CN105838415A - Method for producing alkane by catalytically cracking naphtha - Google Patents
Method for producing alkane by catalytically cracking naphtha Download PDFInfo
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- CN105838415A CN105838415A CN201610401567.9A CN201610401567A CN105838415A CN 105838415 A CN105838415 A CN 105838415A CN 201610401567 A CN201610401567 A CN 201610401567A CN 105838415 A CN105838415 A CN 105838415A
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- 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates (APO compounds)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a method for producing alkane by catalytically cracking naphtha. The naphtha is catalytically cracked to obtain a crack reaction product in the existence of a first catalyst, a second catalyst and a sodium chloride aqueous solution with a mass fraction of 3 to 7 percent. Compared with the prior art, the method has the following advantages: (1) a mesoporous/microporous composite molecular sieve is used as a catalyst, so that the stability of the molecular sieve is improved, an acidic center of the molecular sieve is provided, the catalytic efficiency is improved, and the alkane yield is increased; and (2) the catalytic cracking method is low in reaction temperature and less in energy consumption.
Description
Technical field
The invention belongs to PETROLEUM PROCESSING field, relate to a kind of method that naphtha catalytic cracking produces alkane.
Background technology
Petrochemical industry is one of pillar industry promoting development of world economy, and hydro carbons processing is as petrochemical industry
Tap, its level of development oneself become one of the important symbol weighing a national economic strength, at petrochemical industry or even national warp
Ji development has very important status.
Along with the development of World Economics, the market demand of hydrocarbon resources sharply increases.2005, whole world ethylene requirements amount
Rising to 1.07 hundred million tons, propylene demand reaches 67,100,000 tons, and within 2006, global ethylene requirements amount is about 1.15 hundred million tons, 2006-
2010, ethylene requirements annual rate of growth was about 4.3%, and the average annual growth of propylene demand reaches 5.13%, for keeping this to need
Asking rate of increase, 2006-2010, year is increased by 5.4%, for 1.5 times of GDP growth rate, global second in 2006 by ethylene production capacity
Alkene supply breach is about 2,310,000 tons, will supply falls short of demand, it was predicted that the demand that following 20 years whole world is to plastics in the coming years
To increase further, the demand of ethylene will be quadrupled, be up to 2.16 hundred million tons to the year two thousand twenty.The whole world ethylene requirements growth with
Economic Growth is close, even if petroleum chemicals market is the most saturated, but also will increase substantially the demand of ethylene, whole world ethylene
Industry will enter the high speed development stage.
Catalytic pyrolysis is under conditions of catalyst exists, and in relatively low temperature, petroleum hydrocarbon carries out cracking and comes
Obtain the production process of the low-carbon alkanes of high yield.Compared with steam heat cracking, this process reaction temperature is reacted than Standard cleavage
Temperature is low, therefore cracks less energy consumption than common steam.Cracking furnace pipe inwall coking rate will reduce, thus can extend operation week
Phase, increasing the boiler tube life-span, CO2 emission also can reduce, and alleviates pollution, and product structure can be adjusted flexibly.With traditional
The product yield of steam cracking technology is compared, and this new technique can increase the total recovery of alkane, produces used by equal number alkane
Feed naphtha can reduce nearly 40%, and production cost is greatly lowered.
But catalyst of the prior art is because of the hole wall randomness of its mesopore molecular sieve so that it is easily because of the hydrolysis of local
Or heat effect and cause pore structure to be caved in, therefore can not simply micro porous molecular sieve and mesopore molecular sieve mechanical mixture be used,
Thus reduce catalytic efficiency.Additionally, the cleavage method used in prior art needs to improve reaction temperature, thus energy consumption increases
Height, and the alkane yield obtained is relatively low, is mixed with other hydrocarbon compounds in product.
Summary of the invention
Present invention solves the technical problem that and be: in order to overcome the defect of prior art, it is thus achieved that a kind of alkane yield is high, and energy
Consume few catalytic cracking method, the invention provides a kind of method that naphtha catalytic cracking produces alkane.
