CN104549401B - Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application - Google Patents
Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application Download PDFInfo
- Publication number
- CN104549401B CN104549401B CN201310518594.0A CN201310518594A CN104549401B CN 104549401 B CN104549401 B CN 104549401B CN 201310518594 A CN201310518594 A CN 201310518594A CN 104549401 B CN104549401 B CN 104549401B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetylene
- acetylene hydrochlorination
- metallic catalyst
- hydrochlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nonmetallic catalyst for acetylene hydrochlorination, as well as a preparation method and application. The preparation method comprises the following steps: dissolving a nonmetallic compound containing at least one of N, O, S and P in a solvent, and stirring to dissolve the nonmetallic compound in a water bath at 30-100 DEG C to obtain a steeping liquor; immersing a catalyst carrier in the steeping liquor, stirring and immersing in a sealed state, and filtering out the liquid; drying, and putting into a tube furnace or a muffle furnace, heating at a nitrogen atmosphere, standing, and cooling to room temperature to obtain the nonmetallic catalyst for acetylene hydrochlorination. By using the catalyst, pollution of a metallic catalyst to the environment can be reduced; and the initial conversion rate of acetylene can be increased by 10-200 percent in comparison with an activated carbon catalyst which is not loaded with nonmetallic component under a condition that the reaction temperature is 170 DEG C, the acetylene airspeed is 180h＜-1＞ and the raw material gas proportion VC2H2/ VHC1 is 1:1.15, and the selectivity of generated vinyl chloride is more than 99.0 percent.
Description
Technical field
The present invention relates to a kind of non-metallic catalyst for acetylene hydrochlorination reaction as well as preparation method and application thereof.Belong to organic conjunction
The technology of preparing of one-tenth catalyst and range of application.
Background technology
Development, raising and the raising of environmental protection consciousness, the PVC (polrvinyl chloride) day by day of living standards of the people along with national economy
Demand increasing.PVC is by VCM(Vinyl Chloride Monomer) polymerization obtain, the production method of VCM mainly has second
Alkene method technique, ethane method technique and acetylene method technique.Owing to external oil field preferably obtains rich in ethylene, cheaper starting materials, so abroad
The commonly used ethylene process of developed country produces VCM；Ethane method prepares VCM low raw-material cost, however it is necessary that higher investment,
This technique is also merely resting on the lab scale stage, also has with a certain distance from industrialization；Acetylene method technique is prepared VCM and is restricted master
If because raw material supply situation and the high cost of raw material and the restriction of production capacity.In China due to resource distribution situation, unstripped gas
Ethylene does not enrich, and lacks the most very much and price is the highest, and along with the exhaustion of fossil resources, China has a large amount of low one-tenth
This coal provides raw material and price advantage, so China is suitable for acetylene method route being main production VCM.Therefore in west area,
Such as the area of the rich coal resources such as Xinjiang, Inner Mongol, it is rapid that newly-built or enlarging carbide produces Corvic project development.
But the fatal bottleneck problem that restriction acetylene method becomes Green Chemistry is catalyst problem, industrial its catalyst used at present
Principle active component be mercuric chloride, hydrargyrum easily distils loss, is the carbide severe contamination source that produces in polrvinyl chloride.Carbide
Technique often produces 1 ton of PVC will consume hydrargyrum about 1.4 kilograms, according to statistics, and China's acetylene method PVC industry hydrargyrum in 2010
Usage amount is about 767 tons, accounts for more than the 60% of whole nation hydrargyrum usage amount, accounts for about the 20% of world's hydrargyrum usage amount.The loss of hydrargyrum is not
Only cause catalysqt deactivation, and owing to the loss catalyst of active component cannot regenerate, also have impact on VCM product simultaneously
Quality, also can cause the biggest harm to ecological environment.Additionally hydrargyrum is a heavy metal species, has severe toxicity, and the concentration producing toxicity is
0.01～0.1mg/l, and can not be degraded by microorganisms, can only be with different valence states, Transport And Transformation between water and biology, send out
Estranged dissipate and enrichment, enter and be difficult to again metabolism after human body and go out, be gathered in liver, kidney and brain, damage nervous system, make
Become fearful " minamata disease ".It is predicted that the consumption mercury quantity of acetylene method production polyvinyl chloride resin in 2014 can reach 17.5489 ten thousand tons,
Hydrargyrum also receives much concern because of its potential significant damage.Pollution problem that mercury catalyst causes that the most urgently to be resolved hurrily is, grinds
Study carefully the non-mercury catalyst replacing mercuric chleride catalyst and acetylene method is produced the existence of enterprise of PVC, to environmental problem, economic development,
The raising of living standards of the people, builds a harmonious society and plays huge effect.
