CN107442169A - A kind of catalyst for loading chloride organotin and nitrogen-containing compound and its preparation method and application - Google Patents
A kind of catalyst for loading chloride organotin and nitrogen-containing compound and its preparation method and application Download PDFInfo
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- CN107442169A CN107442169A CN201710696202.8A CN201710696202A CN107442169A CN 107442169 A CN107442169 A CN 107442169A CN 201710696202 A CN201710696202 A CN 201710696202A CN 107442169 A CN107442169 A CN 107442169A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/122—Metal aryl or alkyl 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
The present invention discloses a kind of catalyst for loading chloride organotin and nitrogen-containing compound and its preparation method and application.The catalyst is compound as active component using chloride organotin and nitrogen-containing compound；Under water bath condition, chloride organotin and nitrogen-containing compound mixing are dissolved in solvent and prepare maceration extract, by the isometric open stirring of carrier and maceration extract, obtained sample and be dried, be calcined, finally obtain catalyst；And catalyst is prepared into vinyl chloride applied to acetylene hydrochlorination method.Catalyst activity component is base metal, and without mercury element, catalyst synthesis processes are simple and environmentally-friendly, and synthesis cost is low.Catalyst acetylene and hydrogen chloride one-step method prepare chloroethene alkene reaction, and catalyst reaction activity, selectivity and stable sex expression are excellent：At 200 DEG C, acetylene air speed is 15h‑1‑120 h‑1, feed gas molar ratio is：HCl/C2H2Under conditions of=1.05 1.1, conversion of alkyne is up to 99.5%.
Description
Technical field
The present invention relates to a kind of catalyst for loading chloride organotin and nitrogen-containing compound and its preparation method and application, category
In catalyst and its preparing technical field.
Background technology
The demand and yield of polyvinyl chloride occupy five big synthetic resin first places, because Corvic has anti-chemistry
The features such as burn into is electrically insulated, is quality-high and inexpensive, it is important to be widely used in agricultural, building, chemical industry, machinery, electronics, commodity etc.
Field.
With the rapid development of economy, living standards of the people increasingly improve, the demand of polyvinyl chloride are continuously increased.It is poly-
Vinyl chloride is formed by chloroethylene polymerization.The vinyl chloride yield ranking production area of first three of the world is followed successively by Asia, North America, west
Europe, wherein Asia yield account for Gross World Product more than 50%.In 2009, Chinese vinyl chloride yield occupied the 56.3% of Asia yield.
The technique of production vinyl chloride is divided into three kinds, including acetylene hydrochlorination method, process for oxychlorination of ethylene and ethane method at present.Because China's coal
Charcoal aboundresources, oil and natural gas resource is poorer, so acetylene hydrochlorination method is developed rapidly in China, China is every
Year acetylene method production vinyl chloride about 1.3 × 108T, in 2015, the yield of Chinese acetylene hydrochlorination method production polyvinyl chloride accounted for always
The 80.7% of yield.Traditional acetylene hydrochlorination method prepares vinyl chloride using activated carbon supported mercury chloride as catalyst, because chlorination
Mercury is easy to run off during the course of the reaction, have impact on the stability of catalyst, and the mercury being lost in does great damage to environment, also can
The life health of people is endangered, while the increasingly poor and international convention limit mercury order, therefore study and synthesize cheap, ring of mercury resource be present
Guarantor, the catalyst of good activity are extremely urgent.
Hutchings et al. has delivered paper " Discovery, Development, and
Commercialization of Gold Catalysts for Acetylene Hydrochlorination”（Journal
of the American Chemical Society, 2015, 137(46):14548.）, catalyst is catalyzed in the reaction
Activity and the standard electrode potential of metal link together, and infer that the noble metals such as Au and Pd prepare the process of vinyl chloride in acetylene method
In there is very strong catalytic activity.Its activity is demonstrated in an experiment.Using noble metal as catalyst, such as gold, palladium etc..It is expensive
For metallic catalyst although with higher catalytic activity and vinyl chloride selectivity, cost is too high, can not heavy industrialization.
