CN102069000A - Non-mercury catalyst for production of vinyl chloride and preparation method thereof - Google Patents
Non-mercury catalyst for production of vinyl chloride and preparation method thereof Download PDFInfo
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- CN102069000A CN102069000A CN2010105748025A CN201010574802A CN102069000A CN 102069000 A CN102069000 A CN 102069000A CN 2010105748025 A CN2010105748025 A CN 2010105748025A CN 201010574802 A CN201010574802 A CN 201010574802A CN 102069000 A CN102069000 A CN 102069000A
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Abstract
The invention discloses a non-mercury catalyst for the production of vinyl chloride and a preparation method thereof, belonging to the fields of chemical catalyst and the preparation thereof. The non-mercury catalyst of the invention uses cocoanut active charcoal as carrier and stannous chloride as main active substance, wherein the weight percentage of stannous chloride is 15%-30%; and at least one additive of barium chloride, zinc chloride and copper chloride is added and the total additive weight percentage is 0.5-2%. By using the non-mercury catalyst, the environmental pollution caused by the mercury-containing catalyst can be avoided; the large-scale production can be benefited, the conversion rate and selectivity of the catalyst can be increased, the yield of the product can be increased; by increasing the quality of the carrier, technical guarantee can be provided for the large-scale production device of vinyl chloride, the loss of the active matter can be slowed down, the service life of the catalyst can be prolonged; and the use efficiency of the catalyst can be increased by 500%.
Description
Technical field
The present invention relates to a kind of production catalyst for vinyl chloride, be specifically related to a kind of production vinyl chloride non-mercury catalyst.
Background technology
In the PVC industry,, mainly be two kinds of technologies from present industrialized should being used for---two kinds of carbide acetylene method technology and ethene balancing method technologies.The vinyl chloride that the carbide acetylene method production technology is produced accounts for the 6%-8% of world's vinyl chloride total output; All the other mainly are ethene balancing method explained hereafter.
Carbide is produced the catalyst of vinyl chloride, and mainly being divided into has two kinds of mercury catalyst and non-mercury catalysts.It is carrier with the active carbon exactly mainly that mercury catalyst is arranged, and mercury chloride is main active substances; Non-mercury catalyst mainly is with the catalyst of noble metals such as palladium, platinum as active material.
Analyze from the production actual conditions, mercuric chleride catalyst has following shortcoming: (1), mercury chloride are fast to the synthesizing chloroethylene by acetylene reaction speed, and reaction is fierce, are difficult to control; (2), mercury chloride is a kind of extremely toxic substance; Bigger for environmental pollution; (3), lose activity easily.
Wherein, mercuric chleride catalyst in use, 1), the destruction of toxic gas in the unstripped gas along with the prolongation of service time, its activity is progressively descending, and then causes taking off of catalyst factor alive to mainly contain following 5 aspects:; 2), the foreign material in the production process have stopped up the micropore of catalyst or have been deposited on catalyst surface, and mercury chloride is covered, and make it lose the effect of catalysis; 3), in process of production, the caking of catalyst causes active the reduction; 4), under the reaction temperature condition, the distillation of mercury chloride causes mercury chloride to run off; The excessive mercury chloride that causes of acetylene is reduced into mercury and inactivation when 5), reacting.
Especially along with raising, just increasing for the demand of non-mercury catalyst to environmental requirement.
Someone explores for non-mercury catalyst, such as, application number is 200910228149.4, name is called " a kind of Catalysts and its preparation method that is used for synthesizing chloroethylene by acetylene ", and this patent is to be carrier with the activated carbon, is active component with the chloride that contains 2～15% palladium or gold, 1～5% rare earth-iron-boron is a cocatalyst component, be carried on the pellet type catalyst that makes on the activated carbon through infusion process, more existing mercuric chleride catalyst has higher stability, environmentally safe.In addition, application number is 200810044560.1, name is called the patent application of " can be used for non-mercury catalyst of acetylene hydrochlorination reaction and preparation method thereof ", and disclosed non-mercury catalyst be that the composition of some noble metal and base metal is as active material, equally to not pollution of environment.But, all having used palladium or noble metals such as gold or platinum among both, cost is too high, can not large-scale production.
