CN103894221B - A kind of method utilizing molecular sieve catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination - Google Patents
A kind of method utilizing molecular sieve catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination Download PDFInfo
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Abstract
The present invention relates to a kind of method utilizing molecular sieve catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination.The molecular sieve catalyst without mercury of the present invention comprises FAU type Si-Al molecular sieve and the non-molecular sieve component of 0 50wt% of 50 100wt%, have an advantage in that can under the reaction temperature of 280 350 DEG C catalyzing acetylene hydrochlorination with prepare vinyl chloride and inactivate after can regenerate.
Description
Technical field
The present invention relates to one utilizes molecular sieve catalyst without mercury catalyzing acetylene hydrochlorination to prepare chlorine
The new method of ethylene.
Background technology
Vinyl chloride is the monomer of igelite (PVC) synthesis.Anti-by acetylene and hydrogen chloride
The important route of synthesis that vinyl chloride is Vinyl Chloride Monomer should be prepared.Reaction equation is as follows:
Industrial processes at present use activated carbon supported mercuric chloride as catalyst, reaction temperature
100-200℃.Along with socioeconomic development, the yield of igelite is continuously increased, catalyst
Consumption be also continuously increased.Hydrargyrum is a kind of noxious substance, and environmental pollution is serious.Therefore from acetylene
The course of reaction going out to send synthesis vinyl chloride receives the dual-pressure of hydrargyrum resource and environmental protection.Develop novel
The catalyst without mercury of environmental protection, the catalyst using current industrial process substitutes, is carbide
The pressing problem that method vinyl chloride industry faces.Current industrial is also all paid much attention to academia be catalyzed without hydrargyrum
The development of agent, has made some progress:
Chinese patent 200910196849.X discloses a kind of catalyst without mercury system, the main work of catalyst
Property component be gold salt, can be the halogenide of gold, complex etc., in gold salt, gold content accounts for catalyst weight
The 0.1-10% of amount；Helping active component is base metal salt, can be the halogenation of potassium, barium, lanthanum, copper
Thing, acetate, phosphate, complex etc., base metal salt content accounts for the 0.1-10% of catalyst weight；
Carrier is activated carbon, including coconut husk matter charcoal, ature of coal charcoal, shell matter charcoal, or silica gel.
Chinese patent 200910236255.7 discloses a kind of liquid phase catalyst without mercury system, and solvent is miaow
Azole ionic liquid, catalyst is the one in the chloride of gold, platinum, palladium, stannum, hydrargyrum, copper or rhodium
Or its two or more combination in any.
Chinese patent 200910228149.4 discloses a kind of catalyst without mercury system, and catalyst is with activity
Carbon is carrier, with the chloride of the palladium containing 2～15% or gold as active component, and 1～the rare earth of 5%
Chloride is cocatalyst component, and the method for being through impregnation with is carried on activated carbon the pellet type catalyst prepared.
Chinese patent 201010149180.1 discloses a kind of catalyst without mercury system, and catalyst uses lives
Property charcoal be carrier, dipping absorption barium salt as active component.
Chinese patent 201010185916.0 discloses a kind of liquid phase catalyst without mercury system, reaction dissolvent
For pyridine ionic liquid, muriatic with stannum, palladium, platinum, gold, copper, manganese, bismuth, hydrargyrum or rhodium
One or more are active component.
Chinese patent 201010248348.4 discloses a kind of catalyst without mercury system, and catalyst is with activity
Charcoal and molecular sieve are carrier, and the chloride of noble ruthenium is active component, is prepared by infusion process.
Chinese patent 201010272612.8 discloses a kind of catalyst without mercury system, and catalyst uses
The base metals such as the noble metals such as gold, platinum, rhodium, ruthenium, palladium and copper, zinc, potassium, barium, nickel are activity
Component, activated carbon, molecular sieve, silica gel, CNT etc. are carrier.It is applicable to fluid bed, fixes
The reactors such as bed.
Chinese patent 201010574802.5 discloses a kind of catalyst without mercury system, and catalyst is with coconut husk
Activated carbon is carrier, and stannous chloride is main active substances, and the weight/mass percentage composition of stannous chloride is
15%-30%, at least one additive being added with in barium chloride, zinc chloride and copper chloride.
Chinese patent 201110023364.8 discloses a kind of catalyst without mercury system, and catalyst is with Ni2P
For active center, with activated carbon as carrier, auxiliary agent is iron chloride, Nickel dichloride., barium chloride.
Chinese patent 201110023357.8 discloses a kind of catalyst without mercury system, and catalyst uses lives
Property charcoal is carrier, and the bismuth simple substance of the bismuth trichloride being reduced is active component, ferrous iron, ferrum, nickel, barium,
The chloride auxiliary agent of bismuth.
Chinese patent 201110040369.1 discloses a kind of catalyst without mercury system, and catalyst uses lives
Property charcoal is carrier, and active component is phosphorized copper, and auxiliary agent is the one of copper chloride, Nickel dichloride., barium chloride
Or it is several.
Chinese patent 201110040371.9 discloses a kind of catalyst without mercury system, and catalyst uses lives
Property charcoal is carrier, and active component is phosphating sludge, and auxiliary agent is barium chloride.
