CN104785238B - Hg-La catalyst and preparation method and application for acetylene hydrochlorination - Google Patents
Hg-La catalyst and preparation method and application for acetylene hydrochlorination Download PDFInfo
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Abstract
The invention discloses the Hg-La catalyst and preparation method and application for acetylene hydrochlorination, the step of preparation method for the Hg-La catalyst of acetylene hydrochlorination：（1）Mercury salt is added in solvent, mercury salt solution is obtained；（2）Lanthanum salt is weighed, is dissolved in mercury salt solution, obtains Hg-La mixed solutions；（3）Porous carrier is added into Hg-La mixed solutions, impregnates, liquid evaporation, drying obtains the Hg-La catalyst for acetylene hydrochlorination.A kind of Hg-La catalyst for acetylene hydrochlorination of the present invention is lower than the mercury content of the prior art, can greatly reduce mercury pollution on the environment；Reaction temperature is 140 DEG C, acetylene air speed is 180h‑1, unstripped gas match VC2H2/VHC1=1:Under conditions of 1.1, the initial conversion of acetylene still can reach 99%, and the selectivity for generating vinyl chloride is more than 99.0%.
Description
Technical field
The present invention relates to a kind of Hg-La catalyst and preparation method and application for acetylene hydrochlorination, belong to organic conjunction
At the preparing technical field with catalyst.
Background technology
With the development of national economy, the raising of the increasingly raising and environmental protection consciousness of living standards of the people, PVC is (poly-
Vinyl chloride) demand it is increasing.PVC is obtained by VCM (vinyl chloride monomer) polymerizations, and the production method of VCM mainly has
Ethylene process technique, ethane method technique and acetylene method technique.Since external oil field is rich in ethylene, raw material inexpensively preferably obtains, so state
Outer developed country generally uses ethylene process to produce VCM；Ethane method prepares VCM low raw-material costs, but needs higher investment,
The technique is also merely resting on the lab scale stage, with a certain distance from industrialization also；Acetylene method technique prepares VCM and is restricted mainly
It is because of raw material supply situation and the high cost of raw material and the limitation of production capacity.In China due to resource distribution situation, unstripped gas
Ethylene does not enrich, and all lacks very much always and price is very high, and with the exhaustion of fossil resources, China possess it is a large amount of it is low at
This coal provides raw material and price advantage, so China is suitble to produce VCM based on acetylene method route.Therefore on western ground
Area, such as Xinjiang, Inner Mongol rich coal resources area, create or enlarging carbide produce Corvic project development
Rapidly.The principle active component of industrial its used catalyst at present is mercury chloride (mass fraction 10-13%), and mercury is easy
Distillation loss is the severe contamination source in carbide production polyvinyl chloride.Carbide technique, which often produces 1 ton of PVC, will consume mercury
1.4 kilograms or so, according to statistics, the usage amount of China's acetylene method PVC industry mercury in 2010 is about 767 tons, accounts for national mercury usage amount
60% or more, account for 20% or so of world's mercury usage amount.The loss of mercury not only causes catalyst inactivation, but also due to activearm
The loss catalyst divided can not regenerate, while also affect the quality of VCM products, and prodigious danger can be also caused to ecological environment
Evil.In addition mercury is a heavy metal species, there is severe toxicity, generates a concentration of 0.01~0.1mg/l of toxicity, and cannot be dropped by microorganism
Solution, can only be with different valence states, the Transport And Transformation between water and biology, occur dispersion and enrichment, into human body after again very
Hardly possible is metabolized away, is gathered in liver, kidney and brain, is damaged nervous system, is caused fearful " minamata disease ".It is predicted that by 2014
The consumption mercury quantity of acetylene method production polyvinyl chloride resin can reach 17.5489 ten thousand tons, and mercury is also concerned because of its potential significant damage.
Therefore, pollution problem caused by being mercury catalyst urgently to be resolved hurrily at present, though catalyst without mercury is to solve the problems, such as this
Best method, and the exploitation of catalyst without mercury is also current research hotspot, but active component have focused largely on Au, Pt,
In terms of the noble metals such as Pd, Ru, though catalyst initial activity is good, stability is slightly worse, apart from industrial applications it is also very long one
Therefore Duan Lucheng reduces the dosage of mercury in catalyst, reduce environmental pollution current a kind of good plan of can yet be regarded as.
