CN103962131A - Preparation method of mercury-free catalyst for use in hydrochlorination of acetylene - Google Patents
Preparation method of mercury-free catalyst for use in hydrochlorination of acetylene Download PDFInfo
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- CN103962131A CN103962131A CN201410215117.1A CN201410215117A CN103962131A CN 103962131 A CN103962131 A CN 103962131A CN 201410215117 A CN201410215117 A CN 201410215117A CN 103962131 A CN103962131 A CN 103962131A
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Abstract
The invention discloses a preparation method of a mercury-free catalyst for use in hydrochlorination of acetylene, and belongs to the technical field of catalyst preparation and application. The catalyst is prepared by adopting a precipitation method. Active carbon is taken as a carrier, and a noble metal is taken as an active component, wherein the loading amount of the noble metal is 0.1-5 percent. The preparation method has the advantages that the catalyst is environment-friendly, simple in constitution and small in the using amount of the active component, a preparation process is simple and convenient, the acetylene conversion rate of the prepared catalyst is over 98 percent, and the selectivity of chloroethylene is not lower than 97 percent.
Description
Technical field
The invention belongs to catalyst preparation technology and application, related to the preparation method of a kind of acetylene hydrochlorination catalyst without mercury.
Background technology
Vinyl chloride (VCM) is industrial a kind of important industrial chemicals, and purposes is very extensive, and wherein main purposes is polymerization Heat of Formation plastic resin polyvinyl chloride (PVC) under the effect of initator.In addition vinyl chloride can with the copolymerization such as acrylonitrile, acrylate, vinyl acetate, obtain the resin of various performances, can also be for the production of 1,1, the essential industry raw materials such as 2-trichloroethanes and vinylidene chloride.
Synthetic VCM mainly contains two kinds of production technologies in the world at present: ethylene process and acetylene method (acetylene hydrochlorination).Wherein ethylene process belongs to petrochemical industry route, and it is taking oil as raw material, obtains ethene, then make vinyl chloride through ethylene chlorination through petroleum cracking.And acetylene method belongs to Coal Chemical Industry Route, it is the technique that realizes the earliest in the world suitability for industrialized production VCM, and technical matters is very ripe.For the China of " oil-poor, rich coal ", acetylene hydrochlorination method is produced VCM has become the main flow technique of China PVC industry.
But industrial at present, acetylene method adopts poisonous mercury chloride/active carbon as catalyst, serious harm environment and human health.And solve fundamental way that acetylene hydrochlorination mercury catalyst pollutes be exactly development make new advances applicable to acetylene hydrochlorination legal system VCM without mercury environment-friendly type catalyst, therefore the development of acetylene hydrochlorination catalyst without mercury has important practical significance.
The research of current catalyst without mercury is more extensive, plants the catalytic activity of metal chloride for acetylene hydrochlorination reaction as Graham J. Hutchings etc. has investigated more than 20; Haiyang Zhang etc. has compared the impact of different carriers on acetylene hydrochlorination reaction; East China University of Science has reported the impact on palladium carbon catalyst catalytic performance that adds of auxiliary agent potassium and lanthanum.It is short that but previous research does not thoroughly solve the catalyst without mercury life-span, and the problem of poor stability, need further research.
But the research in early stage concentrates on the aspect such as the screening of carrier and active component and the interpolation of auxiliary agent mostly, but rarely has report for preparation method's research.Based on above factor, the present invention adopts the precipitation method to prepare loaded noble metal catalyst, and is applied in acetylene hydrochlorination reaction, provides a kind of new preparation method to the development for catalyst without mercury and exploitation.
Summary of the invention
The object of the invention is the pollution problem in order to solve industrial mercury catalyst, the preparation method of a kind of acetylene hydrochlorination catalyst without mercury is provided.
The present invention adopts the precipitation method to prepare loaded noble metal catalyst.
It is carrier that the present invention adopts active carbon, and active component is the one in precious metal chloride gold, platinum, palladium, ruthenium, rhodium.
In the present invention, the load capacity of active component is 0.1%-5%.
The present invention's alkaline solution used is sodium carbonate, NaOH, urea, potash, saleratus, the one in ammoniacal liquor.
In the present invention, the pH value of solution maintains between 8-12, and the sedimentation time is 1-12 h, and be 4-24 h drying time.
Reaction condition of the present invention is: the total air speed of unstripped gas is 80-200 h
-1, unstripped gas is than being V (HCl): V (C
2h
2)=1-3, reaction temperature is 100-200 DEG C, pressure is normal pressure.
The present invention is realized by following measures, and concrete technology is as follows:
The preparation of loaded noble metal catalyst
The present invention adopts the precipitation method to prepare loaded noble metal catalyst.
Concrete steps: first active carbon is inserted in precious metal solution and flooded, drip alkaline solution under magnetic agitation, the pH value that maintains solution is constant, after precipitation certain hour, the washing active carbon of carried noble metal, to neutral, is dried at 120 DEG C, both obtained loaded noble metal catalyst.
