CN106008144A - Method for producing vinyl chloride through catalytic cracking - Google Patents
Method for producing vinyl chloride through catalytic cracking Download PDFInfo
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- CN106008144A CN106008144A CN201610400763.4A CN201610400763A CN106008144A CN 106008144 A CN106008144 A CN 106008144A CN 201610400763 A CN201610400763 A CN 201610400763A CN 106008144 A CN106008144 A CN 106008144A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- 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
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- 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)
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- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
Abstract
The invention discloses a method for producing vinyl chloride through catalytic cracking. According to the method, 1,2-dichloroethane is subjected to catalytic cracking in the presence of a first catalyst, a second catalyst and an aqueous ammonium sulfate solution with a mass percentage of 3 to 10% so as to obtain a cracking product, i.e., vinyl chloride. Compared with the prior art, the method provided by the invention has the advantages that (1) a mesoporous/microporous composite molecular sieve is used as a catalyst, stability of a molecular sieve is improved, and an acid center of the molecular sieve is provided, so catalysis efficiency and vinyl chloride yield are improved; and (2) the method is high in conversion rate, low in energy consumption, simple in subsequent separation operation and long in production period.
Description
Technical field
The invention belongs to PETROLEUM PROCESSING field, relate to a kind of method that catalytic pyrolysis produces vinyl chloride.
Background technology
Vinyl chloride is also known as being a kind of colourless gas under vinyl chloride, standard state, and with ethereal odor.Vinyl chloride is a kind of important polymerization monomer being applied to macromolecule chemical industry, and its polymer is mainly used in the manufacture of the products such as elastomer, fiber, coating, adhesive sealant, special type function material.Vinyl chloride monomer can be used to produce Corvic, poly-inclined two koroseals and chlorinated solvent.Additionally, vinyl chloride monomer can also be widely used in the various fields such as chemical fibre and packaging for foodstuff.
Polrvinyl chloride product is by the polymer of Vinyl Chloride Monomer copolymerization, and whole world polrvinyl chloride product 98% is to be produced by vinyl chloride to prepare.Polrvinyl chloride is one of big general-purpose plastics in the world five, has stronger mechanical tenacity nonflammable, owing to having good decay resistance, and contact that therefore can be direct or indirect with all kinds of chemical drugss.Based on above fine quality, polrvinyl chloride is used for manufacturing thin film, leather product, civil electric wire cable etc. used by Building class tubing and sheet material, green house of vegetables in a large number, is that energy consumption is low, cost is few, the most large versatile material of purposes for one.
It is the energy saving and environment friendly advanced production route generally acknowledged the most in the world that ethylene process prepares vinyl chloride, and the production technology of the polrvinyl chloride monomer of developed country all uses the ethylene process based on petrochemical industry route in the world.Current domestic ethylene process Polyvinyl Chloride System only has a few set, the utilization of capacity of process units nearly about 90%, is concentrated mainly on Tianjin and Jiangsu-zhejiang Shanghai Area one band, and relatively representational enterprise is Dagu, Tianjin chemistry and Shanghai chemical industry for making chlorine and alkali.Than acetylene method production technology, second dilute method production capacity is still the most not enough, and therefore, China actively to create conditions from now on, adjusts internal sources structure, accelerates the dilute method of second and prepares the production capacity ratio of polrvinyl chloride.
The dilute method of second produces vinyl chloride and is broadly divided into oxychlorination process and direct chlorination technique, oxychlorination production technology originates in the sixties in last century, and establishing the first set process units with Goodrich technique as technology at Kentucky, USA, this technology path is promoted the most rapidly because production capacity is powerful.Subsequently, three well East Asia companies of Japan develop direct chlorination technique.At present, domestic many producers all use this covering device Joint Production chloroethene dilute.But, numerous second dilute method route is prepared vinyl chloride and is all used dichloroethanes thermal cracking process.The temperature that this method needs is about 500 DEG C, and energy consumption is high.And the highest in order to ensure that the selectivity of vinyl chloride directly results in feed stock conversion, back segment separation circuit costly, the easy coking of boiler tube, with short production cycle wait series of problems.
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 conversion ratio is high, and energy consumption is low, later separation operation is simple and the vinyl chloride production method of production cycle length, the invention provides a kind of method that catalytic pyrolysis produces vinyl chloride.
Technical scheme: a kind of catalytic pyrolysis produces the method for vinyl chloride, and described method is:
The first catalyst, the second catalyst and mass fraction be 3～10% ammonium sulfate solution in the presence of, by 1,2-dichloroethanes carries out catalytic pyrolysis, obtains cleavage reaction product；
Wherein, first catalyst, by weight, composed of the following components: Kaolin 11～27 parts, phosphate aluminium molecular sieve 18～32 parts, calcium carbonate 12～24 parts, lanthana 8～21 parts, titanium dioxide 9～18 parts, sodium phosphate 12～32 parts, silicon dioxide 6～18 parts, hydrochloric acid 8～19 parts；Second catalyst, by weight, composed of the following components: white carbon black 11～19 parts, sodium phosphate 12～26 parts, ZSM-5 zeolite 15～30 parts, sodium hydroxide 7～14 parts, COK-5 zeolite 20～34 parts, sodium silicate 8～21 parts.
Preferably, the detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 12～32 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 2～4 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 1～5 hour, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 1～3.6%, wash 2～4 times.
Preferably, described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 5～35 hours under the conditions of 45～65 DEG C；
(2) step (1) described solution is taken, and with sodium carbonate, pH value is adjusted to 8.6～10.2, then it is added to Kaolin, lanthana and silicon dioxide, after stirring, crystallization 13～55 hours under the conditions of 85～150 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, add titanium dioxide, roasting 2～5 hours under the conditions of 450～600 DEG C, can be prepared by the first catalyst.
Preferably, described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 2.3～4.5MPa at pressure, temperature is reacted 3～6 hours under the conditions of being 212～356 DEG C；
(2) in the reactor of step (1), sodium hydroxide and sodium silicate are added, after stirring, crystallization 12～30 hours under the conditions of 100～150 DEG C, 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 the second catalyst.
Preferably, the first catalyst, by weight, composed of the following components: Kaolin 23 parts, phosphate aluminium molecular sieve 27 parts, calcium carbonate 18 parts, lanthana 17 parts, titanium dioxide 14 parts, sodium phosphate 28 parts, silica 14 parts, hydrochloric acid 16 parts；Second catalyst, by weight, composed of the following components: white carbon black 16 parts, sodium phosphate 23 parts, ZSM-5 zeolite 25 parts, sodium hydroxide 11 parts, 29 parts of COK-5 zeolite, sodium silicate 15 parts.
Further, the detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 25 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 3 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 3.5 hours, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 2.8%, wash 3 times.
Further, described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 28 hours under the conditions of 58 DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is adjusted to 9.6, then be added to Kaolin, lanthana and silicon dioxide, after stirring, crystallization 45 hours under the conditions of 125 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, add titanium dioxide, roasting 3.5 hours under the conditions of 565 DEG C, can be prepared by the first catalyst.
Further, described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 4.0MPa at pressure, temperature is reacted 4.5 hours under the conditions of being 315 DEG C；
(2) in the reactor of step (1), add sodium hydroxide and sodium silicate, after stirring, crystallization 25 hours under the conditions of 140 DEG C, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 4 hours under the conditions of 605 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 provides acidic zeolite center, thus improve catalytic efficiency, improves the yield of vinyl chloride；(2) the method for the invention conversion ratio is high, and energy consumption is low, and later separation operation is simple and the production cycle is long.
Detailed description of the invention
Embodiment 1
A kind of catalytic pyrolysis produces the method for vinyl chloride, and described method is:
In the presence of the first catalyst, the second catalyst and ammonium sulfate solution that mass fraction is 3%, by 1,2-dichloroethanes carries out catalytic pyrolysis, obtains cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 11 parts, phosphate aluminium molecular sieve 18 parts, calcium carbonate 12 parts, lanthana 8 parts, titanium dioxide 9 parts, sodium phosphate 12 parts, silicon dioxide 6 parts, hydrochloric acid 8 parts；Second catalyst, by weight, composed of the following components: white carbon black 11 parts, sodium phosphate 12 parts, ZSM-5 zeolite 15 parts, sodium hydroxide 7 parts, 20 parts of COK-5 zeolite, sodium silicate 8 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 12 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 2 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 1 hour, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 1%, wash 2 times.
Described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 5 hours under the conditions of 45 DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is 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, add titanium dioxide, roasting 2 hours under the conditions of 450 DEG C, can be prepared by the first catalyst.
Described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 2.3MPa at pressure, temperature is reacted 3 hours under the conditions of being 212 DEG C；
(2) in the reactor of step (1), add sodium hydroxide and sodium silicate, after stirring, crystallization 12 hours under the conditions of 100 DEG C, 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 catalytic pyrolysis produces the method for vinyl chloride, and described method is:
In the presence of the first catalyst, the second catalyst and ammonium sulfate solution that mass fraction is 7%, by 1,2-dichloroethanes carries out catalytic pyrolysis, obtains cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 23 parts, phosphate aluminium molecular sieve 27 parts, calcium carbonate 18 parts, lanthana 17 parts, titanium dioxide 14 parts, sodium phosphate 28 parts, silica 14 parts, hydrochloric acid 16 parts；Second catalyst, by weight, composed of the following components: white carbon black 16 parts, sodium phosphate 23 parts, ZSM-5 zeolite 25 parts, sodium hydroxide 11 parts, 29 parts of COK-5 zeolite, sodium silicate 15 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 25 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 3 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 3.5 hours, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 2.8%, wash 3 times.
Described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 28 hours under the conditions of 58 DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is adjusted to 9.6, then be added to Kaolin, lanthana and silicon dioxide, after stirring, crystallization 45 hours under the conditions of 125 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, add titanium dioxide, roasting 3.5 hours under the conditions of 565 DEG C, can be prepared by the first catalyst.
Described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 4.0MPa at pressure, temperature is reacted 4.5 hours under the conditions of being 315 DEG C；
(2) in the reactor of step (1), add sodium hydroxide and sodium silicate, after stirring, crystallization 25 hours under the conditions of 140 DEG C, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 4 hours under the conditions of 605 DEG C, can be prepared by the second catalyst.
Embodiment 3
A kind of catalytic pyrolysis produces the method for vinyl chloride, and described method is:
In the presence of the first catalyst, the second catalyst and ammonium sulfate solution that mass fraction is 10%, by 1,2-dichloroethanes carries out catalytic pyrolysis, obtains cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 27 parts, phosphate aluminium molecular sieve 32 parts, calcium carbonate 24 parts, lanthana 21 parts, titanium dioxide 18 parts, sodium phosphate 32 parts, silica 18 parts, hydrochloric acid 19 parts；Second catalyst, by weight, composed of the following components: white carbon black 19 parts, sodium phosphate 26 parts, ZSM-5 zeolite 30 parts, sodium hydroxide 14 parts, 34 parts of COK-5 zeolite, sodium silicate 21 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 32 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 4 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 5 hours, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 3.6%, wash 4 times.
Described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 35 hours under the conditions of 65 DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is 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, add titanium dioxide, roasting 5 hours under the conditions of 600 DEG C, can be prepared by the first catalyst.
Described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 4.5MPa at pressure, temperature is reacted 6 hours under the conditions of being 356 DEG C；
(2) in the reactor of step (1), add sodium hydroxide and sodium silicate, after stirring, crystallization 30 hours under the conditions of 150 DEG C, 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, is provided without the second catalyst and is catalyzed, and detailed process is as follows:
A kind of catalytic pyrolysis produces the method for vinyl chloride, and described method is:
In the presence of the first catalyst and ammonium sulfate solution that mass fraction is 7%, by 1,2-dichloroethanes carries out catalytic pyrolysis, obtains cleavage reaction product；
Wherein, the first catalyst, by weight, composed of the following components: Kaolin 23 parts, phosphate aluminium molecular sieve 27 parts, calcium carbonate 18 parts, lanthana 17 parts, titanium dioxide 14 parts, sodium phosphate 28 parts, silica 14 parts, hydrochloric acid 16 parts.
The detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 25 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 3 hours, obtain the first catalytic pyrolysis product；
4th step, the potassium hydrogen phosphate aqueous solution using mass fraction to be 2.8% first pyrolysis product, wash 3 times.
Described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 28 hours under the conditions of 58 DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is adjusted to 9.6, then be added to Kaolin, lanthana and silicon dioxide, after stirring, crystallization 45 hours under the conditions of 125 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, add titanium dioxide, roasting 3.5 hours under the conditions of 565 DEG C, can be prepared by the first catalyst.
To embodiment 1～3 and the catalytic pyrolysis effect of reference examples detect, result is as shown in the table:
Claims (8)
1. the method that a catalytic pyrolysis produces vinyl chloride, it is characterised in that described method is:
The first catalyst, the second catalyst and mass fraction be 3～10% ammonium sulfate solution in the presence of, by 1,2-dichloroethanes carries out catalytic pyrolysis, obtains cleavage reaction product；
Wherein, first catalyst, by weight, composed of the following components: Kaolin 11～27 parts, phosphate aluminium molecular sieve 18～32 parts, calcium carbonate 12～24 parts, lanthana 8～21 parts, titanium dioxide 9～18 parts, sodium phosphate 12～32 parts, silicon dioxide 6～18 parts, hydrochloric acid 8～19 parts；Second catalyst, by weight, composed of the following components: white carbon black 11～19 parts, sodium phosphate 12～26 parts, ZSM-5 zeolite 15～30 parts, sodium hydroxide 7～14 parts, COK-5 zeolite 20～34 parts, sodium silicate 8～21 parts.
A kind of catalytic pyrolysis the most according to claim 1 produces the method for vinyl chloride, it is characterised in that the detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 12～32 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 2～4 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 1～5 hour, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 1～3.6%, wash 2～4 times.
A kind of catalytic pyrolysis the most according to claim 1 produces the method for vinyl chloride, it is characterised in that described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 5～35 hours under the conditions of 45～65 DEG C；
(2) step (1) described solution is taken, and with sodium carbonate, pH value is adjusted to 8.6～10.2, then it is added to Kaolin, lanthana and silicon dioxide, after stirring, crystallization 13～55 hours under the conditions of 85～150 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, add titanium dioxide, roasting 2～5 hours under the conditions of 450～600 DEG C, can be prepared by the first catalyst.
A kind of catalytic pyrolysis the most according to claim 1 produces the method for vinyl chloride, it is characterised in that described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 2.3～4.5MPa at pressure, temperature is reacted 3～6 hours under the conditions of being 212～356 DEG C；
(2) in the reactor of step (1), sodium hydroxide and sodium silicate are added, after stirring, crystallization 12～30 hours under the conditions of 100～150 DEG C, 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 the second catalyst.
A kind of catalytic pyrolysis the most according to claim 1 produces the method for vinyl chloride, it is characterized in that, first catalyst, by weight, composed of the following components: Kaolin 23 parts, phosphate aluminium molecular sieve 27 parts, calcium carbonate 18 parts, lanthana 17 parts, titanium dioxide 14 parts, sodium phosphate 28 parts, silica 14 parts, hydrochloric acid 16 parts；Second catalyst, by weight, composed of the following components: white carbon black 16 parts, sodium phosphate 23 parts, ZSM-5 zeolite 25 parts, sodium hydroxide 11 parts, 29 parts of COK-5 zeolite, sodium silicate 15 parts.
A kind of catalytic pyrolysis the most according to claim 2 produces the method for vinyl chloride, it is characterised in that the detailed process of described catalytic pyrolysis is as follows:
1st step, employing nitrogen purging 1,2-dichloroethanes cracker, temperature in device is down to 25 DEG C, and by 1,2-dichloroethanes is in constant flow pump delivers to tube cracking furnace；
2nd step, the first catalyst and ammonium sulfate solution mix homogeneously are placed in fixed bed reactors, separate through condensing unit after reacting 3 hours, obtain the first catalytic pyrolysis product；
3rd step, by the first catalytic pyrolysis product reflux to tube cracking furnace, in fixed bed reactors, send into the second catalyst, react 3.5 hours, obtain the second catalytic pyrolysis product；
4th step, the second pyrolysis product is carried out condensation collect, and the potassium hydrogen phosphate aqueous solution using mass fraction to be 2.8%, wash 3 times.
A kind of catalytic pyrolysis produces the method for vinyl chloride, it is characterised in that described first catalyst is prepared by following methods:
(1) calcium carbonate is added in sodium phosphate aqueous solution, after addition dissolving with hydrochloric acid is uniform, add phosphate aluminium molecular sieve, hydrolyze and aging 28 hours under the conditions of 58 DEG C；
(2) take step (1) described solution, and with sodium carbonate, pH value is adjusted to 9.6, then be added to Kaolin, lanthana and silicon dioxide, after stirring, crystallization 45 hours under the conditions of 125 DEG C, filter, wash acquisition the first catalyst precarsor；
(3) in the first catalyst precarsor that step (2) obtains, add titanium dioxide, roasting 3.5 hours under the conditions of 565 DEG C, can be prepared by the first catalyst.
A kind of catalytic pyrolysis produces the method for vinyl chloride, it is characterised in that described second catalyst is prepared by following methods:
(1) adding ZSM-5 zeolite and COK-5 zeolite in a kettle., add sodium phosphate aqueous solution, be 4.0MPa at pressure, temperature is reacted 4.5 hours under the conditions of being 315 DEG C；
(2) in the reactor of step (1), add sodium hydroxide and sodium silicate, after stirring, crystallization 25 hours under the conditions of 140 DEG C, filter, wash acquisition the second catalyst precarsor；
(3) in the second catalyst precarsor, add white carbon black, roasting 4 hours under the conditions of 605 DEG C, can be prepared by the second catalyst.
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| CN102247884A (en) * | 2011-05-20 | 2011-11-23 | 天津大沽化工股份有限公司 | Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst |
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| CN102247884A (en) * | 2011-05-20 | 2011-11-23 | 天津大沽化工股份有限公司 | Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588532A (en) * | 2016-12-17 | 2017-04-26 | 段清 | Method of producing ethylene through catalytic cracking |
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