Nankai University Deng state in 1994 just wait the people proposed with stannous chloride be main active matter as catalyst, but because its impregnation method tradition, its active matter runs off easily.At air speed 30h
-1The time, catalyst life has only 120 hours.
Therefore but, it is little to seek a kind of environmental pollution, is difficult for inactivation, the life-span is long, service efficiency is high production catalyst for vinyl chloride simultaneously and is those skilled in the art and crave for and solve unsolved always problem.
Summary of the invention
It is little to the purpose of this invention is to provide a kind of environmental pollution, is difficult for inactivation, the life-span is long, service efficiency is high production catalyst for vinyl chloride simultaneously.
The technical scheme that the present invention solves the problems of the technologies described above is: a kind of production vinyl chloride non-mercury catalyst, it is carrier that described non-mercury catalyst adopts cocoanut active charcoal, stannous chloride is a main active substances, and wherein, the quality percentage composition of stannous chloride is 15%-30%.
As preferably: also be added with at least a additive in barium chloride, zinc chloride and the copper chloride, described additive level is 0.5-2% by mass percentage.
As preferably: the active carbon of described cocoanut active charcoal for handling through modification.
As further preferred: the method that described cocoanut active charcoal modification is handled is: earlier through overpickling, again through the oven dry of washing back.
Produce the preparation method of above-mentioned vinyl chloride, may further comprise the steps with non-mercury catalyst:
A, dissolving: according to weight ratio weighing active material, be dissolved in the pure water, obtain maceration extract;
B, dipping: the cocoanut active charcoal after will drying places the resulting maceration extract of A step, normal temperature dipping 12～24 hours in calcining under 300～400 ℃ after 3～6 hours immediately;
C, oven dry: evaporating water, dried 8～12 hours down at 120～150 ℃ then, take out the back and cool off standby.
As preferably: in the described A step, active material and pure water equal-volume solution dipping method are used this method and can be saved the step of filtering unnecessary dipping solution, and are convenient to control the content of active component in the catalyst.
As preferably: in the described B step, whole dipping process carries out under ultrasonic environment, frequency of ultrasonic 80～100Hz, make metal active material " locking " on carrier, it is tightr that active matter is combined with carrier, slowed down the loss of active matter, prolonged the service life of catalyst, the catalyst service efficiency improves greatly.
As preferably: in the described C step, evaporating water in water-bath.
As preferably: described B step and C step are all carried out in closed system.
As further preferred: closed system adopts the pressure-fired environmental pressure that is higher than atmospheric pressure 200～400 handkerchiefs.
Owing to adopted technique scheme, beneficial effect of the present invention is:
1, adopting stannous chloride is main active substances, has avoided having the environmental pollution of mercury catalyst; Simultaneously, employing be base metal, be beneficial to large-scale production;
2, composite elements such as barium chloride, zinc chloride and copper chloride have improved the conversion ratio and the selectivity of catalyst greatly, have improved the yield of product;
3, before the dipping, cocoanut active charcoal is carried out modification to be handled, with active carbon by pickling, the washing after, thereby thereby the catalyst poison that has reduced the some or all of removal activated carbon surface of content of inorganic elements and ash content has improved activated carbon supported activity of such catalysts; Simultaneously, reduced the pulverizing probability of catalyst in the course of reaction, slowed down inactivation, prolonged the service life of catalyst, this catalyst is at air speed 35h
-1, under 150 ℃ of conditions of reaction temperature, catalyst life can reach more than 600 hours; The raising of carrier quality is for the maximization device of vinyl chloride production provides technical guarantee;
4, in the catalyst soakage process, adopted locking dipping modification technology, mainly be in whole dipping process, to have used ultrasonic wave, make metal active material " locking " on carrier, it is tightr that active matter is combined with carrier, slowed down the loss of active matter, prolonged the service life of catalyst, the catalyst service efficiency has improved 500%.