Chinese patent 201110040375.7 discloses a kind of catalyst without mercury system, and catalyst uses lives
Property charcoal is carrier, and active component is tungsten phosphide, and auxiliary agent is the one of Nickel dichloride., barium chloride, copper chloride
Or it is several.
Chinese patent 201110150287.2 discloses a kind of catalyst without mercury system, and catalyst uses lives
Property charcoal be carrier, by supersound process, coupling agent equal solvent carries out carrier surface modification, loads chlorination
Gold or ruthenic chloride, with the chloride of bismuth, barium, manganese, ferrum etc. as auxiliary agent.
Chinese patent 201110199651.4 discloses a kind of catalyst without mercury system, and catalysis uses activity
The porous microstructure material such as charcoal, silicon dioxide is carrier, gold element, cobalt element, the chlorination of lanthanum element
Thing or nitrate are active component, and auxiliary agent is the chloride of potassium, sodium, bismuth, ferrum etc..
Chinese patent 201110257699.6 discloses a kind of catalyst without mercury system, and catalyst is with coconut husk
Charcoal, fruit shell carbon, do not have machine activated carbon to be carrier, active component be copper, nickel, bismuth, zinc-manganese, the one of molybdenum
Plant or several.Metal is with form loads such as oxide, chloride, nitrate, acetate.
Chinese patent 201110257696.2 discloses a kind of catalyst without mercury system, and catalyst is with molecule
Sieve is carrier, the halogenide of supported precious metal palladium or complex.
Chinese patent 201110257697.7 discloses a kind of catalyst without mercury system, and catalyst is with activity
Charcoal is carrier, and noble metal is active component, is prepared by infusion process.
Chinese patent 201110291457.9 discloses a kind of catalyst without mercury system, and catalyst contains chlorine
Changing stannum, rare earth chloride, other metal chlorides, rare earth chloride is cerium chloride or lanthanum chloride, carries
Body is cerium-zirconium powder, zirconium oxide etc..
Chinese patent 201210100688.1 discloses a kind of catalyst without mercury system, and catalyst is by main work
Property component four Hydrogen thiocyanate close potassium aurate, Supplementary active compounds potassium chloride, copper chloride, cobaltous chloride and chlorination
One or more combination of zinc, carrier active carbon composition, wherein gold complex accounts for catalyst weight
The 0.1～2.5% of amount, Supplementary active compounds accounts for the 0.05～15% of total catalyst weight altogether.
In general, the catalyst without mercury system of current document and patent report is mainly characterized by catalyst
Using activated carbon or other oxide is carrier, by loading metal-salt, oxide or phosphatization
Thing isoreactivity component and the loaded catalyst prepared, reaction temperature is generally below 200 DEG C.These are urged
Agent system face active component be easy to run off, the problems such as cost height, complicated process of preparation.
Summary of the invention
For overcoming the problems of the prior art, it is an object of the invention to provide a kind of at acetylene hydrogen chlorine
Change reaction, be especially in the reaction for synthesize vinyl chloride use molecular sieve catalyst without mercury and
Preparation method.This catalyst should be suitable to have catalysis activity in high reaction temperatures, and acetylene converts
Rate is high, vinyl chloride selectivity high, and not easily run off, with low cost, preparation technology is simple.
Therefore, at first aspect, the invention provides a kind of molecule for acetylene hydrochlorination reaction
Sieve catalyst without mercury (the most sometimes referred to simply as " catalyst of the present invention "), it comprises by catalyst
The FAU type Si-Al molecular sieve of total amount meter 50-100wt% and the non-molecular sieve component of 0-50wt%, described
Non-molecule screen banks is divided into silicon dioxide, aluminium oxide or both arbitrary proportion mixture.
One advantage of the catalyst of the present invention is that it has foot under the reaction temperature of 280-350 DEG C
Catalysis activity with effective catalyzing acetylene hydrochlorination.In the present invention, the catalyst of the present invention exists
The conversion of alkyne that can realize in catalyzing acetylene hydrochlorination is not less than 80%.Further,
The catalyst of present invention vinyl chloride selectivity in catalyzing acetylene hydrochlorination is not less than 97%, excellent
Select more than 98%.
Meanwhile, another advantage of the catalyst of the present invention is when can be after this catalyst activity reduction
By method of roasting activity recovery under the sintering temperature of 350-500 DEG C.
Silica alumina ratio (the SiO of FAU type molecular sieve in the catalyst of the present invention2/Al2O3) it is 2-7.
In the catalyst of the present invention on FAU type molecular sieve tradable cation can be hydrion,
One in sodium ion, calcium ion, potassium ion, lithium ion, magnesium ion, strontium ion and barium ions or
Several.
In a preferred embodiment of the catalyst of the present invention, this catalyst can be containing by catalysis
The FAU type Si-Al molecular sieve of the total amount meter 70-100wt% of agent and the non-molecular sieve component of 0-30wt%.
At second aspect, the invention provides the preparation method of the catalyst of the present invention, described method
Carry out as follows: FAU type Si-Al molecular sieve powder body is directly squeezed into solid particle, then
The solid particle obtained 450～600 DEG C of roastings to obtain finished catalyst；And FAU type silicoaluminophosphate molecular
Sieve is then squeezed into solid particle by extruded moulding with the mixture of non-molecular sieve component, then obtains
Solid particle is 450～600 DEG C of roastings to obtain finished catalyst, and wherein said non-molecular sieve component rises
Effect to binding agent.In the present invention, granular size shape does not affect the catalytic reaction work of catalyst
Property.