Deng state ability of Nankai University etc. has delivered paper " development of acetylene method synthesis vinyl chloride thereof solid phase non-mercury catalyst "（Polyvinyl chloride,
1994, 6: 5-9.）, three component stannous chlorides-compound non-catalytic of bismuth trichloride-stannous chloride is filtered out first in acetylene hydrogen
Excellent catalytic activity is shown during chlorination reaction synthesis vinyl chloride thereof, while stannous chloride component is found in research process
Easily it is lost in during the course of the reaction.It is applied to acetylene hydrogen chlorine as catalyst using activated carbon supported stannic chloride or stannous chloride
Change method prepares vinyl chloride, but comes with some shortcomings.On the one hand：Butter of tin toxicity is stronger, and easily environment is polluted, chlorine
Changing stannous has compared with severe corrosive, while can also destroy ecological environment.The boiling point of another aspect butter of tin is 114 DEG C, and second
Alkynes hydrogen chloride industrial production vinyl chloride reaction temperature is 150 DEG C -200 DEG C, therefore butter of tin can not be stabilized.Stannous chloride
Catalytic activity performance is general.Above-mentioned to show, inorganic tin shows certain catalytic activity in acetylene hydrochlorination reaction, but enters
One step improves catalytic activity, and stability, it is key to the issue to reduce pollution.
The content of the invention
The present invention is intended to provide a kind of catalyst for loading chloride organotin and nitrogen-containing compound, has base metal, nothing
The characteristics of mercury, cost are low, building-up process is simple and environmentally-friendly.The invention provides the chloride organotin of above-mentioned load and nitrogen-containing compound
The preparation method of catalyst.Present invention also offers the catalyst of the chloride organotin of above-mentioned load and nitrogen-containing compound in acetylene hydrogen
Chloridising prepares the application in vinyl chloride, and the catalyst is for chloroethylene polymerization process and has no adverse effects, in VCM synthesis
During catalyst activity and selectivity performance it is excellent.
The invention provides a kind of catalyst for loading chloride organotin and nitrogen-containing compound, it is made up of following raw material：
Chloride organotin, nitrogen-containing compound, the mass ratio of carrier are：1-35:1-35:70.
The chloride organotin formula is one kind in formula I, formula II or formula III：
Carbon number is 1-20 wherein in R1, R2, R3, and R1, R2, R3 represent alkyl, cycloalkyl, aryl, ester group, acyl group respectively
In one kind；
Nitrogen-containing compound includes：One or more in dicyandiamide, melamine, methenamine, urea；
Carrier includes：Cocoanut active charcoal, active carbon from coal, asphalt-base spherical activated carbon, column-shaped active carbon, CNT, dioxy
One kind in SiClx, zeolite molecular sieve.
Further, the chloride organotin is triphenyl tin chloride, diphenyl stannous chloride, phenyl tin trichloride, one
Octyl group tin trichloride, dioctyl stannous chloride, trioctylphosphine stannic chloride, tribenzyltin chloride, dibenzyl stannic chloride, a Benzylmagnesium chloride
Tin, tricyclohexyltin chloride, dicyclohexyl stannous chloride, a cyclohexyl tin trichloride, tin dilaurate dibutyl tin oxide, maleic acid
One kind in octyl group stannic chloride, stearic acid tin, tributyltin chloride alkenyl, dibutyl tin dichloride, monobutyl tin tri-chloride.
The invention provides the preparation method of the chloride organotin of above-mentioned load and the catalyst of nitrogen-containing compound, including it is following
Step：
（1）Under 60 DEG C of -90 DEG C of water bath conditions, chloride organotin and nitrogen-containing compound are mixed and are dissolved in solvent, is held in opening
5min-60min is stirred in device and prepares maceration extract, wherein chloride organotin mass percentage concentration is 1%-55%, nitrogen-containing compound matter
Amount percentage concentration is 1%-40%；
（2）Carrier is stirred in open-top receptacle in equal volume with maceration extract, sample is obtained and is dried, is calcined, finally urged
Agent.
The solvent includes：One kind in methanol, ethanol, acetone.
The carrier refers to the isometric open stirring of maceration extract：Under the conditions of 60 DEG C -90 DEG C, the body such as maceration extract and carrier
The open stirring dipping 1h-24h of product；Wherein, chloride organotin and carrier quality ratio are 1-35:70, nitrogen-containing compound and carrier matter
It is 1-35 to measure ratio:70.
The drying refers to：Carrier after dipping is placed in 90 DEG C -120 DEG C of baking oven 6h-24h is dried；Institute
Roasting is stated to refer to：Under nitrogen atmosphere, 150 DEG C of -650 DEG C of holding more than 4h are risen to by 1 DEG C/min-15 DEG C/min of heating rate,
Room temperature is naturally cooled to, finally obtains catalyst.