5, dipping process and drying course all carry out in closed system, and whole closed system employing pressure-fired, thereby it is more firm to guarantee that activity component impregnation gets, and is not easy to run off.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
8.93g stannous chloride, 0.098g barium chloride, 0.105g zinc chloride and 0.099g copper chloride fully are dissolved in the 90ml pure water, stannous chloride concentration is 0.52mol/L, with the cocoanut active charcoal after the 50g pickling at 100 ℃ down after the oven dry, add immediately in the solvent maceration extract after 3 hours in calcining under 300 ℃ of conditions again.Normal temperature dipping 6 hours, between constantly stir.Evaporating water in 100 ℃ water-bath was dried 10 hours down at 150 ℃ then, took out the back and cooled off standby.This catalyst generates in the reaction of vinyl chloride at hydrogen chloride addition acetylene, and the mol ratio of reaction distribution is C2H2/HCl=1/1.15, air speed 30h
-1, react catalyst amount 50g under 150 ℃ of conditions of reaction temperature, hydrogen chloride soak time 3 hours, analytical reactions tail gas, the conversion ratio that obtains acetylene is more than 98%, the selectivity of vinyl chloride 〉=99%, successive reaction is after 590 hours, and reaction conversion ratio drops to 95.2%.
Embodiment 2
14.28g stannous chloride, 0.206g barium chloride, 0.211g zinc chloride and 0.217g copper chloride fully are dissolved in the 90ml pure water, stannous chloride concentration is 0.84mol/L, with the cocoanut active charcoal after the 50g pickling at 100 ℃ down after the oven dry, add immediately in the solvent maceration extract after 3 hours in calcining under 300 ℃ of conditions again.Normal temperature dipping 6 hours, between constantly stir.Evaporating water in 100 ℃ water-bath was dried 10 hours down at 150 ℃ then, took out the back and cooled off standby.This catalyst generates in the reaction of vinyl chloride at hydrogen chloride addition acetylene, and the mol ratio of reaction distribution is C2H2/HCl=1/1.15, air speed 30h
-1, react catalyst amount 50g under 150 ℃ of conditions of reaction temperature, hydrogen chloride soak time 3 hours, analytical reactions tail gas, the conversion ratio that obtains acetylene is more than 98%, the selectivity of vinyl chloride 〉=99%, successive reaction is after 599 hours, and reaction conversion ratio drops to 95.8%.
Embodiment 3
21.89g stannous chloride, 0.436g barium chloride, 0.441g zinc chloride and 0.432g copper chloride fully are dissolved in the 90ml pure water, stannous chloride concentration is 1.28mol/L, with the cocoanut active charcoal after the 50g pickling at 100 ℃ down after the oven dry, add immediately in the solvent maceration extract after 3 hours in calcining under 300 ℃ of conditions again.Normal temperature dipping 6 hours, between constantly stir.Evaporating water in 100 ℃ water-bath was dried 10 hours down at 150 ℃ then, took out the back and cooled off standby.This catalyst generates in the reaction of vinyl chloride at hydrogen chloride addition acetylene, and the mol ratio of reaction distribution is C2H2/HCl=1/1.15, air speed 30h
-1, react catalyst amount 50g under 150 ℃ of conditions of reaction temperature, hydrogen chloride soak time 3 hours, analytical reactions tail gas, the conversion ratio that obtains acetylene is more than 98%, the selectivity of vinyl chloride 〉=99%, successive reaction is after 620 hours, and reaction conversion ratio drops to 95.4%.
Embodiment 4
19.76g stannous chloride, 0.348g barium chloride, 0.369g zinc chloride fully are dissolved in the 90ml pure water, stannous chloride concentration is 1.16mol/L, cocoanut active charcoal after the 50g pickling after oven dry under 100 ℃, is added in the solvent maceration extract after 3 hours in calcining under 300 ℃ of conditions more immediately.Normal temperature dipping 6 hours, between constantly stir.Evaporating water in 100 ℃ water-bath was dried 10 hours down at 150 ℃ then, took out the back and cooled off standby.This catalyst generates in the reaction of vinyl chloride at hydrogen chloride addition acetylene, and the mol ratio of reaction distribution is C2H2/HCl=1/1.15, air speed 30h
-1, react catalyst amount 50g under 150 ℃ of conditions of reaction temperature, hydrogen chloride soak time 3 hours, analytical reactions tail gas, the conversion ratio that obtains acetylene is more than 98%, the selectivity of vinyl chloride 〉=99%, successive reaction is after 595 hours, and reaction conversion ratio drops to 94.8%.
