CN101474567A - Method for producing powdery composite mercury catalyst - Google Patents
Method for producing powdery composite mercury catalyst Download PDFInfo
- Publication number
- CN101474567A CN101474567A CNA200810068917XA CN200810068917A CN101474567A CN 101474567 A CN101474567 A CN 101474567A CN A200810068917X A CNA200810068917X A CN A200810068917XA CN 200810068917 A CN200810068917 A CN 200810068917A CN 101474567 A CN101474567 A CN 101474567A
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- China
- Prior art keywords
- chloride
- catalyst
- mercury
- mixed solution
- activated carbon
- 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 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 30
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 15
- -1 rare earth chloride Chemical class 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 239000011780 sodium chloride Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000007598 dipping method Methods 0.000 abstract description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 229960002523 mercuric chloride Drugs 0.000 abstract description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 235000013399 edible fruits Nutrition 0.000 abstract 2
- 238000012216 screening Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a production method of a powdery composite mercury catalyst, which comprises the steps of taking fruit shell-shaped activated carbon as a carrier, dipping the fruit shell-shaped activated carbon in a mercury chloride mixed solution to obtain a wet catalyst, and drying and screening the wet catalyst to obtain the powdery composite mercury catalyst containing 5-12.5% of mercury chloride, 1-5% of barium chloride, 1-5% of sodium chloride and 2-4% of rare earth chloride; the content of mercuric chloride in the catalyst is relatively low, and a manufacturer using the powdery mercury catalyst combines the corresponding production process, so that the activity and the stability of the catalyst are greatly improved to 5-12%, the use amount of the catalyst is reduced, the service life of the catalyst is prolonged, the catalyst replacement time is saved, and the production cost of vinyl chloride is reduced; except that the catalyst is less consumed and less lost, the mixed solution after dipping is readjusted and prepared, and the mixed solution is used for removing impurities without discarding, so that the environment is not polluted; the catalyst has the advantages of short production process, low energy consumption, easily mastered process conditions and low production cost. In conclusion, the invention has good economic benefit and environmental benefit.
Description
Technical field
The present invention relates to a kind of method of mercury catalyst, particularly carry out addition reaction synthesizing chloroethylene production method used, the multicomponent powdery composite mercury catalyst with hydrogen chloride and acetylene.
Background technology
In the prior art, domestic enterprise carries out addition reaction synthesizing chloroethylene catalyst system therefor in manufacturing with hydrogen chloride and acetylene and adopts the preparation of traditional handicraft method more, promptly adopt infusion process, this method is that mercury chloride is mixed with certain density solution, carrier active carbon floods therein, and mercury chloride is adsorbed in the carrier active carbon; Used carrier active carbon is the column-shaped active carbon of φ 3.5～4mm, L6～9mm, then at mercuric chloride catalyst under 60～90 temperature, through with after the heated-air drying, will contain chlorination mercury catalyst water content and reduce to moisture 0.3%.The shortcoming of this method is the flow process complexity, and production efficiency is low, the energy consumption height, and three wastes treating capacity is bigger, and certain mercury chloride loss is arranged, and contaminated environment also causes its cost higher.This catalyst mercury content height of the prior art, big to the mercury resource consumption, that the distillation of poor heat stability, mercury is run off is fast, it is many to consume, and the decay of catalyst ability is fast, and the part mercury element enters air with reacting gas, contaminated environment, or enter product product is worked the mischief.To this, domestic production enterprise also manages to improve, specifically also in Chinese patent literature, embody to some extent, be called " composite metal chloride catalyst and production technology thereof " as application number for (200610012455.0) name, and for example application number is (02154466.2), name is called " environment-friendly type mercury catalyst and production technology thereof ", also having application (patent) number is (91103854.X), name is called " a kind of method for preparing mercuric chleride catalyst " etc., and process for preparing catalyst and product quality that they introduced have had large increase.But according to the understanding to factory, the catalyst producer that produces with these new methods seldom.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect of above-mentioned prior art, and provide a kind of technological process short, the efficient height, the production method of the powdery composite mercury catalyst of three-waste free pollution, thus avoided the big problem of energy consumption of traditional technology.With the powdery composite mercury catalyst of this process preparation, can fine meeting the needs of production.
The production method of powdery composite mercury catalyst of the present invention is to adopt following technical scheme:
Adopting powdery shell powdered activated carbon is carrier, use mercury chloride, barium chloride, sodium chloride, the mercury chloride mixed solution that the rare earth chloride preparation obtains, in this mixed solution, carrier flooded 8～16 hours under 40～70 ℃ of conditions, had adsorbed the powdered activated carbon of mercury chloride mixed solution, through filtering, separate waste liquid, place drying chamber, or place drying room under 60～150 ℃ of temperature, to be dried to constant weight, obtain containing mercury chloride 5～12.5%, barium chloride 1～5%, sodium chloride 1～5%, the powdery composite mercury catalyst of rare earth chloride 2～4%.