20 various metals components are used for acetylene hydrochlorination reaction by Hutchings etc., draw activity and the standard electrode EMF of component
Relevant, the order of initial activity is Pd2+>Hg2+>Cu2+, Cu+>Ag+；M.Conte etc. have studied in detail activated carbon supported
Bimetallic catalyst and acetylene hydrochlorination that Au catalyst 1wt%Au/C and Pd, Pt, Ir, Rh, Ru compound with Au are anti-
Answer mechanism；Wei Fei etc. are prepared for SiO2Chloride or phosphate as carrier, bismuth, copper, barium, zinc, cadmium etc. are active component
Catalyst without mercury, and test they activity in acetylene hydrochlorination reacts, research draws in catalyst addition PO4 3-Significantly
Improve catalysis activity, the most especially composite phosphate with Bi and Cu preferable, at reaction temperature 200 DEG C, its primary response
Activity is the 1/3 of industrial catalyst, and has certain recyclability.Chen Rongti etc. preparation and investigated three component stannous chlorides-
Bismuth trichloride-Cu-lyt ./activated carbon catalyst without mercury, its initial activity and selectivity are close to mercury bichloride/activated-carbon catalyst, longevity
Order 120 hours, but stannous chloride is also volatile substances, it is impossible to solve catalysqt deactivation.
Therefore, although personage is devoted to the research of catalyst without mercury the most both at home and abroad, but research contents has focused largely on metal active
The screening of component and compounding aspect, it is relatively low that the catalyst developed there is also activity, poor stability, and easily inactivate and be difficult to
The problem of regeneration, the life-span is shorter, and economy is the highest, brings considerable restraint for its industrialized production.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of non-metallic catalyst for acetylene hydrochlorination.
Second object of the present invention is to provide the preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination.
Third object of the present invention is to provide a kind of non-metallic catalyst for acetylene hydrochlorination in acetylene hydrochlorination reacts
Application.
Technical solution of the present invention is summarized as follows:
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) in proportion 0.1-10g at least one nonmetallic compound containing N, O, S and P is dissolved in 10-50ml solvent, stirs
Mix and make to dissolve to obtain impregnation liquid；Described solvent be water, methanol, ethanol, formaldehyde, acetic acid, hot ethylene glycol, glycerol, pyridine, third
Ketone, N-Methyl pyrrolidone, ether, benzene, chloroform；
(2) in proportion 10g catalyst carrier is immersed in described impregnation liquid, at water-bath 30-100 DEG C, seals stirring dipping 2-10h,
Filtration filters liquid；It is dried, puts in tube furnace or Muffle furnace, rise to the heating rate of 4-6 DEG C/min in a nitrogen atmosphere
500-1000 DEG C, keep 1-4h, be cooled to room temperature, obtain a kind of non-metallic catalyst for acetylene hydrochlorination.
The described nonmetallic compound containing N is tripolycyanamide, carbamide, pyrroles, pyridine, pyrimidine or purine.
The described nonmetallic compound containing O is nitric acid or hydrogen peroxide.