Embodiment 5
18.83g stannous chloride, 0.348g barium chloride, 0.332g copper chloride fully are dissolved in the 90ml pure water, stannous chloride concentration is 1.11mol/L, cocoanut active charcoal after the 50g pickling after oven dry under 100 ℃, is added in the solvent maceration extract after 3 hours in calcining under 300 ℃ of conditions more immediately.Normal temperature dipping 6 hours, between constantly stir.Evaporating water in 100 ℃ water-bath was dried 10 hours down at 150 ℃ then, took out the back and cooled off standby.This catalyst generates in the reaction of vinyl chloride at hydrogen chloride addition acetylene, and the mol ratio of reaction distribution is C2H2/HCl=1/1.15, air speed 30h
-1, react catalyst amount 50g under 150 ℃ of conditions of reaction temperature, hydrogen chloride soak time 3 hours, analytical reactions tail gas, the conversion ratio that obtains acetylene is more than 98%, the selectivity of vinyl chloride 〉=99%, successive reaction is after 610 hours, and reaction conversion ratio drops to 95.6%.
Embodiment 6
18.97g stannous chloride, 0.328g copper chloride 0.374g zinc chloride fully are dissolved in the 90ml pure water, stannous chloride concentration is 1.12mol/L, cocoanut active charcoal after the 50g pickling after oven dry under 100 ℃, is added in the solvent maceration extract after 3 hours in calcining under 300 ℃ of conditions more immediately.Normal temperature dipping 6 hours, between constantly stir.Evaporating water in 100 ℃ water-bath was dried 10 hours down at 150 ℃ then, took out the back and cooled off standby.This catalyst generates in the reaction of vinyl chloride at hydrogen chloride addition acetylene, and the mol ratio of reaction distribution is C2H2/HCl=1/1.15, air speed 30h
-1, react catalyst amount 50g under 150 ℃ of conditions of reaction temperature, hydrogen chloride soak time 3 hours, analytical reactions tail gas, the conversion ratio that obtains acetylene is more than 98%, the selectivity of vinyl chloride 〉=99%, successive reaction is after 603 hours, and reaction conversion ratio drops to 95.0%.
Claims (10)
1. produce the vinyl chloride non-mercury catalyst for one kind, it is characterized in that: it is carrier that described non-mercury catalyst adopts cocoanut active charcoal, and stannous chloride is a main active substances, and wherein, the quality percentage composition of stannous chloride is 15%-30%.
2. production vinyl chloride non-mercury catalyst according to claim 1 is characterized in that: also be added with at least a additive in barium chloride, zinc chloride and the copper chloride, described additive level is 0.5-2% by mass percentage.
3. production vinyl chloride non-mercury catalyst according to claim 1 is characterized in that: the active carbon of described cocoanut active charcoal for handling through modification.
4. production vinyl chloride non-mercury catalyst according to claim 3 is characterized in that: the method that described cocoanut active charcoal modification is handled is: earlier through overpickling, again through the oven dry of washing back.
5. any described production vinyl chloride of claim 1 to 4 is characterized in that with the preparation method of non-mercury catalyst, may further comprise the steps:
A, dissolving: according to weight ratio weighing active material, be dissolved in the pure water, obtain maceration extract;
B, dipping: the cocoanut active charcoal after will drying places the resulting maceration extract of A step, normal temperature dipping 12～24 hours in calcining under 300～400 ℃ after 3～6 hours immediately;
C, oven dry: evaporating water, dried 8～12 hours down at 120～150 ℃ then, take out the back and cool off standby.
6. the production vinyl chloride according to claim 5 preparation method of non-mercury catalyst is characterized in that: in the described A step, and active material and pure water equal-volume solution impregnation.
7. the production vinyl chloride according to claim 5 preparation method of non-mercury catalyst, it is characterized in that: in the described B step, whole dipping process carries out under ultrasonic environment, frequency of ultrasonic 80～100Hz.
8. the production vinyl chloride according to claim 5 preparation method of non-mercury catalyst is characterized in that: in the described C step, and evaporating water in water-bath.
9. the production vinyl chloride according to claim 5 preparation method of non-mercury catalyst, it is characterized in that: described B step and C step are all carried out in closed system.
10. the production vinyl chloride according to claim 9 preparation method of non-mercury catalyst is characterized in that: closed system adopts the pressure-fired environmental pressure that is higher than atmospheric pressure 200～400 handkerchiefs.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007972A (en) * | 2012-12-26 | 2013-04-03 | 天津大学 | Non-noble metal mercury-free catalyst for hydrochlorination of acetylene and preparation method thereof |
| CN103170372A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene through acetylene gas phase hydrochlorination |
| CN103170371A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN103386315A (en) * | 2013-08-12 | 2013-11-13 | 湖北随州双星生物科技有限公司 | Environment-friendly non-mercury catalyst for acetylene-method chloroethylene synthesis and preparation method thereof |
| CN104415794A (en) * | 2013-08-27 | 2015-03-18 | 天津大学 | Phosphorus modified catalyst carrier, preparation method and application of phosphorus modified catalyst carrier |
| CN106215977A (en) * | 2016-07-25 | 2016-12-14 | 宁夏新龙蓝天科技股份有限公司 | A kind of high synthesis vinyl chloride of activity that is catalyzed is without mercury catalyst and preparation method thereof |
| CN106902851A (en) * | 2017-03-02 | 2017-06-30 | 北京宇极科技发展有限公司 | A kind of catalyst, Its Preparation Method And Use |
| CN110304981A (en) * | 2019-06-06 | 2019-10-08 | 宜宾天原集团股份有限公司 | The method of chloromethanes conversion producing light olefins |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5083303A (en) * | 1973-11-27 | 1975-07-05 | ||
| CN1994564A (en) * | 2006-12-20 | 2007-07-11 | 内蒙古海吉氯碱化工股份有限公司 | Catalyst for producing vinyl chloride |
-
2010
- 2010-12-06 CN CN2010105748025A patent/CN102069000A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5083303A (en) * | 1973-11-27 | 1975-07-05 | ||
| CN1994564A (en) * | 2006-12-20 | 2007-07-11 | 内蒙古海吉氯碱化工股份有限公司 | Catalyst for producing vinyl chloride |
Non-Patent Citations (3)
| Title |
|---|
| 《聚氯乙烯》 19941231 邓国才等 乙炔法合成氯乙烯固相非汞催化剂的研制 5-9 1 , 第6期 * |
| 王芳超等: "炭载体对乙炔氢氯化反应金催化剂催化性能的影响", 《化工进展》 * |
| 邓国才等: "乙炔法合成氯乙烯固相非汞催化剂的研制", 《聚氯乙烯》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170372A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene through acetylene gas phase hydrochlorination |
| CN103170371A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN103007972A (en) * | 2012-12-26 | 2013-04-03 | 天津大学 | Non-noble metal mercury-free catalyst for hydrochlorination of acetylene and preparation method thereof |
| CN103386315A (en) * | 2013-08-12 | 2013-11-13 | 湖北随州双星生物科技有限公司 | Environment-friendly non-mercury catalyst for acetylene-method chloroethylene synthesis and preparation method thereof |
| CN104415794A (en) * | 2013-08-27 | 2015-03-18 | 天津大学 | Phosphorus modified catalyst carrier, preparation method and application of phosphorus modified catalyst carrier |
| CN104415794B (en) * | 2013-08-27 | 2017-03-01 | 天津大学 | A kind of P Modification catalyst carrier and preparation method and application |
| CN106215977A (en) * | 2016-07-25 | 2016-12-14 | 宁夏新龙蓝天科技股份有限公司 | A kind of high synthesis vinyl chloride of activity that is catalyzed is without mercury catalyst and preparation method thereof |
| CN106902851A (en) * | 2017-03-02 | 2017-06-30 | 北京宇极科技发展有限公司 | A kind of catalyst, Its Preparation Method And Use |
| CN106902851B (en) * | 2017-03-02 | 2019-08-02 | 北京宇极科技发展有限公司 | A kind of catalyst, Its Preparation Method And Use |
| CN110304981A (en) * | 2019-06-06 | 2019-10-08 | 宜宾天原集团股份有限公司 | The method of chloromethanes conversion producing light olefins |
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Application publication date: 20110525 |