Prepared the invention provides the catalyst of the chloride organotin of above-mentioned load and nitrogen-containing compound in acetylene hydrochlorination method
Application in vinyl chloride.
In the application, electric heating control temperature programming to 150 DEG C -200 DEG C of reaction temperature, catalyst quality 1.8g-
17.5g, it is 15/h-120/h in acetylene air speed, feed gas molar ratio is：HCl/C2H2=1.05-1.1:1, reaction pressure is normal
Pressure；Reaction end gas removes unreacted hydrogen chloride gas in gaseous mixture by medical soda lime, then samples, in gas-chromatography
Analyzed.
In catalyst prepares vinyl chloride process for acetylene hydrochlorination method, the conversion ratio of acetylene can reach 99.5%,
Vinyl chloride can selectively reach 99.8%.
Beneficial effects of the present invention：
Catalyst activity component base metal provided by the invention, without mercury element, catalyst synthesis processes are simple and environmentally-friendly, synthesis
Cost is low.Chloride organotin is usually as heat stabilizer, without removing during follow-up chloroethylene polymerization.In acetylene method chloroethene
In alkene building-up process, catalyst activity and selectivity performance is excellent.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：
Pair that 18ml mass percentage concentrations are 11% dioctyl stannous chloride solution and 18ml mass percentage concentrations are 11% is taken first
Cyanamide solution mixes, and methanol is solvent, stirs 30min in 65 DEG C of water bath condition lower open mouths, then adds 16g 20-40 purposes
Activated carbon, isometric open stirring dipping 2h is carried out under 65 DEG C of water bath conditions；Catalyst after dipping is put in 80 DEG C of drying boxes
Middle drying 12h；After drying, under nitrogen atmosphere, put it into tube furnace, be calcined 4h at 500 DEG C, naturally cool to room temperature
Obtain catalyst A.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：It is by above-mentioned catalyst 17.5g loading internal diameters
16mm fixed bed reactors（Glass material）In, it is 15h in gas space velocity-1, reaction temperature is 200 DEG C, feed gas molar ratio
HCl/C2H2=1.05：Acetylene hydrochlorination method test, analytical reactions tail gas, the second of catalyst are carried out to the catalyst under conditions of 1
Alkynes conversion ratio is 99.5%, and the selectivity of vinyl chloride is 98.6%.
Evaluating catalyst is shown in Table 1.
Embodiment 2
Take that 20ml mass percentage concentrations are 10% 1 octyl group tin trichloride solution and 16ml mass percentage concentrations are 12.5% first
Melamine solution mixes, and ethanol is solvent, and 15min is stirred under 80 DEG C of water bath conditions, then adds 18g 20-40 purposes
Activated carbon, isometric open stirring dipping 4h is carried out under 80 DEG C of water bath conditions；Catalyst after dipping is put in 100 DEG C of drying boxes
Middle drying 15h；After drying, under nitrogen atmosphere, put it into tube furnace, be calcined 6h at 450 DEG C, naturally cool to room
Temperature, obtain catalyst B.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：It is 16mm by above-mentioned catalyst 8.8g loading internal diameters
Fixed bed reactors（Glass material）In, it is 30h in gas space velocity-1, reaction temperature is 200 DEG C, and feed gas molar compares HCl/
C2H2=1.05:Acetylene hydrochlorination method test, analytical reactions tail gas are carried out under conditions of 1 to the catalyst, the acetylene of catalyst turns
Rate is 96.6%, and the selectivity of vinyl chloride is 98.9%.
Evaluating catalyst is shown in Table 1.
Embodiment 3
Take that 20ml mass percentage concentrations are 10% diphenyl stannous chloride solution and 16ml mass percentage concentrations are 12.5% first
Melamine solution mixes, and ethanol is solvent, and 5min is stirred under the conditions of 80 DEG C, then adds the activity of 15g 20-40 mesh
Charcoal, isometric open stirring dipping 4h is carried out under 80 DEG C of water bath conditions；Catalyst after dipping, which is put in 100 DEG C of drying boxes, to be dried
Dry 12h；After drying, put it into tube furnace, more than 4h is calcined at 400 DEG C, naturally cool to room temperature, obtain catalyst C
。
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 10.3g is fitted into reactor
It is 30h in gas space velocity-1, reaction temperature is 200 DEG C, and feed gas molar compares HCl/C2H2=1.05:To the catalysis under conditions of 1
Agent carries out acetylene hydrochlorination method test, and analytical reactions tail gas, the conversion of alkyne of catalyst is 94.5%, the selectivity of vinyl chloride
For 98.4%.
Evaluating catalyst is shown in Table 1.
Embodiment 4
It is 18.2% to take a phenyl tin trichloride solution that 25ml mass percentage concentrations are 8% and 11ml mass percentage concentrations first
Dicyandiamide solution mixes, and ethanol is solvent, and 25min is stirred under 80 DEG C of water bath conditions, then adds the work of 18g 20-40 mesh
Property charcoal, isometric open stirring dipping is carried out under 80 DEG C of water bath conditions, is evaporated；Catalyst after dipping is put in 100 DEG C of dryings
12h is dried in case；After drying, but its atmosphere under, put it into tube furnace, be calcined 5h at 500 DEG C, naturally cool to room
Temperature, obtain catalyst D.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：It is 16mm by above-mentioned catalyst 4.4g loading internal diameters
Fixed bed reactors（Glass material）In, it is 60h in gas space velocity-1, reaction temperature is 190 DEG C, and feed gas molar compares HCl/
C2H2=1.05:Acetylene hydrochlorination method test, analytical reactions tail gas are carried out under conditions of 1 to the catalyst, the acetylene of catalyst turns
Rate is 81.6%, and the selectivity of vinyl chloride is 99.1%.
Evaluating catalyst is shown in Table 1.
Embodiment 5
Take that 18ml mass percentage concentrations are 11% dicyclohexyl stannous chloride solution and 18ml mass percentage concentrations are 11% first
Methenamine solution mixes, and ethanol is solvent, and 30min is stirred under 80 DEG C of water bath conditions, then adds 18g 20-40 purposes
Silicon dioxide microsphere, isometric open stirring dipping is carried out under 80 DEG C of water bath conditions, is evaporated；Catalyst after dipping is put in
12h is dried in 100 DEG C of drying boxes；After drying, put it into tube furnace, be calcined 6h at 200 DEG C, naturally cool to room temperature,
Obtain catalyst E.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 6.7g catalyst is loaded and reacted
Device, it is 30h in gas space velocity-1, reaction temperature is 200 DEG C, and feed gas molar compares HCl/C2H2=1.05：This is urged under conditions of 1
Agent carries out acetylene hydrochlorination method test, and analytical reactions tail gas, the conversion of alkyne of catalyst is 94.9%, the selection of vinyl chloride
Property is 98.7%.
Evaluating catalyst is shown in Table 1.
Embodiment 6
Take that 20ml mass percentage concentrations are 10% 1 octyl group tin trichloride solution and 16ml mass percentage concentrations are 12.5% pair first
Cyanamide solution mixes, and ethanol is solvent, and 30min is stirred under 80 DEG C of water bath conditions, then adds the activity of 18g 20-40 mesh
Charcoal, isometric open stirring dipping is carried out under 80 DEG C of water bath conditions, carries out dipping 4h；Catalyst after dipping is put in 100 DEG C
12h is dried in drying box；After drying, put it into tube furnace, be calcined 4h at 450 DEG C, naturally cool to room temperature, urged
Agent F.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 6.1g is loaded into reactor,
Gas space velocity is 20h-1, reaction temperature is 200 DEG C, and feed gas molar compares HCl/C2H2=1.05：To the catalyst under conditions of 1
Acetylene hydrochlorination method test is carried out, analytical reactions tail gas, the conversion of alkyne of catalyst is 98.9%, and the selectivity of vinyl chloride is
98.1%。
Evaluating catalyst is shown in Table 1.
Embodiment 7
Take that 15ml mass percentage concentrations are 13.3% dibutyl tin dichloride solution and 15ml mass percentage concentrations are 13.3% first
Dicyandiamide solution mixes, and ethanol is solvent, and 30min is stirred under 78 DEG C of water bath conditions, then adds 18g 20-40 purposes
ZSM-5, isometric open stirring dipping is carried out under 80 DEG C of water bath conditions, carries out dipping 4h；Catalyst after dipping is put in 100
12h is dried in DEG C drying box；After drying, put it into tube furnace, be calcined 12h at 150 DEG C, naturally cool to room temperature, obtain
Obtain catalyst G.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 9.6g is loaded into reactor,
Gas space velocity is 30h-1, reaction temperature is 170 DEG C, and feed gas molar compares HCl/C2H2=1.1：The catalyst is entered under conditions of 1
Row acetylene hydrochlorination method is tested, analytical reactions tail gas, and the conversion of alkyne of catalyst is 41.8%, and the selectivity of vinyl chloride is
98.9%。
Evaluating catalyst is shown in Table 1.
Embodiment 8
Take that 20ml mass percentage concentrations are 10% stearic acid solution of tin and 16ml mass percentage concentrations are that 1.5% dicyandiamide is molten first
Liquid mixes, and ethanol is solvent, and 30min is stirred under 79 DEG C of water bath conditions, the activated carbon of 18g 20-40 mesh is then added, 79
Isometric open stirring dipping is carried out under DEG C water bath condition, carries out dipping 4h；Catalyst after dipping is put in 100 DEG C of drying boxes
Dry 12h；After drying, put it into tube furnace, 4h is calcined at 200 DEG C, naturally cool to room temperature, obtain catalyst H.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 7.9g is fitted into reactor,
It is 30h in gas space velocity-1, reaction temperature is 150 DEG C, and feed gas molar compares HCl/C2H2=1.05:To the catalysis under conditions of 1
Agent carries out acetylene hydrochlorination method test, and analytical reactions tail gas, the conversion of alkyne of catalyst is 15.7%, the selectivity of vinyl chloride
For 99.0%.
Evaluating catalyst is shown in Table 1.
Embodiment 9
Take that 20ml mass percentage concentrations are 10% maleic acid octyl group tin chloride solution and 16ml mass percentage concentrations are 12.5% first
Urea liquid mixes, and ethanol is solvent, and 30min is stirred under 79 DEG C of water bath conditions, then adds the activity of 18g 20-40 mesh
Charcoal, isometric open stirring dipping is carried out under 60 DEG C of water bath conditions, carries out dipping 4h；Catalyst after dipping is put in 100 DEG C
12h is dried in drying box；After drying, put it into tube furnace, be calcined 4h at 650 DEG C, naturally cool to room temperature, urged
Agent I.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 14.7g is loaded into reactor,
Gas space velocity is 120h-1, reaction temperature is 160 DEG C, and feed gas molar compares HCl/C2H2=1.1:To the catalyst under conditions of 1
Acetylene hydrochlorination method test is carried out, analytical reactions tail gas, the conversion of alkyne of catalyst is 22.53%, and the selectivity of vinyl chloride is
99.8%。
Evaluating catalyst is shown in Table 1.
Embodiment 10
Take that 30ml mass percentage concentrations are 9.0% dioctyl stannous chloride solution and 10ml mass percentage concentrations are 11.3% pair first
Cyanamide and 12ml mass percentage concentrations mix for 11.3% urea liquid, and ethanol is solvent, is stirred under 80 DEG C of water bath conditions
30min, the activated carbon of 18g 20-40 mesh is then added, isometric open stirring dipping is carried out under 90 DEG C of water bath conditions, is entered
Row dipping 4h；Catalyst after dipping is put in 100 DEG C of drying boxes and dries 12h；After drying, put it into tube furnace, 550
4h is calcined at DEG C, naturally cools to room temperature, obtains catalyst J.
The catalyst is used for during acetylene hydrochlorination synthesis vinyl chloride thereof：Above-mentioned catalyst 1.8g is loaded into reactor,
Gas space velocity is 30h-1, reaction temperature is 180 DEG C, and feed gas molar compares HCl/C2H2=1.1:The catalyst is entered under conditions of 1
Row acetylene hydrochlorination method is tested, analytical reactions tail gas, and the conversion of alkyne of catalyst is 79.1%, and the selectivity of vinyl chloride is
98.5%。
Evaluating catalyst is shown in Table 1.
The evaluating catalyst table of table 1
。
Claims (10)
1. a kind of catalyst for loading chloride organotin and nitrogen-containing compound, it is characterised in that be made up of following raw material：
Chloride organotin, nitrogen-containing compound, the mass ratio of carrier are：1-35:1-35:70.
The chloride organotin formula is one kind in formula I, formula II or formula III：
Carbon number is 1-20 wherein in R1, R2, R3, and R1, R2, R3 represent alkyl, cycloalkyl, aryl, ester group, acyl group respectively
In one kind；
Nitrogen-containing compound includes：One or more in dicyandiamide, melamine, methenamine, urea；
Carrier includes：Cocoanut active charcoal, active carbon from coal, asphalt-base spherical activated carbon, column-shaped active carbon, CNT, dioxy
One kind in SiClx, zeolite molecular sieve.
2. the catalyst according to claim 1 for loading chloride organotin and nitrogen-containing compound, it is characterised in that：It is described to contain
Chlorine organotin is triphenyl tin chloride, diphenyl stannous chloride, phenyl tin trichloride, an octyl group tin trichloride, dioctyl dichloro
Change tin, trioctylphosphine stannic chloride, tribenzyltin chloride, dibenzyl stannic chloride, a benzyltin chloride, tricyclohexyltin chloride, two rings
Hexyl stannous chloride, a cyclohexyl tin trichloride, tin dilaurate dibutyl tin oxide, maleic acid octyl group stannic chloride, stearic acid tin, three
One kind in dibutyl tin oxide alkenyl, dibutyl tin dichloride, monobutyl tin tri-chloride.
3. a kind of preparation method of the catalyst of the chloride organotin of load and nitrogen-containing compound described in claim 1 or 2, it is special
Sign is to comprise the following steps：
(1) under 60 DEG C of -90 DEG C of water bath conditions, chloride organotin and nitrogen-containing compound is mixed and are dissolved in solvent, is held in opening
5min-60min is stirred in device and prepares maceration extract, wherein chloride organotin mass percentage concentration is 1%-55%, nitrogen-containing compound
Mass percentage concentration is 1%-40%；
(2) carrier is stirred in open-top receptacle in equal volume with maceration extract, obtains sample and be dried, be calcined, finally urged
Agent.
4. the preparation method of the catalyst according to claim 3 for loading chloride organotin and nitrogen-containing compound, its feature
It is：The solvent is one kind in methanol, ethanol, acetone.
5. the preparation method of the catalyst according to claim 3 for loading chloride organotin and nitrogen-containing compound, its feature
It is：The carrier refers to the isometric open stirring of maceration extract：Under the conditions of 60 DEG C -90 DEG C, maceration extract is isometric with carrier
Opening stirring dipping 1h-24h；Chloride organotin and carrier quality ratio are 1-35:70, nitrogen-containing compound and carrier quality ratio are 1-
35:70。
6. the preparation method of the catalyst according to claim 3 for loading chloride organotin and nitrogen-containing compound, its feature
It is：The drying refers to：Carrier after dipping is placed in 90 DEG C -120 DEG C of baking oven 6h-24h is dried；The roasting
Burning refers to：Under nitrogen atmosphere, 150 DEG C of -650 DEG C of holding more than 4h, nature are risen to by 1 DEG C/min-15 DEG C/min of heating rate
Room temperature is cooled to, finally obtains catalyst.
7. the catalyst of the chloride organotin of load and nitrogen-containing compound described in a kind of claim 1 or 2 is in acetylene hydrochlorination method
Prepare the application in vinyl chloride.
8. application according to claim 7, it is characterised in that：Electric heating control temperature programming to 150 DEG C of reaction temperature-
200 DEG C, catalyst quality 1.8g-17.5g, be 15/h-120/h in acetylene air speed, feed gas molar ratio is：HCl/C2H2=
1.05-1.1:1, reaction pressure is normal pressure；Reaction end gas removes unreacted hydrogen chloride gas in gaseous mixture by medical soda lime
Body, then sample, analyzed in gas-chromatography.
9. application according to claim 8, it is characterised in that：The conversion ratio of acetylene can reach 99.5%.
10. application according to claim 8, it is characterised in that：Vinyl chloride can selectively reach 99.8%.
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| CN101108336A (en) * | 2007-07-11 | 2008-01-23 | 南开大学 | Method of manufacturing nitrogen of high activity, stannum ion codope nano titanium dioxide photocatalyst |
| CN104588112A (en) * | 2015-01-21 | 2015-05-06 | 四川花语精细化工有限公司 | Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115608415A (en) * | 2021-07-16 | 2023-01-17 | 中国科学院大连化学物理研究所 | Supported catalyst, preparation and application thereof |
| CN115608415B (en) * | 2021-07-16 | 2024-04-16 | 中国科学院大连化学物理研究所 | Supported catalyst, preparation and application thereof |
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