The invention has the advantages that: catalyst environmental protection, composition is simple, and active component consumption is few, and preparation process is simple and convenient, and the conversion of alkyne of institute's controlling catalyst is greater than 98%, and vinyl chloride is selectively not less than 97%.
Specific embodiment
Embodiment 1: take 10 g active carbons, immersed PdCl
2in solution, under magnetic agitation, drip Na
2cO
3solution, it is 10 constant that pH value is maintained until, and after precipitation 8 h, catalyst detergent, to neutral, dried to 6 h at 120 DEG C, both palladium carbon catalyst, wherein the load capacity of Pd is 0.3%.
Above-mentioned 5 g palladium carbon catalysts are packed in micro fixed-bed reactor, are 100 h in the total air speed of unstripped gas
-1, reaction temperature is 140 DEG C, unstripped gas is than being V (HCl): V (C
2h
2under the condition of)=1.3, carry out the test of acetylene hydrochlorination reactivity.Gained conversion of alkyne is 98.01%, and vinyl chloride is selectively 98.05%.
Embodiment 2: take 10 g active carbons, immersed AuCl
3in solution, under magnetic agitation, drip NaHCO
3solution, it is 9 constant that pH value is maintained until, after precipitation 4 h, by catalyst detergent to neutral, dry 4 h at 120 DEG C, both golden Pd/carbon catalyst, wherein the load capacity of Au is 0.5%.
Above-mentioned 5 g gold Pd/carbon catalysts are packed in micro fixed-bed reactor, are 180 h in the total air speed of unstripped gas
-1, reaction temperature is 160 DEG C, unstripped gas is than being V (HCl): V (C
2h
2under the condition of)=1.1, carry out the test of acetylene hydrochlorination reactivity.Gained conversion of alkyne is 99.81%, and vinyl chloride is selectively 99.13%.
Take 10 g active carbons, immersed RhCl
3in solution, under magnetic agitation, drip urea liquid, it is 8 constant that pH value is maintained until, after precipitation 2 h, by catalyst detergent to neutral, dry 24 h at 120 DEG C, both rhodium Pd/carbon catalyst, wherein the load capacity of Rh is 1%.
Above-mentioned 5 g rhodium Pd/carbon catalysts are packed in micro fixed-bed reactor, are 80 h in the total air speed of unstripped gas
-1, reaction temperature is 180 DEG C, unstripped gas is than being V (HCl): V (C
2h
2under the condition of)=1.2, carry out the test of acetylene hydrochlorination reactivity.Gained conversion of alkyne is 98.87%, and vinyl chloride is selectively 97.86%.
Take 10 g active carbons, immersed RuCl
3in solution, under magnetic agitation, drip K
2cO
3solution, it is 10 constant that pH value is maintained until, after precipitation 8 h, by catalyst detergent to neutral, dry 16 h at 120 DEG C, both ruthenium Pd/carbon catalyst, wherein the load capacity of Ru is 3%.
Above-mentioned 5 g ruthenium Pd/carbon catalysts are packed in micro fixed-bed reactor, are 120 h in the total air speed of unstripped gas
-1, reaction temperature is 200 DEG C, unstripped gas is than being V (HCl): V (C
2h
2under the condition of)=1.5, carry out the test of acetylene hydrochlorination reactivity.Gained conversion of alkyne is 98.83%, and vinyl chloride is selectively not less than 98.61%.
Take 10 g active carbons, immersed PtCl
4in solution, under magnetic agitation, drip KHCO
3solution, it is 9 constant that pH value is maintained until, after precipitation 10 h, by catalyst detergent to neutral, dry 8 h at 120 DEG C, both platinum carbon catalyst, wherein the load capacity of Pt is 0.8%.
Above-mentioned 5 g platinum carbon catalysts are packed in micro fixed-bed reactor, are 140 h in the total air speed of unstripped gas
-1, reaction temperature is 110 DEG C, unstripped gas is than being V (HCl): V (C
2h
2under the condition of)=1.1, carry out the test of acetylene hydrochlorination reactivity.Gained conversion of alkyne is 99.41%, and vinyl chloride is selectively not less than 98.70%.
Take 10 g active carbons, immersed PdCl
2in solution, drip NaOH solution under magnetic agitation, it is 12 constant that pH value is maintained until, after precipitation 6 h, by catalyst detergent to neutral, dry 10 h at 120 DEG C, both palladium carbon catalyst, wherein the load capacity of Pd is 1.2%.
Above-mentioned 5 g palladium carbon catalysts are packed in micro fixed-bed reactor, are 160 h in the total air speed of unstripped gas
-1, reaction temperature is 160 DEG C, unstripped gas is than being V (HCl): V (C
2h
2under the condition of)=1.2, carry out the test of acetylene hydrochlorination reactivity.Gained conversion of alkyne is 99.31%, and vinyl chloride is selectively not less than 98.70%.
Claims (6)
1. a preparation method who can be used for acetylene hydrochlorination reaction catalyst without mercury, the carrier that it is characterized in that catalyst is active carbon, and active component is the one in precious metal chloride gold, platinum, palladium, ruthenium, rhodium, and preparation method is the precipitation method.
2. the preparation process of catalyst without mercury according to claim 1 is: first active carbon is inserted in precious metal solution and flooded, under magnetic agitation, drip alkaline solution, the pH value that maintains solution is constant, after precipitation certain hour, the washing active carbon of carried noble metal is to neutral, dry at 120 DEG C.
3. according to the catalyst system and catalyzing described in claim 1 and 2, the load capacity that it is characterized in that noble metal is 0.1%-5%.
4. according to the catalyst system and catalyzing described in claim 1 and 2, it is characterized in that alkaline solution is sodium carbonate, NaOH, urea, potash, saleratus, the one in ammoniacal liquor.
5. according to the catalyst system and catalyzing described in claim 1 and 2, it is characterized in that the pH value of solution maintains between 8-12, the sedimentation time is 1-12 h, and be 4-24 h drying time.
6. according to the catalyst system and catalyzing described in claim 1-5, it is characterized in that reaction condition is: the total air speed of unstripped gas is 80-200 h
-1, unstripped gas is than being V (HCl): V (C
2h
2)=1-3, reaction temperature is 100-200 DEG C, pressure is normal pressure.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126833A (en) * | 2015-07-28 | 2015-12-09 | 浙江工业大学 | Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride |
| CN106362741A (en) * | 2016-08-05 | 2017-02-01 | 厦门大学 | Compound gold-based catalyst, and preparation method and application thereof |
| CN106423287A (en) * | 2016-09-10 | 2017-02-22 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination |
| CN107803213A (en) * | 2017-09-29 | 2018-03-16 | 浙江工业大学 | A kind of stable palladium compound of acetylene atmosphere high temperature and its application |
| CN109331869A (en) * | 2018-09-28 | 2019-02-15 | 内蒙古自治区石油化工监督检验研究院 | A kind of low ruthenium content ruthenium-based catalyst for acetylene hydrochlorination reaction |
| CN109876864A (en) * | 2019-02-14 | 2019-06-14 | 西安凯立新材料股份有限公司 | A kind of super low loading noble metal composite catalyst and preparation method thereof for acetylene hydrochlorination reaction |
| CN110465279A (en) * | 2019-08-21 | 2019-11-19 | 福建省鑫森炭业股份有限公司 | Catalyst without mercury carrier active carbon and preparation method thereof for PVC production |
| CN112424150A (en) * | 2018-07-16 | 2021-02-26 | 卡迪夫大学学院顾问有限公司 | Catalyst and process for preparing same |
| CN115572207A (en) * | 2022-10-19 | 2023-01-06 | 鄂尔多斯市瀚博科技有限公司 | Method for preparing vinyl chloride by reducing acetylene hydrochlorination by-product through gold-based catalysis |
-
2014
- 2014-05-21 CN CN201410215117.1A patent/CN103962131A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126833A (en) * | 2015-07-28 | 2015-12-09 | 浙江工业大学 | Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride |
| CN106362741A (en) * | 2016-08-05 | 2017-02-01 | 厦门大学 | Compound gold-based catalyst, and preparation method and application thereof |
| CN106423287A (en) * | 2016-09-10 | 2017-02-22 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination |
| CN107803213A (en) * | 2017-09-29 | 2018-03-16 | 浙江工业大学 | A kind of stable palladium compound of acetylene atmosphere high temperature and its application |
| CN107803213B (en) * | 2017-09-29 | 2020-04-24 | 浙江工业大学 | Palladium compound with high-temperature stability in acetylene atmosphere and application thereof |
| CN112424150A (en) * | 2018-07-16 | 2021-02-26 | 卡迪夫大学学院顾问有限公司 | Catalyst and process for preparing same |
| CN112424150B (en) * | 2018-07-16 | 2024-04-12 | 卡迪夫大学学院顾问有限公司 | Catalyst |
| CN109331869A (en) * | 2018-09-28 | 2019-02-15 | 内蒙古自治区石油化工监督检验研究院 | A kind of low ruthenium content ruthenium-based catalyst for acetylene hydrochlorination reaction |
| CN109876864A (en) * | 2019-02-14 | 2019-06-14 | 西安凯立新材料股份有限公司 | A kind of super low loading noble metal composite catalyst and preparation method thereof for acetylene hydrochlorination reaction |
| CN110465279A (en) * | 2019-08-21 | 2019-11-19 | 福建省鑫森炭业股份有限公司 | Catalyst without mercury carrier active carbon and preparation method thereof for PVC production |
| CN110465279B (en) * | 2019-08-21 | 2022-10-18 | 福建省鑫森炭业股份有限公司 | Mercury-free catalyst carrier activated carbon for PVC production and preparation method thereof |
| CN115572207A (en) * | 2022-10-19 | 2023-01-06 | 鄂尔多斯市瀚博科技有限公司 | Method for preparing vinyl chloride by reducing acetylene hydrochlorination by-product through gold-based catalysis |
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Application publication date: 20140806 |