At the 3rd aspect, the invention provides and utilize the catalyst acetylene hydrochlorination of the present invention anti-
The method that should prepare vinyl chloride, described method is carried out as follows: by this of solid particulate form
Bright catalyst is placed in tubular fixed-bed reactor, and logical nitrogen activates 2～4 hours at 350 DEG C；Enter
The reaction temperature of row acetylene hydrochlorination is 280-350 DEG C, reaction raw materials gas hydrogen chloride and the body of acetylene
Long-pending is 20-240h than the volume ratio for 0.9-1.2, reaction raw materials gas flow rate and catalyst-1, thus
Prepare vinyl chloride.
In fourth aspect, present invention also offers the renovation process of the catalyst of the present invention, described method
Carry out as follows: when the catalyst activity reduction of the present invention, in the reactor containing catalyst
Being passed through air, catalyst in reactor bed temperature is 350-500 DEG C, air velocity and caltalyst
Long-pending ratio is 100-1000h-1, 3-6 hour recovery time.
Beneficial effects of the present invention:
1. the catalyst of the present invention directly use FAU type molecular sieve as the main active component of catalyst,
By fashion of extrusion or extrusion mode molding, it is suitable for the acetylene under the reaction temperature of 280-350 DEG C
Hydrochlorination.
2. the catalyst of present invention acetylene in the reaction of catalyzing acetylene preparing vinyl chloride by hydrochlorination turns
Rate is high, and vinyl chloride selectivity is high.
3. the catalyst low cost of the present invention, preparation technology is simple, inactive component losing issue, catalyst
After inactivation renewable.
Detailed description of the invention
The catalyst of the present invention comprises 50-100wt% based on the total amount of catalyst (preferably 70-100wt%)
FAU type Si-Al molecular sieve and the non-molecular sieve component of 0-50wt% (preferably 0-30wt%), described non-
Molecular sieve component is silicon dioxide, aluminium oxide or both arbitrary proportion mixture.The present invention urges
Agent can occur by effective catalyzing acetylene hydrochlorination under the reaction temperature of 280-350 DEG C, and
Can recover to live by method of roasting under the sintering temperature of 350-500 DEG C after catalyst activity reduction
Property.
The exploitation of the catalyst being effective to catalyzing acetylene preparing vinyl chloride by hydrochlorination of the present invention
Based on following thinking:
First, the feature of acetylene hydrochlorination reaction is that acetylene and product are active, and carbon distribution, chlorination easily occur
Hydrogen has corrosivity, easily causes catalyst activity component and runs off.So hydrochlorination is to catalysis
The requirement of agent is in addition to activity and selectivity, in addition it is also necessary to catalyst has big specific surface area, active group
Anti-current mistake, catalyst is divided not to react with hydrogen chloride.
Stated in the background, of the prior art prepare chloroethene for catalyzing acetylene hydrochlorination
In the catalyst of alkene, often using activated carbon or other oxide is carrier, by loading metal-salt,
Oxide or phosphide isoreactivity component and the loaded catalyst prepared, reaction temperature is the lowest
In 200 DEG C.The shortcoming of catalyst without mercury of the prior art is that stability is low, though when pyroreaction
So activity is high, but catalyst carbon deposition is serious, and the chloride loss of active component of its load is serious；
The catalyst having additionally used absorbent charcoal carrier can not be regenerated by method of roasting, and employs porous oxygen
Compound is that the catalyst of carrier loss of active component when high temperature regeneration is serious, and catalyst can not the most again
Raw.And the present invention uses FAU type molecular sieve as catalyst, being characterized in can be at high-temperature catalytic
Reaction occurs, and does not has loss of active component, and can have substantially at high temperature by roasting regeneration
Advantage.Namely the present invention changes traditional catalyst without mercury Research idea, have employed new high temperature
Reaction, roasting regeneration Research Thinking.
Secondly, FAU type Si-Al molecular sieve is the main active component of the catalyst of the present invention, and other
Non-molecular sieve oxide primarily serves binding agent effect.Acid centre in FAU molecular sieve is acetylene hydrogen
The active center of chlorination reaction, on the active center of molecular sieve, acetylene and hydrogen chloride molecule are adsorbed
Activation, thus there is hydrochlorination.The pore passage structure of FAU type molecular sieve uniqueness and supercage structure pair
Acetylene and the activation of hydrogen chloride molecule and reaction serve facilitation.Compared to metal chloride, phosphorus
The activated carbon of compound even load is the catalyst without mercury of carrier, and FAU type molecular sieve is to acetylene and hydrogen chloride
The activation capacity of molecule is lower, and therefore the molecular sieve catalyst without mercury of the present invention is less than 200 DEG C
Time activity relatively low, but react the high-temperature region of 280-350 DEG C and activity is higher, and selectivity is also
Higher.
3rd, owing to FAU type molecular sieve is main active component, therefore catalyst Middle molecule sieve
The height of content determines the activity of catalytic hydrochlorination reaction.The present inventor grinds through substantial amounts of
Studying carefully discovery, when molecular sieve content is less than 50%, conversion of alkyne (sees following anti-less than 80%
Answer comparative example 1), affect the economy of whole catalytic reaction process, therefore application claims catalysis
Agent Middle molecule sieve content is no less than 50%.