The production method of above-mentioned powdery composite mercury catalyst, its used carrier are that the technical indicator of the carrier that uses is: granularity is 30～150 orders, iodine number mg/g with the powdered activated carbon of the drying of shell manufacturing〉950, Bi Biao Mian Ji ≧ 1000～1500m
2/ g, Ji tool Qiang Du ≧ 90%, unit weight g/cm
30.4～0.55, pH ≧ 7 phenol adsorptive values are mg/g ≧ 450; The raw material carrier powdered activated carbon requires to use the rotary type drier, or the dry processing of drying room is to reach These parameters.
The production method of above-mentioned powdery composite mercury catalyst, it uses mercury chloride, barium chloride, sodium chloride, the mercury chloride mixed solution that the rare earth chloride modulation obtains, its weight proportion is a mercury chloride: barium chloride: sodium chloride: rare earth chloride: water is 45:15:15:15:1800; PH control is modulated pH ≦ 1 with hydrochloric acid.
Advantage that has of the present invention and effect, the content of mercury chloride in catalyst is relatively low in the catalyst, the manufacturer that uses powdery mercury catalyst of the present invention is in conjunction with own corresponding production technology, the activity and the stability of catalyst are greatly improved, be 5%～12%, reduce the use amount of catalyst and prolonged life-span of catalyst, saved the time that catalyst is changed, thereby reduced the production cost of vinyl chloride; Except catalyst consumption is few, outside loss was few, powder catalyst can also recycle through processing, reduces secondary pollution, and the mixed solution behind the dipping can be readjusted preparation, continues after the removal of impurities not use out to abandon, and is free from environmental pollution; Because the catalyst technological process of production is short, energy consumption is low, easy control of technology conditions, and production cost is low.In sum, the present invention has good economic benefit and environmental benefit.
The specific embodiment
The present invention enumerates following example for explanation, but content of the present invention is not limited thereto, and its claimed scope is recorded in the claim of claim.
Embodiment 1: powdery composite mercury catalyst of the present invention, be that employing 550kg shell powdered activated carbon is a carrier, be immersed in pH ≦ 1 and use mercury chloride, barium chloride, sodium chloride, each compositional modulation of rare earth chloride and the mercury chloride mixed solution that obtains, mercury chloride 10.5% in the solution, barium chloride 4.5%, sodium chloride is adjusted pH ≦ 1 with hydrochloric acid, rare earth chloride flooded 10 hours under 70 ℃ of left and right sides temperature conditions, had adsorbed the powdered activated carbon of mercury chloride mixed solution, through filtering, separate waste liquid, the wet-milling shape composite mercury catalyst that obtains behind the dipping places drying chamber, or places drying room to be dried to constant weight for 150 ℃, obtain containing mercury chloride 6%, barium chloride 3%, sodium chloride 2.5%, the powdery composite mercury catalyst of rare earth chloride 2.45%.
Its used carrier is that service index: granularity is 30-150 orders, iodine number mg/g with the powdered activated carbon of the drying of shell manufacturing〉950, Bi Biao Mian Ji ≧ 1100m
2/ g, Ji tool Qiang Du ≧ 90%, unit weight g/cm
30.45 pH ≧ 7 phenol adsorptive values are mg/g ≧ 450, moisture Han Liang ≦ 5%; The raw material carrier powdered activated carbon requires to use the rotary type drier, or 105 ℃ of dryings of drying room, and moisture 0.5% is pulverized, sieved and handle to reach These parameters.
Embodiment 2: powdery composite mercury catalyst of the present invention, be that employing 650kg shell powdered activated carbon is a carrier, be immersed in pH ≦ 1 and use mercury chloride, barium chloride, sodium chloride, each compositional modulation of rare earth chloride and the mercury chloride mixed solution that obtains, mercury chloride 7.5% in the solution, barium chloride 3%, sodium chloride, rare earth chloride is adjusted pH ≦ 1 with hydrochloric acid, and carrier was put into dipping 10 hours under 70 ℃ of left and right sides temperature conditions, the powdered activated carbon that has adsorbed the mercury chloride mixed solution, through filtering, separate waste liquid, the wet-milling shape composite mercury catalyst that obtains behind the dipping, place drying chamber, or place drying room to be dried to constant weight for 150 ℃, obtain containing mercury chloride 7%, barium chloride 3%, sodium chloride 3%, the powdery composite mercury catalyst of rare earth chloride 3%.
Its used carrier is that the technical indicator of the carrier that uses is: granularity is 30-150 orders, iodine number mg/g with the powdered activated carbon of the drying of shell manufacturing〉950, Bi Biao Mian Ji ≧ 1100m
2/ g, Ji tool Qiang Du ≧ 90%, unit weight g/cm
30.45 pH ≧ 7 phenol adsorptive values are mg/g ≧ 450, moisture Han Liang ≦ 5%; The raw material carrier powdered activated carbon requires to use the rotary type drier, or 105 ℃ of dryings of drying room, and moisture 0.5% is pulverized, sieved and handle to reach These parameters.
Claims (3)
1, a kind of production method of powdery composite mercury catalyst, it is characterized in that adopting powdery shell powdered activated carbon is carrier, use mercury chloride, barium chloride, sodium chloride, the mercury chloride mixed solution that the rare earth chloride preparation obtains is in this mixed solution, carrier flooded 8～16 hours under 40～70 ℃ of conditions, the powdered activated carbon that has adsorbed the mercury chloride mixed solution through filtering, separates waste liquid, place drying chamber, or place drying room under 60～150 ℃ of temperature, to be dried to constant weight, obtain containing mercury chloride 5～12.5%, barium chloride 1～5%, sodium chloride 1～5%, the powdery composite mercury catalyst of rare earth chloride 2～4%.
2, the production method of powdery composite mercury catalyst according to claim 1, it is characterized in that used carrier is the powdered activated carbon with the drying of shell manufacturing, the technical indicator of the carrier that uses is: granularity is 30～150 orders, iodine number mg/g〉950, Bi Biao Mian Ji ≧ 1000～1500m2/g, Ji tool Qiang Du ≧ 90%, unit weight g/cm30.4～0.55, pH ≧ 7 phenol adsorptive values are mg/g ≧ 450; The raw material carrier powdered activated carbon requires to use the rotary type drier, or the drying room drying, pulverizes, sieves and handle to reach These parameters.
3, the production method of powdery composite mercury catalyst according to claim 1, it is characterized in that using mercury chloride, barium chloride, sodium chloride, the mercury chloride mixed solution that the rare earth chloride modulation obtains, its weight proportion is a mercury chloride: barium chloride: sodium chloride: rare earth chloride: water is 45:15:15:15:1800; The control of pH ≦ 1 is with hydrochloric acid modulation pH value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810068917XA CN101474567B (en) | 2008-09-19 | 2008-09-19 | Method for producing powdery composite mercury catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810068917XA CN101474567B (en) | 2008-09-19 | 2008-09-19 | Method for producing powdery composite mercury catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101474567A true CN101474567A (en) | 2009-07-08 |
| CN101474567B CN101474567B (en) | 2012-01-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810068917XA Expired - Fee Related CN101474567B (en) | 2008-09-19 | 2008-09-19 | Method for producing powdery composite mercury catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101474567B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890360A (en) * | 2010-08-05 | 2010-11-24 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
| CN102085484A (en) * | 2010-06-11 | 2011-06-08 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | High-stability composite mercury catalyst for hydrochlorination of acetylene |
| CN102085485A (en) * | 2010-06-11 | 2011-06-08 | 新疆天业（集团）有限公司 | High-stability composite mercury catalyst for hydrochlorination of acetylene |
| CN102151573A (en) * | 2011-01-21 | 2011-08-17 | 南开大学 | Preparation method of low-mercury catalyst for preparing vinyl chloride |
| CN102489306A (en) * | 2011-11-25 | 2012-06-13 | 贵州大学 | Low-mercury catalyst for synthesizing vinyl chloride |
| CN102527415A (en) * | 2010-12-14 | 2012-07-04 | 新晃新中化工有限责任公司 | Low-mercury compound mercury catalyst and its preparation method |
| CN103539876A (en) * | 2013-10-16 | 2014-01-29 | 贵州大龙银星汞业有限责任公司 | Environment-friendly catalytic agent for synthesizing polyvinyl chloride |
| CN104785238A (en) * | 2014-01-20 | 2015-07-22 | 天津大学 | Hg-La catalyst for acetylene hydrochlorination, and preparation method and application thereof |
-
2008
- 2008-09-19 CN CN200810068917XA patent/CN101474567B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085484A (en) * | 2010-06-11 | 2011-06-08 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | High-stability composite mercury catalyst for hydrochlorination of acetylene |
| CN102085485A (en) * | 2010-06-11 | 2011-06-08 | 新疆天业（集团）有限公司 | High-stability composite mercury catalyst for hydrochlorination of acetylene |
| CN101890360A (en) * | 2010-08-05 | 2010-11-24 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
| CN101890360B (en) * | 2010-08-05 | 2012-07-25 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
| CN102527415A (en) * | 2010-12-14 | 2012-07-04 | 新晃新中化工有限责任公司 | Low-mercury compound mercury catalyst and its preparation method |
| CN102151573A (en) * | 2011-01-21 | 2011-08-17 | 南开大学 | Preparation method of low-mercury catalyst for preparing vinyl chloride |
| CN102151573B (en) * | 2011-01-21 | 2012-10-03 | 南开大学 | Preparation method of low-mercury catalyst for preparing vinyl chloride |
| CN102489306A (en) * | 2011-11-25 | 2012-06-13 | 贵州大学 | Low-mercury catalyst for synthesizing vinyl chloride |
| CN103539876A (en) * | 2013-10-16 | 2014-01-29 | 贵州大龙银星汞业有限责任公司 | Environment-friendly catalytic agent for synthesizing polyvinyl chloride |
| CN104785238A (en) * | 2014-01-20 | 2015-07-22 | 天津大学 | Hg-La catalyst for acetylene hydrochlorination, and preparation method and application thereof |
| CN104785238B (en) * | 2014-01-20 | 2018-11-09 | 天津大学 | Hg-La catalyst and preparation method and application for acetylene hydrochlorination |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101474567B (en) | 2012-01-04 |
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Granted publication date: 20120104 Termination date: 20120919 |