Group Co., Ltd of Xingjiang Tianye Co. discloses a kind of acetylene hydrochlorination reaction compound mercury catalyst of high stability, this is urged
Agent mainly by 100 parts of carrier active carbon, 1~15 part of main catalytic ingredient mercury chloride, potassium, barium, lithium chloride in one kind
Or a variety of mixtures or strontium, chromium, praseodymium chloride in one or more mixtures composition, catalyst dispersity is good, thermostabilization
Property it is high, the more simple mercuric chleride catalyst of stability improves 0.1~0.5 times.They further disclose a kind of answering for high activity simultaneously
Close mercury catalyst, the catalyst is mainly by 100 parts of carrier active carbon, 1~15 part of main catalytic ingredient mercury chloride, cobalt, manganese, gadolinium
One or more mixtures or bismuth, cadmium in chloride, the composition of one or more mixtures in the chloride of copper, catalyst are lived
Property more simple mercuric chleride catalyst improve 5%~50%.Xin Huangxinzhong chemical industry Co., Ltd discloses a kind of low mercury of compound
Mercury catalyst and preparation method thereof, catalyst weight part proportioning are activated carbon 1.05, mercury chloride 0.085, barium chloride 0.72, potassium chloride
0.40, Hg chloride content is low, effect of catalyst is good, environmental pollution is small.Nankai University, as carrier, is made using treated coal quality charcoal
The mercury chloride of lower content and other auxiliary agents are carried on carrier with vacuum impregnation technology, and pass through the drying means such as rotary evaporation
New catalyst is obtained, at low cost, safety and environmental protection is simple for process.Zhejiang University discloses a kind of environment friendly chlorinated mercury metal and urges
Agent is coated on by heterogeneous mercury chloride metallic catalyst and in membrane form heterogeneous mercury chloride metallic catalyst surfaces
Polymer composition, reduce the environment and health problem that Hg sublimation ribbon is come, there is high catalytic efficiency, small toxicity, catalyst to release
It is laid flat the features such as slow.Generation of Shihezi Univ is refined etc. to disclose one kind using mercury chloride as active component, and nickel chloride is urging for auxiliary agent
Agent, the wherein content of mercury chloride are 3%~5%, and the addition of auxiliary agent nickel is so that the activity of mercury catalyst increases.Tian Jinhai
Chemical Industry Science Co., Ltd speed by first being impregnated with chloroazotic acid and in the aqueous solution of triethylamine while flowing back and stir pretreatment coal
Then a certain amount of surfactant hexadecyltrimethylammonium chloride, mercury chloride and auxiliary agent nickel chloride is added in matter high-area carbon, with
Rotary evaporation in vacuo mode is impregnated, and the content of mercury chloride is 4~6.5%, improves the active, steady of low mercury composite catalyst
It is qualitative and selective.Yibin Tianyuan Group Co., Ltd and Nankai University, the research of Xin Huangxinzhong chemical industry Co., Ltd
With HgCl2、BaCl2With FeCoP compounding ingredients good activity and selectivity is shown for the composite catalyst in activated centre.
Guizhou University and the activity of Co., Ltd of Shaanxi North Yuan Chemical Group and Guizhou Siver Star Group Co., Ltd.'s joint study
The HgCl of load 2.5~3.5% on charcoal2And BiCl3、ZnCl2、TiCl4、CuCl2、VCl3, rare earth chloride and BaCl2Low mercury touch
Matchmaker, using distribution infusion process, simple for process, effective, energy-saving and environmental protection.Zhonghao (Dalian) Research & Design Institute of Chemical Industry Co., Ltd. grinds
Studied carefully it is a kind of with mercury chloride for main active component, noble metal Au, Pd, Pt, Ru, Rh, Os, Ir salt or one kind in its complex compound or
A variety of is active regulator, one or more for co-catalyst in potassium chloride, iron chloride, zinc chloride, copper chloride.In mercury chloride
Micro precious metal salt is added and forms stable complex metal compound, fixed and activation can be played to mercury chloride.
It is mercury chloride 8.0%~10.0%, rare earth-iron-boron auxiliary agent that Guizhou Siver Star Group Co., Ltd., which is investigated a kind of be formulated,
A8%~13%, alkali earth chloride auxiliary agent B 5%~25%, auxiliary agent C10%~20%, the remaining low-mercury catalyst for activated carbon should
Catalyst can reduce resource consumption, reduce the pressure for administering mercury pollution, while reducing production cost, and its anti-toxicity
Energy, resistance to reduction energy and leach resistance increase.But or to still have mercury content higher for all above-mentioned mercury catalysts,
Catalyst activity and the bad disadvantage of stability.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of mercury content it is low for acetylene hydrochlorination
Hg-La catalyst.
Second object of the present invention is to provide a kind of preparation method of the Hg-La catalyst for acetylene hydrochlorination.
Third object of the present invention is to provide a kind of applications of the Hg-La catalyst for acetylene hydrochlorination.
Technical solution of the present invention is summarized as follows：
The preparation method of a kind of Hg-La catalyst for acetylene hydrochlorination, it is characterized in that including the following steps：
(1) mercury salt is added in solvent, heating stirring make to dissolve mercury molar concentration be 0.02053mol/L~
The mercury salt solution of 0.32053mol/L；
(2) La in molar ratio:Hg=0.5~3 weighs lanthanum salt, is dissolved in the mercury salt solution, and it is molten to obtain Hg-La mixing
Liquid；
(3) 10g porous carriers are added into the Hg-La mixed solutions of 10~30mL in proportion, impregnate 5~24 hours,
50~100 DEG C of stirred in water bath to liquid evaporations finish, and are put into 110~180 DEG C of drying in baking oven, obtain being used for acetylene hydrochlorination
Hg-La catalyst.
The preferred mercuric nitrate of the mercury salt, mercuric acetate, mercuric sulfate or mercury chloride.
The preferred lanthanum nitrate of the lanthanum salt, lanthanum acetate, lanthanum sulfate or lanthanum chloride.
The aqueous hydrochloric acid solution of the preferred water of the solvent, ethyl alcohol or a concentration of 0.1-1.0mol/L.
The preferred asphalt based active carbon of the porous carrier, active carbon from coal, shell matrix activated carbon or coconut shell based activated carbon.
A kind of Hg-La catalyst for acetylene hydrochlorination prepared by the above method.
A kind of application of the above-mentioned Hg-La catalyst for acetylene hydrochlorination in acetylene hydrochlorination reaction.
Advantages of the present invention：
A kind of Hg-La catalyst for acetylene hydrochlorination of the present invention is lower than the mercury content of the prior art, can be significantly
Reduce mercury pollution on the environment；Reaction temperature is 140 DEG C, acetylene air speed is 180h-1, unstripped gas match VC2H2/VHC1=
1:Under conditions of 1.1, the initial conversion of acetylene still can reach 99%, and the selectivity for generating vinyl chloride is more than
99.0%；
When the load capacity of mercury is 4%, La:When Hg molar ratios are 1.5, the service life of catalyst is more than 480h.
Specific implementation mode
The present invention is specifically described below by embodiment, to keep those skilled in the art better
Understand the present invention.But illustrated embodiment is not as a limitation of the invention.
Embodiment 1
A kind of preparation method of Hg-La catalyst for acetylene hydrochlorination, includes the following steps：
(1) 0.1666g Hg (NO are weighed3)2It is dissolved in the dilute hydrochloric acid of 25ml 0.1mol/L, 50 DEG C of stirred in water bath make molten
Solution forms the Hg (NO that Hg molar concentrations are 0.02053mol/L3)2Solution；
(2) La is pressed:Molar ratio=1 Hg weighs 0.1813g LaCl3·6H2O is dissolved in Hg (NO3)2In solution, shape
At Hg-La aqueous hydrochloric acid solutions；
(3) 10g active carbon from coal is impregnated into Hg-La aqueous hydrochloric acid solutions, dip time is 5 hours；In 50 DEG C of water-baths
Heating stirring to liquid evaporation finishes, and is then placed in 180 DEG C of drying in baking oven, obtains being catalyzed for the Hg-La of acetylene hydrochlorination
Agent.
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, 140 DEG C of reaction temperature, unstripped gas proportioning VC2H2/
VHC1=1:1.1.Above-mentioned loaded catalyst is 5ml；Catalyst catalyzing acetylene hydrochlorination under these conditions, obtains
The initial conversion of acetylene is 60%, and the selectivity of vinyl chloride is more than 99%.