The preparation of the catalyst of the present invention can use following preferred embodiment:
Take a certain amount of FAU type Si-Al molecular sieve powder body, be individually squeezed into solid particle,
450～600 DEG C, preferably 500 DEG C roastings i.e. obtain after 3 hours the molecular sieve of molecular sieve content 100% without
Mercury catalyst finished product.Why take squeezing and pressing method, be because use 100% molecular sieve time do not have
Binding agent, it is impossible to use kneading and compacting technique.By extruded, certain intensity can be obtained
Pellet type catalyst, thus it is suitable for fixed bed catalyst.
Take a certain amount of Ludox to mix homogeneously with a certain amount of FAU type Si-Al molecular sieve powder body, logical
The mode crossing extruded moulding obtains bar column solid particle, at 450～600 DEG C, and preferably 500～550 DEG C
Roasting i.e. obtains silica containing molecular sieve catalyst without mercury finished product after 3 hours.
Take a certain amount of Alumina gel to mix homogeneously with a certain amount of FAU type Si-Al molecular sieve powder body, logical
The mode crossing extruded moulding obtains bar column solid particle, at 450～600 DEG C, and preferably 500～550 DEG C
Roasting i.e. obtains salic molecular sieve catalyst without mercury finished product after 3 hours.
Take a certain amount of Kaolin to mix homogeneously with a certain amount of FAU type Si-Al molecular sieve powder body, logical
The mode crossing extruded moulding obtains bar column solid particle, at 450～600 DEG C, and preferably 500～550 DEG C
Roasting i.e. obtains the molecular sieve catalyst without mercury finished product containing silica/alumina mixture after 3 hours.
The catalyst utilizing the present invention can be joined by the method for preparing vinyl chloride by hydrochlorination of acetylene
Examine following preferred embodiment to carry out:
Take a certain amount of above-mentioned molecular sieve catalyst without mercury finished product and load tubular fixed-bed reactor, first lead to nitrogen
Gas activates 2～4 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by reaction bed temperature control
At 280-350 DEG C, being passed through reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (body
Long-pending ratio)=0.9-1.2, reaction raw materials gas flow rate and volume ratio (the volume space velocity)=20-240 of catalyst
h-1, reaction afterproduct analyzes conversion of alkyne and vinyl chloride selectivity by gas chromatography.
The renovation process of the catalyst of the present invention can refer to following preferred embodiment to be carried out:
When the catalyst activity reduction of the present invention, in the reactor containing catalyst, it is passed through air, instead
Answering device inner catalyst bed temperature to be 350-500 DEG C, (volume is empty for air velocity and catalyst volume ratio
Speed)=100-1000h-1, 3-6 hour recovery time.
Further describe technical scheme and effect, this area skill by the following examples
Art personnel, it should be understood that following embodiment is merely to illustrate the present invention, are not intended to limit the model of the present invention
Enclose.
Catalyst Preparation Example 1
Take 100 grams of Hydrogen FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=7, will
This powdered molecular sieve raw material is put into and is squeezed into bulk in metal die, squeeze pressure 20Mpa, then
Crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content 100%
Hydrogen FAU molecular sieve catalyst without mercury finished product, by reaction embodiment 1 be evaluated.
Catalyst Preparation Example 2
Take 100 grams of sodium form FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2, will
This powdered molecular sieve raw material is put into and is squeezed into bulk in metal die, squeeze pressure 20Mpa, then
Crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content 100%
Sodium form FAU molecular sieve catalyst without mercury finished product, by reaction embodiment 2 be evaluated.
Catalyst Preparation Example 3
Take 100 grams of calcium type FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
This powdered molecular sieve raw material is put into metal die is squeezed into bulk, squeeze pressure 20Mpa, so
Rear crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content
The calcium type FAU molecular sieve catalyst without mercury finished product of 100%, is evaluated by reaction embodiment 3.
Catalyst Preparation Example 4
Take 100 grams of potassium type FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
This powdered molecular sieve raw material is put into metal die is squeezed into bulk, squeeze pressure 20Mpa, so
Rear crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content
The potassium type FAU molecular sieve catalyst without mercury finished product of 100%, is evaluated by reaction embodiment 4.
Catalyst Preparation Example 5
Take 100 grams of lithium type FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
This powdered molecular sieve raw material is put into metal die is squeezed into bulk, squeeze pressure 20Mpa, so
Rear crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content
The lithium type FAU molecular sieve catalyst without mercury finished product of 100%, is evaluated by reaction embodiment 5.
Catalyst Preparation Example 6
Take 100 grams of magnesium types FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
This powdered molecular sieve raw material is put into metal die is squeezed into bulk, squeeze pressure 20Mpa, so
Rear crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content
The magnesium types FAU molecular sieve catalyst without mercury finished product of 100%, is evaluated by reaction embodiment 6.
Catalyst Preparation Example 7
Take 100 grams of strontium type FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
This powdered molecular sieve raw material is put into metal die is squeezed into bulk, squeeze pressure 20Mpa, so
Rear crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content
The strontium type FAU molecular sieve catalyst without mercury finished product of 100%, is evaluated by reaction embodiment 7.
