CN102151580A - Tungsten phosphide catalyst for synthesizing vinyl chloride and preparation method thereof - Google Patents
Tungsten phosphide catalyst for synthesizing vinyl chloride and preparation method thereof Download PDFInfo
- Publication number
- CN102151580A CN102151580A CN2011100403757A CN201110040375A CN102151580A CN 102151580 A CN102151580 A CN 102151580A CN 2011100403757 A CN2011100403757 A CN 2011100403757A CN 201110040375 A CN201110040375 A CN 201110040375A CN 102151580 A CN102151580 A CN 102151580A
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- CN
- China
- Prior art keywords
- catalyst
- tungsten phosphide
- synthetic method
- phosphide catalyst
- chloride
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 26
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 17
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 6
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052753 mercury Inorganic materials 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000005997 Calcium carbide Substances 0.000 abstract 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 7
- 238000007038 hydrochlorination reaction Methods 0.000 description 7
- 150000001345 alkine derivatives Chemical class 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001009 interstitial alloy Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a tungsten phosphide catalyst for preparing vinyl chloride by a calcium carbide method. The catalyst is characterized in that a carrier of the catalyst is activated carbon, an active component is WP (tungsten phosphide), and auxiliaries refers to one or more than one of copper chloride, nickel chloride and barium chloride. The catalyst belongs to loaded metal interstitial compounds and is more green and environment friendly in comparison with a mercury catalyst. The catalyst has good activity and selectively in the reaction of synthesizing the vinyl chloride by the calcium carbide method.
Description
Technical field
The present invention proposes a kind of tungsten phosphide catalyst that carbide prepares vinyl chloride that is used for, and it is characterized in that: the carrier of this catalyst is an active carbon, and active component is WP, and auxiliary agent is one or more in copper chloride, nickel chloride, the barium chloride.Catalyst proposed by the invention belongs to load type metal interstitial compound classification, compares environmental protection more with mercury catalyst.This catalyst has good active and selectivity in the reaction of carbide synthesizing chloroethylene.
Background technology
Having now under the constant condition of vinyl chloride manufacturing condition, adopting catalyst without mercury to produce vinyl chloride is current research focus.So just can by only more catalyst changeout realize the mercuryless production of vinyl chloride, it is theoretical and practical significance is self-evident.As everyone knows, because the cumulative year after year of polyvinyl chloride (PVC) demand, its synthetic required monomer also presents the trend of cumulative year after year.At the most vinyl chloride of China is to adopt acetylene hydrochlorination method (carbide) preparation, because the scarcity of current China mercury pollution and mercury resource, catalyst without mercury is produced vinyl chloride has become inevitable development trend.Support type WP catalyst is applied to carbide and prepares in the vinyl chloride reaction among the present invention, and has shown good active and selectivity.
Summary of the invention
The present invention proposes a kind of tungsten phosphide catalyst that carbide prepares vinyl chloride that is used for, and it is characterized in that: the carrier of this catalyst is an active carbon, and active component is WP, and auxiliary agent is one or more in copper chloride, nickel chloride, the barium chloride.
The preparation process of tungsten phosphide catalyst:
At first, under the stirring at room state, sodium tungstate and sodium hypophosphite are dissolved in the deionized water, afterwards with solution impregnation in absorbent charcoal carrier, and in 60 ℃ of down oven dry; Precursor after will drying is then packed in the reactor, in temperature required roasting down, and drops to room temperature at nitrogen atmosphere and obtains catalyst precarsor in the nitrogen atmosphere of static state; At last compounding agent solution is impregnated in the catalyst precarsor, and oven dry obtains required catalyst under 120 ℃.
H described in the preparation process
2PO
2 -: WO
4 2-Mol ratio is in 4.5～5.0 scopes; The quality percentage composition of described WP component is 5-15%; Described precursor bake out temperature is 60 ℃; Described precursor sintering temperature is 400～500 ℃; Described precursor roasting time is 30-120min; The quality percentage composition of described auxiliary agent is 1-10%.
The specific embodiment
Below the Preparation of catalysts scheme is carried out more detailed specific description.
Embodiment one:
At first, under the stirring at room state, the sodium tungstate of 3.3g and the sodium hypophosphite of 4.28g are dissolved in the 25.0g deionized water, afterwards with solution impregnation in the 23g absorbent charcoal carrier, and 60 ℃ of down oven dry; Precursor after will drying is then packed in the reactor, at 400 ℃ of following roasting 30min, and drops to room temperature at nitrogen atmosphere and obtains catalyst precarsor in nitrogen atmosphere; Be 5% CuCl at last with 10g concentration
2Solution for vacuum is impregnated in the precursor, and oven dry gained sample is named as A under 120 ℃.Catalyst A is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 86%, and the vinyl chloride selectivity is 77%.
Embodiment two:
Preparation process is identical with the preparation process of catalyst A, and the amount that only changes sodium hypophosphite is 5.36g, and other condition is constant, and the gained sample is named as B.Catalyst B is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 88%, and the vinyl chloride selectivity is 79%.
Embodiment three:
Preparation process is identical with the preparation process of catalyst A, and only changing the precursor sintering temperature is 500 ℃, and other condition is constant, and the gained sample is named as C.Catalyst C is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 87%, and the vinyl chloride selectivity is 78%.
Embodiment four:
Preparation process is identical with the preparation process of catalyst A, and only changing quality of activated carbon is 11.5g, and other condition is constant, and the gained sample is named as D.Catalyst D is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 90%, and the vinyl chloride selectivity is 81%.
Embodiment five:
Preparation process is identical with the preparation process of catalyst A, only increases 10g concentration and be 5% NiCl
2Auxiliary agent, other condition is constant, and the gained sample is named as E.Catalyst E is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 79%, and the vinyl chloride selectivity is 68%.
Embodiment six:
Preparation process is identical with the preparation process of catalyst A, only increases 10g concentration and be 5% BaCl
2Auxiliary agent, other condition is constant, and the gained sample is named as F.Catalyst F is used for the preparing chloroethylene by acetylene hydrochlorination reaction, and 170 ℃ of following conversion of alkyne are 78%, and the vinyl chloride selectivity is 67%.
Claims (8)
1. the present invention proposes a kind of tungsten phosphide catalyst that carbide prepares vinyl chloride that is used for, and it is characterized in that: the carrier of this catalyst is an active carbon, and active component is WP, and auxiliary agent is one or more in copper chloride, nickel chloride, the barium chloride.
2. the present invention proposes the preparation method of tungsten phosphide catalyst described in a kind of claim 1; Its concrete implementation step is: at first, under the stirring at room state, sodium tungstate and sodium hypophosphite are dissolved in the deionized water, afterwards with solution impregnation in absorbent charcoal carrier, and in 60 ℃ of down oven dry; Precursor after will drying is then packed in the reactor, in temperature required roasting down, and drops to room temperature at nitrogen atmosphere and obtains catalyst precarsor in the nitrogen atmosphere of static state; At last compounding agent solution is impregnated in the catalyst precarsor, and oven dry obtains required catalyst under 120 ℃.
3. the synthetic method of tungsten phosphide catalyst according to claim 2 is characterized in that H
2PO
2 -: WO
4 2-Mol ratio is in 4.5～5.0 scopes.
4. the synthetic method of tungsten phosphide catalyst according to claim 2, the quality percentage composition that it is characterized in that the WP component is 5-15%.
5. the synthetic method of tungsten phosphide catalyst according to claim 2 is characterized in that the precursor bake out temperature is 60 ℃.
6. the synthetic method of tungsten phosphide catalyst according to claim 2 is characterized in that the precursor sintering temperature is 400～500 ℃.
7. the synthetic method of tungsten phosphide catalyst according to claim 2 is characterized in that the precursor roasting time is 30-120min.
8. the synthetic method of tungsten phosphide catalyst according to claim 2, the quality percentage composition that it is characterized in that auxiliary agent is 1-10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110040375.7A CN102151580B (en) | 2011-02-18 | 2011-02-18 | Tungsten phosphide catalyst for synthesizing vinyl chloride and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110040375.7A CN102151580B (en) | 2011-02-18 | 2011-02-18 | Tungsten phosphide catalyst for synthesizing vinyl chloride and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102151580A true CN102151580A (en) | 2011-08-17 |
| CN102151580B CN102151580B (en) | 2014-07-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110040375.7A Active CN102151580B (en) | 2011-02-18 | 2011-02-18 | Tungsten phosphide catalyst for synthesizing vinyl chloride and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430420A (en) * | 2011-11-15 | 2012-05-02 | 宜宾天原集团股份有限公司 | Low-mercury composite catalyst for synthesizing chloroethylene, and preparation method for low-mercury composite catalyst |
| CN113215818A (en) * | 2021-03-31 | 2021-08-06 | 浙江工业大学 | Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6596624B1 (en) * | 1999-07-31 | 2003-07-22 | International Business Machines Corporation | Process for making low dielectric constant hollow chip structures by removing sacrificial dielectric material after the chip is joined to a chip carrier |
| CN1470326A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Load tungsten phosphide catalyst and its preparing method |
| CN101905157A (en) * | 2010-08-09 | 2010-12-08 | 南开大学 | Method for preparing mercury-free catalyst for preparing chloroethylene by acetylene hydrochlorination |
-
2011
- 2011-02-18 CN CN201110040375.7A patent/CN102151580B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6596624B1 (en) * | 1999-07-31 | 2003-07-22 | International Business Machines Corporation | Process for making low dielectric constant hollow chip structures by removing sacrificial dielectric material after the chip is joined to a chip carrier |
| CN1470326A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Load tungsten phosphide catalyst and its preparing method |
| CN101905157A (en) * | 2010-08-09 | 2010-12-08 | 南开大学 | Method for preparing mercury-free catalyst for preparing chloroethylene by acetylene hydrochlorination |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430420A (en) * | 2011-11-15 | 2012-05-02 | 宜宾天原集团股份有限公司 | Low-mercury composite catalyst for synthesizing chloroethylene, and preparation method for low-mercury composite catalyst |
| CN102430420B (en) * | 2011-11-15 | 2013-07-17 | 宜宾天原集团股份有限公司 | Low-mercury composite catalyst for synthesizing chloroethylene, and preparation method for low-mercury composite catalyst |
| CN113215818A (en) * | 2021-03-31 | 2021-08-06 | 浙江工业大学 | Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof |
| CN113215818B (en) * | 2021-03-31 | 2022-05-24 | 浙江工业大学 | Metal interstitial compound/activated carbon fiber composite material and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN102151580B (en) | 2014-07-09 |
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Effective date of registration: 20210218 Address after: 012100 Intersection of Sanjing Road and Liuwei Road, High-tech Fluorine Industrial Park, Fengzhen City, Inner Mongolia Autonomous Region Inner Mongolia Haichi Fine Chemical Co.,Ltd. Patentee after: Inner Mongolia Haichi Fine Chemical Co.,Ltd. Address before: College of chemistry Nankai University Nankai District 94 Tianjin City No. 300071 Weijin Road Patentee before: Li Wei |
|
| CP01 | Change in the name or title of a patent holder | ||
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Address after: 012100 Intersection of Sanjing Road and Liuwei Road, High-tech Fluorine Industrial Park, Fengzhen City, Inner Mongolia Autonomous Region Inner Mongolia Haichi Fine Chemical Co.,Ltd. Patentee after: Inner Mongolia Haichi High-tech New Materials Co.,Ltd. Address before: 012100 Intersection of Sanjing Road and Liuwei Road, High-tech Fluorine Industrial Park, Fengzhen City, Inner Mongolia Autonomous Region Inner Mongolia Haichi Fine Chemical Co.,Ltd. Patentee before: Inner Mongolia Haichi Fine Chemical Co.,Ltd. |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A tungsten phosphide catalyst for synthesizing vinyl chloride and its preparation method Granted publication date: 20140709 Pledgee: Mongolian Commercial Bank Co.,Ltd. Ulanqab Fengzhen Branch Pledgor: Inner Mongolia Haichi High-tech New Materials Co.,Ltd. Registration number: Y2024150000011 |