The described nonmetallic compound containing S is thiourea or mercaptan.
The described nonmetallic compound containing P is triphenylphosphine, sodium hypophosphite, pyrophosphoric acid or sodium pyrophosphate.
Described catalyst carrier be cocoanut active charcoal, active carbon from coal, asphalt-base spherical activated carbon, CNT, carborundum,
ZTCMS-185 type molecular sieve, ZTCMS-200 type molecular sieve or ZTCMS-220 type molecular sieve.
A kind of non-metallic catalyst for acetylene hydrochlorination prepared by said method.
The application in acetylene hydrochlorination reacts of a kind of non-metallic catalyst for acetylene hydrochlorination.
Advantages of the present invention:
Substitute traditional metallic catalyst with a kind of non-metallic catalyst of the present invention, decrease what environment was caused by metallic catalyst
Pollute；Reaction temperature be 170 DEG C, acetylene air speed be 180h-1, unstripped gas proportioning VC2H2/VHC1Under conditions of=1:1.15,
The initial conversion of its acetylene compares the activated-carbon catalyst of unsupported nonmetallic ingredient can improve 10%-200%, generates chloroethene
The selectivity of alkene is more than 99.0%.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, in order to make those skilled in the art can be better understood from this
Invention.But illustrated embodiment is not as a limitation of the invention.
Embodiment 1
The test that cocoanut active charcoal (reference) reacts as catalyst acetylene hydrochlorination
In a device, reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas
Proportioning VC2H2/VHC1=1:1.15, activated carbon loadings after pretreatment is 5ml；
This activated carbon catalyzing acetylene hydrochlorination under these conditions, the initial conversion obtaining acetylene is 15.0%, vinyl chloride
Selectivity more than 99.0%.
Embodiment 2
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1), during tripolycyanamide 1g is dissolved in 25ml formaldehyde, at water-bath 60 DEG C, impregnation liquid it is stirred to dissolve to obtain；
(2) 10g cocoanut active charcoal is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 2h, filter filter
Fall liquid；It is dried, puts in tube furnace, rise to 500 DEG C with the heating rate of 4 DEG C/min in a nitrogen atmosphere, keep 4h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 25%, and the selectivity of vinyl chloride is more than 99%.Compare unsupported any non-gold of embodiment 1
Belonging to the catalyst of active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 66.7%.
It is demonstrated experimentally that substitute the formaldehyde in the present embodiment with acetic acid, hot ethylene glycol, glycerol or pyridine to make solvent, the dipping of preparation
Liquid, it is also possible to for the preparation of the non-metallic catalyst of acetylene hydrochlorination.
Embodiment 3
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) during 3g triphenylphosphine is dissolved in 20ml methanol, under 100 DEG C of water-baths, impregnation liquid it is stirred to dissolve to obtain；
(2) 10g CNT is immersed in described impregnation liquid, under 100 DEG C of water-baths, seal stirring dipping 2h, filter filter
Fall liquid；It is dried, puts in Muffle furnace, rise to 1000 DEG C with the heating rate of 6 DEG C/min in a nitrogen atmosphere, keep 1h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 20.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 33.3%.
It is demonstrated experimentally that the methanol substituted in the present embodiment with chloroform makees solvent, the impregnation liquid of preparation, it is also possible to for acetylene
The preparation of the non-metallic catalyst of hydrogen chloride.
Embodiment 4
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) weigh the hydrogen peroxide 10g of 30% to be dissolved in 20ml ether, under 30 DEG C of water-baths, be stirred to dissolve and to obtain dipping
Liquid；
(2) 10g asphalt-base spherical activated carbon is immersed in described impregnation liquid, at water-bath 30 DEG C, seals stirring dipping 10h,
Filtration filters liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep
2h, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 30.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 100.0%.