Catalyst Preparation Example 8
Take 100 grams of barium type FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
This powdered molecular sieve raw material is put into metal die is squeezed into bulk, squeeze pressure 20Mpa, so
Rear crushing and screening becomes 20-40 mesh granule, after 500 DEG C of roastings 3 hours, i.e. obtains molecular sieve content
The barium type FAU molecular sieve catalyst without mercury finished product of 100%, is evaluated by reaction embodiment 8.
Catalyst Preparation Example 9
Take 80 grams of sodium form FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, add
Entering 200 grams of silicon dioxide quality content is the Ludox of 40%, adds 5 milliliters of mass concentrations 5%
Dust technology, adds 5 grams of lignins, by said mixture mix homogeneously on kneading machine, is then squeezing
Extruding strip-shaped product on bar machine, banded extruder orifice plate is circular, diameter 3 millimeters；Above-mentioned strip-shaped product exists
Dry 6 hours at 60 DEG C, then roasting 6 hours at 550 DEG C；Strip-shaped product after roasting is broken
The broken cylindrical pellet being sieved into a length of 3 millimeter, i.e. obtains molecular sieve content 50%, dioxy
The sodium form FAU molecular sieve catalyst without mercury finished product of SiClx content 50%, is entered by reaction embodiment 9
Row is evaluated.
Catalyst Preparation Example 10
Take 80 grams of sodium form FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, add
Enter 80 grams of alumina powders, add 120 milliliters of water, add the dust technology of 5 milliliters of mass concentrations 5%,
Add 5 grams of lignins, by said mixture mix homogeneously on kneading machine, then squeeze on banded extruder
Going out strip-shaped product, banded extruder orifice plate is circular, diameter 3 millimeters；Above-mentioned strip-shaped product dries at 60 DEG C
Dry 6 hours, then roasting 6 hours at 550 DEG C；Strip-shaped product crushing and screening after roasting is become
The cylindrical pellet of a length of 3 millimeter, i.e. obtains molecular sieve content 50%, alumina content 50%
Sodium form FAU molecular sieve catalyst without mercury finished product, by reaction embodiment 10 be evaluated.
Catalyst Preparation Example 11
Take 80 grams of sodium form FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, add
Enter 80 grams of Kaolin, add 120 milliliters of water, add the dust technology of 5 milliliters of mass concentrations 5%, add
Enter 5 grams of lignins, by said mixture mix homogeneously on kneading machine, then extrude on banded extruder
Strip-shaped product, banded extruder orifice plate is circular, diameter 3 millimeters；Above-mentioned strip-shaped product is dried at 60 DEG C
6 hours, then roasting 6 hours at 550 DEG C；Strip-shaped product crushing and screening after roasting is grown up
Degree is the cylindrical pellet of 3 millimeter, i.e. obtains molecular sieve content 50%, Kaolin content 50%
Sodium form FAU molecular sieve catalyst without mercury finished product, by reaction embodiment 11 be evaluated.
Catalyst Preparation Example 12
Take 70 grams of sodium form FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, add
Enter 30 grams of Kaolin, add 75 milliliters of water, add the dust technology of 5 milliliters of mass concentrations 5%, add
Enter 5 grams of lignins, by said mixture mix homogeneously on kneading machine, then extrude on banded extruder
Strip-shaped product, banded extruder orifice plate is circular, diameter 3 millimeters；Above-mentioned strip-shaped product is dried at 60 DEG C
6 hours, then roasting 6 hours at 550 DEG C；Strip-shaped product crushing and screening after roasting is grown up
Degree is the cylindrical pellet of 3 millimeter, i.e. obtains molecular sieve content 70%, Kaolin content 30%
Sodium form FAU molecular sieve catalyst without mercury finished product, by reaction embodiment 12 be evaluated.
CATALYST PREPARATION Comparative's embodiment 1
Take 45 grams of sodium form FAU molecular sieve powder, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, add
Enter 55 grams of Kaolin, add 75 milliliters of water, add the dust technology of 5 milliliters of mass concentrations 5%, add
Enter 5 grams of lignins, by said mixture mix homogeneously on kneading machine, then extrude on banded extruder
Strip-shaped product, banded extruder orifice plate is circular, diameter 3 millimeters；Above-mentioned strip-shaped product is dried at 60 DEG C
6 hours, then roasting 6 hours at 550 DEG C；Strip-shaped product crushing and screening after roasting is grown up
Degree is the cylindrical pellet of 3 millimeter, i.e. obtains molecular sieve content 45%, Kaolin content 55%
Sodium form FAU molecular sieve catalyst without mercury finished product, by reaction comparative example 1 be evaluated.
Reaction embodiment 1
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is hydrion, molecular sieve silica alumina ratio (SiO2/Al2O3)=7, load tubular fixed-bed reaction
Device, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by beds
Temperature controls at 280 DEG C, is passed through reactor feed gas, and reaction raw materials gas ratio is: hydrogen chloride/acetylene
Volume ratio (the volume space velocity)=20h of (volume ratio)=0.9, reaction raw materials gas flow rate and catalyst-1,
Reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 98.5%, and vinyl chloride selects
Property 98%.When conversion of alkyne is less than 80%, being first passed through nitrogen in hydrogen-catalyst reactor, to purge 1 little
Time, nitrogen flow rate 100ml/min, then it is passed through air, controlling catalyst in reactor bed temperature is
350 DEG C, air velocity and catalyst volume ratio (volume space velocity)=100h-1, 6 hours recovery times.
It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, is passed through reactor feed gas,
Reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: conversion of alkyne
98.4%, vinyl chloride selectivity 98.0%.
