CN102489306B - Low-mercury catalyst for synthesizing vinyl chloride - Google Patents
Low-mercury catalyst for synthesizing vinyl chloride Download PDFInfo
- Publication number
- CN102489306B CN102489306B CN201110380027.4A CN201110380027A CN102489306B CN 102489306 B CN102489306 B CN 102489306B CN 201110380027 A CN201110380027 A CN 201110380027A CN 102489306 B CN102489306 B CN 102489306B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- low
- mercury catalyst
- 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.)
- Expired - Fee Related
Links
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- -1 rare earth chloride Chemical class 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 26
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 20
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 19
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 abstract description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 abstract 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 abstract 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 abstract 2
- 229910001626 barium chloride Inorganic materials 0.000 abstract 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 abstract 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 abstract 2
- 239000011592 zinc chloride Substances 0.000 abstract 2
- 235000005074 zinc chloride Nutrition 0.000 abstract 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005997 Calcium carbide Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 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 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a low-mercury catalyst for synthesizing vinyl chloride. The catalyst is characterized by comprising the following components, by weight: 2.5-3.5% of HgCl2; 0.1-12.5% of BiCl3; 0.15-15% of ZnCl2; 0.1-7.00% of TiCl4; 2.75-3.25% of CuCl2; 0.3-8.3% of VCl3; 0.3-8.3% of rare earth chloride; 3-8.5% of BaCl2; and 62.5-75% of C. In the invention, BiCl3, ZnCl2, TiCl4, CuCl2, VCl3, as well as BaCl2 that are cheap and has catalytic performance and rare earth chloride are employed to substitute part of HgCl2 for preparing the low-mercury catalyst, the HgCl2 content of which can be reduced to less than 3.5% while the catalytic performance is fully guaranteed. Thus, not only is the energy consumption reduced, but the product cost of the catalyst is also lowered. Prepared by a step impregnation method, the low-mercury catalyst in the invention is characterized by simple process, effectiveness, energy saving, environmental protection, and convenient operation, and simultaneously can overcome problems existing in prior art, thus being suitable for the second-stage process of vinyl chloride synthesis.
Description
Technical field
The present invention relates to a kind of preparation method of low mercury catalyst of synthesizing chloroethylene; Belong to synthesizing chloroethylene technical field.
Background technology
Mercury pollution is a serious Global Environmental Problems.The cry of international taboo mercury is more and more surging.China's year mercury use accounts for 30% ~ 40% of the whole world, and wherein generated by polyvinyl chloride by calcium carbide mercury use accounts for 60% of national mercury use.At present, Production of PVC enterprise of China 104, aggregated capacity is 1,781 ten thousand tons, wherein carbide 94, and production capacity is 1,362 ten thousand tons, accounts for 76.5% of aggregated capacity.Within 2009, China's polyvinyl chloride total output is 9,150,000 tons, and wherein generated by polyvinyl chloride by calcium carbide output 5,800,000 tons, accounts for 63.4% of total output.Restrict by resource structures, the situation of China's Production of PVC industry based on calcium carbide cannot change.
The Chinese government to mercury pollution control pay much attention to: Environmental Protection Department, the Ministry of Industry and Information Technology etc. 8 department combine issue literary composition, proposed for the end of the year 2015, generated by polyvinyl chloride by calcium carbide manufacturing enterprise all will use low mercury catalyst, specifies Heavy Metal Pollution target.
The patent of inventor herein's earlier application: mercuric chloride low-mercury catalyst and preparation method thereof, number of patent application 200910102437, active carbon is adopted to be carrier adsorption mercury chloride, mercury chloride in this catalyst formulation is 8.0% ~ 10.0%, its Hg chloride content is still higher, can not meet the demands.
In addition, VCM synthesis technique mostly adopts two-stage method, and one section is high concentration synthesis, and two sections is low concentration synthesis.The synthesizing chloroethylene under the effect at mercury catalyst at one section of operation middle and high concentration HCl and high concentration acetylene, reaction is violent, and release large calorimetric, after entering two sections of operations, the concentration of HCl and acetylene reduces greatly, reaction temperature and.Thus the mercury catalyst needed for a section and two sections is also because of difference.
Summary of the invention
The object of the invention is: the preparation method providing a kind of low mercury catalyst of synthesizing chloroethylene, reaches the HgCl reduced further in catalyst
2the object of content.
The present invention is formed like this: the low mercury catalyst of synthesizing chloroethylene, by weight, comprises following composition: HgCl
2: 2.5 ~ 3.5%; BiCl
3: 0.1 ~ 12.5%; ZnCl
2: 0.15 ~ 15%; TiCl
4: 0.1 ~ 7.00%; CuCl
2: 2.75 ~ 3.25%; VCl
3: 0.3 ~ 8.3%; Rare earth chloride: 0.3 ~ 8.3%; BaCl
23 ~ 8.5%; C:62.5 ~ 75%.
The low mercury catalyst of above-mentioned a kind of synthesizing chloroethylene, described BiCl
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl
2with rare earth chloride total amount≤32%.
The low mercury catalyst of above-mentioned a kind of synthesizing chloroethylene, by weight, comprises following composition: HgCl
2: 3.5%; BiCl
3: 3%; ZnCl
2: 4%; TiCl
4: 3%; CuCl
2: 3%; VCl
3: 4%; Rare earth chloride: 4%; BaCl
24%; Surplus is C.
The low mercury catalyst of above-mentioned a kind of synthesizing chloroethylene, described rare earth chloride is one of chloride of scandium, yttrium, lanthanum and/or cerium, or mixtures two or more arbitrarily.
Applicant finds through experiment, the BiCl in raw material of the present invention
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl
2under the process conditions of synthesizing chloroethylene, certain catalytic action itself is possessed with rare earth chloride.Choose reasonable BiCl
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl
2with the proportioning of rare earth chloride, utilize its cooperative effect, can be used for Substitute For Partial HgCl
2catalysis, reduce the consumption of mercury chloride.Compared with the existing technology, the cheap chloride BiCl of the present invention
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3and BaCl
2substitute expensive HgCl
2, environmental protection more.TiCl in formula
4good with the cooperative effect of rare earth chloride, the advantages such as low mercury catalyst long not easily deliquescence service time of preparation, has environmental protection, easy to operate, safe; The consumption of mercury can be reduced simultaneously further, overcome prior art Problems existing.
Through test, this reasonable mixture ratio scope is as follows, by weight, and HgCl
2: 2.5 ~ 3.5%; BiCl
3: 0.1 ~ 12.5%; ZnCl
2: 0.15 ~ 15%; TiCl
4: 0.1 ~ 7.00%; CuCl
2: 2.75 ~ 3.25%; VCl
3: 0.3 ~ 8.3%; Rare earth chloride: 0.3 ~ 8.3%; BaCl
23 ~ 8.5%; C:62.5 ~ 75%.Rare earth chloride is one of chloride of scandium, yttrium, lanthanum and/or cerium, or any two or more muriatic mixture.
The present invention develops the new low mercury catalyst of synthesis, with a large amount of cheap BiCl
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl
2with rare earth chloride Substitute For Partial HgCl
2produce low mercury catalyst, make to reduce HgCl in catalyst while fully ensureing catalytic performance
2content≤3.5%, not only reduces resource consumption, reduces the production cost of catalyst simultaneously.The low mercury catalyst of a kind of synthesizing chloroethylene prepared by the present invention is applicable to synthesizing chloroethylene two sections of operations.
Detailed description of the invention
Embodiments of the invention 1: according to following proportioning, HgCl
2: 3.5%; BiCl
3: 3%; ZnCl
2: 4%; TiCl
4: 3.5%; CuCl
2: 3%; VCl
3: 4.5%; Rare earth chloride: 4.4%; BaCl
26%; All the other are C.C selects active carbon.First by BiCl
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl and rare earth chloride dissolve, and then in the saturated solution dissolved, adds the active carbon (C) soaked by hydrochloric acid solution at low temperature; Be heated to 50 DEG C of dippings after 24 hours, the active carbon after dipping is put into containing HgCl
2solution for continuous carry out dipping 8 hours and take out, the predrying rear continuation drying of low temperature obtains product.
