CN105195225B - A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption - Google Patents
A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption Download PDFInfo
- Publication number
- CN105195225B CN105195225B CN201510704051.7A CN201510704051A CN105195225B CN 105195225 B CN105195225 B CN 105195225B CN 201510704051 A CN201510704051 A CN 201510704051A CN 105195225 B CN105195225 B CN 105195225B
- Authority
- CN
- China
- Prior art keywords
- chloride
- activated carbon
- mercury
- palladium bichloride
- acid
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption, including the preparation of activated carbon, the processing of activated carbon, the preparation of adsorption liquid, adsorption treatment；The adsorption treatment is adsorbed including vacuum infiltration.Low-mercury catalyst prepared by the present invention, by weight percentage, potassium sulfonate 2.25%, water 0.16%, mechanical strength 99.0%, 3~6mm of granularity between chloride containing mercury 4.5%, zinc chloride 8.1%, palladium bichloride 2.7%, platinum chloride 2.7%, tetrabutylammonium chloride 2.25%, triphenylphosphine（99.2%）, bulk density 480g/l；Low-mercury catalyst prepared by the present invention, mercury chloride burn tinctuer is low, and heat endurance is good；For vinyl chloride synthesis reaction, the conversion ratio of acetylene is obtained up to 99.95%, and the yield of vinyl chloride is up to 95.9%；Catalytic efficiency improves；Reaction temperature reduces, and the unit consumption of catalyst is low.
Description
Technical field
The present invention relates to a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption, belong to and become more meticulous
Learn technical field.
Background technology
The reaction principle of acetylene method synthesis vinyl chloride thereof is acetylene and the hydrogen chloride gas under the catalytic action of mercuric chleride catalyst
Phase reaction generates vinyl chloride, the preparation method of existing mercuric chleride catalyst, makees carrier with activated carbon, in 85-90 DEG C of condition
Under, activated carbon is immersed in 8-24 hours in mercuric chloride solution, in a manner of physical absorption after adsorbing chlorinated mercury, then through dry
It is dry, water content in activated carbon is less than 0.3%, chloride containing mercury 4-12%, mercuric chleride catalyst is made.
The Hg chloride content 10-12% of high mercury catalyst, because the Hg chloride content of high mercury catalyst is high, mercury consumption is big, existing
Progressively it is being eliminated, the application scale of low-mercury catalyst is progressively expanding.
Existing low-mercury catalyst, has the following disadvantages：
（1）The poor performance of catalyst itself；
（2）Mercury chloride burn tinctuer is high, and heat endurance is poor；
（3）For vinyl chloride synthesis reaction, the conversion ratio of acetylene is low, and the yield of vinyl chloride is low；Catalytic efficiency is low；It is required anti-
Answer temperature high, the unit consumption of catalyst is high.
The content of the invention
The present invention is solution the shortcomings of the prior art, there is provided one kind is prepared low using palladium bichloride collaboration accelerator absorption
The method of mercury catalyst, to realize following goal of the invention：
（1）Low-mercury catalyst prepared by the present invention, by weight percentage, chloride containing mercury 4.5%, zinc chloride 8.1%, chlorination
Potassium sulfonate 2.25%, water 0.16%, mechanical strength between palladium 2.7%, platinum chloride 2.7%, tetrabutylammonium chloride 2.25%, triphenylphosphine
99.0%, 3~6mm of granularity（99.2%）, bulk density 480g/l.
（2）Low-mercury catalyst prepared by the present invention, mercury chloride burn tinctuer is low, and heat endurance is good.
（3）Low-mercury catalyst prepared by the present invention, for vinyl chloride synthesis reaction, the conversion ratio for obtaining acetylene reaches
99.95%, the yield of vinyl chloride is up to 95.9%；Catalytic efficiency improves；Reaction temperature reduces, and the unit consumption of catalyst is low.
To solve above technical problem, the present invention uses following technical scheme：
A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption, includes preparation, the work of activated carbon
The property processing of charcoal, the preparation of adsorption liquid, adsorption treatment；The adsorption treatment is adsorbed including vacuum infiltration.