Embodiment 5
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) during thiourea 5g is dissolved in 30ml dehydrated alcohol, under 60 DEG C of water-baths, impregnation liquid it is stirred to dissolve to obtain；
(2) 10g asphalt-base spherical activated carbon is immersed in described impregnation liquid, at water-bath 60 DEG C, seals stirring dipping 4h,
Filtration filters liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep
2h, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 28.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 86.7%.
Embodiment 6
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) during carbamide 0.1g is dissolved in 10ml dehydrated alcohol, under 60 DEG C of water-baths, impregnation liquid it is stirred to dissolve to obtain；
(2) immersing in described impregnation liquid by 10g carborundum, at water-bath 60 DEG C, seal stirring dipping 4h, filtration filters
Liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 16.5%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 10.0%.
Embodiment 7
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) pyrroles 3g+ sodium hypophosphite 3g is dissolved in 45ml dehydrated alcohol, under 60 DEG C of water-baths, is stirred to dissolve to obtain leaching
Stain liquid；
(2) 10g ZTCMS-200 type molecular sieve is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 4
H, filters liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere,
Keep 2h, be cooled to room temperature, obtain the non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 33.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 120.0%.
Embodiment 8
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) tripolycyanamide 3g+ mercaptan 1g is dissolved in 30ml dehydrated alcohol, under 60 DEG C of water-baths, is stirred to dissolve to obtain leaching
Stain liquid；
(2) 10g ZTCMS-185 type molecular sieve is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 4
H, filters liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere,
Keep 2h, be cooled to room temperature, obtain a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 27.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 80.0%.
Embodiment 9
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) concentrated nitric acid 3g+ thiourea 3g is dissolved in 35ml water, under 60 DEG C of water-baths, is stirred to dissolve to obtain impregnation liquid；
(2) 10g ZTCMS-220 type molecular sieve is immersed in described impregnation liquid, at water-bath 60 DEG C, seals stirring dipping 4h,
Filtration filters liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep
2h, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 22.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 46.7%.
Embodiment 10
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) concentrated nitric acid 3g+ sodium pyrophosphate 2g is dissolved in 40ml water, under 60 DEG C of water-baths, is stirred to dissolve to obtain impregnation liquid；
(2) 10g active carbon from coal is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 4h, filter
Filter liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2
H, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 38.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 153.3%.
Embodiment 11
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) thiourea 3g+ triphenylphosphine 1g is dissolved in 35ml dehydrated alcohol, under 60 DEG C of water-baths, is stirred to dissolve to obtain leaching
Stain liquid；
(2) 10g cocoanut active charcoal is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 4h, filter
Filter liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 21.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 40.0%.
Embodiment 12
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) the hydrogen peroxide 3g+ thiourea 1g of tripolycyanamide 3g+30% is dissolved in 30ml dehydrated alcohol, 60 DEG C of water-baths
Under, it is stirred to dissolve to obtain impregnation liquid；
(2) 10g active carbon from coal is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 6h, filter
Filter liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 40.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 166.7%.
Embodiment 13
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) pyridine 3g+ concentrated nitric acid 3g+ sodium hypophosphite 3g is dissolved in 40ml water, and under 60 DEG C of water-baths, stirring makes molten
Solve impregnation liquid；
(2) 10g active carbon from coal is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 6h, filter
Filter liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2
H, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 42.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 180.0%.
Embodiment 14
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) concentrated nitric acid 3g+ thiourea 1g+ pyrophosphoric acid 2g is dissolved in 50ml water, under 60 DEG C of water-baths, is stirred to dissolve
Impregnation liquid；
(2) 10g cocoanut active charcoal is immersed in described impregnation liquid, at water-bath 60 DEG C, seal stirring dipping 6h, filter
Filter liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 29.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 93.3%.