Technical scheme: a kind of naphtha catalytic cracking produces the method for alkane, and described method is:
The first catalyst, the second catalyst and mass fraction be 3～7% sodium-chloride water solution in the presence of, Petroleum is carried out
Catalytic pyrolysis, obtains cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 13～26 parts, phosphate aluminium molecular sieve 17～31
Part, aluminium oxide 8～22 parts, lanthana 7～21 parts, titanium dioxide 6～18 parts, sodium phosphate 9～32 parts, silicon dioxide 7～15 parts,
Hydrochloric acid 8～19 parts；Second catalyst, by weight, composed of the following components: white carbon black 9～17 parts, sodium phosphate 11～28 parts,
ZSM-5 zeolite 14～28 parts, sodium bicarbonate 8～14 parts, COK-5 zeolite 21～34 parts, sodium silicate 7～19 parts.
Preferably, the detailed process of described catalytic pyrolysis is as follows:
1st step, under conditions of pressure is 0.12～0.95MPa, the volume ratio of Petroleum and sodium-chloride water solution is 2～7:1
～3, naphtha feed weight (hourly) space velocity (WHSV) is 3～12h-1, temperature is 25～32 DEG C, adds the first catalyst, and catalytic reaction obtains the
One catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.23～1.2MPa, with sodium-chloride water solution by volume 2～
5:1～3 mixing, naphtha feed weight (hourly) space velocity (WHSV) is 16～35h-1, temperature is 37～45 DEG C, adds the second catalyst, and catalysis is anti-
The second catalytic pyrolysis product should be obtained；
3rd step, the second catalytic pyrolysis product is added in reactor, under the conditions of 0.01～0.32MPa, spray quality wherein
Mark is the potassium hydrogen phosphate aqueous solution of 1～3.6%, washes 2～4 times.
Preferably, described first catalyst is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, 45～65
Hydrolyze and aging 5～35 hours under the conditions of DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is adjusted to 8.6～10.2, then be added to Kaolin, oxygen
Change lanthanum and silicon dioxide, after stirring, crystallization 13～55 hours under the conditions of 85～150 DEG C, filter, wash acquisition first and urge
Agent precursor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide, roasting 2～5 under the conditions of 450～600 DEG C are added
Hour, can be prepared by the first catalyst.
Preferably, described second catalyst is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, pressure be 2.3～
4.5MPa, temperature is reacted 3～6 hours under the conditions of being 212～356 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate are added, after stirring, under the conditions of 100～150 DEG C
Crystallization 12～30 hours, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 2～5 hours under the conditions of 565～625 DEG C, can be prepared by second
Catalyst.
Preferably, described first catalyst, by weight, composed of the following components: Kaolin 21 parts, phosphate aluminium molecular sieve
23 parts, aluminium oxide 16 parts, lanthana 15 parts, titanium dioxide 13 parts, sodium phosphate 25 parts, silica 12 parts, hydrochloric acid 16 parts；Second
Catalyst, by weight, composed of the following components: white carbon black 12 parts, sodium phosphate 24 parts, ZSM-5 zeolite 22 parts, sodium bicarbonate 11
Part, 31 parts of COK-5 zeolite, sodium silicate 14 parts.
Further, the detailed process of described catalytic pyrolysis is as follows:
1st step, under conditions of pressure is 0.75MPa, the volume ratio of Petroleum and sodium-chloride water solution is 5:2, and Petroleum enters
Material weight (hourly) space velocity (WHSV) is 9h-1, temperature is 28 DEG C, adds the first catalyst, and catalytic reaction obtains the first catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.89MPa, mix with sodium-chloride water solution 3:1 by volume,
Naphtha feed weight (hourly) space velocity (WHSV) is 28h-1, temperature is 40 DEG C, adds the second catalyst, and catalytic reaction obtains the second catalytic pyrolysis and produces
Thing；
3rd step, being added in reactor by the second catalytic pyrolysis product, under the conditions of 0.25MPa, spraying mass fraction wherein is
The potassium hydrogen phosphate aqueous solution of 2.7%, washes 3 times.
Further, described first catalyst is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, at 58 DEG C of bars
Hydrolyze and aging 27 hours under part；
(2) take step (1) described solution, and with sodium carbonate pH value be adjusted to 9.5, then be added to Kaolin, lanthana and
Silicon dioxide, after stirring, crystallization 40 hours under the conditions of 128 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide is added, roasting 4 hours under the conditions of 545 DEG C, i.e.
The first catalyst can be prepared.
Further, described second catalyst is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 3.7MPa at pressure, temperature
Degree reacts 4.5 hours under the conditions of being 312 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate, after stirring, crystallization 24 under the conditions of 138 DEG C are added
Hour, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 4 hours under the conditions of 590 DEG C, can be prepared by the second catalyst.
Beneficial effect: (1) present invention uses mesoporous/mesoporous-microporous composite molecular sieve as catalyst, improves the stability of molecular sieve,
And provide acidic zeolite center, thus improve catalytic efficiency so that alkane yield improves；(2) catalysis of the present invention
Cleavage method reaction temperature is low, power consumption is few.
Detailed description of the invention
Embodiment 1
A kind of naphtha catalytic cracking produces the method for alkane, and described method is:
In the presence of the first catalyst, the second catalyst and sodium-chloride water solution that mass fraction is 3%, Petroleum is urged
Change cracking, obtain cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 13 parts, phosphate aluminium molecular sieve 17 parts, oxidation
8 parts of aluminum, lanthana 7 parts, titanium dioxide 6 parts, sodium phosphate 9 parts, silicon dioxide 7 parts, hydrochloric acid 8 parts；Second catalyst, by weight
Meter, composed of the following components: white carbon black 9 parts, sodium phosphate 11 parts, ZSM-5 zeolite 14 parts, sodium bicarbonate 8 parts, 21 parts of COK-5 zeolite,
Sodium silicate 7 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, under conditions of pressure is 0.12MPa, the volume ratio of Petroleum and sodium-chloride water solution is 2:1, and Petroleum enters
Material weight (hourly) space velocity (WHSV) is 3h-1, temperature is 25 DEG C, adds the first catalyst, and catalytic reaction obtains the first catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.23MPa, mix with sodium-chloride water solution 2:1 by volume,
Naphtha feed weight (hourly) space velocity (WHSV) is 16h-1, temperature is 37 DEG C, adds the second catalyst, and catalytic reaction obtains the second catalytic pyrolysis and produces
Thing；
3rd step, being added in reactor by the second catalytic pyrolysis product, under the conditions of 0.01MPa, spraying mass fraction wherein is
The potassium hydrogen phosphate aqueous solution of 1%, washes 2 times.
Described first catalyst is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, at 45 DEG C of bars
Hydrolyze and aging 5 hours under part；
(2) take step (1) described solution, and with sodium carbonate pH value be adjusted to 8.6, then be added to Kaolin, lanthana and
Silicon dioxide, after stirring, crystallization 13 hours under the conditions of 85 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide is added, roasting 2 hours under the conditions of 450 DEG C, i.e.
The first catalyst can be prepared.
Described second catalyst is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 2.3MPa at pressure, temperature
Degree reacts 3 hours under the conditions of being 212 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate, after stirring, crystallization 12 under the conditions of 100 DEG C are added
Hour, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 2 hours under the conditions of 565 DEG C, can be prepared by the second catalyst.
Embodiment 2
A kind of naphtha catalytic cracking produces the method for alkane, and described method is:
In the presence of the first catalyst, the second catalyst and sodium-chloride water solution that mass fraction is 5%, Petroleum is urged
Change cracking, obtain cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 21 parts, phosphate aluminium molecular sieve 23 parts, oxidation
16 parts of aluminum, lanthana 15 parts, titanium dioxide 13 parts, sodium phosphate 25 parts, silica 12 parts, hydrochloric acid 16 parts；Second catalyst, presses
Weight portion meter, composed of the following components: white carbon black 12 parts, sodium phosphate 24 parts, ZSM-5 zeolite 22 parts, sodium bicarbonate 11 parts, COK-5
31 parts of zeolite, sodium silicate 14 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, under conditions of pressure is 0.75MPa, the volume ratio of Petroleum and sodium-chloride water solution is 5:2, and Petroleum enters
Material weight (hourly) space velocity (WHSV) is 9h-1, temperature is 28 DEG C, adds the first catalyst, and catalytic reaction obtains the first catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.89MPa, mix with sodium-chloride water solution 3:1 by volume,
Naphtha feed weight (hourly) space velocity (WHSV) is 28h-1, temperature is 40 DEG C, adds the second catalyst, and catalytic reaction obtains the second catalytic pyrolysis and produces
Thing；
3rd step, being added in reactor by the second catalytic pyrolysis product, under the conditions of 0.25MPa, spraying mass fraction wherein is
The potassium hydrogen phosphate aqueous solution of 2.7%, washes 3 times.
Described first catalyst is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, at 58 DEG C of bars
Hydrolyze and aging 27 hours under part；
(2) take step (1) described solution, and with sodium carbonate pH value be adjusted to 9.5, then be added to Kaolin, lanthana and
Silicon dioxide, after stirring, crystallization 40 hours under the conditions of 128 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide is added, roasting 4 hours under the conditions of 545 DEG C, i.e.
The first catalyst can be prepared.
Described second catalyst is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 3.7MPa at pressure, temperature
Degree reacts 4.5 hours under the conditions of being 312 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate, after stirring, crystallization 24 under the conditions of 138 DEG C are added
Hour, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 4 hours under the conditions of 590 DEG C, can be prepared by the second catalyst.
Embodiment 3
A kind of naphtha catalytic cracking produces the method for alkane, and described method is:
In the presence of the first catalyst, the second catalyst and sodium-chloride water solution that mass fraction is 7%, Petroleum is urged
Change cracking, obtain cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 26 parts, phosphate aluminium molecular sieve 31 parts, oxidation
22 parts of aluminum, lanthana 21 parts, titanium dioxide 18 parts, sodium phosphate 32 parts, silica 15 parts, hydrochloric acid 19 parts；Second catalyst, presses
Weight portion meter, composed of the following components: white carbon black 17 parts, sodium phosphate 28 parts, ZSM-5 zeolite 28 parts, sodium bicarbonate 14 parts, COK-5
34 parts of zeolite, sodium silicate 19 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, under conditions of pressure is 0.95MPa, the volume ratio of Petroleum and sodium-chloride water solution is 7:3, and Petroleum enters
Material weight (hourly) space velocity (WHSV) is 12h-1, temperature is 32 DEG C, adds the first catalyst, and catalytic reaction obtains the first catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 1.2MPa, mix with sodium-chloride water solution 5:3 by volume, stone
Cerebrol charging weight (hourly) space velocity (WHSV) is 35h-1, temperature is 45 DEG C, adds the second catalyst, and catalytic reaction obtains the second catalytic pyrolysis and produces
Thing；
3rd step, being added in reactor by the second catalytic pyrolysis product, under the conditions of 0.32MPa, spraying mass fraction wherein is
The potassium hydrogen phosphate aqueous solution of 3.6%, washes 4 times.
Described first catalyst is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, at 65 DEG C of bars
Hydrolyze and aging 35 hours under part；
(2) take step (1) described solution, and with sodium carbonate pH value be adjusted to 10.2, then be added to Kaolin, lanthana and
Silicon dioxide, after stirring, crystallization 55 hours under the conditions of 150 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide is added, roasting 5 hours under the conditions of 600 DEG C, i.e.
The first catalyst can be prepared.
Described second catalyst is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 4.5MPa at pressure, temperature
Degree reacts 6 hours under the conditions of being 356 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate, after stirring, crystallization 30 under the conditions of 150 DEG C are added
Hour, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 5 hours under the conditions of 625 DEG C, can be prepared by the second catalyst.
Reference examples
Difference with embodiment 2 is, without titanium dioxide in the first catalyst, without white carbon black in the second catalyst, specifically urges
Change cracking process as follows:
A kind of naphtha catalytic cracking produces the method for alkane, and described method is:
In the presence of the first catalyst, the second catalyst and sodium-chloride water solution that mass fraction is 5%, Petroleum is urged
Change cracking, obtain cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 21 parts, phosphate aluminium molecular sieve 23 parts, oxidation
16 parts of aluminum, lanthana 15 parts, sodium phosphate 25 parts, silica 12 parts, hydrochloric acid 16 parts；Second catalyst, by weight, by with
Lower component forms: sodium phosphate 24 parts, ZSM-5 zeolite 22 parts, sodium bicarbonate 11 parts, 31 parts of COK-5 zeolite, sodium silicate 14 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, under conditions of pressure is 0.75MPa, the volume ratio of Petroleum and sodium-chloride water solution is 5:2, and Petroleum enters
Material weight (hourly) space velocity (WHSV) is 9h-1, temperature is 28 DEG C, adds the first catalyst, and catalytic reaction obtains the first catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.89MPa, mix with sodium-chloride water solution 3:1 by volume,
Naphtha feed weight (hourly) space velocity (WHSV) is 28h-1, temperature is 40 DEG C, adds the second catalyst, and catalytic reaction obtains the second catalytic pyrolysis and produces
Thing；
3rd step, being added in reactor by the second catalytic pyrolysis product, under the conditions of 0.25MPa, spraying mass fraction wherein is
The potassium hydrogen phosphate aqueous solution of 2.7%, washes 3 times.
Described first catalyst is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, at 58 DEG C of bars
Hydrolyze and aging 27 hours under part；
(2) take step (1) described solution, and with sodium carbonate pH value be adjusted to 9.5, then be added to Kaolin, lanthana and
Silicon dioxide, after stirring, crystallization 40 hours under the conditions of 128 DEG C, filter, wash acquisition the first catalyst.
Described second catalyst is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 3.7MPa at pressure, temperature
Degree reacts 4.5 hours under the conditions of being 312 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate, after stirring, crystallization 24 under the conditions of 138 DEG C are added
Hour, filter, wash acquisition the second catalyst.
Detecting embodiment 1～3 with reference examples catalytic pyrolysis effect, result is as shown in the table:
Claims (8)
1. the method that a naphtha catalytic cracking produces alkane, it is characterised in that described method is:
The first catalyst, the second catalyst and mass fraction be 3～7% sodium-chloride water solution in the presence of, Petroleum is carried out
Catalytic pyrolysis, obtains cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 13～26 parts, phosphate aluminium molecular sieve 17～31
Part, aluminium oxide 8～22 parts, lanthana 7～21 parts, titanium dioxide 6～18 parts, sodium phosphate 9～32 parts, silicon dioxide 7～15 parts,
Hydrochloric acid 8～19 parts；Second catalyst, by weight, composed of the following components: white carbon black 9～17 parts, sodium phosphate 11～28 parts,
ZSM-5 zeolite 14～28 parts, sodium bicarbonate 8～14 parts, COK-5 zeolite 21～34 parts, sodium silicate 7～19 parts.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that described catalytic pyrolysis
Detailed process as follows:
1st step, under conditions of pressure is 0.12～0.95MPa, the volume ratio of Petroleum and sodium-chloride water solution is 2～7:1
～3, naphtha feed weight (hourly) space velocity (WHSV) is 3～12h-1, and temperature is 25～32 DEG C, adds the first catalyst, and catalytic reaction obtains the
One catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.23～1.2MPa, with sodium-chloride water solution by volume 2～
5:1～3 mixing, naphtha feed weight (hourly) space velocity (WHSV) is 16～35h-1, and temperature is 37～45 DEG C, adds the second catalyst, and catalysis is anti-
The second catalytic pyrolysis product should be obtained；
3rd step, the second catalytic pyrolysis product is added in reactor, under the conditions of 0.01～0.32MPa, spray quality wherein
Mark is the potassium hydrogen phosphate aqueous solution of 1～3.6%, washes 2～4 times.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that described first catalysis
Agent is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, 45～65
Hydrolyze and aging 5～35 hours under the conditions of DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is adjusted to 8.6～10.2, then be added to Kaolin, oxygen
Change lanthanum and silicon dioxide, after stirring, crystallization 13～55 hours under the conditions of 85～150 DEG C, filter, wash acquisition first and urge
Agent precursor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide, roasting 2～5 under the conditions of 450～600 DEG C are added
Hour, can be prepared by the first catalyst.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that described second catalysis
Agent is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, pressure be 2.3～
4.5MPa, temperature is reacted 3～6 hours under the conditions of being 212～356 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate are added, after stirring, under the conditions of 100～150 DEG C
Crystallization 12～30 hours, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 2～5 hours under the conditions of 565～625 DEG C, can be prepared by second
Catalyst.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that the first catalyst,
By weight, composed of the following components: Kaolin 21 parts, phosphate aluminium molecular sieve 23 parts, aluminium oxide 16 parts, lanthana 15 parts, two
Titanium oxide 13 parts, sodium phosphate 25 parts, silica 12 parts, hydrochloric acid 16 parts；Second catalyst, by weight, by following components
Composition: white carbon black 12 parts, sodium phosphate 24 parts, ZSM-5 zeolite 22 parts, sodium bicarbonate 11 parts, 31 parts of COK-5 zeolite, sodium silicate 14 parts.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that described catalytic pyrolysis
Detailed process as follows:
1st step, under conditions of pressure is 0.75MPa, the volume ratio of Petroleum and sodium-chloride water solution is 5:2, and Petroleum enters
Material weight (hourly) space velocity (WHSV) is 9h-1, and temperature is 28 DEG C, adds the first catalyst, and catalytic reaction obtains the first catalytic pyrolysis product；
2nd step, by the first catalysate under the conditions of pressure is 0.89MPa, mix with sodium-chloride water solution 3:1 by volume,
Naphtha feed weight (hourly) space velocity (WHSV) is 28h-1, and temperature is 40 DEG C, adds the second catalyst, and catalytic reaction obtains the second catalytic pyrolysis
Product；
3rd step, being added in reactor by the second catalytic pyrolysis product, under the conditions of 0.25MPa, spraying mass fraction wherein is
The potassium hydrogen phosphate aqueous solution of 2.7%, washes 3 times.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that described first catalysis
Agent is prepared by following methods:
(1) aluminium oxide is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, at 58 DEG C of bars
Hydrolyze and aging 27 hours under part；
(2) take step (1) described solution, and with sodium carbonate pH value be adjusted to 9.5, then be added to Kaolin, lanthana and
Silicon dioxide, after stirring, crystallization 40 hours under the conditions of 128 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, titanium dioxide is added, roasting 4 hours under the conditions of 545 DEG C, i.e.
The first catalyst can be prepared.
A kind of naphtha catalytic cracking produces the method for alkane, it is characterised in that described second catalysis
Agent is prepared by following methods:
(1) add ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 3.7MPa at pressure, temperature
Degree reacts 4.5 hours under the conditions of being 312 DEG C；
(2) in the reactor of step (1), sodium bicarbonate and sodium silicate, after stirring, crystallization 24 under the conditions of 138 DEG C are added
Hour, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 4 hours under the conditions of 590 DEG C, can be prepared by the second catalyst.
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| CN106588532A (en) * | 2016-12-17 | 2017-04-26 | 段清 | Method of producing ethylene through catalytic cracking |
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