Through test, this reasonable mixture ratio scope is as follows, by weight, and HgCl
2: 2.5 ~ 3.5%; BiCl
3: 0.1 ~ 12.5%; ZnCl
2: 0.15 ~ 15%; TiCl
4: 0.1 ~ 7.00%; CuCl
2: 2.75 ~ 3.25%; VCl
3: 0.3 ~ 8.3%; Rare earth chloride: 0.3 ~ 8.3%; BaCl
23 ~ 8.5%; C:62.5 ~ 75%.Rare earth chloride is one of chloride of scandium, yttrium, lanthanum and/or cerium, or any two or more muriatic mixture.In formula, BiCl
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl
2≤ 32% is answered, good catalytic activity with rare earth chloride total amount.
Embodiments of the invention 2: according to following proportioning, HgCl
2: 3.5%; BiCl
3: 0.1%; ZnCl
2: 0.15%; TiCl
4: 0.1%; CuCl
2: 3.25%; VCl
3: 8.3%; Rare earth chloride: 8.3%; BaCl
28.5%; All the other are C.First by BiCl
3, ZnCl
2, TiCl
4dissolve, containing BiCl
3, ZnCl
2, TiCl
4the active carbon soaked by hydrochloric acid solution at low temperature is added in saturated solution; Be heated to 50 DEG C of dippings after 12 hours, the active carbon after dipping is put into containing CuCl
2, VCl
3, BaCl
2proceed dipping with control temperature in the solution of rare earth chloride 50 DEG C to take out for 12 hours, then the Product Activity charcoal after dipping is put into containing 3.5%HgCl
2solution in dipping 8 hours, take out low temperature predrying rear continuation drying and obtain product.Rare earth chloride is lanthanum chloride.
Embodiments of the invention 3: optimum proportioning is, by weight, by weight, comprise following composition: HgCl
2: 3.5%; BiCl
3: 3%; ZnCl
2: 4%; TiCl
4: 3%; CuCl
2: 3%; VCl
3: 4%; Rare earth chloride: 4%; BaCl
24%; All the other are C.First containing BiCl
3, ZnCl
2saturated solution in add the active carbon soaked by hydrochloric acid solution at low temperature; Be heated to 50 DEG C of dippings after 8 hours, the active carbon after dipping is put into containing TiCl
4, CuCl
2saturated solution in proceed dipping 8 hours, control temperature 50 DEG C, then by dipping after active carbon put into containing VCl
3, BaCl
2within 8 hours, take out with dipping in the solution of rare earth chloride, this stage is control temperature 50 DEG C still, then puts it into containing 3%HgCl
2solution in dipping 8 hours, take out after the predrying rear continuation drying of low temperature obtain product.Rare earth chloride is the chlorate mixture of scandium, yttrium and cerium.
Claims (5)
1. a low mercury catalyst for synthesizing chloroethylene, is characterized in that: by weight, comprises following composition: HgCl
2: 2.5 ~ 3.5%; BiCl
3: 0.1 ~ 12.5%; ZnCl
2: 0.15 ~ 15%; TiCl
4: 0.1 ~ 7.00%; CuCl
2: 2.75 ~ 3.25%; VCl
3: 0.3 ~ 8.3%; Rare earth chloride: 0.3 ~ 8.3%; BaCl
23 ~ 8.5%; C:62.5 ~ 75%.
2. according to the low mercury catalyst of a kind of synthesizing chloroethylene according to claim 1, it is characterized in that: described BiCl
3, ZnCl
2, TiCl
4, CuCl
2, VCl
3, BaCl
2with rare earth chloride total amount≤32%.
3. according to the low mercury catalyst of synthesizing chloroethylene according to claim 1, it is characterized in that: by weight, comprise following composition: HgCl
2: 3.5%; BiCl
3: 3%; ZnCl
2: 4%; TiCl
4: 3%; CuCl
2: 3%; VCl
3: 4%; Rare earth chloride: 4%; BaCl
24%; Surplus is C.
4. according to the low mercury catalyst of synthesizing chloroethylene according to claim 1, it is characterized in that: described C is active carbon.
5. according to the low mercury catalyst of synthesizing chloroethylene according to claim 1, it is characterized in that: described rare earth chloride is one of chloride of scandium, yttrium, lanthanum and/or cerium, or mixtures two or more arbitrarily.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110380027.4A CN102489306B (en) | 2011-11-25 | 2011-11-25 | Low-mercury catalyst for synthesizing vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110380027.4A CN102489306B (en) | 2011-11-25 | 2011-11-25 | Low-mercury catalyst for synthesizing vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102489306A CN102489306A (en) | 2012-06-13 |
| CN102489306B true CN102489306B (en) | 2015-04-08 |
Family
ID=46181190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110380027.4A Expired - Fee Related CN102489306B (en) | 2011-11-25 | 2011-11-25 | Low-mercury catalyst for synthesizing vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102489306B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785285A (en) * | 2015-05-07 | 2015-07-22 | 温县三陵化工厂 | Low-mercury catalyst for synthesizing vinyl chloride and preparation method of low-mercury catalyst |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551155B (en) * | 2013-10-16 | 2015-08-19 | 贵州大龙银星汞业有限责任公司 | A kind of synthesizing polyvinyl chloride low mercury catalyst and preparation method thereof |
| CN105080581B (en) * | 2015-09-11 | 2017-05-17 | 浙江工业大学 | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof |
| CN107486224A (en) * | 2017-08-29 | 2017-12-19 | 贵州重力科技环保有限公司 | A kind of ultralow solid mercury catalyst of high catalytic conversion and preparation method thereof |
| CN109317169A (en) * | 2018-11-20 | 2019-02-12 | 湖北随州双星生物科技有限公司 | A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof |
| CN113131031B (en) * | 2021-04-09 | 2022-07-15 | 贵州理工学院 | Method for preparing ultra-low mercury catalyst by recycling waste batteries |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059438A (en) * | 1973-12-13 | 1977-11-22 | Hoechst Aktiengesellschaft | Process for the work-up of a contaminated inactive mercury(II)chloride/active carbon-catalyst |
| CN101474567B (en) * | 2008-09-19 | 2012-01-04 | 贵州省万山特区矿产公司 | Method for producing powdery composite mercury catalyst |
| CN101890360B (en) * | 2010-08-05 | 2012-07-25 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
-
2011
- 2011-11-25 CN CN201110380027.4A patent/CN102489306B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785285A (en) * | 2015-05-07 | 2015-07-22 | 温县三陵化工厂 | Low-mercury catalyst for synthesizing vinyl chloride and preparation method of low-mercury catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102489306A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102489306B (en) | Low-mercury catalyst for synthesizing vinyl chloride | |
| CN102631942B (en) | Composite metal salt catalyst for hydrochlorination reaction of acetylene | |
| RU2580580C1 (en) | Method for extraction ruthenium from spent catalyst in form of aluminium oxide loaded with ruthenium | |
| CN102441409B (en) | Composite low mercury catalyst used for synthesizing vinyl chloride | |
| CN103933994B (en) | A kind of for CO and CO 2the preparation method of the high-temperature methanation catalyst of methane is produced with hydrogen reaction | |
| CN103785470B (en) | A kind of preparation method for the synthesis of acrylic acid catalyst | |
| CN102698806B (en) | A kind of catalyst without mercury synthesizing vinyl chloride for acetylene hydrochlorination | |