Embodiment 2
A kind of preparation method of Hg-La catalyst for acetylene hydrochlorination, includes the following steps：
(1) 0.5452g HgSO are weighed4It is dissolved in the dilute hydrochloric acid of 30ml 1mol/L, 60 DEG C of stirred in water bath make dissolving shape
At the HgSO that Hg molar concentrations are 0.06126mol/L4Solution；
(2) La is pressed:Molar ratio=3 Hg weigh 1.7424g La (CH3COO)3, it is dissolved in HgSO4In solution, formed
Hg-La aqueous hydrochloric acid solutions；
(3) 10g shell matrix activated carbons are impregnated into Hg-La aqueous hydrochloric acid solutions, dip time is 12 hours；In 60 DEG C of water-baths
Middle heating stirring to liquid evaporation finishes, and is then placed in 180 DEG C of drying in baking oven, obtains urging for the Hg-La of acetylene hydrochlorination
Agent.
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, 140 DEG C of reaction temperature, unstripped gas proportioning VC2H2/
VHC1=1:1.1.Above-mentioned loaded catalyst is 5ml；Catalyst catalyzing acetylene hydrochlorination under these conditions, obtains
The initial conversion of acetylene is 82%, and the selectivity of vinyl chloride is more than 99%.
Embodiment 3
A kind of preparation method of Hg-La catalyst for acetylene hydrochlorination, includes the following steps：
(1) 0.8910g Hg (CH are weighed3COO)2It is dissolved in 20ml water, 100 DEG C of stirred in water bath make dissolving form Hg moles
Hg (the CH of a concentration of 0.17159mol/L3COO)2Solution；
(2) La is pressed:Molar ratio=0.5 Hg weighs La2(SO4)3, it is dissolved in Hg (CH3COO)2In solution, Hg-La water is formed
Solution；
(3) 10g coconut shell based activated carbons are impregnated into Hg-La aqueous solutions, dip time is 24 hours；In 100 DEG C of water-baths
Heating stirring to liquid evaporation finishes, and is then placed in 140 DEG C of drying in baking oven, obtains being catalyzed for the Hg-La of acetylene hydrochlorination
Agent.
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, 140 DEG C of reaction temperature, unstripped gas proportioning VC2H2/
VHC1=1:1.1.Above-mentioned loaded catalyst is 5ml；Catalyst catalyzing acetylene hydrochlorination under these conditions, obtains
The initial conversion of acetylene is 88%, and the selectivity of vinyl chloride is more than 99%.Compared to the catalyst of embodiment 1, Hg- of the invention
The acetylene initial conversion of La catalyst has to be improved to a certain degree.
Embodiment 4
A kind of preparation method of Hg-La catalyst for acetylene hydrochlorination, includes the following steps：
(1) 0.8703g HgCl are weighed2It is dissolved in 10ml ethyl alcohol, 60 DEG C of stirred in water bath make dissolving form Hg molar concentrations
For the HgCl of 0.32053mol/L2Solution；
(2) La is pressed:Molar ratio=1.5 Hg weigh 2.0819g La (NO3)3·6H2O is dissolved in HgCl2In solution,
Form Hg-La ethanol solutions；
(3) 10g asphaltic base ball-type activated carbons are impregnated into Hg-La ethanol solutions, dip time is 18 hours；In 60 DEG C of water
Heating stirring to liquid evaporation finishes in bath, is then placed in 110 DEG C of drying in baking oven, obtains the Hg-La for acetylene hydrochlorination
Catalyst.
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 180h-1, 140 DEG C of reaction temperature, unstripped gas proportioning VC2H2/
VHC1=1:1.1.Above-mentioned loaded catalyst is 5ml；Catalyst catalyzing acetylene hydrochlorination under these conditions, obtains
The initial conversion of acetylene is 99%, and the selectivity of vinyl chloride is more than 99%.
Embodiment 5
A kind of preparation method of Hg-La catalyst for acetylene hydrochlorination, includes the following steps：
(1) 0.6206g HgCl are weighed2It is dissolved in 10ml water, 60 DEG C of stirred in water bath make dissolving form Hg molar concentrations to be
The HgCl of 0.22857mol/L2Solution；
(2) La is pressed:Molar ratio=1.5 Hg weigh 1.2111g LaCl3·6H2O is dissolved in HgCl2In solution, formed
Hg-La aqueous solutions；
(3) 10g asphaltic base ball-type activated carbons are impregnated into Hg-La aqueous solutions, dip time is 24 hours；In 60 DEG C of water-baths
Middle heating stirring to liquid evaporation finishes, and is then placed in 110 DEG C of drying in baking oven, obtains urging for the Hg-La of acetylene hydrochlorination
Agent.
Reaction condition is that hydrogen chloride activates 30min, acetylene air speed 36h-1, 140 DEG C of reaction temperature, unstripped gas proportioning VC2H2/
VHC1=1:1.1.Above-mentioned loaded catalyst is 5ml；Catalyst catalyzing acetylene hydrochlorination under these conditions, obtains
The conversion ratio of acetylene is 99%, and the selectivity of vinyl chloride is more than 99%, 480 hours conversion of alkyne of continuous operation still greater than
97%, i.e. the service life of Hg-La catalyst of the invention is more than 480 hours.
Claims (6)
1. the preparation method of a kind of Hg-La catalyst for acetylene hydrochlorination, it is characterized in that including the following steps：
(1) mercury salt is added in solvent, heating stirring make to dissolve mercury molar concentration be 0.02053mol/L~
The mercury salt solution of 0.32053mol/L；
(2) La in molar ratio:Hg=0.5~3 weighs lanthanum salt, is dissolved in the mercury salt solution, obtains Hg-La mixed solutions；
(3) 10g porous carriers are added into the Hg-La mixed solutions of 10~30mL in proportion, impregnate 5~24 hours, 50~
100 DEG C of stirred in water bath to liquid evaporations finish, and are put into 110~180 DEG C of drying in baking oven, obtain for acetylene hydrochlorination
Hg-La catalyst；The solvent is the aqueous hydrochloric acid solution of water, ethyl alcohol or a concentration of 0.1-1.0mol/L.
2. the preparation method of a kind of Hg-La catalyst for acetylene hydrochlorination according to claim 1, it is characterized in that institute
It is mercuric nitrate, mercuric acetate, mercuric sulfate or mercury chloride to state mercury salt.
3. the preparation method of a kind of Hg-La catalyst for acetylene hydrochlorination according to claim 1, it is characterized in that institute
It is lanthanum nitrate, lanthanum acetate, lanthanum sulfate or lanthanum chloride to state lanthanum salt.
4. the preparation method of a kind of Hg-La catalyst for acetylene hydrochlorination according to claim 1, it is characterized in that institute
It is asphalt based active carbon, active carbon from coal, shell matrix activated carbon or coconut shell based activated carbon to state porous carrier.
5. a kind of Hg-La catalyst for acetylene hydrochlorination prepared by the method for one of claim 1-4.
6. a kind of application of the Hg-La catalyst for acetylene hydrochlorination of claim 5 in acetylene hydrochlorination reaction.
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Cited By (1)
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| CN107497496A (en) * | 2017-08-29 | 2017-12-22 | 贵州重力科技环保有限公司 | Micro- solid mercury catalyst of a kind of high degree of dispersion of acetylene hydrochlorination and preparation method thereof |
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| CN106362741B (en) * | 2016-08-05 | 2019-02-22 | 厦门大学 | A kind of compound Au-based catalyst and the preparation method and application thereof |
| CN112121809B (en) * | 2020-09-30 | 2023-06-23 | 宁夏新龙蓝天科技股份有限公司 | Catalyst for preparing chloroethylene by calcium carbide method and preparation method thereof |
| CN112844433B (en) * | 2021-01-14 | 2023-04-14 | 石河子大学 | Nonmetal catalyst for acetylene hydrochlorination and preparation method thereof |
| CN115025790B (en) * | 2022-05-12 | 2024-04-12 | 上海交通大学 | High-stability low-mercury catalyst for hydrochlorination of acetylene and preparation method thereof |
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| WO2012057794A1 (en) * | 2010-10-29 | 2012-05-03 | Tda Research, Inc. | Low temperature sulphur dioxide oxidation catalyst for sulfuric acid manufacture |
| CN102794174A (en) * | 2011-05-24 | 2012-11-28 | 代斌 | Au-La catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method thereof |
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| CN101474567A (en) * | 2008-09-19 | 2009-07-08 | 贵州省万山特区矿产公司 | Method for producing powdery composite mercury catalyst |
| CN101596459A (en) * | 2009-02-11 | 2009-12-09 | 贵阳白云银星化工有限公司 | Mercuric chloride low-mercury catalyst and preparation method thereof |
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| CN107497496A (en) * | 2017-08-29 | 2017-12-22 | 贵州重力科技环保有限公司 | Micro- solid mercury catalyst of a kind of high degree of dispersion of acetylene hydrochlorination and preparation method thereof |
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