Embodiment 15
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) the hydrogen peroxide 10g+ thiourea 2g+ triphenylphosphine 2g of tripolycyanamide 3g+30% is dissolved in the anhydrous second of 50ml
In alcohol, under 60 DEG C of water-baths, it is stirred to dissolve to obtain impregnation liquid；
(2) 10g asphalt-base spherical activated carbon is immersed in described impregnation liquid, at water-bath 60 DEG C, seals stirring dipping 6h,
Filtration filters liquid；It is dried, puts in tube furnace, rise to 800 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, protect
Hold 2h, be cooled to room temperature, obtain a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 45.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 200.0%.
Embodiment 16
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) during 3g pyrimidine is dissolved in 20ml water, under 70 DEG C of water-baths, impregnation liquid it is stirred to dissolve to obtain；
(2) 10g asphalt-base spherical activated carbon is immersed in described impregnation liquid, under 70 DEG C of water-baths, seals stirring dipping 4h,
Filtration filters liquid；It is dried, puts in Muffle furnace, rise to 700 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep
2h, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 38.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 153.3%.
Embodiment 17
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) during 2g purine is dissolved in 20ml water, under 60 DEG C of water-baths, impregnation liquid it is stirred to dissolve to obtain；
(2) 10g active carbon from coal is immersed in described impregnation liquid, under 60 DEG C of water-baths, seal stirring dipping 4h, filter filter
Fall liquid；It is dried, puts in Muffle furnace, rise to 600 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep 2h,
It is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 26.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 73.3%.
Embodiment 18
The preparation method of a kind of non-metallic catalyst for acetylene hydrochlorination, comprises the steps:
(1) during 2g pyrroles is dissolved in 20ml acetone, under 70 DEG C of water-baths, impregnation liquid it is stirred to dissolve to obtain；
(2) 10g asphalt-base spherical activated carbon is immersed in described impregnation liquid, under 70 DEG C of water-baths, seals stirring dipping 4h,
Filtration filters liquid；It is dried, puts in Muffle furnace, rise to 700 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere, keep
2h, is cooled to room temperature, obtains a kind of non-metallic catalyst for acetylene hydrochlorination；
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, reaction temperature 170 DEG C, unstripped gas proportioning
VC2H2/VHC1=1:1.15.Above-mentioned loaded catalyst is 5ml；This catalyst catalyzing acetylene hydrochlorination under these conditions,
The initial conversion obtaining acetylene is 32.0%, and the selectivity of vinyl chloride is more than 99.0%.Compare the unsupported any of embodiment 1
The catalyst of nonmetal active component, the acetylene initial conversion of the non-metallic catalyst of the present invention improves 113.3%.
It is demonstrated experimentally that the acetone substituted in the present embodiment with N-Methyl pyrrolidone, benzene makees solvent, the impregnation liquid of preparation, it is possible to
Preparation for the non-metallic catalyst of acetylene hydrochlorination.
Claims (3)
1. it is used for a preparation method for the non-metallic catalyst of acetylene hydrochlorination, it is characterized in that comprising the steps:
(1) in proportion 0.1-10g at least one nonmetallic compound containing N, O, S and P is dissolved in 10-50ml solvent, stirs
Mix and make to dissolve to obtain impregnation liquid；Described solvent be water, methanol, ethanol, formaldehyde, acetic acid, hot ethylene glycol, glycerol, pyridine, third
Ketone, N-Methyl pyrrolidone, ether, benzene, chloroform；
(2) in proportion 10g catalyst carrier is immersed in described impregnation liquid, at water-bath 30-100 DEG C, seals stirring dipping 2-10h,
Filtration filters liquid；It is dried, puts in tube furnace or Muffle furnace, rise to the heating rate of 4-6 DEG C/min in a nitrogen atmosphere
500-1000 DEG C, keep 1-4h, be cooled to room temperature, obtain a kind of non-metallic catalyst for acetylene hydrochlorination；Described containing N's
Nonmetallic compound is tripolycyanamide, carbamide, pyrroles, pyridine, pyrimidine or purine；The described nonmetallic compound containing O is nitre
Acid or hydrogen peroxide；The described nonmetallic compound containing S is thiourea or mercaptan；The described nonmetallic compound containing P is triphenyl
Phosphine, sodium hypophosphite, pyrophosphoric acid or sodium pyrophosphate；Described catalyst carrier is cocoanut active charcoal, active carbon from coal, asphaltic base ball
Shape activated carbon, CNT, carborundum, ZTCMS-185 type molecular sieve, ZTCMS-200 type molecular sieve or ZTCMS-220
Type molecular sieve.
2. a kind of non-metallic catalyst for acetylene hydrochlorination that prepared by method described in claim 1.
3. a kind of non-metallic catalyst for acetylene hydrochlorination of claim 2 application in acetylene hydrochlorination reacts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518594.0A CN104549401B (en) | 2013-10-28 | 2013-10-28 | Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518594.0A CN104549401B (en) | 2013-10-28 | 2013-10-28 | Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549401A CN104549401A (en) | 2015-04-29 |
| CN104549401B true CN104549401B (en) | 2017-01-11 |
Family
ID=53067106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310518594.0A Active CN104549401B (en) | 2013-10-28 | 2013-10-28 | Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549401B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238095A (en) * | 2015-06-05 | 2016-12-21 | 天津大学 | Sulfur non-metallic catalyst and preparation method and application is mixed for what acetylene hydrochlorination reacted |
| CN108187712B (en) * | 2016-12-08 | 2021-02-02 | 中国科学院大连化学物理研究所 | Non-metal boron nitride catalyst, preparation and application thereof, and regeneration method |
| CN108246340B (en) * | 2016-12-28 | 2021-03-26 | 南开大学 | Preparation and use method of metal-free catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination |
| CN108246327B (en) * | 2016-12-28 | 2020-11-10 | 南开大学 | Preparation method and use method of nitrogen-doped carbon material catalyst for fixed bed acetylene hydrochlorination |
| CN108339569B (en) * | 2017-01-23 | 2020-07-28 | 天津大学 | Supported quaternary phosphonium salt non-metallic catalyst, preparation method and application |
| CN107930691B (en) * | 2017-11-21 | 2020-09-15 | 厦门中科易工化学科技有限公司 | Catalyst for preparing chloroethylene from acetylene dichloroethane and preparation method and application thereof |
| CN108097308B (en) * | 2018-01-10 | 2021-02-09 | 南开大学 | Preparation method and use method of nonmetal catalyst for acetylene hydrochlorination |
| CN108187721B (en) * | 2018-01-10 | 2020-11-24 | 南开大学 | Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination |
| CN108067282B (en) * | 2018-01-10 | 2020-11-10 | 南开大学 | Catalyst for hydrochlorination of acetylene and using method |
| CN108160097B (en) * | 2018-01-10 | 2021-02-09 | 南开大学 | Metal-free catalyst for acetylene hydrochlorination and using method thereof |
| CN108097251B (en) * | 2018-01-10 | 2021-03-26 | 南开大学 | Catalyst for fixed bed acetylene hydrochlorination and use method thereof |
| CN112871207B (en) * | 2019-11-29 | 2022-06-21 | 中国科学院大连化学物理研究所 | Supported non-metal catalyst and preparation method and application thereof |
| CN111330621A (en) * | 2020-03-18 | 2020-06-26 | 鄂尔多斯市瀚博科技有限公司 | Supported mercury-free catalyst for synthesizing chloroethylene and preparation method thereof |
| CN111389441A (en) * | 2020-04-17 | 2020-07-10 | 鄂尔多斯市瀚博科技有限公司 | Catalyst for acetylene hydrochlorination reaction and preparation method and application thereof |
| CN112844433B (en) * | 2021-01-14 | 2023-04-14 | 石河子大学 | Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof |
| CN112973799A (en) * | 2021-03-01 | 2021-06-18 | 内蒙古大学 | Preparation method and application of uracil modified gold-based catalyst |
| CN115069284A (en) * | 2022-06-08 | 2022-09-20 | 鄂尔多斯市瀚博科技有限公司 | Metal-free catalyst and preparation method and application thereof |
| CN115888786A (en) * | 2022-10-26 | 2023-04-04 | 鄂尔多斯市瀚博科技有限公司 | Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014947A (en) * | 1969-06-03 | 1977-03-29 | Inst Neftechimicheskogo Sintez | Method of producing vinyl chloride |