It is the further improvement to above-mentioned technical proposal below：
The preparation of the activated carbon, include the selection of raw material, selected raw material is coconut husk, containing ash content 0.61%, lignin
36.51%, cellulose 53.06%, cellulose contains pentosan 20.54%.
The preparation of the activated carbon, including acid treatment, the acid treatment, with acid dip coconut shell flour, acid and coconut shell flour quality
Than for 3:1, soak 3 hours, wash, dry, be then 10ml/mim, at 480 DEG C in N2 flows, activate 2 hours.
Described acid, including：60% phosphoric acid, citric acid, oxalic acid, mass ratio 4:1:2；Described coconut shell flour, it is
100 mesh.
The preparation of the activated carbon, including microwave treatment, the microwave treatment, coconut shell flour and liquor zinci chloridi are mixed,
The concentration of liquor zinci chloridi is 35%, and the mass ratio of coconut shell flour and zinc chloride is 1:3, using microwave treatment, microwave power is
610w, irradiate 10 minutes, activated carbon is made.
The activated carbon, iodine number 1350mg/g, methylene blue value 115mg/g, up to 95.2%, carbon tetrachloride adsorbs mesoporous
It is worth for 130%, moisture content 2%, ash 1.6%, bulk density 400g/L, specific surface area 1700m2/ g, average pore size 2.5-
2.7nm。
The preparation of the adsorption liquid, the chlorine that mass fraction is 3.8%, pH=2.9 is prepared with mercury chloride, hydrochloric acid and desalted water
Change mercury salt acid solution, add appropriate palladium bichloride collaboration accelerator, it is 1 that mercury chloride and palladium bichloride, which cooperate with the mass ratio of accelerator,:
4。
Between palladium bichloride the collaboration accelerator, including zinc chloride, palladium bichloride, platinum chloride, tetrabutylammonium chloride, triphenylphosphine
Potassium sulfonate, mass ratio 1.8:0.6:0.6:0.5:0.5.
Using above technical scheme, beneficial effects of the present invention are：
（1）Low-mercury catalyst prepared by the present invention, by weight percentage, chloride containing mercury 4.5%, zinc chloride 8.1%, chlorination
Potassium sulfonate 2.25%, water 0.16%, mechanical strength between palladium 2.7%, platinum chloride 2.7%, tetrabutylammonium chloride 2.25%, triphenylphosphine
99.0%, 3~6mm of granularity（99.2%）, bulk density 480g/l.
（2）Low-mercury catalyst prepared by the present invention, mercury chloride burn tinctuer 0.28%, heat endurance is good, under the conditions of 260 DEG C
After 100h, the content of mercury chloride is 4.26%, and mercury chloride loss late is 5.3%.
（3）Low-mercury catalyst prepared by the present invention, for vinyl chloride synthesis reaction, the conversion ratio for obtaining acetylene is
99.95%, the yield of vinyl chloride is up to 95.9%, and catalytic efficiency improves, and catalytic efficiency improves 4.6 m3/h；Reaction temperature reduces, drop
To 108 DEG C, the reaction temperature of prior art is more than 130 DEG C；The unit consumption of catalyst is low, catalyst consumption 0.0012-
0.0013 g/ml vinyl chloride.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption of embodiment 1
The preparation of step 1 activated carbon
（1）The selection of raw material
Selected raw material is coconut husk, poly- containing penta containing ash content 0.61%, lignin 36.51%, cellulose 53.06%, cellulose
Sugar 20.54%.
Coconut husk is crushed, 100 mesh sieves is crossed, obtains coconut shell flour.
（2）Acid treatment
With the above-mentioned coconut shell flour of acid dip, described acid, including：60% phosphoric acid, citric acid, oxalic acid, mass ratio 4:1:
2, acid is 3 with coconut shell flour mass ratio:1, soak 3 hours, wash, dry, be then 10ml/mim, at 480 DEG C in N2 flows, it is living
Change 2 hours.
（3）Microwave treatment
Coconut shell flour and liquor zinci chloridi are mixed, the concentration of liquor zinci chloridi is 35%, the mass ratio of coconut shell flour and zinc chloride
Example is 1:3, using microwave treatment, microwave power 610w, irradiate 10 minutes, activated carbon is made.
The activated carbon iodine number 1350mg/g of preparation, methylene blue value 115mg/g, up to 95.2%, carbon tetrachloride adsorbs mesoporous
It is worth for 130%, moisture content 2%, ash 1.6%, bulk density 400g/L, specific surface area 1700m2/ g, average pore size 2.5-
2.7nm。
The processing of step 2 activated carbon
It is in 2.2mol/L nitric acid by the concentration that activated carbon prepared by the present invention is placed in 6 times of volumes, heating stirring is extremely returned
Activated carbon is washed to pH=6 with distilled water, surface moisture is dried at 50 DEG C, be dried under vacuum to then at 88 DEG C by stream after 3 hours
Constant weight；It is heating stirring to backflow 2.5 ~ 3.5 in 2% ~ 4wt% urea liquid by the concentration that the activated carbon is placed in 4 times of its volume
After hour, filter and dry surface moisture in 55 DEG C, be dried under vacuum to constant weight then at 82 DEG C, be subsequently placed in Muffle furnace in 160
℃（The decomposition temperature of urea）Constant weight is fired to, obtains the activated carbon that pretreatment is completed, it is standby.
The preparation of step 3 adsorption liquid
The mercury chloride hydrochloric acid solution that mass fraction is 3.8%, pH=2.9 is prepared with mercury chloride, hydrochloric acid and desalted water, is added
The mass ratio of appropriate palladium bichloride collaboration accelerator, mercury chloride and palladium bichloride collaboration accelerator is 1:4；The palladium bichloride collaboration
Potassium sulfonate between accelerator, including zinc chloride, palladium bichloride, platinum chloride, tetrabutylammonium chloride, triphenylphosphine, mass ratio 1.8:
0.6:0.6:0.5:0.5。
Step 4 adsorption treatment
A, ultrasonic wave added adsorbs
Activated carbon is put into the adsorption liquid that step 3 is prepared, the mass ratio of activated carbon and adsorption liquid is 1:6, at 140 DEG C
Temperature conditionss under soak 1.5 hours, use ultrasonic assistant adsorption process, ultrasonic power density 138W/L, supersonic frequency
Rate is 86KHz, while is passed through compressed air, and the air pressure of air-flow is 1.30MPa, and the flow velocity of air draught is 33kg/L, is during which made
Adsorbent solution is constantly flowed with circulating pump, then take out filtering or be filtered dry with centrifuge drying dehydration, baking oven is put into, 125
DEG C temperature conditionss under dry to aqueous less than 0.2%；
B, microwave radiation technology adsorbs
Then the activated carbon Jing Guo ultrasonic wave added adsorption treatment is placed again into the adsorption liquid that step 3 is prepared, activated carbon
Mass ratio with adsorption liquid is 1:4,58 DEG C of temperature, microwave wavelength are 135 millimeters, and frequency is 2630 megahertzs, power 300w,
Adsorption treatment 10 minutes, during which makes adsorbent solution constantly flow using circulating pump, then takes out filtering or is dried with centrifuge de-
Water is filtered dry, and is put into baking oven, is dried under 120 DEG C of temperature conditionss to aqueous less than 0.2%；
C, vacuum infiltration adsorbs
Then the activated carbon Jing Guo microwave radiation technology adsorption treatment is placed again into the adsorption liquid that step 3 is prepared, activated carbon
Mass ratio with adsorption liquid is 1:6, place into stainless-steel vacuum tank, vacuumized with vavuum pump, after reaching -0.039MPa pressure
28s is kept, then is recovered to normal pressure, soaks 5min under normal pressure, filtering is then taken out or is filtered dry with centrifuge drying dehydration, put
Enter baking oven, it is 0.16% to be dried under 120 DEG C of temperature conditionss to water content, and low-mercury catalyst of the present invention is made.
Low-mercury catalyst prepared by the present invention, by weight percentage, wherein chloride containing mercury 4.5%, zinc chloride 8.1%, chlorine
Change potassium sulfonate 2.25%, water 0.16% between palladium 2.7%, platinum chloride 2.7%, tetrabutylammonium chloride 2.25%, triphenylphosphine, mechanical strength
99.0%, 3~6mm of granularity（99.2%）, bulk density 480g/l, mercury chloride burn tinctuer 0.28%, heat endurance is good, in 260 DEG C of bars
Under part after 100h, the content of mercury chloride is 4.26%, and mercury chloride loss late is 5.3%.
2 above-mentioned catalyst of embodiment is used for vinyl chloride synthesis reaction
In the reaction for preparing chloroethylene by acetylene hydrochlorination, the mol ratio of reactor feed gas is catalyst of the present invention
C2H2/ HCl=1/1.18, acetylene air speed are 69h-1, 108 DEG C of reaction temperature, hydrogen chloride soak time is 30 minutes.
For reaction end gas through chromatography, the conversion ratio for obtaining acetylene is 99.95%, and the yield of vinyl chloride is catalyzed up to 95.9%
Efficiency improves, and catalytic efficiency improves 4.6 m3/h；Reaction temperature reduces, and is down to 108 DEG C, the reaction temperature of prior art is 130
More than DEG C；The unit consumption of catalyst is low, and catalyst consumption is 0.0012-0.0013 g/ml vinyl chloride.
Unless otherwise indicated, the percentage employed in the present invention is percetage by weight, ratio of the present invention,
For mass ratio.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
For art personnel it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (7)
- A kind of 1. method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption, it is characterised in that：Including activated carbon Preparation, the processing of activated carbon, the preparation of adsorption liquid, adsorption treatment；The adsorption treatment is adsorbed including vacuum infiltration；The low-mercury catalyst, by weight percentage, wherein chloride containing mercury 4.5%, zinc chloride 8.1%, palladium bichloride 2.7%, chlorination Potassium sulfonate 2.25%, water 0.16% between platinum 2.7%, tetrabutylammonium chloride 2.25%, triphenylphosphine；The processing of the activated carbon, it is in 2.2mol/L nitric acid by the concentration that activated carbon is placed in 6 times of volumes, heating stirring is extremely returned Activated carbon is washed to pH=6 with distilled water, surface moisture is dried at 50 DEG C, be dried under vacuum to then at 88 DEG C by stream after 3 hours Constant weight；By the activated carbon be placed in 4 times of its volume concentration be 2%~4wt% urea liquid in, heating stirring to flow back 2.5~ After 3.5 hours, filter simultaneously in 55 DEG C dry surface moistures, be dried under vacuum to constant weight then at 82 DEG C, be subsequently placed in Muffle furnace in 160 DEG C are fired to constant weight, obtain the activated carbon that pretreatment is completed, standby.
- 2. a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption according to claim 1, its It is characterised by：The preparation of the activated carbon, include the selection of raw material, selected raw material is coconut husk, wooden containing ash content 0.61% Element 36.51%, cellulose 53.06%, cellulose contains pentosan 20.54%.
- 3. a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption according to claim 1, its It is characterised by：The preparation of the activated carbon, including acid treatment, the acid treatment, with acid dip coconut shell flour, acid and coconut shell flour quality Than for 3:1, soak 3 hours, wash, dry, then in N2Flow is 10ml/min, at 480 DEG C, is activated 2 hours.
- 4. a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption according to claim 3, its It is characterised by：Described acid, including：60% phosphoric acid, citric acid, oxalic acid, mass ratio 4:1:2；Described coconut shell flour is 100 mesh.
- 5. a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption according to claim 1, its It is characterised by：The preparation of the activated carbon, including microwave treatment, the microwave treatment, coconut shell flour and liquor zinci chloridi are mixed, The concentration of liquor zinci chloridi is 35%, and the mass ratio of coconut shell flour and zinc chloride is 1:3, using microwave treatment, microwave power is 610w, irradiate 10 minutes, activated carbon is made.
- 6. a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption according to claim 1, its It is characterised by：The activated carbon, iodine number 1350mg/g, methylene blue value 115mg/g, up to 95.2%, carbon tetrachloride adsorbs mesoporous It is worth for 130%, moisture content 2%, ash 1.6%, bulk density 400g/L, specific surface area 1700m2/ g, average pore size 2.5- 2.7nm。
- 7. a kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption according to claim 1, its It is characterised by：The preparation of the adsorption liquid, the chlorine that mass fraction is 3.8%, pH=2.9 is prepared with mercury chloride, hydrochloric acid and desalted water Change mercury salt acid solution, add appropriate palladium bichloride collaboration accelerator, is 1 that mercury chloride and palladium bichloride, which cooperate with the mass ratio of accelerator,: 4；Sulfonic acid between palladium bichloride the collaboration accelerator, including zinc chloride, palladium bichloride, platinum chloride, tetrabutylammonium chloride, triphenylphosphine Potassium, mass ratio 1.8:0.6:0.6:0.5:0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510704051.7A CN105195225B (en) | 2015-10-27 | 2015-10-27 | A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510704051.7A CN105195225B (en) | 2015-10-27 | 2015-10-27 | A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105195225A CN105195225A (en) | 2015-12-30 |
| CN105195225B true CN105195225B (en) | 2017-11-17 |
Family
ID=54943383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510704051.7A Active CN105195225B (en) | 2015-10-27 | 2015-10-27 | A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105195225B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179428B (en) * | 2016-08-12 | 2017-03-22 | 宁夏新龙蓝天科技股份有限公司 | Preparation method of low-mercury catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5912090B2 (en) * | 1978-04-26 | 1984-03-21 | 三井東圧化学株式会社 | Method for recovering vinyl chloride from vinyl chloride vinyl acetate copolymer solution |
| CN102962082A (en) * | 2012-11-26 | 2013-03-13 | 中昊(大连)化工研究设计院有限公司 | Low-mercury catalyst used for synthesizing vinyl chloride |
| CN103551139B (en) * | 2013-11-17 | 2015-08-12 | 那风换 | Ultralow mercury catalyst and production technology thereof |
-
2015
- 2015-10-27 CN CN201510704051.7A patent/CN105195225B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105195225A (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103551139B (en) | Ultralow mercury catalyst and production technology thereof | |
| CN109926044A (en) | A kind of manganese oxide-active carbon composite catalyst and its preparation method and application | |
| CN102786050A (en) | Method for preparing microporous cocoanut active charcoal by pyrolysis and activation | |
| CN109734089A (en) | A kind of high-specific surface area vinasse method for preparation of active carbon | |
| CN102500421B (en) | Preparation method of low-mercury compound catalyst for producing vinyl chloride | |
| CN105060290A (en) | Preparation method of coal-based activated carbon with low ash and high specific surface area | |
| CN105413746B (en) | A kind of preparation of the high ultralow mercury catalyst of catalytic activity and its recovery method | |
| CN101885486A (en) | Technology for producing acid granular activated carbon by air activation method | |
| CN102614829A (en) | Method for preparing mycotoxin adsorbent for efficient carbon silicon feed by taking rice hulls as raw materials | |
| CN105195224B (en) | A kind of preparation method of the good low-mercury catalyst of heat endurance | |
| CN105195184B (en) | A method of low-mercury catalyst is prepared using high mesoporosity activated carbon | |
| CN105195225B (en) | A kind of method for preparing low-mercury catalyst using palladium bichloride collaboration accelerator absorption | |
| CN105251531B (en) | A kind of preparation of ultralow mercury catalyst with long service life and its recovery method | |
| CN105233875B (en) | A kind of preparation method of ultralow mercury catalyst for VCM synthesis | |
| CN108163823A (en) | A kind of method for preparing 4N purity nitric oxide gas | |
| CN107804848A (en) | A kind of preparation method of the straw base porous activated carbon of surface active | |
| JP2006225231A (en) | Activated carbon from chitinous matter as raw material and its manufacturing method | |
| CN107840334A (en) | A kind of atomic hole porous carbon materials and preparation method thereof | |
| CN105771891B (en) | It is a kind of for adsorbing the modified activated carbon preparation method of dioxin | |
| CN102583370B (en) | Production process of phosphate method activated carbon of rotary kiln | |
| CN105195229B (en) | A kind of method that activated carbon using low ash content prepares low-mercury catalyst | |
| CN107128915A (en) | A kind of preparation method of the activated carbon of high absorption capacity | |
| CN114436258B (en) | Preparation method of graphitized porous carbon for removing earthy and musty substances | |
| CN107999136B (en) | Preparation method of solid-phase mercury-free catalyst for chloroethylene synthesis | |
| CN105195230B (en) | A kind of method that low-mercury catalyst is prepared using high iodine number activated carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |