CN1332756C - Hydrocarbon conversion catalyst containing zeolite - Google Patents
Hydrocarbon conversion catalyst containing zeolite Download PDFInfo
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- CN1332756C CN1332756C CNB2004100689364A CN200410068936A CN1332756C CN 1332756 C CN1332756 C CN 1332756C CN B2004100689364 A CNB2004100689364 A CN B2004100689364A CN 200410068936 A CN200410068936 A CN 200410068936A CN 1332756 C CN1332756 C CN 1332756C
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a hydrocarban converting catalyst. According to the reference of the total amount of the catalyst, the weight percentage of the zeolite is from 1 to 60, and counted by the oxides, the weight percentage of the auxiliary agent content is from 0.1 to 10, the weight percentage of the content of the inorganic oxides of heat resistance is from 5 to 99, and the weight percentage of the clay content is from 0 to 70, wherein the zeolite is the zeolite which comprises phosphorus and bimetallic ingredients and has an MFI structure or the zeolite is the mixture of the zeolite and macropore zeolite. Counted by the total amount of the zeolite, the weight percentage of the content of the zeolite which has an MFI structure is from 75 to 100, and the weight percentage of the content of the macropore zeolite is from 0 to 25. Counted by the mass of the oxides, the zeolite which comprises phosphorus and bimetallic ingredients and has an MFI structure has the following anhydrous chemical expression: ((0-0.3) Na2O. (0.3-5.5)Al2O3. (1.0-10)P2O5. (0.7-15)Ml<x>O<y>. (0.01-5)M2<m>O<n>. (0-10)RE2O3. (70-97)SiO2. The auxiliary agent is selected from one or a plurality of alkaline earth metal, the metal in the IV B group, and the non-precious metal and the rare earth metal in the VIII group in the periodic table. The catalyst has high converting ability of petroleum hydrocarbon, and the yields of propene, ethene and light aromatic hydrocarbon are high.
Description
Technical field
The invention relates to a kind of Hydrocarban coversion catalysts that contains molecular sieve and preparation method thereof, more particularly, is about a kind of Hydrocarban coversion catalysts that contains zeolite and preparation method thereof.
Background technology
Low-carbon alkene, as ethene and propylene, and light aromatics is important petrochemical materials, its demand is increasing day by day.In the prior art, the maturation process method of production ethene and propylene has: hydro carbons is produced ethene, propylene by the thermal conversion processes of radical reaction, as the tube furnace steam cracking process of lighter hydrocarbons; The catalytic pyrolysis or the catalytic pyrolysis technology of the heavy hydrocarbon by carbonium ion mechanism can a certain amount of propylene of by-product and ethene.In addition, also have and use the catalyst that contains zeolite, produce the method for ethene and propylene from the hydrocarbon raw material that contains alkene by catalyzed conversion.And the production of aromatic hydrocarbons mainly is the catalytic reforming by direct steaming gasoline.
With the petroleum hydrocarbon be raw material when adopting cracking or cleavage method to produce low-carbon alkene employed catalyst three classes are roughly arranged.One class is to be the metal load type catalyst of carrier with the oxide, and their carrier can be SiO
2, Al
2O
3Or other oxide, mostly the metallic element of institute's load is to belong to IIB, VB, VIIB and VIII family element (US3541179, US3647682, DD225135, SU1214726).When using this class catalyst because the dehydrogenation of institute's carried metal, the also corresponding quickening of polymerization coking reaction when carrying out cracking reaction, therefore, generally can only use boiling range when adopting this type of catalyst is＜220 ℃ lightweight material.
The employed second class catalyst is composite oxides.As with ZrO
2And/or HfO
2Catalyst for main component is aided with Al
2O
3, Cr
2O
3, MnO and/or Fe
2O
3And alkali metal or alkaline earth oxide (USP3725495, USP3839485); Be catalyst and for example with potassium vanadate, potassium stannate or potassium niobate, low-carbon alkene that can about 56 weight % after the naphtha cracking, the therein ethylene productive rate can reach 36.5 weight %, and productivity of propylene is 12.5 weight % (SU523133, SU487927, SU410073); Contain small amount of Fe for another example
2O
3, TiO
2, CaO, MgO, Na
2O, K
2The SiO of O
2Al
2O
3Catalyst is used for the cracking (SU550173, SU559946) of various hydrocarbon-fractions.Composite oxides commonly used are amorphous Si O
2Al
2O
3(DD152356)
Along with zeolite increasingly extensive application in petrochemical industry and PETROLEUM PROCESSING field, the 3rd class catalyst has appearred, promptly contain the catalyst that strokes stone, particularly contain have the MFI structural zeolite catalyst of (five-membered ring silica-rich zeolite).
US3758403 discloses a kind of method of catalytically crack hydrocarbons raw material, this method is included under the cracking conditions, described hydro carbons is contacted with a kind of catalyst, described catalyst contains a kind of ZSM-5 zeolite and the aperture mixture greater than the zeolite of 7 dusts, this method can in improving product in the octane number, make (C
3 =+ C
4 =) productive rate increase.
CN1042201C discloses a kind of voluminous C
3-C
5The Cracking catalyst of alkene, be the ZSM-5 zeolite that is selected from modifications such as P, RE, Ca, Mg, H, Al by y-type zeolite, the 2-40% of 10-50% lattice constant≤2.450nm, β zeolite and composition thereof, 20-80% are made up of the semi-synthetic carrier that kaolin and al binder are formed.This catalyst can voluminous ethene and propylene, and makes gasoline yield keep higher level.
CN1055301C discloses the Cracking catalyst of a kind of voluminous isomeric olefine and gasoline, it is made up of the zeolite of the clay of the composite aluminum base binding agent of 5-70%, 5-65% and 23-50%, and said zeolite is that the phosphorus content of the y-type zeolite of 15-82% and surplus is (with P
2O
5Meter) is the mixture that contains rare-earth five-membered ring silica-rich zeolite and/or HZSM-5 zeolite of 0-10 weight %, when containing rare-earth five-membered ring silica-rich zeolite and HZSM-5 zeolite and exist simultaneously, contains rare-earth five-membered ring silica-rich zeolite content and be no more than 65%.This catalyst is mainly used in the productive rate that improves isomeric olefine and gasoline.
CN1102634C discloses a kind of catalyst for catalytic thermal cracking process to prepare lower olefine, this catalyst has the clay of following composition: 10-70%, the inorganic oxide of 5-85% and the zeolite of 1-50%, its mesolite is y-type zeolite and the phosphorous and aluminium of 75-100% or the five-membered ring structure high-silicon zeolite of magnesium or calcium of 0-25%, this silica-rich zeolite is the ZSM-5 that contains the aluminium of the phosphorus of 2-8% and 0.3-3% or magnesium or calcium (in oxide) ,-8 or the zeolite of-11 types, and its silica alumina ratio is 15-60.This catalyst is mainly used in catalytic pyrolysis and produces ethene.
CN1317543A discloses the method for a kind of petroleum hydrocarbon catalytic pyrolysis fecund ethene and propylene, this method comprises that heavy petroleum hydrocarbon with preheating is in reactor, contacting with the catalyst that contains the ZSM-5 molecular sieve in the presence of high-temperature steam, is that 650-750 ℃, reaction pressure are 1.5-4 * 10 in reaction temperature
5Handkerchief, reaction time are that the weight ratio of 0.2-5 second, catalyst and feedstock oil is 15-40: 1, the weight ratio of water vapour and feedstock oil is 0.3-1: carry out the catalytic pyrolysis reaction under 1 the condition, described ZSM-5 molecular sieve contains Ag or the Cu of 0.1-8 weight %.
US 5006497 discloses a kind of multi-zeolite catalyzer, this catalyst contains (1) at least a large pore molecular sieve, (2) a kind of restricted index (constraint index) is the shape-selective molecular sieve of 1-12, this shape-selective molecular sieve does not contain the hydrogenation/dehydrogenation component substantially, and has cracking/isomerization activity, (3) restricted index is the shape-selective molecular sieve of 1-12, and this shape-selective molecular sieve has aromatization activity and (4) a kind of matrix.Wherein, described large pore molecular sieve is selected from conventional large pore zeolite, as L zeolite, X zeolite, Y zeolite.The shape-selective molecular sieve that described restricted index is 1-12 is selected from the ZSM-5 of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48, ZSM-57, boracic, gallium, zirconium, titanium.This catalyst can improve octane number, yield of gasoline.
Reported at SiO among the US 5236880
2/ Al
2O
3The paraffin hydrocarbon Cracking catalyst that adds VIIIB family metal component, preferred nickel in＞5 the zeolite with MFI or MEL structure, this catalyst can improve the paraffin hydrocarbon conversion of raw material, increase the aromatic component in the gasoline fraction, improve the octane number and the gasoline yield of gasoline.
CN1048428C discloses a kind of multi-zeolite catalyzer of producing low-carbon alkene, be made up of the clay of 0-70 weight %, the inorganic oxide of 5-90 weight % and the zeolite of 10-35% weight %, its mesolite is made up of the five-membered ring silica-rich zeolite of the phosphorous and rare earth of 20-75 weight %, the Y-type high-Si zeolite of 20-75 weight % and the y-type zeolite that contains rare earth of 1-25 weight %.This catalyst is mainly used in the productive rate that improves isobutene and iso-amylene.
CN1053918C discloses a kind of double zeolite catalyst of producing low-carbon alkene, be made up of the clay of 0-70 weight %, the inorganic oxide of 5-90 weight % and the zeolite of 10-40 weight %, its mesolite is made up of the Y-type high-Si zeolite of the five-membered ring silica-rich zeolite of the phosphorous and rare earth of 25-75 weight % and 25-75 weight % or the y-type zeolite that contains rare earth.This catalyst is mainly used in the productive rate that improves propylene, isobutene and iso-amylene.
CN1043520A discloses a kind of catalyst for cracking, and its carrier is the clay of 0-70 weight % and the inorganic oxide of 5-99 weight %, and its active component is the ZSM-5 of 1-50 weight % and the mixture of Y zeolite.The ZSM-5 molecular sieve accounts for 75-100 weight % in the active component, and the Y type divides in sieve and accounts for 0-25 weight %.This catalyst for cracking is applicable to production low-carbon alkene, particularly propylene and butylene, and double oil and the diesel oil of steaming.
CN1034223C discloses a kind of catalyst for cracking, this catalyst is made up of the clay of 0-70%, the inorganic oxide of 5-99% and the zeolite of 1-50%, and zeolite wherein is the mixture of five-membered ring silica-rich zeolite of the phosphorous and rare earth of the REY of 0-25 weight % or Y-type high-Si zeolite and 75-100 weight %.This catalyst is applicable to that the petroleum hydrocarbon cracking produces ethene, propylene and butylene, mainly is propylene and butylene, and double oil and the diesel oil of steaming.
Summary of the invention
The purpose of this invention is to provide a kind of higher petroleum hydrocarbon conversion capability that has, propylene, ethene and the higher catalyst of light aromatics productive rate.Another object of the present invention provides this Preparation of catalysts method.
Catalyst provided by the invention contains zeolite, heat-resistant inorganic oxide, contain or argillaceous not, wherein, described zeolite is to contain the zeolite with MFI structure of phosphorus and bimetallic component or this contains the zeolite with MFI structure of phosphorus and bimetallic component and the mixture of large pore zeolite, total amount in zeolite, the content that contains the zeolite with MFI structure of phosphorus and bimetallic component is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide, the described zeolite with MFI structure that contains phosphorus and bimetallic component has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5.5) Al
2O
3(1.0-10) P
2O
5(0.7-15) M1
xO
y(0.01-5) M2
mO
n(0-10) RE
2O
3(70-97) SiO
2, wherein, M1 is selected from a kind of metal among Fe, Co and the Ni, M2 is selected from a kind of metal among Zn, Mn, Ga and the Sn, and RE represents rare earth metal, and x is 1 or 2, when x is 1, the numerical value of y be metal M 1 valent half, when x is 2, the numerical value of y is metal M 1 chemical valence, m is 1 or 2, when m is 1, the numerical value of n be metal M 2 valent half, when m was 2, the numerical value of n was metal M 2 chemical valences; This catalyst also contains a kind of auxiliary agent, and described auxiliary agent is selected from one or more in barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, the nickel; With the catalyst total amount is benchmark, and the content of zeolite is 1-60 weight %, in oxide, and the content of auxiliary agent is that the content of 0.1-10 weight %, heat-resistant inorganic oxide is that the content of 5-70 weight %, clay is 0-70 weight %.
Preparation of catalysts method provided by the invention comprises all or part of heat-resistant inorganic oxide and/or its precursor and water mixing making beating, add or do not add clay, add zeolite, the slurries that drying obtains, roasting then, wherein, before adding zeolite, add before or after the clay, also add a kind of auxiliary compound, and add the pH value that a kind of acid makes slurries and be 1-5, and under 30-90 ℃ temperature aging 0.1-10 hour; Aging back adds remaining heat-resistant inorganic oxide and/or its precursor; Described zeolite is to contain the zeolite with MFI structure of phosphorus and bimetallic component or this contains the zeolite with MFI structure of phosphorus and bimetallic component and the mixture of large pore zeolite, total amount in zeolite, the content that contains the zeolite with MFI structure of phosphorus and bimetallic component is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide, the described zeolite with MFI structure that contains phosphorus and bimetallic component has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5.5) Al
2O
3(1.0-10) P
2O
5(0.7-15) M1
xO
y(0.01-5) M2
mO
n(0-10) RE
2O
3(70-97) SiO
2, wherein, M1 is selected from a kind of metal among Fe, Co and the Ni, M2 is selected from a kind of metal among Zn, Mn, Ga and the Sn, and RE represents rare earth metal, and x is 1 or 2, when x is 1, the numerical value of y be metal M 1 valent half, when x is 2, the numerical value of y is metal M 1 chemical valence, m is 1 or 2, when m is 1, the numerical value of n be metal M 2 valent half, when m was 2, the numerical value of n was metal M 2 chemical valences; The consumption of each component makes in the final catalyst and contains, and is benchmark with the catalyst total amount, the zeolite of 1-60 weight %, in oxide, the heat-resistant inorganic oxide of 0.1-10 weight % auxiliary agent, 5-70 weight % and the clay of 0-70 weight %.
Because maybe this has the zeolite of MFI structure and the mixture of large pore zeolite is an active component to the zeolite with MFI structure that catalyst provided by the invention adopts phosphorous and bimetallic component modification, contain a kind of auxiliary agent that improves performance that has simultaneously in the catalyst, therefore, catalyst provided by the invention has good activity stability and selectivity, show through the aging catalyst of steam to have higher petroleum hydrocarbon conversion capability, propylene, ethene and light aromatics productive rate are higher.
The specific embodiment
According to catalyst provided by the invention, be benchmark with the catalyst total amount, the content of zeolite is that the content of 1-60 weight %, auxiliary agent is that the content of 0.1-10 weight %, heat-resistant inorganic oxide is that the content of 5-99 weight %, clay is 0-70 weight %.Under the preferable case, the content of zeolite is that the content of 10-50 weight %, auxiliary agent is that the content of 0.5-8 weight %, heat-resistant inorganic oxide is that the content of 10-70 weight %, clay is 0-60 weight %.
Under the preferable case, in the quality of oxide, the described zeolite with MFI structure that contains phosphorus and bimetallic component has following anhydrous chemical expression: (0-0.2) Na
2O (0.9-5) Al
2O
3(1.5-7) P
2O
5(0.9-10) M1
xO
y(0.5-2) M2
mO
n(0.5-10) RE
2O
3(82-92) SiO
2
M1 is preferably Fe, and M2 is preferably Zn, and more preferably under the situation, M1 is Fe, and M2 is Zn simultaneously.
Described rare earth metal (RE) is preferably lanthanum, cerium or contains lanthanum and/or the norium of cerium.
Described auxiliary agent is preferably one or more in barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, the nickel.Described auxiliary agent can exist with the oxide of above-mentioned metal and/or the form of salt, also can with heat-resistant inorganic oxide and/or clay effect, exist with the form of complex compound.Described auxiliary agent can be dispersed in the heat-resistant inorganic oxide, also can be dispersed in the clay, can also be dispersed in heat-resistant inorganic oxide and the clay.
Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujasite, L zeolite, Beta zeolite, omega zeolite, modenite, the ZSM-18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.
Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of Cracking catalyst matrix and binder component one or more, as in aluminium oxide, silica, the amorphous silicon aluminium one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.Preferred clay is one or more in kaolin, halloysite, the imvite.These clays are conventionally known to one of skill in the art.
According to Preparation of catalysts method provided by the invention, before aging, heat-resistant inorganic oxide and/or its precursor all can be added or partly add, in order to make catalyst have the better wear resistance energy, preferably before aging, add part heat-resistant inorganic oxide and/or its precursor earlier, add remaining heat-resistant inorganic oxide and/or its precursor again after aging, earlier to make the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide that adds earlier in the catalyst and back add be 1 to the part that adds of the part that adds and back: 0.1-10, more preferably 1: 0.1-5.
Described clay can add before aging or after aging, and the order that described clay adds is to the not influence of performance of catalyst.
Described acid is selected from one or more in water-soluble inorganic acid and the organic acid, is preferably hydrochloric acid, nitric acid, phosphoric acid, carbon number and is in the carboxylate of 1-10 one or more.The consumption of acid makes the pH value of slurries for 1-5, is preferably 1.5-4.
Described aging temperature is 30-90 ℃, is preferably 40-80 ℃, and the aging time is 0.1-10 hour, is preferably 0.5-8 hour.
The precursor of described heat-resistant inorganic oxide refers in described catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminium oxide can be selected from hydrated alumina and/or aluminium colloidal sol; Described hydrated alumina is selected from one or more in boehmite (boehmite), false boehmite (boehmite), hibbsite, the amorphous hydroted alumina.The precursor of silica can be selected from Ludox, one or more in silicon gel and the waterglass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of Ludox and aluminium colloidal sol, one or more in the silica-alumina gel.The precursor of these heat-resistant inorganic oxides is conventionally known to one of skill in the art.
Described auxiliary compound is selected from one or more in one or more in water soluble or water-fast alkaline-earth metal, IVB family metal, group VIII base metal and the rare earth compound, particularly water soluble or water-fast barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel compound.As the halide of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel, one or more in nitrate, sulfate, the phosphate.Wherein, the halide of described barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel is preferably the chloride of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel.
The consumption of each component makes in the final catalyst and contains, and is benchmark with the catalyst total amount, the heat-resistant inorganic oxide of the zeolite of 1-60 weight %, 0.1-10 weight % auxiliary agent, 5-99 weight % and the clay of 0-70 weight %.Under the preferable case, the consumption of each component makes in the final catalyst and contains, and is benchmark with the catalyst total amount, the heat-resistant inorganic oxide that strokes stone, 0.5-8 weight % auxiliary agent, 10-70 weight % of 10-50 weight % and the clay of 0-60 weight %.
The drying means of slurries and condition are conventionally known to one of skill in the art, for example, dry method can be dry, oven dry, forced air drying or spray-drying, preferably spray drying.Dry temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.For the ease of spray-drying, the solid content of dry preceding slurries is preferably 10-50 weight %, more preferably 20-50 weight %.
Roasting condition after the described slurry dried also is conventionally known to one of skill in the art, and in general, the sintering temperature after the described slurry dried is 400-700 ℃, be preferably 450-650 ℃, roasting time was at least 0.5 hour, was preferably 0.5-100 hour, more preferably 0.5-10 hour.
The described prepare zeolite method with MFI structure that contains phosphorus and bimetallic component is included in and introduces phosphorus and above-mentioned bimetallic component in the zeolite with MFI structure that contains or do not contain rare earth.
The method of introducing phosphorus and bimetallic component in the zeolite with MFI structure that contains or do not contain rare earth can adopt the whole bag of tricks, as in the process of synthesizing the zeolite that contains or do not contain rare earth, introducing with MFI structure, perhaps adopt the mode of dipping, mixing and/or ion-exchange, in the zeolite that contains or do not contain rare earth, introduce phosphorus and bimetallic component with MFI structure.Describedly introduce phosphorus and bimetallic component in the process of the synthetic zeolite with MFI structure that contains or do not contain rare earth, the method that perhaps adopts the mode of dipping, mixing and/or ion-exchange to introduce phosphorus and bimetallic component is conventionally known to one of skill in the art.
For example, the described zeolite with MFI structure that contains phosphorus and bimetallic component can be prepared as follows: conventional crystallization is resulting, and the sodium type molecular sieve with MFI structure that contains or do not contain rare earth is according to molecular sieve: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (5～10) obtains the filter cake after ammonium exchanges in room temperature to 100 ℃ exchange filtration after 0.3～1 hour down.Then, adopt the method for dipping or ion-exchange to introduce phosphorus and be selected from a kind of among Fe, Co, the Ni and be selected from a kind of compound among Metal Zn, Mn, Ga, the Sn, drying, and in 400～800 ℃ of following roastings or roasting 0.5～8 hour under steam atmosphere.