| CN100998949A (en) * | 2006-01-10 | 2007-07-18 | 李群生 | Catalyst for preparing chloroethylene from acetylene hydrochlorination and its preparation method |
| CN102029189A (en) * | 2009-09-29 | 2011-04-27 | 华东理工大学 | Non-mercuric catalyst used in hydrochlorination of acetylene and method for preparing vinyl chloride by using catalyst |
| CN102921473A (en) * | 2012-09-28 | 2013-02-13 | 石河子大学 | Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof |
-
2013
- 2013-10-28 CN CN201310518594.0A patent/CN104549401B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549401A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549401B (en) | Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application | |
| CN104415794B (en) | A kind of P Modification catalyst carrier and preparation method and application | |
| CN105148989B (en) | A kind of cellular solid load-type ion liquid-Au catalyst and its preparation and application | |
| CN104415793B (en) | A kind of oxygen modified catalyst supports and preparation method and application | |
| CN106694046B (en) | A kind of preparation method of modified class zeolite imidazole skeleton material and its application in carbon dioxide hydrogenation reaction | |
| CN102921473A (en) | Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof | |
| CN103691442B (en) | A kind of synthesis gas isobutanol catalyst and preparation method thereof | |
| CN102380380A (en) | Mercury-free catalyst system for acetylene hydrochlorination and use thereof | |
| CN105693490B (en) | It is a kind of to aoxidize the method for preparing 2,3,5 trimethylbenzoquinones | |
| CN105126930B (en) | A kind of preparation method of catalyst carrier and its application in the catalytic oxidation of hydrogen chloride | |
| CN107029764B (en) | A kind of preparation method and application of support type P Modification palladium catalyst | |
| CN102069000A (en) | Non-mercury catalyst for production of vinyl chloride and preparation method thereof | |
| CN104307523B (en) | A kind of method being prepared year Fischer-Tropsch synthesis by rice husk thermal decomposition charcoal one step | |
| CN105797719A (en) | Load type duplex metal/multi-metal catalyst for hydrogenation synthesis of metanilic acid from m-Nitrobenzenesulfonic acid and preparation method and application | |
| CN107759441A (en) | A kind of method that 1,2 dichloropropane catalysis dechlorination hydrogen prepares 1 chloropropene | |
| CN102357366B (en) | For the non-mercury catalyst of acetylene hydrochlorination reaction | |
| CN104971758B (en) | A kind of azepine of high activity activated carbon supported palladium catalyst, its preparation method and application | |
| CN104785238A (en) | Hg-La catalyst for acetylene hydrochlorination, and preparation method and application thereof | |
| CN104387271B (en) | Purifying technique is adsorbed in the cyclic regeneration of tricarboxymethyl propane oleate | |
| JP2013144644A (en) | Method for producing high purity boron trichloride | |
| CN102294240A (en) | Pd/C catalyst for producing 2,3,5-trimethylhydroquinone (TMHQ) by virtue of hydrogenation of 2,3,5-trimethylbenzoquinone (TMBQ) and preparation method thereof | |
| CN107602369A (en) | A kind of preparation method of acrylic acid or acrylate | |
| CN106693958B (en) | A kind of hydrogenating alkyl anthraquinone catalyst and preparation method thereof | |
| CN108752170A (en) | A method of catalysis benzalcohol derivatives etherificate | |
| CN102942548A (en) | Delta-dodecalactone synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |