CA2015209C - Production of olefins - Google Patents
Production of olefinsInfo
- Publication number
- CA2015209C CA2015209C CA002015209A CA2015209A CA2015209C CA 2015209 C CA2015209 C CA 2015209C CA 002015209 A CA002015209 A CA 002015209A CA 2015209 A CA2015209 A CA 2015209A CA 2015209 C CA2015209 C CA 2015209C
- Authority
- CA
- Canada
- Prior art keywords
- olefins
- mixture
- propylene
- conversion
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to the conversion of saturated paraffin hydrocarbons having 4 or more carbon atoms to olefins having fewer carbon atoms. In particular, the invention provides for contact of a mixture of 40 to 95 wt % paraffin hydrocarbons having 4 or more carbon atoms and 5 to 60 wt % olefins having 4 or more carbon atoms with solid zeolitic catalyst such as ZSM-5 at conditions effective to form propylene and the separation of light olefins from the reaction mixture.
Description
2 ~
PRODUCTION OF OLEFINS
Background of the Invention Field of the Invention The present invention relates to the conversion of saturated paraffinic hydrocarbons to olefins having fewer carbon atoms. In particular, the invention provides for contact of a mixture of saturated and unsaturated hydrocar~ons comprised of 40~ to 95% saturated hydrocarbons with solid zeolitic catalyst such as ZSM-5 at conditions effective to form propylene. In preferred practice, light olefins are separated from the reaction mixture, and unreacted saturated feed and product olefin other than the desired light olefin~ product are recycled for further reactive contact over the zeollte cataly~t.
Degcri~tion o~ ~he Prior Art M-thods are currently known for the productlon o~
commercially important olefins such as propylene from parafflnic feed materials. Such methods include steam cracking, propane dehydrogenation, and various refinery catalytic cracking operations.
.
.
2 ~
Each of these procedures has certain disadvantages For example, propylene yields from steam cracking are not very high, and are not substantially improved by recycling Purification of non-propylene products is required which is costly or such products have only fuel value Propane dehydrogenation processes are characterized by rapid catalyst coking requiring frequent, costly regenerations Also, reasonable conversions require sub-atmospheric pressures, and propane is difficult to separate from propylene Propylene supplies from catalytic conversions are uncertain Transportation and purification are significant problems.
SummarY of the Invention The present invention provides an improved process for the selective production of propylene from C4 and higher saturated paraf~in hydrocarbon feed, especially C5-C20 paraffin According to th- invention, the saturated paraffin feed is combined with 5-60 wt ~ of olefins having 4 to 20 carbon atom- and th- mixture contact-d with a zeolitic cataly-t such as ZSM-5, at condltions which favor propylene formatlon, i ~ high temperatur- and low con~r~ion per pa--, and low hydlocarbon partial p~ ~r-- Preferably combined with the saturated fe-d hydrocarbon i~ a recycle stream cont~n~ng unreacted f-ed a~ well as C4+ olefins which are formed during the contact with the zeolitic , , ,: :,.i ... . .. .
' , : ,. ' : :'. .. ~ . '.
. , - : . . . . . .
2~2~
_3_ catalyst and which are not the desired reaction product Surprisingly, conditions which favor propylene formation from the saturated paraffin hydrocarbons also favor propylene formation from butenes and higher olefins, thus providing enhanced selectivity and yields through practice of the invention It has been found that the provision of olefins in the feed mixture in the designated amounts results in a very substantial enhancement of saturated hydrocarbon conversion Descri~tion of Drawing The attached drawing illustrates in schematic fashion pre~erred practice of the invention Detailed Description of the Invention Although it is known to convert paraffins to lower olefin-containing mixtures, as above described, prior p~ocedures have not been entirely satisfactor~ Yields via steam cracking are not high Paraffins can be converted by reaction over acedic zeolite~, but onc- again yields are not high In accordance with the inv-ntion, saturatQd hydrocarbon cGAv~r-lon to ~olubl- light olefins can b- dramatically im~ov~ by lncorporat-d C4 to C20 ol-fins in the feed mlxtur- and pas~ing the resulting mix-d f--d ov-r a zeolitic catalyst at conditlon~ favoring propyl-n- formation 2S Saturated hydrocarbons employed a~ feed ar- paraffins havlng at least four carbon atoms and ar- preferably C5 to .. ... ..
. -. .. ~ . ; ;
,, , . .
2 ~ ~
C20 paraffins. It is essential that the feed mixture to the conversion zone contain between 40 and 95 wt.% of these paraffins based on the total of paraffins and olefins for the advantages of the present invention to be realized.
Combined with the paraffins in the conversion feed mixture are C4 to C20 olefins in amount of 5 to 60 wt.%
based on the total of paraffins and olefins, preferably 10 to 50 wt.~ olefins.
The feed mixture may also contain aromatics, naphthenes and inerts such as nitrogen, but the benzene content should not exceed 30 wt.% of the total feed. At benzene concentrations above 40 wt.%, alkylation becomes significant and light olefin yields are reduced. The feed mixture may also contain steam in amount up to 30 mol. %, preferably 1 to 20 mol. ~.
The accompanying drawing illustrates a particularly preferred practice of the invention involving recycle of C4 and higher olefins formed during the paraffin conversion.
Referring to the drawing, the paraffin hydrocarbon feedstock, e.g., C6-C20 paraffin hydrocarbons, pa98e8 via line 1 to reaction zone 2. Recycle compri~ed of unreacted paraffins and C4+ olefins pa~se~ via line 3 and is combined with ths net paraffin feed to form a mixture of 40 to 95 wt.% paraffins, and this mixture i~ fed to zone 2. In zone 2 the mixed hydrocarbon feedstock is contacted with the zeollte solid contact catalyst at reaction conditions which ~' , ' ' ' ' .
, ' ' : ' ' ~,~, .
2~ 2~
favor production of propylene from both the paraffin and olefin feed materials Conditions favoring propylene production involve low hydrocarbon partial pressure, high temperatures and low per pass conversions as described later The product mixture from reaction zone 2 passes via line 4 to separation zone 5 wherein the components of the product mixture are separated by conventional means such as fractional distillation An overhead mixed ethylene and propylene stream is removed from zone 5 via line 6 and comprises the preferred product mixture Higher boiling compounds are removed via lin- 7; a small purge of hydrocarbons suitable as gasoline blsn~ng stock is separated as by distillation (not shown) via line 8 with the remainder ot the materials boiling higher than propylene being recycled via line 3 ~or further r-action in zone 2 after being combined with the fresh pararfin feed intro~ucs~ via lin- 1 In ord-r to more clearly d-scrib- th- invention particularly tn comparison to pr~c~ r-- whlch ar- not in accordance with th- lnvention, rer-r-nce i~ made to the rollowlng example-Comparative ~Y~mpl- A
H ZSM-5, 20 x 40 me~h, in amount Or 0 25 grams was admlxed with 3 5 grams or similar m-sh siz- alpha alumina and loaded into a 36 inch tubular reactor made from 5/8 inch .
~ . ; ; .
~3 ~9 OD tubing having 0.065 inch wall thickness. Reactor heating was by an electric tube furnace.
Normal octane was fed to the top of the reactor where it was preheated to 510~C before contacting the catalyst.
Conditions in the catalyst bed were maintained at about S27~C and 6 psig. octane feed rate was 250 cc/hr giving a WHSV of about 700 hr~l based on the ZSM-S. Residence time was about 0.1 second.
The reactor was operated for 1 hour between regenerations. Regeneration consisted of feeding 5% ~2 for 28 minutes and full air for 28 minute~ followed by 4 minutes o~ nitrogen purge.
~ : . .. ... -,, . :
''i. '''. '. ~
Octane conversion was 22%, and the wt. % selectivities achieved on a hydrogen-free and coke-free basis were:
Methane 0.4 S Ethylene 4.59 Ethane 2.03 Propylene 15.55 Propane 9.95 Butenes 21.89 3utanes 16.14 Pentenes 9.77 Pentanes 6.36 C6~s 3.46 C7's 2.93 Cg+ 6.94 Example 1 Comparative Example A was repeated except that, pursuant to the instant invention, an equal volume of the C4+ reaction producte (containing unreacted octane and olefins) wae continuou~ly recycled to the roaction and combin-d with the fresh octane ~eed. The combined ~eed contAlned 2.4 wt.% propylene and 7.2 wt.% C4 plus C5 olefins. The n-octane concsntration in the combined feed was 85 wt.%. Residence time was 0.05 ss~:n~. The WHSV
including the recycle was about 1400 hr 1, : .
PRODUCTION OF OLEFINS
Background of the Invention Field of the Invention The present invention relates to the conversion of saturated paraffinic hydrocarbons to olefins having fewer carbon atoms. In particular, the invention provides for contact of a mixture of saturated and unsaturated hydrocar~ons comprised of 40~ to 95% saturated hydrocarbons with solid zeolitic catalyst such as ZSM-5 at conditions effective to form propylene. In preferred practice, light olefins are separated from the reaction mixture, and unreacted saturated feed and product olefin other than the desired light olefin~ product are recycled for further reactive contact over the zeollte cataly~t.
Degcri~tion o~ ~he Prior Art M-thods are currently known for the productlon o~
commercially important olefins such as propylene from parafflnic feed materials. Such methods include steam cracking, propane dehydrogenation, and various refinery catalytic cracking operations.
.
.
2 ~
Each of these procedures has certain disadvantages For example, propylene yields from steam cracking are not very high, and are not substantially improved by recycling Purification of non-propylene products is required which is costly or such products have only fuel value Propane dehydrogenation processes are characterized by rapid catalyst coking requiring frequent, costly regenerations Also, reasonable conversions require sub-atmospheric pressures, and propane is difficult to separate from propylene Propylene supplies from catalytic conversions are uncertain Transportation and purification are significant problems.
SummarY of the Invention The present invention provides an improved process for the selective production of propylene from C4 and higher saturated paraf~in hydrocarbon feed, especially C5-C20 paraffin According to th- invention, the saturated paraffin feed is combined with 5-60 wt ~ of olefins having 4 to 20 carbon atom- and th- mixture contact-d with a zeolitic cataly-t such as ZSM-5, at condltions which favor propylene formatlon, i ~ high temperatur- and low con~r~ion per pa--, and low hydlocarbon partial p~ ~r-- Preferably combined with the saturated fe-d hydrocarbon i~ a recycle stream cont~n~ng unreacted f-ed a~ well as C4+ olefins which are formed during the contact with the zeolitic , , ,: :,.i ... . .. .
' , : ,. ' : :'. .. ~ . '.
. , - : . . . . . .
2~2~
_3_ catalyst and which are not the desired reaction product Surprisingly, conditions which favor propylene formation from the saturated paraffin hydrocarbons also favor propylene formation from butenes and higher olefins, thus providing enhanced selectivity and yields through practice of the invention It has been found that the provision of olefins in the feed mixture in the designated amounts results in a very substantial enhancement of saturated hydrocarbon conversion Descri~tion of Drawing The attached drawing illustrates in schematic fashion pre~erred practice of the invention Detailed Description of the Invention Although it is known to convert paraffins to lower olefin-containing mixtures, as above described, prior p~ocedures have not been entirely satisfactor~ Yields via steam cracking are not high Paraffins can be converted by reaction over acedic zeolite~, but onc- again yields are not high In accordance with the inv-ntion, saturatQd hydrocarbon cGAv~r-lon to ~olubl- light olefins can b- dramatically im~ov~ by lncorporat-d C4 to C20 ol-fins in the feed mlxtur- and pas~ing the resulting mix-d f--d ov-r a zeolitic catalyst at conditlon~ favoring propyl-n- formation 2S Saturated hydrocarbons employed a~ feed ar- paraffins havlng at least four carbon atoms and ar- preferably C5 to .. ... ..
. -. .. ~ . ; ;
,, , . .
2 ~ ~
C20 paraffins. It is essential that the feed mixture to the conversion zone contain between 40 and 95 wt.% of these paraffins based on the total of paraffins and olefins for the advantages of the present invention to be realized.
Combined with the paraffins in the conversion feed mixture are C4 to C20 olefins in amount of 5 to 60 wt.%
based on the total of paraffins and olefins, preferably 10 to 50 wt.~ olefins.
The feed mixture may also contain aromatics, naphthenes and inerts such as nitrogen, but the benzene content should not exceed 30 wt.% of the total feed. At benzene concentrations above 40 wt.%, alkylation becomes significant and light olefin yields are reduced. The feed mixture may also contain steam in amount up to 30 mol. %, preferably 1 to 20 mol. ~.
The accompanying drawing illustrates a particularly preferred practice of the invention involving recycle of C4 and higher olefins formed during the paraffin conversion.
Referring to the drawing, the paraffin hydrocarbon feedstock, e.g., C6-C20 paraffin hydrocarbons, pa98e8 via line 1 to reaction zone 2. Recycle compri~ed of unreacted paraffins and C4+ olefins pa~se~ via line 3 and is combined with ths net paraffin feed to form a mixture of 40 to 95 wt.% paraffins, and this mixture i~ fed to zone 2. In zone 2 the mixed hydrocarbon feedstock is contacted with the zeollte solid contact catalyst at reaction conditions which ~' , ' ' ' ' .
, ' ' : ' ' ~,~, .
2~ 2~
favor production of propylene from both the paraffin and olefin feed materials Conditions favoring propylene production involve low hydrocarbon partial pressure, high temperatures and low per pass conversions as described later The product mixture from reaction zone 2 passes via line 4 to separation zone 5 wherein the components of the product mixture are separated by conventional means such as fractional distillation An overhead mixed ethylene and propylene stream is removed from zone 5 via line 6 and comprises the preferred product mixture Higher boiling compounds are removed via lin- 7; a small purge of hydrocarbons suitable as gasoline blsn~ng stock is separated as by distillation (not shown) via line 8 with the remainder ot the materials boiling higher than propylene being recycled via line 3 ~or further r-action in zone 2 after being combined with the fresh pararfin feed intro~ucs~ via lin- 1 In ord-r to more clearly d-scrib- th- invention particularly tn comparison to pr~c~ r-- whlch ar- not in accordance with th- lnvention, rer-r-nce i~ made to the rollowlng example-Comparative ~Y~mpl- A
H ZSM-5, 20 x 40 me~h, in amount Or 0 25 grams was admlxed with 3 5 grams or similar m-sh siz- alpha alumina and loaded into a 36 inch tubular reactor made from 5/8 inch .
~ . ; ; .
~3 ~9 OD tubing having 0.065 inch wall thickness. Reactor heating was by an electric tube furnace.
Normal octane was fed to the top of the reactor where it was preheated to 510~C before contacting the catalyst.
Conditions in the catalyst bed were maintained at about S27~C and 6 psig. octane feed rate was 250 cc/hr giving a WHSV of about 700 hr~l based on the ZSM-S. Residence time was about 0.1 second.
The reactor was operated for 1 hour between regenerations. Regeneration consisted of feeding 5% ~2 for 28 minutes and full air for 28 minute~ followed by 4 minutes o~ nitrogen purge.
~ : . .. ... -,, . :
''i. '''. '. ~
Octane conversion was 22%, and the wt. % selectivities achieved on a hydrogen-free and coke-free basis were:
Methane 0.4 S Ethylene 4.59 Ethane 2.03 Propylene 15.55 Propane 9.95 Butenes 21.89 3utanes 16.14 Pentenes 9.77 Pentanes 6.36 C6~s 3.46 C7's 2.93 Cg+ 6.94 Example 1 Comparative Example A was repeated except that, pursuant to the instant invention, an equal volume of the C4+ reaction producte (containing unreacted octane and olefins) wae continuou~ly recycled to the roaction and combin-d with the fresh octane ~eed. The combined ~eed contAlned 2.4 wt.% propylene and 7.2 wt.% C4 plus C5 olefins. The n-octane concsntration in the combined feed was 85 wt.%. Residence time was 0.05 ss~:n~. The WHSV
including the recycle was about 1400 hr 1, : .
3 2 ~ 9 Overall octane conversion was 31% and overall wt %
selectivities on a hydrogen-free and coke-free basis were Methane 0 59 Ethylene 6 32 Ethane 2 s5 Propylene 27 88 Propane 14 90 Butenes 21 34 Butanes 6 86 Pentenes 5 66 Pentanes 4 70 C6's 2 28 C7'9 2 06 Cg+ 3 96 It will be seen from a comparison of Example l and Comparative Example A that practice of the invention dramatically improved ov-rall octane conversion as well as ov-rall propylene ~electivity The butane and pentane ~electiviti-s w r- ~harply ~-du~-~
~Qm~ratlv- ~Y~
Comparativ- Exa~pl- A wa- r-p-ated r~ Ft that the feed W~8 ci-/trana but-ne-2 rather than n-octane ~utene conver~ion was 65% and th- wt % selectivities on ~ . - ,~ . i , . . .
a hydrogen-free and coke-free basis were:
Methane 0.05 Ethylene - 4.26 Ethane 0.12 Propylene 29.55 Propane 3.20 Butanes 6.56 C5+ 56.26 This Comparative Example B demonstrates about the same selectivity to propylene as Example 1 and illustrates that surprisingly both saturated hydrocarbons and olefins are converted to propylene with good efficiency at the same reaction conditions.
.
, .
Com~arative Exam~le C
A full range naptha (C5 to C12), condensed from an Algerian natural gas well, was fed to a steam cracker at an 0 75 steam to oil ratio The weight % yields are shown 5 below at the indicated coil temperatures Coil Outlet Temp, ~C 815 849 Yields, wt %
~ydrogen 0 8 1 0 Methane 12 8 16 S
Acetylene 0 3 0 6 Ethylene 25 0 30 0 Ethane 3 7 3 4 Methylacetylene/Propadiene 0 6 0 7 Propylene 16 9 12 1 Propane 0,7 0 5 Butenes 5 7 3 2 Butanes 1 1 0 4 Butadiene 4 6 3 9 CS g 5 4 3 2 Benzene 6 6 9 1 Toluene 3 7 4 1 C8 Aromatics 2 5 2 7 C6lto C8 Non-aromatics 4 1 1 0 Cg 5 5 7 5 Comn~rativo Exam~le D
0 15 gramJ o~ ZSM-5 catalyst, 100 x 140 mesh was mixed with 4 5 grams o~ Alcoa T-64 alpha alumina and loaded into the reactor Or Example A The r-actor was heatQd with an ~lectric tub- ~urnac- Temp-ratures in the catalyst bed w-r- m-asur-d with an axial thermowell Algerian condensate as in Exampl- C was pumped into the top o~ the reactor at the rate o~ 60 cc/hr The catalyst bed was maintaine~ at 621~C and 0 5 psig The gas and llguid reaction products .. . ~ ~ ' ' .: , "" ~ :
i., .
~,.
: , ., , ~ , ~: , , . ; -. ~ , . . ..
--ll--were analyzed and the results are shown below:
overall conversion, % 54 Yield, Wt%
Methane 3.8 Ethylene 9.8 Ethane 3.5 Propylene 18.3 Propane 2.3 Butenes 8.2 Butane 4.3 Butadiene 0.2 C5 olefins 2.5 C5 paraffins 1.1 C6+ aromatics 3.3 C6+ paraffins (unreacted feed) 42.7 Exam~le 2 The process of the present invention was carried out using the Algerian condensate al~o used in Comparative Example~ C and D. Conditions of the reaction were the same as tho~e in Comparative Example D. In carrying out the process, effluent from the reactor was distilled to separate a C3 and lighter product stream from a C4 and heavier stream which was recycled. The volume ratio of fresh feed to - - ~ , . . .
~ . . . ..
. ' . . ~ . ~ ,, ' .: .. ,,' .