If contain organic formwork agent in the na-pretreated zeolite of the described MFI of having structure, should behind removed template method, carry out operation as above again, wherein said ammonium salt can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture for inorganic ammonium salt commonly used.
Wherein, the method for described dipping or ion-exchange can adopt following any one mode:
Mode 1: filter cake after the ammonium exchange and phosphorous compound aqueous solution is even in room temperature to 95 ℃ making beating, drying, roasting or not roasting under 400～800 ℃ of conditions; ℃ mix in room temperature to 95 with the mixed aqueous solution of the compound of one of the compound of one of Fe, Co, Ni and Metal Zn, Mn, Ga, Sn, drying, roasting or not roasting.Wherein, the order of twice mixing can be put upside down.
Mode 2: filter cake after the ammonium exchange and phosphorous compound aqueous solution is even in room temperature to 95 ℃ making beating, drying, roasting or not roasting under 400～800 ℃ of conditions; ℃ mix in room temperature to 95 with the compound water solution that contains one of Fe, Co, Ni, drying, roasting or not roasting under 400～800 ℃ of conditions; ℃ mix in room temperature to 95 with the compound water solution of one of containing metal Zn, Mn, Ga, Sn, drying, roasting or not roasting.Wherein, the order of above-mentioned three mixing can be arbitrarily.
Mode 3: with the mixed aqueous solution of the compound of one of the filter cake after the ammonium exchange and the compound that contains one of phosphorus compound, metal Fe, Co, Ni and Metal Zn, Mn, Ga, Sn after room temperature to 95 ℃ mixes, drying, roasting or not roasting.
Mode 4: filter cake after the ammonium exchange and phosphorous compound aqueous solution is even in room temperature to 95 ℃ making beating, dry, roasting or not roasting under 400～800 ℃ of conditions, with contain metal Fe, Co, the aqueous solution of one of Ni compound, or contain Metal Zn, Mn, Ga, the compound water solution of one of Sn or contain metal Fe simultaneously, Co, one of Ni compound and Metal Zn, Mn, Ga, the mixed aqueous solution of the compound of one of Sn is by 1: after the solid-to-liquid ratio of (5～20) mixes, at 80～95 ℃, pH=4～7, under agitation carry out ion-exchange 2～3 hours, filter, dry, roasting or not roasting.Wherein, described ion-exchange can repeat repeatedly.
Described phosphorus-containing compound is selected from one or more in water-soluble phosphorus compound, is preferably in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and the ammonium phosphate one or more.
Described Fe, Co, Ni compound and Zn, Mn, Ga, Sn compound are selected from their water soluble salt, a kind of as in their sulfate, nitrate, hydrochloride.
Wherein, a kind of compound of described dipping or carry out ion-exchange after drying can adopt the method for any drying, as dry, method such as oven dry.Dry temperature can be a room temperature to 350 ℃, is preferably 100-200 ℃.Dried sintering temperature is conventional sintering temperature, is 400-800 ℃ in general, is preferably 450-700 ℃.
The consumption of each component should guarantee to make the composition of the zeolite with MFI structure that contains phosphorus and bimetallic component that obtains to meet the anhydrous chemical expression of this zeolite.If sodium content wherein is undesirable, the method that can adopt the method for water washing filter cake or carry out ammonium exchange is removed sodium wherein.The method that the method that adopts the method for water washing filter cake or carry out the ammonium exchange is removed sodium wherein is conventionally known to one of skill in the art.
Catalyst provided by the invention can be applicable to existing catalytic cracking or Deep Catalytic Cracking process, be used to produce low-carbon alkene, improve the productive rate of low-carbon alkene, the productive rate of propylene and ethene particularly, increase the content of light aromatics in the gasoline simultaneously, also can be used for a kind of brand-new hydrocarbon conversion process, be about to heavy distillate and carry out catalyzed conversion, produce low-carbon alkene, particularly propylene and ethene and light aromatics.
Following example will the present invention is described further, but therefore do not limit the present invention.
Example 1-8 illustrates zeolite with MFI structure of phosphorous and bimetallic component and preparation method thereof.
Example 1
With 2 kilograms of NH
4Cl is dissolved in 100 kg of water, and (zeolite with MFI structure that contains rare earth, the Qilu Petrochemical catalyst plant is produced, SiO to add 10 kilograms of (butt) ZRP-1 zeolites in this solution
2With Al
2O
3Mol ratio be 30, rare earth oxide RE
2O
3Content is 4.0 weight %, and wherein, lanthana content is 2.12 weight %, and cerium oxide content is 0.52 weight %, and other rare earth oxide content is 1.36 weight %, Na
2O content is 1.7 weight %), carry out ion-exchange after 0.5 hour at 90 ℃, filter filter cake; Contain 0.34 kilogram of H with 9.8 kilograms
3PO
4, 0.29 kilogram of Fe (NO
3)
3With 0.15 kilogram of Zn (NO
3)
2Mixed solution and filter cake mix, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain the zeolite Z1 with MFI structure of phosphorous and metallic iron, zinc.The anhydrous chemical expression of Z1 is: 0.1Na
2O4.9Al
2O
32.4P
2O
50.9Fe
2O
30.6ZnO3.8RE
2O
387.3SiO
2Wherein, the anhydrous chemical expression of the zeolite with MFI structure of phosphorous and bimetallic component is to form with the element that x-ray fluorescence spectrometry strokes stone, obtains through conversion again.