Reaction embodiment 2
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is sodium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2, load tubular fixed-bed reaction
Device, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by beds
Temperature controls at 350 DEG C, is passed through reactor feed gas, and reaction raw materials gas ratio is: hydrogen chloride/acetylene
The volume ratio (volume space velocity)=240 of (volume ratio)=1.2, reaction raw materials gas flow rate and catalyst
h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 92.5%, vinyl chloride
Selectivity 98.0%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen blows
Sweep 1 hour, nitrogen flow rate 100ml/min, then be passed through air, control catalyst in reactor bed
Temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time
3 hours.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, is passed through reaction
Unstripped gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene turns
Rate 92.4%, vinyl chloride selectivity 98.0%.
Reaction embodiment 3
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is calcium ion molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load tubular fixed-bed reactor,
First lead to nitrogen to activate 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by reaction bed temperature
Controlling at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (body
Long-pending ratio)=1.1, reaction raw materials gas flow rate and volume ratio (the volume space velocity)=120h of catalyst-1,
Reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 93.9%, and vinyl chloride selects
Property 98.1%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen purging 1
Hour, nitrogen flow rate 100ml/min, then it is passed through air, control catalyst in reactor bed temperature
It is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time 3
Hour.Being passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, being passed through, reaction is former
Material gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene converts
Rate 93.6%, vinyl chloride selectivity 98.0%.
Reaction embodiment 4
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is potassium ion molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load tubular fixed-bed reactor,
First lead to nitrogen to activate 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by reaction bed temperature
Controlling at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio is: hydrogen chloride/acetylene (body
Long-pending ratio)=1.1, reaction raw materials gas flow rate and volume ratio (the volume space velocity)=120h of catalyst-1,
Reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 99.1%, and vinyl chloride selects
Property 98.2%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen purging 1
Hour, nitrogen flow rate 100ml/min, then it is passed through air, control catalyst in reactor bed temperature
It is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time 3
Hour.Being passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, being passed through, reaction is former
Material gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene converts
Rate 98.9%, vinyl chloride selectivity 98.1%.
Reaction embodiment 5
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is lithium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load tubular fixed-bed reaction
Device, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by beds
Temperature controls at 320 DEG C, is passed through reactor feed gas, and reaction raw materials gas ratio is: hydrogen chloride/acetylene
The volume ratio (volume space velocity)=120 of (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 96.9%, vinyl chloride
Selectivity 98.1%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen blows
Sweep 1 hour, nitrogen flow rate 100ml/min, then be passed through air, control catalyst in reactor bed
Temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time
6 hours.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, is passed through reaction
Unstripped gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene turns
Rate 96.8%, vinyl chloride selectivity 98.1%.
Reaction embodiment 6
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is magnesium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load tubular fixed-bed reaction
Device, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by beds
Temperature controls at 320 DEG C, is passed through reactor feed gas, and reaction raw materials gas ratio is: hydrogen chloride/acetylene
The volume ratio (volume space velocity)=120 of (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 90.9%, vinyl chloride
Selectivity 98.1%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen blows
Sweep 1 hour, nitrogen flow rate 100ml/min, then be passed through air, control catalyst in reactor bed
Temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time
3 hours.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, is passed through reaction
Unstripped gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene turns
Rate 91.0%, vinyl chloride selectivity 98.0%.
Reaction embodiment 7
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is strontium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load tubular fixed-bed reaction
Device, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by beds
Temperature controls at 320 DEG C, is passed through reactor feed gas, and reaction raw materials gas ratio is: hydrogen chloride/acetylene
The volume ratio (volume space velocity)=120 of (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 93.7%, vinyl chloride
Selectivity 98.1%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen blows
Sweep 1 hour, nitrogen flow rate 100ml/min, then be passed through air, control catalyst in reactor bed
Temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time
3 hours.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, is passed through reaction
Unstripped gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene turns
Rate 93.8%, vinyl chloride selectivity 98.1%.
Reaction embodiment 8
Take the molecular sieve catalyst without mercury finished product of 10ml molecular sieve content 100%, commutative on molecular sieve
Cation is barium ions, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load tubular fixed-bed reaction
Device, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.Then by beds
Temperature controls at 320 DEG C, is passed through reactor feed gas, and reaction raw materials gas ratio is: hydrogen chloride/acetylene
The volume ratio (volume space velocity)=120 of (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne 96.8%, vinyl chloride
Selectivity 98.1%.When conversion of alkyne is less than 80%, in hydrogen-catalyst reactor, first it is passed through nitrogen blows
Sweep 1 hour, nitrogen flow rate 100ml/min, then be passed through air, control catalyst in reactor bed
Temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)=1000h-1, the recovery time
3 hours.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate 100ml/min, is passed through reaction
Unstripped gas, reaction condition is identical, and reaction afterproduct by gas chromatography analysis result is: acetylene turns
Rate 96.5%, vinyl chloride selectivity 98.0%.