| CN104087354B (en) | A kind of technique utilizing yellow phosphoric tail gas synthetic natural gas | |
| CN102205961A (en) | Method for adjusting pore structure of activated carbon | |
| CN106866349B (en) | Method for preparing vinyl chloride by low-temperature hydrochlorination of acetylene | |
| CN102806095B (en) | Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant | |
| CN114716347B (en) | Method for preparing adiponitrile | |
| CN102658149A (en) | Copper oxide catalyst for preparing chlorine gas from chlorine hydride by catalytic oxidation, and preparation method and application thereof | |
| US8202353B2 (en) | Separation, purification and recovery method of SF6, HFCs and PFCs | |
| CN104785238A (en) | Hg-La catalyst for acetylene hydrochlorination, and preparation method and application thereof | |
| CN110227507B (en) | High-stability ultralow-mercury catalyst and preparation method and application thereof | |
| CN102962060A (en) | Catalyst for synthetizing dimethyl oxalate and preparation method thereof | |
| CN102125830B (en) | Mercury-free catalyst for use in production of chloroethylene by calcium carbide method | |
| CN106944110A (en) | A kind of hydrogen chloride synthesis vinyl chloride thereof catalyst without mercury and preparation method | |
| CN103721717B (en) | A kind of catalyst and preparation method thereof improving coal ethyl glycol product quality | |
| CN103551155B (en) | A kind of synthesizing polyvinyl chloride low mercury catalyst and preparation method thereof | |
| CN105664949A (en) | Preparation method of Cu/Zn catalyst | |
| CN103920511A (en) | Catalyst for preparing vinyl chloride by acetylene hydrochlorination and preparation method thereof | |
| CN102059117B (en) | Two types of catalysts for synthesizing methyl chlorosilane and preparation method thereof | |
| CN102039180A (en) | Catalyst for producing vinyl acetate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHAANXI BEIYUAN CHEMICAL GROUP CO., LTD. GUIZHOU D Free format text: FORMER OWNER: SHAANXI BEIYUAN CHEMICAL GROUP CO., LTD. GUIZHOU SIVER STAR GROUP CO., LTD. Effective date: 20150708 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150708 Address after: 550025 Department of science and technology, Guizhou University, Huaxi District, Guizhou, Guiyang Patentee after: Guizhou University Patentee after: Shaanxi Beiyuan Chemical Group Co., Ltd. Patentee after: GUIZHOU DALONG MERCURY SILVER STAR INDUSTRY CO., LTD. Address before: 550025 Department of science and technology, Guizhou University, Huaxi District, Guizhou, Guiyang Patentee before: Guizhou University Patentee before: Shaanxi Beiyuan Chemical Group Co., Ltd. Patentee before: Guizhou Siver Star Group Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 550025 Department of science and technology, Guizhou University, Huaxi District, Guizhou, Guiyang Co-patentee after: Shaanxi Beiyuan chemical group Limited by Share Ltd Patentee after: Guizhou University Co-patentee after: GUIZHOU DALONG MERCURY SILVER STAR INDUSTRY CO., LTD. Address before: 550025 Department of science and technology, Guizhou University, Huaxi District, Guizhou, Guiyang Co-patentee before: Shaanxi Beiyuan Chemical Group Co., Ltd. Patentee before: Guizhou University Co-patentee before: GUIZHOU DALONG MERCURY SILVER STAR INDUSTRY CO., LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180614 Address after: 719319 Jinshi Industrial Park, Shenmu county, Yulin, Shaanxi Co-patentee after: GUIZHOU DALONG MERCURY SILVER STAR INDUSTRY CO., LTD. Patentee after: Shaanxi Beiyuan chemical group Limited by Share Ltd Address before: 550025 science and technology office, Guizhou University, Huaxi District, Guiyang, Guizhou Co-patentee before: Shaanxi Beiyuan chemical group Limited by Share Ltd Patentee before: Guizhou University Co-patentee before: GUIZHOU DALONG MERCURY SILVER STAR INDUSTRY CO., LTD. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 Termination date: 20201125 |