Example 2
With 5 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-1 zeolites (with example 1) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.8 kilograms are contained 0.8 kilogram of NH
4H
2PO
4Solution mix, 120 ℃ of oven dry were 550 ℃ of roastings 2 hours; With the sample after the roasting in 5: 1 ratio of liquid-solid ratio and FeCl
3Concentration is 6.5 weight %, ZnCl
2Concentration is that the mixed solution of 4.7 weight % carries out ion-exchange 2 hours under 80-90 ℃, filter, under similarity condition, carry out ion-exchange again, until reaching aim parameter, 550 ℃ of roastings 2 hours, obtain the zeolite Z2 with MFI structure phosphorous and metallic iron, zinc again.The anhydrous chemical expression of Z2 is: 0.03Na
2O4.7Al
2O
34.5P
2O
51.6Fe
2O
31.4ZnO3.7RE
2O
384.1SiO
2
Example 3
With 2 kilograms of NH
4Cl is dissolved in 100 kg of water, and (zeolite with MFI structure, the Qilu Petrochemical catalyst plant is produced, SiO to add 10 kilograms of (butt) ZRP-5 zeolites in this solution
2With Al
2O
3Mol ratio be 60), carry out ion-exchange after 0.5 hour at 90 ℃, filter filter cake; The filter cake that obtains and 6.7 kilograms are contained 0.69 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 11.3 kilograms contain 2.26 kilograms of FeSO
4Solution mix, 120 ℃ of oven dry were 550 ℃ of roastings 2 hours; Sample after the roasting and 9.5 kilograms are contained 0.47 kilogram of ZnSO
4Solution mix, 120 ℃ of oven dry again 550 ℃ of roastings 2 hours, obtain the zeolite Z3 with MFI structure of phosphorous and metallic iron, zinc.The anhydrous chemical expression of Z3 is: 0.1Na
2O2.3Al
2O
33.6P
2O
510.0Fe
2O
32.0ZnO82.0SiO
2
Example 4
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-5 zeolites (with example 3) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.7 kilograms are contained 0.69 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.7 kilograms contain 0.49 kilogram of Fe (NO
3)
3With 0.24 kilogram of Mn (NO
3)
2Mixed solution mix, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain the zeolite Z4 with MFI structure of phosphorous and metallic iron, manganese.Z4's.Its anhydrous chemical expression is: 0.1Na
2O2.6Al
2O
34.0P
2O
51.5Fe
2O
31.1Mn
2O
390.7SiO
2
Example 5
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, and (zeolite with MFI structure, the Qilu Petrochemical catalyst plant is produced, SiO to add 10 kilograms of (butt) ZRP-5 zeolites in this solution
2With Al
2O
3Mol ratio be 70), carried out ion-exchange 0.5 hour at 85 ℃, filter filter cake; The filter cake that obtains and 6.3 kilograms are contained 0.26 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 10.1 kilograms contain 0.82 kilogram of Co (NO
3)
2With 0.24 kilogram of Mn (NO
3)
2Mixed solution mix, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain the zeolite Z5 with MFI structure of phosphorous and metallic cobalt, manganese.The anhydrous chemical expression of Z5 is: 0.1Na
2O2.2Al
2O
31.5P
2O
53.5Co
2O
31.1Mn
2O
391.6SiO
2
Example 6
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-5 zeolites (with example 3) in this solution, carries out ion-exchange after 0.5 hour at 85 ℃, filter filter cake; The filter cake that obtains and 6.7 kilograms are contained 0.70 kilogram of (NH
4)
2HPO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.7 kilograms contain 0.52 kilogram of Ni (NO
3)
2With 0.22 kilogram of Mn (NO
3)
2Mixed solution mix, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain the zeolite Z6 with MFI structure of phosphorous and metallic nickel, manganese.The anhydrous chemical expression of Z6 is: 0.1Na
2O2.6Al
2O
33.5P
2O
52.0NiO1.0Mn
2O
390.8SiO
2
Example 7
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-1 zeolites (with example 1) in this solution, carries out ion-exchange after 0.5 hour at 85 ℃, filter filter cake; The filter cake that obtains and 6.5 kilograms are contained 0.47 kilogram of (NH
4)
2HPO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.8 kilograms contain 0.51 kilogram of Fe (NO
3)
3With 0.32 kilogram of Ga (NO
3)
3Mixed solution mix, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain the zeolite Z7 with MFI structure of phosphorous and metallic iron, gallium.The anhydrous chemical expression of Z7 is: 0.1Na
2O4.9Al
2O
32.4P
2O
51.6Fe
2O
31.1Ga
2O
33.8RE
2O
386.1SiO
2
Example 8
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-5 zeolites (with example 3) in this solution, carries out ion-exchange after 0.5 hour at 85 ℃, filter filter cake; The filter cake that obtains and 7.0 kilograms are contained 0.95 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.5 kilograms contain 0.35 kilogram of FeCl
3With 0.14 kilogram of SnCl
2Mixed solution mix, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain the zeolite Z8 with MFI structure of phosphorous and metallic iron, tin.The anhydrous chemical expression of Z8 is: 0.07Na
2O2.5Al
2O
35.4P
2O
51.6Fe
2O
31.0SnO
289.4SiO
2
Example 9
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.34 kilogram of Ba (NO
3)
2Be dissolved in 18 kilograms of decationized Y sieve water, add 4.2 kilograms of halloysites (Suzhou china clay company industrial products, solid content 71.6 weight %) making beating, add 3.2 kilograms of boehmites (Shandong Aluminum Plant's industrial products, solid content 62.0 weight %) again, its pH is transferred to 2 with hydrochloric acid, stir, under 70 ℃, left standstill aging 1 hour, and added 3.7 kilograms of aluminium colloidal sols (Qilu Petrochemical company catalyst plant product, Al
2O
3Content is 21.5 weight %, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.4), stir, (the industrial trade mark is DASY2.0 to add the zeolite Z1 with MFI structure of phosphorous and metallic iron, zinc of 3.5 kilograms of (butt) examples 1 preparation and 0.5 kilogram of (butt) overstable gamma zeolite, Qilu Petrochemical catalyst plant industrial products, lattice constant is 2.446 nanometers, rare earth oxide RE
2O
3Content is 2.0 weight %, wherein, lanthana content is 1.06 weight %, cerium oxide content is 0.26 weight %, and other rare earth oxide content is 0.68 weight %) mixture and 11.4 kilograms of slurries obtaining of water making beating, stir, obtain the slurries that solid content is 24.5 weight %, with the slurries spray drying forming under 250 ℃ temperature that obtains is that diameter is the particle of 20-150 micron, 550 ℃ of roastings 2 hours, catalyst C1 provided by the invention.The composition of C1 sees Table 1.
Example 10
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 9 prepares catalyst, and different is with 0.46 kilogram of LaCl
37H
2O replaces 0.34 kilogram of Ba (NO
3)
2, replace Z1 with the phosphorous and metallic iron of example 2 preparation of equivalent, the zeolite Z2 with MFI structure of zinc, catalyst C2 provided by the invention.The composition of C2 sees Table 1.
Example 11
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 9 prepares catalyst, and different is with 0.17 kilogram of Ba (NO
3)
2With 0.34 kilogram of FeCl
3.6H
2O replaces 0.34 kilogram of Ba (NO
3)
2, replace Z1 with the phosphorous and metallic iron of example 7 preparation of equivalent, the zeolite Z7 with MFI structure of gallium, catalyst C3 provided by the invention.The composition of C3 sees Table 1.
Comparative Examples 1
The explanation of this Comparative Examples contains the reference catalyst and the preparation thereof of the zeolite with MFI structure of not phosphorous and bimetallic component.
Method by example 9 prepares catalyst, and different is to replace the phosphorous and metallic iron of example 1 preparation, the zeolite Z1 with MFI structure of zinc with ZRP-1 zeolite (with example 1), obtains reference catalyst CB1.The composition of CB1 sees Table 1.
Comparative Examples 2
The explanation of this Comparative Examples does not contain reference catalyst of auxiliary agent and preparation method thereof.
Method by example 9 prepares catalyst, and different is not add Ba (NO
3)
2, the consumption of aluminium colloidal sol is 4.7 kilograms, obtains reference catalyst CB2.The composition of CB2 sees Table 1.
Comparative Examples 3
This Comparative Examples illustrates the zeolite with MFI structure of not phosphorous and bimetallic component, and does not contain reference catalyst of auxiliary agent and preparation method thereof.
Method by example 9 prepares catalyst, and different is not add Ba (NO
3)
2, the consumption of aluminium colloidal sol is 4.7 kilograms, replaces the phosphorous and metallic iron of example 1 preparation, the zeolite Z1 with MFI structure of zinc with ZRP-1 zeolite (with example 1), obtains reference catalyst CB3.The composition of CB3 sees Table 1.
Table 1
| Example number | Example 9 | Example 10 | Example 11 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Catalyst | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| Clay types | Halloysite | Halloysite | Halloysite | Halloysite | Halloysite | Halloysite |
| Clay content, weight % | 30 | 30 | 30 | 30 | 30 | 30 |
| The heat-resistant inorganic oxide kind | Aluminium oxide | Aluminium oxide | Aluminium oxide | Aluminium oxide | Aluminium oxide | Aluminium oxide |
| Heat-resistant inorganic oxide content, weight % | 28 | 28 | 28 | 28 | 30 | 30 |
| The auxiliary agent kind | Barium | Lanthanum | Iron+barium | Barium | - | - |
| Auxiliary agent content (in oxide), weight % | 2 | 2 | 2 | 2 | - | - |
| Zeolite type with MFI structure | Z1 | Z2 | Z7 | ZRP-1 | Z1 | ZRP-1 |
| Zeolite content with MFI structure, weight % | 35 | 35 | 35 | 35 | 35 | 35 |
| The large pore zeolite kind | DASY2.0 | DASY2.0 | DASY2.0 | DASY2.0 | DASY2.0 | DASY2.0 |
| Large pore zeolite content, weight % | 5 | 5 | 5 | 5 | 5 | 5 |
Example 12
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.17 kilogram of Ba (NO
3)
2Be dissolved in 12.5 kilograms of decationized Y sieve water, add 4.0 kilograms of boehmites (with example 9), its pH is transferred to 2, stir, under 50 ℃, left standstill aging 5 hours, the product after obtaining wearing out with nitric acid.
In 2.5 kilograms of decationized Y sieve water, add 1.9 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.16), (solid content is 76 weight % to add 4.0 kilograms of kaolin again, Suzhou kaolin company produces) making beating, stir, add above-mentioned product after aging, phosphorous and the metallic iron that adds 3 preparations of 3 kilograms of (butt) examples again, (the industrial trade mark is USY for have MFI structural zeolite Z3 and 1 kilogram of (butt) overstable gamma zeolite of zinc, Qilu Petrochemical Zhou village catalyst plant industrial products, lattice constant is 2.445 nanometers, sodium oxide content is 0.36 weight %) 11.4 kilograms of slurries obtaining with decationized Y sieve water making beating, stir, obtaining the slurries that solid content is 27.4 weight %, under 220 ℃, is that diameter is the particle of 20-150 micron with the slurries spray drying forming that obtains, 520 ℃ of roastings 4 hours obtain catalyst C4 provided by the invention.The composition of C4 sees Table 2.
Example 13
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.17 kilogram of Ba (NO
3)
2Be dissolved in 18 kilograms of decationized Y sieve water, (solid content is 95 weight % to add 3.0 kilograms of halloysites (with example 9) and 0.9 kilogram of imvite, Zhejiang Feng Hong clay chemical industry Co., Ltd produces) making beating, add 4.0 kilograms of boehmites (with example 9) again, with hydrochloric acid its pH is transferred to 3.5, stir, add and Ba (NO
3)
2Equimolar sulfuric acid, make barium wherein be completed into barium sulfate precipitate, under 75 ℃, left standstill aging 0.5 hour, add 1.8 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.16), stir, phosphorous and the metallic iron that adds 4 preparations of 3.0 kilograms of (butt) examples, have MFI structural zeolite Z4 and 1.0 kilograms (butt) of manganese contain rare earth hydrogen Y zeolite (the industrial trade mark are REHY, Qilu Petrochemical Zhou village catalyst plant industrial products, lattice constant is 2.465 nanometers, sodium oxide content is 3.2 weight %, rare earth oxide content is 7.0 weight %, wherein, lanthana content is 3.71 weight %, cerium oxide content is 0.91 weight %, other rare earth oxide content is 2.38 weight %) 11.4 kilograms of slurries obtaining with water making beating, stir, obtain the slurries that solid content is 25.5 weight %, under 280 ℃, with the slurries spray drying forming that obtains is that diameter is the particle of 20-150 micron, 580 ℃ of roastings 2.5 hours obtain catalyst C5 provided by the invention.The composition of C5 sees Table 2.
Example 14
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.22 kilogram of CeCl
37H
2O is dissolved in 5.0 kilograms of decationized Y sieve water, floods 7.0 kilograms of halloysites (with example 9), and 120 ℃ of oven dry obtain containing CeO
22.0 the halloysite of weight %.
In 21.8 kilograms of decationized Y sieve water, add the above-mentioned CeO that contains
2Halloysite making beating, add 3.9 kilograms of boehmites again (with example 9, the heat-resistant inorganic oxide precursor all adds before aging), with hydrochloric acid its pH is transferred to 3, stir, under 60 ℃, left standstill aging 2 hours, phosphorous and the metallic cobalt that adds 5 preparations of 2.0 kilograms of (butt) examples, 7.2 kilograms of slurries that the zeolite Z5 with MFI structure of manganese and 0.5 kilogram of (butt) overstable gamma zeolite (with example 9) and water making beating obtain, stir, obtain the slurries that solid content is 25.2 weight %, under 250 ℃, with the slurries spray drying forming that obtains is that diameter is the particle of 20-150 micron, 600 ℃ of roastings 1 hour obtain catalyst C6 provided by the invention.The composition of C6 sees Table 2.
Example 15
This example illustrates Catalysts and its preparation method provided by the invention.
With 1.44 kilograms of Zr (SO
4)
24H
2O is dissolved in 18 kilograms of decationized Y sieve water, add 5.6 kilograms of halloysites (with example 9) making beating, add 3.2 kilograms of boehmites (with example 9) again, with hydrochloric acid its pH is transferred to 4, stir, under 60 ℃, left standstill aging 1 hour, add 2.3 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.25), stir, phosphorous and the metallic nickel that adds 6 preparations of 2.5 kilograms of (butt) examples, 8.6 kilograms of slurries that the zeolite Z6 with MFI structure of manganese and 0.5 kilogram of (butt) overstable gamma zeolite (with example 9) and water making beating obtain, stir, obtain the slurries that solid content is 25.6 weight %, under 220 ℃, with the slurries spray drying forming that obtains is that diameter is the particle of 20-150 micron, and 550 ℃ of roastings 2 hours obtain catalyst C7 provided by the invention.The composition of C7 sees Table 2.
Example 16
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.43 kilogram of Ba (NO
3)
2With 0.57 kilogram of LaCl
37H
2O is dissolved in 12 kilograms of decationized Y sieve water, add 3.2 kilograms of boehmites (with example 9) making beating, with hydrochloric acid its pH is transferred to 3, stir, under 55 ℃, left standstill aging 6 hours, (silica content is 16.0 weight % to add 25.0 kilograms of Ludox again, the Beijing Chemical Plant produces), with 2.3 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 2.25), stir, phosphorous and the metallic iron that adds 8 preparations of 3.0 kilograms of (butt) examples, 8.6 kilograms of slurries that the zeolite Z8 with MFI structure of tin and water making beating obtain, stir, obtaining the slurries that solid content is 19.2 weight %, under 250 ℃, is that diameter is the particle of 20-150 micron with the slurries spray drying forming that obtains, 550 ℃ of roastings 2 hours obtain catalyst C8 provided by the invention.The composition of C8 sees Table 2.
Table 2
| Example number | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 |
| Catalyst | C4 | C5 | C6 | C7 | C8 |
| Clay types | Kaolin | Halloysite+imvite | Halloysite | Halloysite | - |
| Clay content, weight % | 30 | 30 | 50 | 40 | - |
| The heat-resistant inorganic oxide kind | Aluminium oxide | Aluminium oxide | Aluminium oxide | Aluminium oxide | Aluminium oxide+silica |
| Heat-resistant inorganic oxide content, weight % | 29 | 29 | 24 | 25 | 65 |
| The auxiliary agent kind | Barium | Barium | Cerium | Zirconium | Barium+lanthanum |
| Auxiliary agent content (in oxide), weight % | 1 | 1 | 1 | 5 | 5 |
| Zeolite type with MFI structure | Z3 | Z4 | Z5 | Z6 | Z8 |
| What have the MFI structure strokes stone content, weight % | 30 | 30 | 20 | 25 | 30 |
| The large pore zeolite kind | USY | REHY | DASY2.0 | DASY2.0 | - |
| Large pore zeolite content, weight % | 10 | 10 | 5 | 5 | - |
Example 17-19
Following example illustrates the catalytic performance of catalyst provided by the invention.
At 800 ℃, with 100% steam aging 17 hours, in the reactor of the small fixed flowing bed device of packing into, the catalyst loading amount was 180 grams, is 580 ℃ in reaction temperature with catalyst C1-C3, and agent weight of oil ratio is 10, and weight (hourly) space velocity (WHSV) is 10 hours
-1Condition under, feed the mixture of vacuum gas oil (VGO) shown in the table 3 and water vapour, the amount of steam is 25 weight % of vacuum gas oil (VGO), the results are shown in Table 4.
Comparative Examples 4-6
The catalytic performance of following Comparative Examples explanation reference catalyst.
Method by example 17 is carried out catalyzed conversion to identical feedstock oil, and different is that catalyst system therefor is respectively reference catalyst CB1, CB2 and CB3, the results are shown in Table in 4.
Table 3
| The feedstock oil title | Vacuum gas oil (VGO) | Reduced crude |
| Density (20 ℃), gram per centimeter 3 | 0.8730 | 0.8906 |
| Viscosity, millimeter 2/ second | 8.04 | 24.84 |
| Asphalitine, weight % | - | 0.8 |
| Conradson carbon residue, weight % boiling range, ℃ | 0.15 | 4.3 |
| IBP | 346 | 282 |
| 10％ | 411 | 370 |
| 30％ | 437 | 482 |
| 50％ | 462 | 553 |
| 70％ | 489 | - |
| 90％ | 523 | - |
| FBP | 546 | - |
Table 4
| Example number | Example 17 | Example 18 | Example 19 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 |
| Catalyst | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| Conversion ratio | 92.2 | 92.0 | 91.9 | 86.8 | 91.7 | 88.1 |
| Product distributes, weight % | ||||||
| Cracked gas | 67.5 | 67.0 | 67.2 | 63.4 | 66.8 | 63.9 |
| Gasoline | 18.8 | 18.7 | 18.6 | 18.5 | 18.4 | 19.1 |
| Diesel oil | 4.5 | 4.6 | 4.6 | 8.1 | 4.8 | 6.9 |
| Heavy oil | 3.3 | 3.4 | 3.5 | 5.1 | 3.5 | 5.0 |
| Coke | 5.9 | 6.3 | 6.1 | 4.9 | 6.5 | 5.1 |
| Wherein, third is rare | 31.3 | 31.0 | 31.4 | 28.3 | 29.5 | 27.8 |
| Wherein, ethene | 10.2 | 10.1 | 9.9 | 8.8 | 9.2 | 8.6 |
| Wherein, BTX * | 6.1 | 6.0 | 5.9 | 5.7 | 5.8 | 5.7 |
*BTX represents benzene, toluene and dimethylbenzene.
The presentation of results of table 4, identical with aging under the same conditions zeolite content, the catalyst of the zeolite with MFI structure of not phosphorous and bimetallic component is compared, the heavy oil cracking ability of catalyst provided by the invention significantly improves, the cracked gas productive rate is higher, and particularly propylene and ethene and BTX productive rate are higher; Identical with zeolite content and type, the catalyst that does not contain auxiliary agent is compared, and catalyst provided by the invention has higher propylene, ethene and BTX productive rate and lower coke yield.This illustrates that catalyst provided by the invention has good activity stability and selectivity.
Example 20-24
Following example illustrates the catalytic performance of catalyst provided by the invention.
Method by example 1 is carried out catalyzed conversion to feedstock oil, and different is, uses catalyst C4-C8 replaced C 1 respectively, and raw materials used oil is reduced crude shown in the table 3, and reaction condition and reaction result see Table 5.
Table 5
| Example number | Example 20 | Example 21 | Example 22 | Example 23 | Example 24 |
| Catalyst | C4 | C5 | C6 | C7 | C8 |
| Reaction temperature, ℃ | 550 | 580 | 620 | 620 | 680 |
| Agent weight of oil ratio | 10 | 10 | 10 | 15 | 25 |
| Weight (hourly) space velocity (WHSV), hour -1 | 10 | 10 | 15 | 15 | 20 |
| The amount of steam is the percetage by weight of reduced crude, weight % | 25 | 25 | 50 | 80 | 80 |
| Conversion ratio | 79.8 | 83.4 | 86.4 | 88.5 | 92.4 |
| Product distributes, weight % | |||||
| Cracked gas | 50.1 | 53.5 | 54.9 | 57.6 | 61.5 |
| Gasoline | 21.6 | 20.2 | 19.4 | 18.3 | 16.4 |
| Diesel oil | 12.6 | 10.5 | 9.0 | 7.5 | 5.9 |
| Heavy oil | 7.6 | 6.1 | 4.6 | 4.0 | 1.7 |
| Coke | 8.1 | 9.7 | 12.1 | 12.6 | 14.5 |
| Wherein, propylene | 21.3 | 23.2 | 24.1 | 25.3 | 22.8 |
| Wherein, ethene | 7.6 | 10.1 | 12.3 | 12.9 | 21.5 |
| Wherein, BTX | 6.2 | 6.8 | 6.9 | 7.1 | 6.8 |
Claims (17)
1. Hydrocarban coversion catalysts that contains zeolite, this catalyst contains zeolite, heat-resistant inorganic oxide, contain or argillaceous not, it is characterized in that, described zeolite is to contain the zeolite with MFI structure of phosphorus and bimetallic component or this contains the zeolite with MFI structure of phosphorus and bimetallic component and the mixture of large pore zeolite, in the total amount of zeolite, the content that contains the zeolite with MFI structure of phosphorus and bimetallic component is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide, the described zeolite with MFI structure that contains phosphorus and bimetallic component has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5.5) Al
2O
3(1.0-10) P
2O
5(0.7-15) Ml
xO
y(0.01-5) M2
mO
n(0-10) RE
2O
3(70-97) SiO
2, wherein, M1 is selected from a kind of metal among Fe, Co and the Ni, M2 is selected from a kind of metal among Zn, Mn, Ga and the Sn, and RE represents rare earth metal, and x is 1 or 2, when x is 1, the numerical value of y be metal M 1 valent half, when x is 2, the numerical value of y is metal M 1 chemical valence, m is 1 or 2, when m is 1, the numerical value of n be metal M 2 valent half, when m was 2, the numerical value of n was metal M 2 chemical valences; This catalyst also contains a kind of auxiliary agent, and described auxiliary agent is selected from one or more in barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, the nickel; With the catalyst total amount is benchmark, and the content of zeolite is 1-60 weight %, in oxide, and the content of auxiliary agent is that the content of 0.1-10 weight %, heat-resistant inorganic oxide is that the content of 5-70 weight %, clay is 0-70 weight %.
2. catalyst according to claim 1, it is characterized in that, with the catalyst total amount is benchmark, and the content of zeolite is that the content of 10-50 weight %, auxiliary agent is that the content of 0.5-8 weight %, heat-resistant inorganic oxide is that the content of 10-70 weight %, clay is 0-60 weight %.
3. catalyst according to claim 1 is characterized in that, in the quality of oxide, the described zeolite with MFI structure that contains phosphorus and bimetallic component has following anhydrous chemical expression: (0-0.2) Na
2O (0.9-5) Al
2O
3(1.5-7) P
2O
5(0.9-10) Ml
xO
y(0.5-2) M2
mO
n(0.5-10) RE
2O
3(82-92) SiO
2
4. catalyst according to claim 1 is characterized in that, M1 is Fe.
5. catalyst according to claim 1 is characterized in that, M2 is Zn.
6. catalyst according to claim 1 is characterized in that, M1 is Fe, and M2 is Zn.
7. catalyst according to claim 1 is characterized in that, described large pore zeolite is selected from one or more in y-type zeolite, overstable gamma zeolite, the Beta zeolite.
8. catalyst according to claim 1 is characterized in that, described large pore zeolite is selected from one or more in faujasite, L zeolite, Beta zeolite, omega zeolite, modenite, the ZSM-18 zeolite.
9. catalyst according to claim 7 is characterized in that, described y-type zeolite is selected from the overstable gamma zeolite that the y-type zeolite of phosphorous and/or rare earth, described overstable gamma zeolite are selected from phosphorous and/or rare earth.
10. catalyst according to claim 1 is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica, the amorphous silicon aluminium.
11. catalyst according to claim 1 is characterized in that, described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
12. claim 1 Preparation of catalysts method, this method comprises all or part of heat-resistant inorganic oxide and/or its precursor and water mixing making beating, adds or do not add clay, adds zeolite, the slurries that drying obtains, roasting then is characterized in that, before adding zeolite, add before or after the clay, also add a kind of auxiliary compound, add a kind of acid and make the pH value of slurries be 1-5, and under 30-90 ℃ temperature, wore out 0.1-10 hour; Aging back adds remaining heat-resistant inorganic oxide and/or its precursor; Described zeolite is to contain the zeolite with MFI structure of phosphorus and bimetallic component or this contains the zeolite with MFI structure of phosphorus and bimetallic component and a kind of mixture of large pore zeolite, total amount in zeolite, the content that contains the zeolite with MFI structure of phosphorus and bimetallic component is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide, the described zeolite with MFI structure that contains phosphorus and bimetallic component has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5.5) Al
2O
3(1.0-10) P
2O
5(0.7-15) M1
xO
y(0.01-5) M2
mO
n(0-10) RE
2O
3(70-97) SiO
2, wherein, M1 is selected from a kind of metal among Fe, Co and the Ni, M2 is selected from a kind of metal among Zn, Mn, Ga and the Sn, and RE represents rare earth metal, and x is 1 or 2, when x is 1, the numerical value of y be metal M 1 valent half, when x is 2, the numerical value of y is metal M 1 chemical valence, m is 1 or 2, when m is 1, the numerical value of n be metal M 2 valent half, when m was 2, the numerical value of n was metal M 2 chemical valences; The consumption of each component makes in the final catalyst and contains, and is benchmark with the catalyst total amount, the zeolite of 1-60 weight %, in oxide, the heat-resistant inorganic oxide of 0.1-10 weight % auxiliary agent, 5-70 weight % and the clay of 0-70 weight %.
13. method according to claim 12, it is characterized in that, before aging, add part heat-resistant inorganic oxide and/or its precursor earlier, add remaining heat-resistant inorganic oxide and/or its precursor again after aging, the part that adds and back add part to make the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide that adds earlier in the catalyst and back add are 1: 0.1-10 earlier.
14. method according to claim 13 is characterized in that, described weight ratio is 1: 0.1-5.
15. method according to claim 12 is characterized in that, described acid is selected from one or more in hydrochloric acid, nitric acid, the phosphoric acid; The consumption of acid makes the pH value of slurries be 1.5-4.
16. method according to claim 12 is characterized in that, described aging temperature is 40-80 ℃, and the aging time is 0.5-8 hour.
17. method according to claim 12 is characterized in that, described auxiliary compound is selected from one or more in the halide, nitrate, sulfate, phosphate of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100689364A CN1332756C (en) | 2004-07-14 | 2004-07-14 | Hydrocarbon conversion catalyst containing zeolite |
| EP05733042.5A EP1762299B1 (en) | 2004-03-31 | 2005-03-31 | A catalyst containing zeolite for hydrocarbon converting and preparation thereof, and a hydrocarbon oil converting method using said catalyst |
| PCT/CN2005/000427 WO2005094992A1 (en) | 2004-03-31 | 2005-03-31 | A catalyst containing zeolite for hydrocarbon converting and preparation thereof, and a hydrocarbon oil converting method using said catalyst |
| CA2563262A CA2563262C (en) | 2004-03-31 | 2005-03-31 | A zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst |
| BRPI0509507-7A BRPI0509507B1 (en) | 2004-03-31 | 2005-03-31 | hydrocarbon conversion catalyst containing zeolite, the process for preparing them, and a process for converting hydrocarbon oils with the catalyst |
| JP2007505361A JP4987693B2 (en) | 2004-03-31 | 2005-03-31 | Zeolite-containing hydrocarbon conversion catalyst, method for producing the same, and method for converting hydrocarbon oil with the catalyst |
| US11/547,209 US7923399B2 (en) | 2004-03-31 | 2005-03-31 | Zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst |
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|---|---|---|---|
| CNB2004100689364A CN1332756C (en) | 2004-07-14 | 2004-07-14 | Hydrocarbon conversion catalyst containing zeolite |
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| CN1721072A CN1721072A (en) | 2006-01-18 |
| CN1332756C true CN1332756C (en) | 2007-08-22 |
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| CN107974286B (en) * | 2016-10-21 | 2020-11-13 | 中国石油化工股份有限公司 | Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon |
| CN114425376B (en) * | 2020-09-27 | 2024-03-12 | 中国石油化工股份有限公司 | Hydrocarbon conversion catalyst containing MFI zeolite and its preparation method |
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| US5318696A (en) * | 1992-12-11 | 1994-06-07 | Mobil Oil Corporation | Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component |
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