Reaction embodiment 9
Taking 10ml molecular sieve content 50%, the molecular sieve catalyst without mercury of dioxide-containing silica 50% becomes
Product, on molecular sieve, exchangeable cations is sodium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4,
Load tubular fixed-bed reactor, first lead to nitrogen and activate 2 hours at 350 DEG C, nitrogen air speed 1000h-1。
Then reaction bed temperature is controlled at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio
Example is: hydrogen chloride/acetylene (volume ratio)=1.1, reaction raw materials gas flow rate and the volume ratio of catalyst
(volume space velocity)=120h-1, reaction afterproduct by gas chromatography analysis result is: acetylene converts
Rate 80.6%, vinyl chloride selectivity 98.1%.When conversion of alkyne is less than 80%, to catalyst reaction
First it is passed through nitrogen in device to purge 1 hour, nitrogen flow rate 100ml/min, then is passed through air, control anti-
Answering device inner catalyst bed temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)
=1000h-1, 3 hours recovery times.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate
100ml/min, is being passed through reactor feed gas, and reaction condition is identical, and reaction afterproduct is by gas phase color
Chromatography result is: conversion of alkyne 80.2%, vinyl chloride selectivity 98.0%.
Reaction embodiment 10
Take 10ml molecular sieve content 50%, the molecular sieve catalyst without mercury finished product of alumina content 50%,
On molecular sieve, exchangeable cations is sodium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load
Tubular fixed-bed reactor, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.So
After reaction bed temperature is controlled at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio
For: the volume ratio (body of hydrogen chloride/acetylene (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
Long-pending air speed)=120h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne
81.2%, vinyl chloride selectivity 98.1%.When conversion of alkyne is less than 80%, to hydrogen-catalyst reactor
The most first it is passed through nitrogen to purge 1 hour, nitrogen flow rate 100ml/min, then is passed through air, control reaction
Device inner catalyst bed temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)
=1000h-1, 3 hours recovery times.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate
100ml/min, is being passed through reactor feed gas, and reaction condition is identical, and reaction afterproduct is by gas phase color
Chromatography result is: conversion of alkyne 81.0%, vinyl chloride selectivity 98.0%.
Reaction embodiment 11
Take 10ml molecular sieve content 50%, the molecular sieve catalyst without mercury finished product of Kaolin content 50%,
On molecular sieve, exchangeable cations is sodium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load
Tubular fixed-bed reactor, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.So
After reaction bed temperature is controlled at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio
For: the volume ratio (body of hydrogen chloride/acetylene (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
Long-pending air speed)=120h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne
85.3%, vinyl chloride selectivity 98.1%.When conversion of alkyne is less than 80%, to hydrogen-catalyst reactor
The most first it is passed through nitrogen to purge 1 hour, nitrogen flow rate 100ml/min, then is passed through air, control reaction
Device inner catalyst bed temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)
=1000h-1, 3 hours recovery times.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate
100ml/min, is being passed through reactor feed gas, and reaction condition is identical, and reaction afterproduct is by gas phase color
Chromatography result is: conversion of alkyne 85.1%, vinyl chloride selectivity 98.0%.
Reaction embodiment 12
Take 10ml molecular sieve content 70%, the molecular sieve catalyst without mercury finished product of Kaolin content 30%,
On molecular sieve, exchangeable cations is sodium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load
Tubular fixed-bed reactor, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.So
After reaction bed temperature is controlled at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio
For: the volume ratio (body of hydrogen chloride/acetylene (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
Long-pending air speed)=120h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne
89.3%, vinyl chloride selectivity 98.1%.When conversion of alkyne is less than 80%, to hydrogen-catalyst reactor
The most first it is passed through nitrogen to purge 1 hour, nitrogen flow rate 100ml/min, then is passed through air, control reaction
Device inner catalyst bed temperature is 500 DEG C, air velocity and catalyst volume ratio (volume space velocity)
=1000h-1, 6 hours recovery times.It is passed through nitrogen after regeneration to purge 1 hour, nitrogen flow rate
100ml/min, is being passed through reactor feed gas, and reaction condition is identical, and reaction afterproduct is by gas phase color
Chromatography result is: conversion of alkyne 89.1%, vinyl chloride selectivity 98.0%.
Reaction comparative example 1
Take 10ml molecular sieve content 45%, the molecular sieve catalyst without mercury finished product of Kaolin content 55%,
On molecular sieve, exchangeable cations is sodium ion, molecular sieve silica alumina ratio (SiO2/Al2O3)=2.4, load
Tubular fixed-bed reactor, first leads to nitrogen and activates 2 hours at 350 DEG C, nitrogen air speed 1000h-1.So
After reaction bed temperature is controlled at 320 DEG C, be passed through reactor feed gas, reaction raw materials gas ratio
For: the volume ratio (body of hydrogen chloride/acetylene (volume ratio)=1.1, reaction raw materials gas flow rate and catalyst
Long-pending air speed)=120h-1, reaction afterproduct by gas chromatography analysis result is: conversion of alkyne
79.2%, vinyl chloride selectivity 97.1%.
Claims (10)
1. the method utilizing molecular sieve catalyst without mercury catalyzing acetylene preparing vinyl chloride by hydrochlorination, institute
Method of stating is carried out as follows: the described molecular sieve catalyst without mercury of solid particulate form is placed in pipe
In formula fixed bed reactors, logical nitrogen is 350 DEG C of activation；It is passed through reaction raw materials gas hydrogen chloride and second
Alkynes, the reaction temperature carrying out acetylene hydrochlorination is 280-350 DEG C, reaction raw materials gas hydrogen chloride and second
The volume ratio of alkynes is 0.9-1.2, and reaction raw materials gas flow rate is 20-240h with the volume ratio of catalyst-1；
Wherein said molecular sieve catalyst without mercury comprises the FAU type of 50-100wt% based on the total amount of catalyst
Si-Al molecular sieve and the non-molecular sieve component of 0-50wt%, described non-molecule screen banks be divided into silicon dioxide,
Aluminium oxide or both arbitrary proportion mixture.
Method the most according to claim 1, it is characterised in that the silicon of described FAU type Si-Al molecular sieve
Aluminum ratio SiO2/Al2O3For 2-7.
Method the most according to claim 1, it is characterised in that can on described FAU type Si-Al molecular sieve
Exchange cation selected from hydrion, sodium ion, calcium ion, potassium ion, lithium ion, magnesium ion,
One or more in strontium ion and barium ions.
Method the most according to claim 1, it is characterised in that it is total that described catalyst contains by catalyst
The FAU type Si-Al molecular sieve of gauge 70-100wt% and the non-molecular sieve component of 0-30wt%.
Method the most according to claim 1, it is characterised in that the acetylene in the reaction of described acetylene hydrochlorination
Conversion ratio is not less than 80%.
Method the most according to claim 1, it is characterised in that the chloroethene in the reaction of described acetylene hydrochlorination
Alkene selectivity is not less than 97%.
Method the most according to claim 1, it is characterised in that the chloroethene in the reaction of described acetylene hydrochlorination
Alkene selectivity is more than 98%.
8. the method according to any one of claim 1-7, it is characterised in that when described molecular sieve is catalyzed without hydrargyrum
When agent contains the FAU type Si-Al molecular sieve of 100wt%, it is made by the following method: by FAU
Type Si-Al molecular sieve powder body is directly squeezed into solid particle, and the solid particle then obtained exists
450～600 DEG C of roastings obtain finished catalyst.
9. the method according to any one of claim 1-7, it is characterised in that when described molecular sieve is catalyzed without hydrargyrum
When agent contains FAU type Si-Al molecular sieve and two kinds of components of non-molecular sieve component, it is by the following method
Make: the mixture of FAU type Si-Al molecular sieve with non-molecular sieve component is extruded by extruded moulding
Becoming solid particle, the solid particle then obtained obtains finished catalyst 450～600 DEG C of roastings.
10., according to the method according to any one of claim 1-7, described method is further comprising the steps of:
When described molecular sieve catalyst without mercury activity decrease, in the reactor containing catalyst, it is passed through air,
Catalyst in reactor bed temperature is 350-500 DEG C, and air velocity with catalyst volume ratio is
100-1000h-1, 3-6 hour recovery time.
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| CN104744207B (en) * | 2015-02-12 | 2018-05-22 | 石家庄市科创助剂有限公司 | Without mercury catalyst synthesis vinyl chloride thereof technique |
| CN109806905B (en) * | 2017-11-20 | 2020-10-09 | 中国科学院大连化学物理研究所 | Mercury-free catalyst, preparation method thereof and application thereof in preparation of chloroethylene |
| CN112844460B (en) * | 2019-11-27 | 2022-06-03 | 中国科学院大连化学物理研究所 | Catalyst for preparing chloroethylene by acetylene and dichloroethane coupling reaction and application thereof |
| CN112973764A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane, preparation method, application and regeneration method |
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|---|---|---|---|---|
| DE2353437A1 (en) * | 1973-10-25 | 1975-05-15 | Basf Ag | Ethylene oxychlorination with oxygen and hydrogen chloride - purified from acetylene by catalytic hydrogenation |
| JPS5988434A (en) * | 1982-11-12 | 1984-05-22 | ユリイ・アントノビチ・パズデルスキイ | Manufacture of vinyl chloride |
| CN101670293A (en) * | 2009-03-06 | 2010-03-17 | 清华大学 | Method for synthesizing and regenerating mercury-free catalyst for hydrochlorination of acetylene and application thereof |
| CN101890360A (en) * | 2010-08-05 | 2010-11-24 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
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2012
- 2012-12-25 CN CN201210571448.XA patent/CN103894221B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2353437A1 (en) * | 1973-10-25 | 1975-05-15 | Basf Ag | Ethylene oxychlorination with oxygen and hydrogen chloride - purified from acetylene by catalytic hydrogenation |
| JPS5988434A (en) * | 1982-11-12 | 1984-05-22 | ユリイ・アントノビチ・パズデルスキイ | Manufacture of vinyl chloride |
| CN101670293A (en) * | 2009-03-06 | 2010-03-17 | 清华大学 | Method for synthesizing and regenerating mercury-free catalyst for hydrochlorination of acetylene and application thereof |
| CN101890360A (en) * | 2010-08-05 | 2010-11-24 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
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