- .: , .: . .
, . .
2 ~ ~ ~ 6~
recycle was varied The results achieved are as follows Recycle Ratio Recycle/Fresh Feed 1 0 2 0 4 0 Overall Yields, wt %
(based on fresh feed) Methane 6 1 6 7 7 0 Ethylene 16 3 18 2 19 2 Ethane 5 6 6 1 6 4 Propylene 32 9 37 5 40 1 Propane 3 9 4 3 4 6 Butanes 7 3 8 2 8 8 Bu~enes 4 6 2 5 1 2 As shown in Comparative Example C, steam cracking is capable of a 17% propylene yield and this will not increase b-yond 20~ with recycle becausQ the once through C4+ steam cracking products are not well suited for making propylene Through practice o~ the present invention, propylene yields as high as 40% can be achieved thus demonstrating the surprising superiority of the invention ÇQmnArative Exam~le E
10 0 grAm~ o~ Intercat Zcat-plu~, 40XCO m-sh, was loaded into a 3/4" ID Alumlna tub- Th- cat_lyst bed was surport-d with a 1/2" OD alumin_ tub- ~rom the bottom A
lay-r o~ D-nston- 57 inert spheres wa~ placed on top The ceramic tub- wa~ plac-d insid- a 1 8" OD stainless steel shield The entire assembly wa~ mounted in an electric tube ~urnace 93 g~/hr o~ n-butane and 6 gm/hr o~ distilled water were ~ed to the catalyst bed, which was maintained at ., ~ , ~ . .
;, ... ..
2~ 3.
about 593~C and 1 psig. After 30 minutes the butane ~eed was stopped and the catalyst bed was regenerated using air, steam and nitrogen. The regeneration was conducted for 30 minutes also. Following this, the reaction-regeneration cycle would repeat indefinitely, until steady state was searched. When steady state was reached, the following data were obtained:
Conversion of N-butane, ~ 7.2 10.9 10 Selectivity, wt %
Methane 14.05 15.90 Ethylene 15.66 19.14 Ethane 12.51 10.23 Propylene 38.35 40.72 15 Propane 1.21 1.62 Butanes 16.12 9.54 IsobutanQ 0.80 0.24 Pentenes ~-~ 0-93 Pentanes o.o o.o 20 c6+ 0.25 0.79 Com~arative Exam~le F
The procedure of Example E above was repeated, except the temperature was raised to 635~C and the feed was changed to isobutane.
~ .
;. . ' Conversion of Isobutane, %16 1 Selectivity, wt %
Methane 12 6 Ethylene 3 7 s Ethane 0 26 Propylene 34 13 Propane 1 95 n-butane 1 38 Butenes 39 21 c5+ 6 77 Example 3 Using the same procedure as Example E, gasoline hydrocarbon mixture was fed to the catalyst bed at a rate of 108 grams per hour The temperature and pre~sure in the catalyst bed were maintained at 593~C and 2 psig, Livsly The feed, analyzed by FIA and GC had the ~ollowing - ,_sition Olefins 10 5 vol% Isobutane 3 6 Wt%
Saturates 61 0% N-butan- S 6%
Aromatlcs 28 5% Pentanes 15 3%
At steady state, the overall conv-rsion was 20 3% The compor- t s-l-ctlvities and conv-rsions are p~e~ ed below ... . ..
2~ 7 Component Selectivity, wt % Conversion H2 + Coke1 44 Methane3 68 Ethylene16 20 Ethane 2 97 Propylene42 02 Propane2 67 Isobutane 32 3 N-butane 21 9 Butenes12 32 Pentenes 62 4 Pentanes 19 4 C6's 33 2 Benzene5 44 C7 s 36 7 Toluene7 23 C8 Non-Aromatics 21 7 C8 Aromatics 4 28 C9+ 1 52 Comparing Example 3 with Examples E and F indicates that th- con~rslons Or N-butane and lsobutane are doubled ~n th- presqnce Or oler1ns - . . ,~. .
. .
, . .~ - ~
~ & ~
Example 4 A C4-C6 cut was taken from an ECC unit and reacted using the same procedure as Example E. The olefin concentration in this stream was 55 wt%. The balance was paraffins, including 17.1 wt% isobutane and 7.6 wt% n-butane. 100 gm/hr of this mixture was fed to the catalyst bed, which was held at 593~C and 1 psig. The results are summarized below:
. . .. ..
~ 5~c3~
Overall Conversion: 34%
Component Selectivity, wt ~ Conversion, %
Methane 1.51 Ethylene 16.04 Ethane 0.60 Propylene 53.22 Propane 2.10 Isobutane 25.5 BD 59.3 N-butane 3.2 Butenes 46.0 Pentenes 59.2 Pentanes 14.36 C6's 35.0 benzene 1.84 C7~8 2.86 Toluene 4.10 C8 3.18 The isobutane conversion here is nearly double that of ExamplQ E, in spite of the lower tempQrature and lower isobutane concentration. This suggests olefins in the feed are increasing the rats of paraffin consumption.
, ~ , . , ;
: . .. . ~. . "-- . .
. . ~. , .
~, . - , .
Com~arative Example G
BT Raffinate, containing the components listed below, was reacted according to the procedure of Example E at feed rate of 210 gm/hr:
Feed, wt%
Butenes 0.19 Pentenes 0.21 Pentanes 5.91 HPY~nes 65.88 Benzene 1.51 Hextanes 19.20 Toluene 2.10 C8+ 3.00 The total olefin content o~ this stream is 0.4 wt~.
The catalyst bed was maint~1ned at 538~C and 9 psig. The results are shown below:
" , . , . . .,, . ".. " ,, 2~5~
Component Selectivity, wt % Conversion, %
Coke + H2 1.25 Methane 2.82 Ethylene 7.84 Ethane 3-35 Propylene38.05 Propane 4.45 Butenes 28.65 Butanes 1.40 Pentenes 7.80 Pentanes 2.99 ~eYAne~ 15.04 Benzene 1.53 Hextanes 18.13 Toluene 1.71 c8+ 2.87 The relative conversions o~ C5, C6 and C7 paraf~inY are not surpri~ing, ~ince reactlvity ino w ~ with molecular w-ight.
~. : . , . . ..
,. . . - . , ~ , .
2~ 2~
Exam~le 5 According to the invention, a c4-C6 cut containing 55 wt% olefins was taken from an FCC unit and fed according to the procedure of Example E at the rate of 195 gm/hr The 5 composition of the stream is presented below Feed, wt%
Propylene 0 10 Propane 0 14 Isobutane 17 11 N-butane 1 60 Butenes 39 23 Pentenes 16 36 Pentanes 13 80 The catalyst bed was maintAine~ at 538~C and 9 psig The C3 and lighter portion of the reactor e~luent was separated by cont~n~ol~ rractionation and removed as product The C4~ portlon o~ the e~rluent was recycled back to th- r-actor inl-t at a rate Or 256 gm/hr and mix-d wlth th- rr-~h r--d prior to contact wlth th- catalyst bed, bringing th- total reed rate to 451 gm/hr The composition - . . ....
. , , . ~ .
2 ~ ~
of the combined feed is shown below:
Feed, wt%
Propylene 1.61 Propane 0.06 Isobutane 13.25 N-butane 7.59 Butenes 26.39 Pentenes 21.49 Pentanes 15.27 C6 14.34 The total concentration of olef$ns in the reactor feed was 49.5 wt%.
The overall conversion of the fresh feed was 32%. The overall selectivities and component conver~ion~ are shown below:
. . .
", Overall Selectivity, wt% Overall Conversion %
Methane 0.26 Ethylene 11.05 Ethane 0.23 Propylene 75.09 Propane 1.83 Isobutane 6.35 N-butane 3.65 Butenes 56.03 Pentenes 26.53 Pentanes 29.56 C6+ 11.43 Comparing Example G with Example 5 shows tho increase in C5 paraffin conversion resulting from the prosence of olefins in the feed. It is surprising that the C5 paraffin conversion in Example 5 is ten times higher than Example G, in spite of the fact that tho space volocity is twics ais high. This result show~ the beneficial effoct of olefins on the conversion of parafrins.
Exam~le H
The procedure of Example E was repeated, except the feed was isobutane, the temperature was raised to 635~C and the pressure was raised to 12 psig.
Conversion of Isobutane, % 23.7 Selectivity, wt%
Methane 12.47 Ethylene 8.03 Ethane 0.62 Propylene 35.83 Propane 4.26 N-butane 1.77 Butenes 29.02 c5+ 5.96 Exam~le 6 Example 4 was repeated, except at 12 psig pressure.
The overall conversion was 42.3%
';
2 ~
component Selectivity, wt % conversion, %
Methane 7.9 Ethylene 18.8 Ethane 2.6 Propylene 51. 4 Propane 4.6 Isobutane 33.1 BD 57.8 N-butane 13.5 Butenes 61.8 Pentenes 65.7 Pentanes 2.8 C6+ 11.4 A comparison of Example 6 with example H shows that the isobutane conversion in Example 6 is measurably higher even though the temperature was 24~C lower. This is due to the olefins present in the f~ed to Example 6.
Saturated paraffin hydrocarbons used as feed in accordance wlth the invention are those having 4 or more carbon atoms, especially C5-C20. Individual hydrocarbons or mlxtures can be employed. Preforred hydro¢arbons are those having fro~ about 6 to 20 carbons, espocially petroleum ~: .
.: ..' ' ' 2 ~
fractions for reasons of costs. Specific hydrocarbons include hexane, the methyl pentanes, cetane, etc.
The conversion is carried out at elevated temperatures in the range of about 400 to 800~C, preferably 500 to 700~C.
Low hydrocarbon partial pressures and low conversions per pass favor propylene production. The feed hydrocarbon can be admixed with steam or inert gas such as nitrogen. The hydrocarbon partial pressure is as low as practical, illustratively 1 to 30 psia. Where no diluents are employed, system pressures ranqing from about -12 to 50 psig, preferably -5 to 30 psig are suitable. Higher pressures can be used when diluents are employed.
High space velocity and short residence times are preferred in order to maintain thQ desired low conversions per pass. Para~fin hydrocarbon conversions per pass are le~s than 50%. Space velocities de~- ' on the particular zeolite us-d and are 1 to 5000 preferably S to 200~ hr 1 WHSV. Reactor res1der.~- tim-s are 0.001 to 20 ~Dnd~, pref-rably 0.01 to 5 ss~n~.
The conversion reaction of the instant invention i~ highly endothermic. Preferably fluidized solid catalyst conv~r-lon proc-dure~ are uaed with th- f-ed hyd~oc~rbon vapor contacting fluidized particle~ of the zeolite 2S catalyst. Heat necs~s~ry to maintain th- reaction is provided by separately heating the catalyst particles in a 2 ~ r~
fluidized regeneration zone as by combustion of appropriate fuel hydrocarbon.
Fixed bed procedures can be employed. In such cases, the use of reaction zones in series with interstage heating is advantageous.
Zeolite catalysts used in the invention can be silaceous, crystalline molecular sieves. Such silica-containing crystalline materials include materials which contain, in addition to silica, significant amounts of alumina. These crystalline materials are frequently named "zeolites, i.e., crystalline aluminosilicates. Silica-containing crystalline materials also include essentially aluminum-free silicates. These crystalline materials are exemplified by crystalline silica polymorphs (e.g., silicalite, disclosed in U.S. Pat. No. 4,061,724 and organosilicates, disclosed ln U.S. Pat. No. Re. 29948), chromia silicatQs (e.g., CZM), ferrosilicates and galliosilicates (see U.S. Pat. No. 4,238,318), and borosilicates (see U.S. Pat. Nos. 4,226,420; 4,269,813: and 4,327,236).
Crystalllne aluminosillcate zQolltes are best exemplifiod by ZSM-5 (see U.S. Pat. Nos. 3,702,886 and 3,770,614), ZSM-ll (see U.S. Pat. No. 3,709,979), ZSM-12 (see U.S. Pat. No. 3,832,449), ZSM-21 and ZSM-38 (see U.S.
Pat. No. 3,948,7S8), ZSM-23 (seo U.S. Pat. No. 4,076,842), and ZSM-3S (see U.S. Pat. No. 4,016,246).
.: ' . .
. , . :
'. ' " ~ .
2~ ~,9 Phosphorous containing zeolites are suitably used (see u S> Patent 3,972,832) and in such cases it is especially advantageous to add steam to the feed mixture Acid aeolites are especially preferred, particularly the ZSM type and borosilicates ZSM-5 is especially useful In addition to the above, zeolite containing materials can be used Representative of such materials are zeolite A (U S Patent 2,882,243), zeolite X (U S Patent 2,882,244), zeolite Y (U S Patent 3,130,007), zeolite ZK-5 (U S Patent 3,247,195), zeolite ZK-4 (U S Patent 3,314,752), synthetic mordenite, and dealuminized mordenite, as well as naturally occurring zeolites, including chabazite, fau;asite, mordenite, and the like In general, the zeolites are ordinarily ion exchanged with a desired cation to replace alkali metal present in the zeolite as found naturally or as synthetically prepared The eY~Ange treatment is such as to reduce the alkali m-tal cont-nt ot the flnal catalyst to l-oo than about 1 5 w-lght p-rc-nt, and pr-f-rably less than about 0 5 w-ight p-rc-nt Pref-rr-d exchanging cations are hyd~ , a~moniu~, rare earth metals and mixtures thereof, with particular preference belng accorded rare earth metals Ion exchange 19 suitably accomplished by conventional contact of the zeolite with a suitable salt solution of the 2 ~ ~ ~ rg ~ ~
desired cation, such as, for example, the sulfate, chloride or nitrate salts It is preferred to have the crystalline zeolite of a suitable matrix, since the catalyst form is generally characterized by a high resistance to attrition, high activity and exceptional steam stability Such catalysts are readily prepared by dispersing the crystalline zeolite in a suitable siliceous sol and gelling the sol by various means The inorganic oxide which serves as the matrix in which the above crystalline zeolite is distributed includes silica gel or a cogel of silica and a suitable metal oxide Representative cogels include silica-aluminia, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary combinations, such as silica-alumina- - lesia, silica-aluminia-zirconia and silica-magnesia-zirconia Preferred cogels include silica-alumina, silica-zirconia or ~ilica-alumina-zirconia The above gQls and cogels will gen-rally comprise a major proportion Or silica and a minor proportion of the other a~orem-ntioned oxid- or oxide~ Thu~, tho ~ilica content of th- sillceou~ q-l or coq-l matrix will generally ~all within th- rang- o~ 55 to lO0 weight percent, preferably 60 to 95 w-ight perc-nt, and the other metal oxide or oxides content will generally be within th- rang- o~ 0 to 45 weight p-rc-nt, and pre~erably 5 to 40 weight percent In addition to the above, the matrix may also compri~- natural or . . . .
. . .. . .
.. ... .
- , - .. . . . ..
-, 2 3 ~iL r ~
synthetic clays, such as kaolin type clays, montmorillonite, bentonite or halloysite. ~hese clays may be used either alone or in combination with silica or any of the above specified cogels in a matrix formulation.
:. , .:, . , . .
selectivities on a hydrogen-free and coke-free basis were Methane 0 59 Ethylene 6 32 Ethane 2 s5 Propylene 27 88 Propane 14 90 Butenes 21 34 Butanes 6 86 Pentenes 5 66 Pentanes 4 70 C6's 2 28 C7'9 2 06 Cg+ 3 96 It will be seen from a comparison of Example l and Comparative Example A that practice of the invention dramatically improved ov-rall octane conversion as well as ov-rall propylene ~electivity The butane and pentane ~electiviti-s w r- ~harply ~-du~-~
~Qm~ratlv- ~Y~
Comparativ- Exa~pl- A wa- r-p-ated r~ Ft that the feed W~8 ci-/trana but-ne-2 rather than n-octane ~utene conver~ion was 65% and th- wt % selectivities on ~ . - ,~ . i , . . .
a hydrogen-free and coke-free basis were:
Methane 0.05 Ethylene - 4.26 Ethane 0.12 Propylene 29.55 Propane 3.20 Butanes 6.56 C5+ 56.26 This Comparative Example B demonstrates about the same selectivity to propylene as Example 1 and illustrates that surprisingly both saturated hydrocarbons and olefins are converted to propylene with good efficiency at the same reaction conditions.
.
, .
Com~arative Exam~le C
A full range naptha (C5 to C12), condensed from an Algerian natural gas well, was fed to a steam cracker at an 0 75 steam to oil ratio The weight % yields are shown 5 below at the indicated coil temperatures Coil Outlet Temp, ~C 815 849 Yields, wt %
~ydrogen 0 8 1 0 Methane 12 8 16 S
Acetylene 0 3 0 6 Ethylene 25 0 30 0 Ethane 3 7 3 4 Methylacetylene/Propadiene 0 6 0 7 Propylene 16 9 12 1 Propane 0,7 0 5 Butenes 5 7 3 2 Butanes 1 1 0 4 Butadiene 4 6 3 9 CS g 5 4 3 2 Benzene 6 6 9 1 Toluene 3 7 4 1 C8 Aromatics 2 5 2 7 C6lto C8 Non-aromatics 4 1 1 0 Cg 5 5 7 5 Comn~rativo Exam~le D
0 15 gramJ o~ ZSM-5 catalyst, 100 x 140 mesh was mixed with 4 5 grams o~ Alcoa T-64 alpha alumina and loaded into the reactor Or Example A The r-actor was heatQd with an ~lectric tub- ~urnac- Temp-ratures in the catalyst bed w-r- m-asur-d with an axial thermowell Algerian condensate as in Exampl- C was pumped into the top o~ the reactor at the rate o~ 60 cc/hr The catalyst bed was maintaine~ at 621~C and 0 5 psig The gas and llguid reaction products .. . ~ ~ ' ' .: , "" ~ :
i., .
~,.
: , ., , ~ , ~: , , . ; -. ~ , . . ..
--ll--were analyzed and the results are shown below:
overall conversion, % 54 Yield, Wt%
Methane 3.8 Ethylene 9.8 Ethane 3.5 Propylene 18.3 Propane 2.3 Butenes 8.2 Butane 4.3 Butadiene 0.2 C5 olefins 2.5 C5 paraffins 1.1 C6+ aromatics 3.3 C6+ paraffins (unreacted feed) 42.7 Exam~le 2 The process of the present invention was carried out using the Algerian condensate al~o used in Comparative Example~ C and D. Conditions of the reaction were the same as tho~e in Comparative Example D. In carrying out the process, effluent from the reactor was distilled to separate a C3 and lighter product stream from a C4 and heavier stream which was recycled. The volume ratio of fresh feed to - - ~ , . . .
~ . . . ..
. ' . . ~ . ~ ,, ' .: .. ,,' .
- .: , .: . .
, . .
2 ~ ~ ~ 6~
recycle was varied The results achieved are as follows Recycle Ratio Recycle/Fresh Feed 1 0 2 0 4 0 Overall Yields, wt %
(based on fresh feed) Methane 6 1 6 7 7 0 Ethylene 16 3 18 2 19 2 Ethane 5 6 6 1 6 4 Propylene 32 9 37 5 40 1 Propane 3 9 4 3 4 6 Butanes 7 3 8 2 8 8 Bu~enes 4 6 2 5 1 2 As shown in Comparative Example C, steam cracking is capable of a 17% propylene yield and this will not increase b-yond 20~ with recycle becausQ the once through C4+ steam cracking products are not well suited for making propylene Through practice o~ the present invention, propylene yields as high as 40% can be achieved thus demonstrating the surprising superiority of the invention ÇQmnArative Exam~le E
10 0 grAm~ o~ Intercat Zcat-plu~, 40XCO m-sh, was loaded into a 3/4" ID Alumlna tub- Th- cat_lyst bed was surport-d with a 1/2" OD alumin_ tub- ~rom the bottom A
lay-r o~ D-nston- 57 inert spheres wa~ placed on top The ceramic tub- wa~ plac-d insid- a 1 8" OD stainless steel shield The entire assembly wa~ mounted in an electric tube ~urnace 93 g~/hr o~ n-butane and 6 gm/hr o~ distilled water were ~ed to the catalyst bed, which was maintained at ., ~ , ~ . .
;, ... ..
2~ 3.
about 593~C and 1 psig. After 30 minutes the butane ~eed was stopped and the catalyst bed was regenerated using air, steam and nitrogen. The regeneration was conducted for 30 minutes also. Following this, the reaction-regeneration cycle would repeat indefinitely, until steady state was searched. When steady state was reached, the following data were obtained:
Conversion of N-butane, ~ 7.2 10.9 10 Selectivity, wt %
Methane 14.05 15.90 Ethylene 15.66 19.14 Ethane 12.51 10.23 Propylene 38.35 40.72 15 Propane 1.21 1.62 Butanes 16.12 9.54 IsobutanQ 0.80 0.24 Pentenes ~-~ 0-93 Pentanes o.o o.o 20 c6+ 0.25 0.79 Com~arative Exam~le F
The procedure of Example E above was repeated, except the temperature was raised to 635~C and the feed was changed to isobutane.
~ .
;. . ' Conversion of Isobutane, %16 1 Selectivity, wt %
Methane 12 6 Ethylene 3 7 s Ethane 0 26 Propylene 34 13 Propane 1 95 n-butane 1 38 Butenes 39 21 c5+ 6 77 Example 3 Using the same procedure as Example E, gasoline hydrocarbon mixture was fed to the catalyst bed at a rate of 108 grams per hour The temperature and pre~sure in the catalyst bed were maintained at 593~C and 2 psig, Livsly The feed, analyzed by FIA and GC had the ~ollowing - ,_sition Olefins 10 5 vol% Isobutane 3 6 Wt%
Saturates 61 0% N-butan- S 6%
Aromatlcs 28 5% Pentanes 15 3%
At steady state, the overall conv-rsion was 20 3% The compor- t s-l-ctlvities and conv-rsions are p~e~ ed below ... . ..
2~ 7 Component Selectivity, wt % Conversion H2 + Coke1 44 Methane3 68 Ethylene16 20 Ethane 2 97 Propylene42 02 Propane2 67 Isobutane 32 3 N-butane 21 9 Butenes12 32 Pentenes 62 4 Pentanes 19 4 C6's 33 2 Benzene5 44 C7 s 36 7 Toluene7 23 C8 Non-Aromatics 21 7 C8 Aromatics 4 28 C9+ 1 52 Comparing Example 3 with Examples E and F indicates that th- con~rslons Or N-butane and lsobutane are doubled ~n th- presqnce Or oler1ns - . . ,~. .
. .
, . .~ - ~
~ & ~
Example 4 A C4-C6 cut was taken from an ECC unit and reacted using the same procedure as Example E. The olefin concentration in this stream was 55 wt%. The balance was paraffins, including 17.1 wt% isobutane and 7.6 wt% n-butane. 100 gm/hr of this mixture was fed to the catalyst bed, which was held at 593~C and 1 psig. The results are summarized below:
. . .. ..
~ 5~c3~
Overall Conversion: 34%
Component Selectivity, wt ~ Conversion, %
Methane 1.51 Ethylene 16.04 Ethane 0.60 Propylene 53.22 Propane 2.10 Isobutane 25.5 BD 59.3 N-butane 3.2 Butenes 46.0 Pentenes 59.2 Pentanes 14.36 C6's 35.0 benzene 1.84 C7~8 2.86 Toluene 4.10 C8 3.18 The isobutane conversion here is nearly double that of ExamplQ E, in spite of the lower tempQrature and lower isobutane concentration. This suggests olefins in the feed are increasing the rats of paraffin consumption.
, ~ , . , ;
: . .. . ~. . "-- . .
. . ~. , .
~, . - , .
Com~arative Example G
BT Raffinate, containing the components listed below, was reacted according to the procedure of Example E at feed rate of 210 gm/hr:
Feed, wt%
Butenes 0.19 Pentenes 0.21 Pentanes 5.91 HPY~nes 65.88 Benzene 1.51 Hextanes 19.20 Toluene 2.10 C8+ 3.00 The total olefin content o~ this stream is 0.4 wt~.
The catalyst bed was maint~1ned at 538~C and 9 psig. The results are shown below:
" , . , . . .,, . ".. " ,, 2~5~
Component Selectivity, wt % Conversion, %
Coke + H2 1.25 Methane 2.82 Ethylene 7.84 Ethane 3-35 Propylene38.05 Propane 4.45 Butenes 28.65 Butanes 1.40 Pentenes 7.80 Pentanes 2.99 ~eYAne~ 15.04 Benzene 1.53 Hextanes 18.13 Toluene 1.71 c8+ 2.87 The relative conversions o~ C5, C6 and C7 paraf~inY are not surpri~ing, ~ince reactlvity ino w ~ with molecular w-ight.
~. : . , . . ..
,. . . - . , ~ , .
2~ 2~
Exam~le 5 According to the invention, a c4-C6 cut containing 55 wt% olefins was taken from an FCC unit and fed according to the procedure of Example E at the rate of 195 gm/hr The 5 composition of the stream is presented below Feed, wt%
Propylene 0 10 Propane 0 14 Isobutane 17 11 N-butane 1 60 Butenes 39 23 Pentenes 16 36 Pentanes 13 80 The catalyst bed was maintAine~ at 538~C and 9 psig The C3 and lighter portion of the reactor e~luent was separated by cont~n~ol~ rractionation and removed as product The C4~ portlon o~ the e~rluent was recycled back to th- r-actor inl-t at a rate Or 256 gm/hr and mix-d wlth th- rr-~h r--d prior to contact wlth th- catalyst bed, bringing th- total reed rate to 451 gm/hr The composition - . . ....
. , , . ~ .
2 ~ ~
of the combined feed is shown below:
Feed, wt%
Propylene 1.61 Propane 0.06 Isobutane 13.25 N-butane 7.59 Butenes 26.39 Pentenes 21.49 Pentanes 15.27 C6 14.34 The total concentration of olef$ns in the reactor feed was 49.5 wt%.
The overall conversion of the fresh feed was 32%. The overall selectivities and component conver~ion~ are shown below:
. . .
", Overall Selectivity, wt% Overall Conversion %
Methane 0.26 Ethylene 11.05 Ethane 0.23 Propylene 75.09 Propane 1.83 Isobutane 6.35 N-butane 3.65 Butenes 56.03 Pentenes 26.53 Pentanes 29.56 C6+ 11.43 Comparing Example G with Example 5 shows tho increase in C5 paraffin conversion resulting from the prosence of olefins in the feed. It is surprising that the C5 paraffin conversion in Example 5 is ten times higher than Example G, in spite of the fact that tho space volocity is twics ais high. This result show~ the beneficial effoct of olefins on the conversion of parafrins.
Exam~le H
The procedure of Example E was repeated, except the feed was isobutane, the temperature was raised to 635~C and the pressure was raised to 12 psig.
Conversion of Isobutane, % 23.7 Selectivity, wt%
Methane 12.47 Ethylene 8.03 Ethane 0.62 Propylene 35.83 Propane 4.26 N-butane 1.77 Butenes 29.02 c5+ 5.96 Exam~le 6 Example 4 was repeated, except at 12 psig pressure.
The overall conversion was 42.3%
';
2 ~
component Selectivity, wt % conversion, %
Methane 7.9 Ethylene 18.8 Ethane 2.6 Propylene 51. 4 Propane 4.6 Isobutane 33.1 BD 57.8 N-butane 13.5 Butenes 61.8 Pentenes 65.7 Pentanes 2.8 C6+ 11.4 A comparison of Example 6 with example H shows that the isobutane conversion in Example 6 is measurably higher even though the temperature was 24~C lower. This is due to the olefins present in the f~ed to Example 6.
Saturated paraffin hydrocarbons used as feed in accordance wlth the invention are those having 4 or more carbon atoms, especially C5-C20. Individual hydrocarbons or mlxtures can be employed. Preforred hydro¢arbons are those having fro~ about 6 to 20 carbons, espocially petroleum ~: .
.: ..' ' ' 2 ~
fractions for reasons of costs. Specific hydrocarbons include hexane, the methyl pentanes, cetane, etc.
The conversion is carried out at elevated temperatures in the range of about 400 to 800~C, preferably 500 to 700~C.
Low hydrocarbon partial pressures and low conversions per pass favor propylene production. The feed hydrocarbon can be admixed with steam or inert gas such as nitrogen. The hydrocarbon partial pressure is as low as practical, illustratively 1 to 30 psia. Where no diluents are employed, system pressures ranqing from about -12 to 50 psig, preferably -5 to 30 psig are suitable. Higher pressures can be used when diluents are employed.
High space velocity and short residence times are preferred in order to maintain thQ desired low conversions per pass. Para~fin hydrocarbon conversions per pass are le~s than 50%. Space velocities de~- ' on the particular zeolite us-d and are 1 to 5000 preferably S to 200~ hr 1 WHSV. Reactor res1der.~- tim-s are 0.001 to 20 ~Dnd~, pref-rably 0.01 to 5 ss~n~.
The conversion reaction of the instant invention i~ highly endothermic. Preferably fluidized solid catalyst conv~r-lon proc-dure~ are uaed with th- f-ed hyd~oc~rbon vapor contacting fluidized particle~ of the zeolite 2S catalyst. Heat necs~s~ry to maintain th- reaction is provided by separately heating the catalyst particles in a 2 ~ r~
fluidized regeneration zone as by combustion of appropriate fuel hydrocarbon.
Fixed bed procedures can be employed. In such cases, the use of reaction zones in series with interstage heating is advantageous.
Zeolite catalysts used in the invention can be silaceous, crystalline molecular sieves. Such silica-containing crystalline materials include materials which contain, in addition to silica, significant amounts of alumina. These crystalline materials are frequently named "zeolites, i.e., crystalline aluminosilicates. Silica-containing crystalline materials also include essentially aluminum-free silicates. These crystalline materials are exemplified by crystalline silica polymorphs (e.g., silicalite, disclosed in U.S. Pat. No. 4,061,724 and organosilicates, disclosed ln U.S. Pat. No. Re. 29948), chromia silicatQs (e.g., CZM), ferrosilicates and galliosilicates (see U.S. Pat. No. 4,238,318), and borosilicates (see U.S. Pat. Nos. 4,226,420; 4,269,813: and 4,327,236).
Crystalllne aluminosillcate zQolltes are best exemplifiod by ZSM-5 (see U.S. Pat. Nos. 3,702,886 and 3,770,614), ZSM-ll (see U.S. Pat. No. 3,709,979), ZSM-12 (see U.S. Pat. No. 3,832,449), ZSM-21 and ZSM-38 (see U.S.
Pat. No. 3,948,7S8), ZSM-23 (seo U.S. Pat. No. 4,076,842), and ZSM-3S (see U.S. Pat. No. 4,016,246).
.: ' . .
. , . :
'. ' " ~ .
2~ ~,9 Phosphorous containing zeolites are suitably used (see u S> Patent 3,972,832) and in such cases it is especially advantageous to add steam to the feed mixture Acid aeolites are especially preferred, particularly the ZSM type and borosilicates ZSM-5 is especially useful In addition to the above, zeolite containing materials can be used Representative of such materials are zeolite A (U S Patent 2,882,243), zeolite X (U S Patent 2,882,244), zeolite Y (U S Patent 3,130,007), zeolite ZK-5 (U S Patent 3,247,195), zeolite ZK-4 (U S Patent 3,314,752), synthetic mordenite, and dealuminized mordenite, as well as naturally occurring zeolites, including chabazite, fau;asite, mordenite, and the like In general, the zeolites are ordinarily ion exchanged with a desired cation to replace alkali metal present in the zeolite as found naturally or as synthetically prepared The eY~Ange treatment is such as to reduce the alkali m-tal cont-nt ot the flnal catalyst to l-oo than about 1 5 w-lght p-rc-nt, and pr-f-rably less than about 0 5 w-ight p-rc-nt Pref-rr-d exchanging cations are hyd~ , a~moniu~, rare earth metals and mixtures thereof, with particular preference belng accorded rare earth metals Ion exchange 19 suitably accomplished by conventional contact of the zeolite with a suitable salt solution of the 2 ~ ~ ~ rg ~ ~
desired cation, such as, for example, the sulfate, chloride or nitrate salts It is preferred to have the crystalline zeolite of a suitable matrix, since the catalyst form is generally characterized by a high resistance to attrition, high activity and exceptional steam stability Such catalysts are readily prepared by dispersing the crystalline zeolite in a suitable siliceous sol and gelling the sol by various means The inorganic oxide which serves as the matrix in which the above crystalline zeolite is distributed includes silica gel or a cogel of silica and a suitable metal oxide Representative cogels include silica-aluminia, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary combinations, such as silica-alumina- - lesia, silica-aluminia-zirconia and silica-magnesia-zirconia Preferred cogels include silica-alumina, silica-zirconia or ~ilica-alumina-zirconia The above gQls and cogels will gen-rally comprise a major proportion Or silica and a minor proportion of the other a~orem-ntioned oxid- or oxide~ Thu~, tho ~ilica content of th- sillceou~ q-l or coq-l matrix will generally ~all within th- rang- o~ 55 to lO0 weight percent, preferably 60 to 95 w-ight perc-nt, and the other metal oxide or oxides content will generally be within th- rang- o~ 0 to 45 weight p-rc-nt, and pre~erably 5 to 40 weight percent In addition to the above, the matrix may also compri~- natural or . . . .
. . .. . .
.. ... .
- , - .. . . . ..
-, 2 3 ~iL r ~
synthetic clays, such as kaolin type clays, montmorillonite, bentonite or halloysite. ~hese clays may be used either alone or in combination with silica or any of the above specified cogels in a matrix formulation.
:. , .:, . , . .
Claims (4)
1. The method of preparing olefins from paraffin hydrocarbon feedstock which comprises:
a) forming a mixture of 40 to 95 wt % paraffin hydrocarbons having 4 or more carbon atoms and 5 to 60 wt %
olefins having 4 or more carbon atoms, and feeding said mixture to a reaction zone containing a catalyst consisting essentially of a zeolite, b) contacting said mixture with said catalyst at reaction conditions favoring conversion of said mixed stream to propylene, said conditions including a reaction temperature in the range 500-700°C, a hydrocarbon partial pressure in the range of 1 to 30 psig and a paraffin hydrocarbon conversion per pass of less than 50%, and c) separating product C2-C3 olefins from the reaction mixture.
a) forming a mixture of 40 to 95 wt % paraffin hydrocarbons having 4 or more carbon atoms and 5 to 60 wt %
olefins having 4 or more carbon atoms, and feeding said mixture to a reaction zone containing a catalyst consisting essentially of a zeolite, b) contacting said mixture with said catalyst at reaction conditions favoring conversion of said mixed stream to propylene, said conditions including a reaction temperature in the range 500-700°C, a hydrocarbon partial pressure in the range of 1 to 30 psig and a paraffin hydrocarbon conversion per pass of less than 50%, and c) separating product C2-C3 olefins from the reaction mixture.
2. The method of claim 1 wherein the paraffin hydrocarbon feedstock is a C5 to C20 paraffin hydrocarbon or hydrocarbon mixture.
3. The method of claim 1 wherein the zeolite catalyst is ZSM-5.
4. The method of preparing olefins from paraffin hydrocarbon feedstock which comprises:
a) forming a mixture of 40 to 95 wt % paraffin hydrocarbons having 4 or more carbon atoms and 5 to 60 wt % olefins having 4 or more carbon atoms, and feeding said mixture to a reaction zone containing a catalyst consisting essentially of a zeolite, b) contacting said mixture with said catalyst at reaction conditions favoring conversion of said mixed stream to propylene, said conditions including a reaction temperature in the range 500-700 °C, a hydrocarbon partial pressure in the range of 1 to 30 psig and a paraffin hydrocarbon conversion per pass of less than 50%, c) separating product C2-C3 olefins from the reaction mixture, and d) recycling unreacted paraffin hydrocarbon and olefins formed in step b) and having 4 or more carbon atoms to step a).
a) forming a mixture of 40 to 95 wt % paraffin hydrocarbons having 4 or more carbon atoms and 5 to 60 wt % olefins having 4 or more carbon atoms, and feeding said mixture to a reaction zone containing a catalyst consisting essentially of a zeolite, b) contacting said mixture with said catalyst at reaction conditions favoring conversion of said mixed stream to propylene, said conditions including a reaction temperature in the range 500-700 °C, a hydrocarbon partial pressure in the range of 1 to 30 psig and a paraffin hydrocarbon conversion per pass of less than 50%, c) separating product C2-C3 olefins from the reaction mixture, and d) recycling unreacted paraffin hydrocarbon and olefins formed in step b) and having 4 or more carbon atoms to step a).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34309789A | 1989-04-25 | 1989-04-25 | |
| US07/343,097 | 1989-04-25 | ||
| US07/500,172 US5043522A (en) | 1989-04-25 | 1990-03-27 | Production of olefins from a mixture of Cu+ olefins and paraffins |
| US07/500,172 | 1990-03-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2015209A1 CA2015209A1 (en) | 1990-10-25 |
| CA2015209C true CA2015209C (en) | 1998-02-24 |
Family
ID=26993328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002015209A Expired - Fee Related CA2015209C (en) | 1989-04-25 | 1990-04-23 | Production of olefins |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5043522A (en) |
| EP (1) | EP0395345B1 (en) |
| JP (1) | JP2779689B2 (en) |
| KR (1) | KR0143411B1 (en) |
| CA (1) | CA2015209C (en) |
| DE (1) | DE69000210T2 (en) |
Families Citing this family (100)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5107042A (en) * | 1989-07-03 | 1992-04-21 | Arco Chemical Technology, L.P. | Preparation of olefins using selectively protonated zeolite |
| US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
| US5234875A (en) * | 1991-12-11 | 1993-08-10 | Mobil Oil Corporation | Coke-selectivated porous acidic crystalline catalyst, its preparation, and use in olefin oligomerization |
| CN1034223C (en) * | 1993-03-29 | 1997-03-12 | 中国石油化工总公司 | Cracking catalyst for processing low-carbon olefines |
| CN1034586C (en) * | 1993-11-05 | 1997-04-16 | 中国石油化工总公司 | Catalytic conversion method of low-carbon olefines high-output |
| US5628978A (en) * | 1994-12-23 | 1997-05-13 | Intevep, S.A. | MTW zeolite for cracking feedstock into olefins and isoparaffins |
| US5846403A (en) * | 1996-12-17 | 1998-12-08 | Exxon Research And Engineering Company | Recracking of cat naphtha for maximizing light olefins yields |
| US6033555A (en) * | 1997-06-10 | 2000-03-07 | Exxon Chemical Patents Inc. | Sequential catalytic and thermal cracking for enhanced ethylene yield |
| JP2002504169A (en) * | 1997-06-10 | 2002-02-05 | エクソン・ケミカル・パテンツ・インク | Hydrocarbon cracking with positive reactor temperature gradient |
| EP0921177A1 (en) * | 1997-12-05 | 1999-06-09 | Fina Research S.A. | Production of olefins |
| EP0920911A1 (en) * | 1997-12-05 | 1999-06-09 | Fina Research S.A. | Production of catalysts for olefin conversion |
| EP0921179A1 (en) * | 1997-12-05 | 1999-06-09 | Fina Research S.A. | Production of olefins |
| EP0921180A1 (en) * | 1997-12-05 | 1999-06-09 | Fina Research S.A. | Production of olefins |
| US6049017A (en) * | 1998-04-13 | 2000-04-11 | Uop Llc | Enhanced light olefin production |
| US6602403B1 (en) | 1998-05-05 | 2003-08-05 | Exxonmobil Chemical Patents Inc. | Process for selectively producing high octane naphtha |
| CA2331613A1 (en) * | 1998-05-05 | 1999-11-11 | Johannes P. Verduijn (Deceased) | Hydrocarbon conversion to propylene with high silica medium pore zeolite catalysts |
| US6315890B1 (en) | 1998-05-05 | 2001-11-13 | Exxonmobil Chemical Patents Inc. | Naphtha cracking and hydroprocessing process for low emissions, high octane fuels |
| US6106697A (en) * | 1998-05-05 | 2000-08-22 | Exxon Research And Engineering Company | Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C4 olefins |
| US6118035A (en) * | 1998-05-05 | 2000-09-12 | Exxon Research And Engineering Co. | Process for selectively producing light olefins in a fluid catalytic cracking process from a naphtha/steam feed |
| US6803494B1 (en) | 1998-05-05 | 2004-10-12 | Exxonmobil Chemical Patents Inc. | Process for selectively producing propylene in a fluid catalytic cracking process |
| US6093867A (en) * | 1998-05-05 | 2000-07-25 | Exxon Research And Engineering Company | Process for selectively producing C3 olefins in a fluid catalytic cracking process |
| US6339180B1 (en) | 1998-05-05 | 2002-01-15 | Exxonmobil Chemical Patents, Inc. | Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process |
| US6388152B1 (en) | 1998-05-05 | 2002-05-14 | Exxonmobil Chemical Patents Inc. | Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process |
| US6069287A (en) * | 1998-05-05 | 2000-05-30 | Exxon Research And Engineering Co. | Process for selectively producing light olefins in a fluid catalytic cracking process |
| US6429348B1 (en) * | 1998-05-05 | 2002-08-06 | Exxonmobil Chemical Patents, Inc. | Method for selectively producing propylene by catalytically cracking an olefinic hydrocarbon feedstock |
| US6455750B1 (en) * | 1998-05-05 | 2002-09-24 | Exxonmobil Chemical Patents Inc. | Process for selectively producing light olefins |
| US6313366B1 (en) | 1998-05-05 | 2001-11-06 | Exxonmobile Chemical Patents, Inc. | Process for selectively producing C3 olefins in a fluid catalytic cracking process |
| US6294493B1 (en) | 1998-05-26 | 2001-09-25 | Exxon Mobil Chemical Patents Inc. | Silicoaluminophosphates having an AEL structure |
| CN1149185C (en) | 1998-08-25 | 2004-05-12 | 旭化成株式会社 | process for producing ethylene and propylene |
| WO2000026163A1 (en) * | 1998-11-04 | 2000-05-11 | Equistar Chemicals, L.P. | Process for making propylene and ethylene |
| EP1061117A1 (en) * | 1999-06-16 | 2000-12-20 | Fina Research S.A. | Production of olefins |
| EP1061116A1 (en) * | 1999-06-16 | 2000-12-20 | Fina Research S.A. | Production of olefins |
| US6339181B1 (en) | 1999-11-09 | 2002-01-15 | Exxonmobil Chemical Patents, Inc. | Multiple feed process for the production of propylene |
| US6565739B2 (en) | 2000-04-17 | 2003-05-20 | Exxonmobil Research And Engineering Company | Two stage FCC process incorporating interstage hydroprocessing |
| US6569316B2 (en) | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process incorporating shape-selective zeolite catalysts |
| US6569315B2 (en) | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
| US20010042702A1 (en) * | 2000-04-17 | 2001-11-22 | Stuntz Gordon F. | Cycle oil conversion process |
| US20010042701A1 (en) | 2000-04-17 | 2001-11-22 | Stuntz Gordon F. | Cycle oil conversion process |
| CN1179022C (en) * | 2001-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Catalytic modification process of light petroleum hydrocarbon accompanied by low temperature regeneration of catalyst |
| US20030116471A1 (en) * | 2001-08-29 | 2003-06-26 | China Petroleum & Chemical Corporation | Catalytic cracking process of petroleum hydrocarbons |
| US6797851B2 (en) | 2001-08-30 | 2004-09-28 | Exxonmobil Chemical Patents Inc. | Two catalyst process for making olefin |
| US6888038B2 (en) * | 2002-03-18 | 2005-05-03 | Equistar Chemicals, Lp | Enhanced production of light olefins |
| US7145051B2 (en) * | 2002-03-22 | 2006-12-05 | Exxonmobil Chemical Patents Inc. | Combined oxydehydrogenation and cracking catalyst for production of olefins |
| US6867341B1 (en) * | 2002-09-17 | 2005-03-15 | Uop Llc | Catalytic naphtha cracking catalyst and process |
| US7011740B2 (en) * | 2002-10-10 | 2006-03-14 | Kellogg Brown & Root, Inc. | Catalyst recovery from light olefin FCC effluent |
| US7153479B2 (en) * | 2002-10-10 | 2006-12-26 | Kellogg Brown & Root Llc | Catalyst regenerator with a centerwell |
| JP4112943B2 (en) | 2002-10-28 | 2008-07-02 | 出光興産株式会社 | Process for producing olefins by catalytic cracking of hydrocarbons |
| US7122494B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| EP1622719A1 (en) * | 2003-02-05 | 2006-02-08 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| US7122493B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| US7125817B2 (en) * | 2003-02-20 | 2006-10-24 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| US7122492B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| JP4953817B2 (en) * | 2004-07-16 | 2012-06-13 | 旭化成ケミカルズ株式会社 | Process for producing ethylene and propylene |
| US7459596B1 (en) | 2005-07-26 | 2008-12-02 | Uop Llc | Nanocrystalline silicalite for catalytic naphtha cracking |
| CN100404484C (en) * | 2005-07-28 | 2008-07-23 | 中国石油化工股份有限公司 | Method of preparing propylene by olefine containing gasoline catalytic cracking |
| EP1935865B1 (en) | 2005-09-16 | 2016-11-16 | Asahi Kasei Kabushiki Kaisha | Process for production of ethylene and propylene |
| KR100651418B1 (en) | 2006-03-17 | 2006-11-30 | 에스케이 주식회사 | Catalytic cracking process using fast fluidization for the production of light olefins from hydrocarbon feedstock |
| DE102006020293B4 (en) * | 2006-04-27 | 2013-07-11 | Wirtgen Gmbh | Road construction machine, leveling device and method for controlling the cutting depth or milling inclination in a road construction machine |
| US7799834B2 (en) * | 2006-05-30 | 2010-09-21 | Starchem Technologies, Inc. | Methanol production process and system |
| CN101490216B (en) * | 2006-07-26 | 2013-04-17 | 道达尔石油化学产品研究弗吕公司 | Production of olefins |
| US7491315B2 (en) * | 2006-08-11 | 2009-02-17 | Kellogg Brown & Root Llc | Dual riser FCC reactor process with light and mixed light/heavy feeds |
| WO2008055185A2 (en) * | 2006-10-30 | 2008-05-08 | Metabank | Computer-based fund transmittal system and method |
| US8608942B2 (en) * | 2007-03-15 | 2013-12-17 | Kellogg Brown & Root Llc | Systems and methods for residue upgrading |
| US7820033B2 (en) * | 2007-04-30 | 2010-10-26 | Kellogg Brown & Root Llc | Method for adjusting yields in a light feed FCC reactor |
| US8324441B2 (en) * | 2007-10-16 | 2012-12-04 | Uop Llc | Pentane catalytic cracking process |
| US20090112031A1 (en) * | 2007-10-30 | 2009-04-30 | Eng Curtis N | Method for olefin production from butanes using a catalyst |
| US8080698B2 (en) * | 2007-10-30 | 2011-12-20 | Kellogg Brown & Root Llc | Method for olefin production from butanes and cracking refinery hydrocarbons and alkanes |
| US20090112032A1 (en) * | 2007-10-30 | 2009-04-30 | Eng Curtis N | Method for olefin production from butanes and cracking refinery hydrocarbons |
| US20090112030A1 (en) * | 2007-10-30 | 2009-04-30 | Eng Curtis N | Method for olefin production from butanes |
| US7943038B2 (en) * | 2008-01-29 | 2011-05-17 | Kellogg Brown & Root Llc | Method for producing olefins using a doped catalyst |
| US8137533B2 (en) | 2008-10-24 | 2012-03-20 | Uop Llc | Mixture of catalysts for cracking naphtha to olefins |
| WO2010053482A1 (en) * | 2008-11-06 | 2010-05-14 | Uop Llc | Nanocrystalline silicalite for catalytic naphtha cracking |
| BRPI0805207B1 (en) * | 2008-11-25 | 2019-11-12 | Petroleo Brasileiro Sa Petrobras | catalytic cracking process of a hydrocarbon stream for maximizing light olefins |
| ES2645694T3 (en) | 2008-12-10 | 2017-12-07 | Reliance Industries Limited | Catalytic fluidized bed cracking (FCC) process for manufacturing propylene and ethylene with increased performance |
| US8007728B2 (en) * | 2008-12-11 | 2011-08-30 | Uop Llc | System, apparatus, and process for cracking a hydrocarbon feed |
| US20110230333A1 (en) * | 2010-03-16 | 2011-09-22 | Uop Llc | Olefin Cracking Catalyst and Manufacturing Process |
| US8383052B2 (en) | 2010-04-16 | 2013-02-26 | Kellogg Brown & Root Llc | System for a heat balanced FCC forlight hydrocarbon feeds |
| US9040763B2 (en) | 2010-06-28 | 2015-05-26 | Uop Llc | Method for quenching paraffin dehydrogenation reaction in counter-current reactor |
| US9150465B2 (en) | 2010-09-21 | 2015-10-06 | Uop Llc | Integration of cyclic dehydrogenation process with FCC for dehydrogenation of refinery paraffins |
| US8889942B2 (en) | 2010-12-23 | 2014-11-18 | Kellogg Brown & Root Llc | Integrated light olefin separation/cracking process |
| US9452404B2 (en) | 2012-07-12 | 2016-09-27 | Lummus Technology Inc. | Fluid cracking process and apparatus for maximizing light olefins or middle distillates and light olefins |
| US9745519B2 (en) | 2012-08-22 | 2017-08-29 | Kellogg Brown & Root Llc | FCC process using a modified catalyst |
| US9328298B2 (en) | 2013-06-04 | 2016-05-03 | Uop Llc | Naphtha cracking |
| US9328299B2 (en) | 2013-06-04 | 2016-05-03 | Uop Llc | Naphtha cracking |
| US10689586B2 (en) | 2015-12-21 | 2020-06-23 | Sabic Global Technologies B.V. | Methods and systems for producing olefins and aromatics from coker naphtha |
| US9981888B2 (en) | 2016-06-23 | 2018-05-29 | Saudi Arabian Oil Company | Processes for high severity fluid catalytic cracking systems |
| KR102305664B1 (en) | 2016-09-16 | 2021-09-28 | 루머스 테크놀로지 엘엘씨 | Fluid Catalytic Cracking Process and Apparatus and Other Applications to Maximize Light Olefin Yields |
| US10870802B2 (en) | 2017-05-31 | 2020-12-22 | Saudi Arabian Oil Company | High-severity fluidized catalytic cracking systems and processes having partial catalyst recycle |
| CN110997876A (en) | 2017-07-18 | 2020-04-10 | 鲁姆斯科技有限责任公司 | Integrated thermal and catalytic cracking for olefin production |
| US10889768B2 (en) | 2018-01-25 | 2021-01-12 | Saudi Arabian Oil Company | High severity fluidized catalytic cracking systems and processes for producing olefins from petroleum feeds |
| TW202104562A (en) | 2019-04-03 | 2021-02-01 | 美商魯瑪斯科技有限責任公司 | Staged fluid catalytic cracking processes incorporating a solids separation device for upgrading naphtha range material |
| AR119323A1 (en) | 2019-07-02 | 2021-12-09 | Lummus Technology Inc | FLUID CATALYTIC CRACKING PROCESSES AND APPARATUS |
| US11352575B2 (en) | 2020-09-01 | 2022-06-07 | Saudi Arabian Oil Company | Processes for producing petrochemical products that utilize hydrotreating of cycle oil |
| US11242493B1 (en) | 2020-09-01 | 2022-02-08 | Saudi Arabian Oil Company | Methods for processing crude oils to form light olefins |
| US11434432B2 (en) | 2020-09-01 | 2022-09-06 | Saudi Arabian Oil Company | Processes for producing petrochemical products that utilize fluid catalytic cracking of a greater boiling point fraction with steam |
| US11230672B1 (en) | 2020-09-01 | 2022-01-25 | Saudi Arabian Oil Company | Processes for producing petrochemical products that utilize fluid catalytic cracking |
| US11505754B2 (en) | 2020-09-01 | 2022-11-22 | Saudi Arabian Oil Company | Processes for producing petrochemical products from atmospheric residues |
| US11230673B1 (en) | 2020-09-01 | 2022-01-25 | Saudi Arabian Oil Company | Processes for producing petrochemical products that utilize fluid catalytic cracking of a lesser boiling point fraction with steam |
| US11332680B2 (en) | 2020-09-01 | 2022-05-17 | Saudi Arabian Oil Company | Processes for producing petrochemical products that utilize fluid catalytic cracking of lesser and greater boiling point fractions with steam |
| CN113070093B (en) * | 2021-03-31 | 2023-08-04 | 陕西科技大学 | GaN-loaded Ga modified-Silicalite-1 catalyst and application thereof |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE229418C (en) * | 1908-07-25 | 1910-12-19 | Mauser Paul | Recoil loader with fixed barrel and locking support levers that can be swung in and out in the manner of flaps by means of cam control |
| US4054510A (en) * | 1958-06-13 | 1977-10-18 | Exxon Research And Engineering Company | Selective conversion of normal paraffins |
| GB964918A (en) * | 1961-10-02 | 1964-07-29 | British Petroleum Co | Improvements relating to the cracking of hydrocarbons |
| US3409701A (en) * | 1964-01-06 | 1968-11-05 | Dow Chemical Co | Catalyst and method for dehydrogenating and cracking alkanes and olefins |
| FR1567284A (en) * | 1968-03-15 | 1969-05-16 | ||
| US3761538A (en) * | 1971-02-11 | 1973-09-25 | Chem Systems | Butane cracking |
| GB1397315A (en) * | 1972-08-14 | 1975-06-11 | Haldor Topsoe As | Process for catalytic steam cracking |
| US3926781A (en) * | 1973-10-09 | 1975-12-16 | Shell Oil Co | Catalytic cracking of paraffinic naphtha |
| RO64554A2 (en) * | 1976-12-07 | 1980-01-15 | Institutul De Inginerie Tehnologica Si Proiectare Pentru Industria Chimica,Ro | CATALYTIC PROCESS FOR OBTAINING OLEFINS AND LOW DIOLEFINES THROUGH HYDROCARBON PIROLYSIS |
| US4282085A (en) * | 1978-10-23 | 1981-08-04 | Chevron Research Company | Petroleum distillate upgrading process |
| US4247386A (en) * | 1979-08-06 | 1981-01-27 | Mobil Oil Corporation | Conversion of hydrocarbons to olefins |
| US4251348A (en) * | 1979-12-26 | 1981-02-17 | Chevron Research Company | Petroleum distillate upgrading process |
| EP0109059B1 (en) * | 1982-11-10 | 1987-07-15 | MONTEDIPE S.p.A. | Process for converting olefins having 4 to 12 carbon atoms into propylene |
| JPH0816072B2 (en) * | 1984-02-24 | 1996-02-21 | 東ソー株式会社 | Method of manufacturing olefin |
| JPS60222428A (en) * | 1984-04-19 | 1985-11-07 | Res Assoc Util Of Light Oil | Catalytic conversion of hydrocarbon |
| JPH0672111B2 (en) * | 1984-06-15 | 1994-09-14 | 新燃料油開発技術研究組合 | Propylene production method |
| FR2614220B1 (en) * | 1987-04-24 | 1989-07-21 | Inst Francais Du Petrole | HYDROCARBON CHARGE CRACKING CATALYST COMPRISING A DEALUMINATED MORDENITY, A Y ZEOLITE AND A MATRIX. |
| JPS642705A (en) * | 1987-06-23 | 1989-01-06 | Kawasaki Steel Corp | Cold rolled steel sheet having high resistance to die galling and its manufacturing method |
-
1990
- 1990-03-27 US US07/500,172 patent/US5043522A/en not_active Expired - Lifetime
- 1990-04-23 CA CA002015209A patent/CA2015209C/en not_active Expired - Fee Related
- 1990-04-24 KR KR1019900005927A patent/KR0143411B1/en not_active IP Right Cessation
- 1990-04-24 DE DE9090304364T patent/DE69000210T2/en not_active Expired - Fee Related
- 1990-04-24 EP EP90304364A patent/EP0395345B1/en not_active Expired
- 1990-04-25 JP JP2109967A patent/JP2779689B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR900016072A (en) | 1990-11-12 |
| US5043522A (en) | 1991-08-27 |
| CA2015209A1 (en) | 1990-10-25 |
| DE69000210D1 (en) | 1992-08-27 |
| JP2779689B2 (en) | 1998-07-23 |
| KR0143411B1 (en) | 1998-07-15 |
| JPH0327327A (en) | 1991-02-05 |
| EP0395345A1 (en) | 1990-10-31 |
| EP0395345B1 (en) | 1992-07-22 |
| DE69000210T2 (en) | 1993-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2015209C (en) | Production of olefins | |
| US5026936A (en) | Enhanced production of propylene from higher hydrocarbons | |
| US5026935A (en) | Enhanced production of ethylene from higher hydrocarbons | |
| US4052479A (en) | Conversion of methanol to olefinic components | |
| US8137533B2 (en) | Mixture of catalysts for cracking naphtha to olefins | |
| EP1078025B1 (en) | Hydrocarbon conversion to propylene with high silica medium pore zeolite catalysts | |
| AU577371B2 (en) | Two stage catalytic conversion of olefins to higher hydrocarbons | |
| US4899015A (en) | Process for olefins to gasoline conversion | |
| JPS59227976A (en) | Conversion of methanol, dimethyl ether or both to olefins | |
| US4605807A (en) | Process for catalytic conversion of ethylene to higher hydrocarbons | |
| JPH04352731A (en) | Method for manufacturing olefin-containing hydrocarbon mixture | |
| JP2002504169A (en) | Hydrocarbon cracking with positive reactor temperature gradient | |
| JPS60222428A (en) | Catalytic conversion of hydrocarbon | |
| US5059735A (en) | Process for the production of light olefins from C5 + hydrocarbons | |
| EP0410600B1 (en) | Propylene oxide production | |
| EP3558907A1 (en) | Process to prepare propylene | |
| RU2191204C1 (en) | Method of processing olefin-containing feedstock | |
| EP3863993A1 (en) | Process to prepare propylene | |
| US5107001A (en) | Propylene oxide production | |
| RU2191203C1 (en) | Method of processing olefin-containing feedstock (options) | |
| RU2119473C1 (en) | Method of refining ethylene-containing gas from c3-olefins and above | |
| WO2018117820A1 (en) | Process to prepare propylene | |
| JPH03199293A (en) | Method for converting olefin into gasoline | |
| CA2004906A1 (en) | Process for olefins to gasoline conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 20090423 |