CN104926592A - Method for producing chloroethylene by homogeneous mercury-free catalysis - Google Patents
Method for producing chloroethylene by homogeneous mercury-free catalysis Download PDFInfo
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- CN104926592A CN104926592A CN201510277690.XA CN201510277690A CN104926592A CN 104926592 A CN104926592 A CN 104926592A CN 201510277690 A CN201510277690 A CN 201510277690A CN 104926592 A CN104926592 A CN 104926592A
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- acetylene
- vinylchlorid
- chloroethylene
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Abstract
The invention provides a method for producing chloroethylene by homogeneous mercury-free catalysis. According to the method, acetylene and hydrogen chloride are taken as raw materials and chloroethylene is generated under the effect of a homogeneous catalyst. One or more of PdCl2, AuCl3, FeCl3, ZnCl2 and CuCl2 are taken as catalysts, one or more of NH4Cl, NaCl, KCl, BaCl2, MgCl2 and CaCl2 are taken as cocatalysts, o-nitrochlorobenzene, o-chlorotoluene or o-dichlorobenzene is taken as a solvent, and a homogeneous catalysis system is formed. Under the reaction conditions of normal pressure and temperature of 130 DEG C, the acetylene conversion rate and the chloroethylene selectivity can reach about 95% and more than 95%, and the catalyst life is more than 3,000 hours. The method adopts the nontoxic and mercury-free homogeneous catalyst for producing the chloroethylene, so that a supported catalyst for producing chloroethylene by hydrochlorination of acetylene in existing production is avoided, the problems of easiness for generating carbon deposit sintering and the like in a conventional process carrier are avoided, and homogeneous production of the chloroethylene is realized.
Description
Technical field
The present invention relates to a kind of with acetylene be carbon source, hydrogenchloride for chlorine source homogeneous phase is without the method for mercury catalytic production vinylchlorid, belong to chemical field.
Technical background
Vinylchlorid is a kind of basic industrial chemicals, and its polymkeric substance (PVC) is one of five large general-purpose plastics, has a wide range of applications at numerous areas.Along with the increase gradually of vinylchlorid demand, the Technology that exploitation vinylchlorid is produced has great importance.
At present, global PVC output is more than 5,000 ten thousand t/a, and only the production capacity of Chinese polyvinyl chloride is more than 2,000 ten thousand t/a.Due to resource reason, China's ethylene process technique working rate is obviously not enough, and its production capacity is only about 25% of aggregated capacity, and the production capacity close to 75% derives from carbide acetylene method technique.Carbide acetylene method is produced vinylchlorid and is all adopted loading type mercuric chleride catalyst, due to mercury highly volatile, it to be prevented to be in process of production brought in product impact quality product, simultaneously easily there is carbon distribution sintering thus affect catalytic activity in the method support of the catalyst, and the process of catalyzer and be also a great difficult problem to the pollution at water source.Therefore, developing a kind of catalyzer that is nontoxic or low toxicity, to substitute mercury chloride catalytic production process for vinyl chloride extremely urgent.
Current industrial vinylchlorid production method mainly contains ethylene process, ethane oxychlorination method and acetylene method three kinds.Acetylene method technique synthesizing chloroethylene realizes industrialized technological line the earliest.The thirties in 20th century, Germany scientist makes catalyzer with mercury chloride, and acetylene and hydrogenchloride are reaction raw materials synthesizing chloroethylene, and finally achieve suitability for industrialized production.What this Technology was walked is a typical Coal Chemical Industry Route, first utilize coke and unslaked lime reaction to produce calcium carbide, then with the calcium carbide generated for raw material and water react obtained acetylene, last acetylene and hydrogenchloride is that catalyzer addition obtains vinylchlorid with mercury chloride.This technical matters is simple, it is little to invest, and technology maturation, is applicable to China's development and application, and problem adopts acetylene method to produce vinylchlorid fundamentally to solve mercury pollution.Therefore, the non-mercury catalyst of technique and exploitation asepsis environment-protecting that developing green produces vinylchlorid becomes pendulum problem demanding prompt solution in face of whole vinylchlorid industry, is also foundation stone and the core of the innovation of acetylene method synthesizing polyvinyl chloride resin Technology and Sustainable development.
Large quantifier elimination is had both at home and abroad about the acetylene hydrochlorination reaction exploitation of non-mercury catalyst and the exploitation of vinylchlorid green production process.After the nineties, external most of developed country eliminates carbide acetylene method substantially, uses ethylene process instead, and external research report mainly concentrated on before the nineties.In recent years, due to environmental requirement increasingly stringent, the domestic research in this field enlivens gradually.Nineteen sixty-eight Smith etc. (J.Catal., 1968,11 (2): 113 ~ 130) using metal chloride as active ingredient, SiO
2for carrier, prepared the catalyzer of multiple acetylene gas solid phase hydrogen chlorination reaction by pickling process, 181 DEG C, normal pressure, C
2h
2under the condition of/HCl=l:1.3, find that the hydrochlorinate activity of metal chloride has following order: Hg
2+>Bi
3+>Ni
2+>Zn
2+>Cd
2+>Cu
2+>Mn
2+>Ca
2+.1975 Shinoda (Chem.Lett., 1975,4 (3): 219 ~ 22) at 200 DEG C, C
2h
2/ HCl=l:1.3, air speed 150h
-1under, the activity of 20 various metals muriates/activated-carbon catalyst catalyzing acetylene hydrochlorination is studied, finds that the activity order of different metal ion is: Pd
2+>Hg
2+>Cu
2+>Cu
+>Ag
+.The rugged filial piety hero of rock (JP, clear 51-101905,1976.9.8) iodide exist under, with HAuC1
44H
2o is active precursor, take activated carbon as support of the catalyst, temperature 120 ~ 140 DEG C, and HCl/C
2h
2react under the condition of=1.1, conversion of alkyne 95%, selectivity reaches 99.5%, and within 120 hours, catalyst activity is unchanged, generates in reaction process without acetylene polymer.Within 2008, people such as Sichuan University Jiang Wen big grade discloses patent of invention (CN10124945lA, 2008.8.2), take gac as carrier, with precious metal chloride (any one in Palladous chloride, platinum chloride, gold trichloride or rhodium chloride) and base metal muriate (in cuprous chloride, Cerium II Chloride and bismuth chloride at least one) for active ingredient, pickling process is adopted to prepare the non-mercury catalyst of acetylene hydrochlorination reaction, react in fixed-bed reactor, temperature of reaction 110 ~ 160 DEG C, HCl/C
2h
2=1.05 ~ 1.25, air speed 500 ~ l000h
-1, conversion of alkyne 95 ~ 98%, vinylchlorid selectivity is greater than 99%.Owing to will keep the stable of catalyst activity, need the state of oxidation in the active centre of managing rugged catalyst, the stability of non-mercury catalyst becomes and is difficult to industrialized main cause.In addition, compared with current mercury catalyst, non-mercury catalyst many employings precious metal is active ingredient, and costly, Cost Problems is also the industrialized important factor of restriction non-mercury catalyst to noble metal catalyst price general charged.Therefore, need manage to develop new vinylchlorid production technique, avoid the use of mercury catalyst.
The exploitation report that homogeneous method produces vinylchlorid novel process is less.United States Patent (USP) (US5233108,1993.8.3) is reported, with PdCl
2for catalyzer, Shellsol K and Pramene 81-R is mixed solvent, is made into the catalyst system that fusing point is about 25 DEG C, temperature of reaction 150 DEG C, and pressure 1.5bar, HCl/C
2h
2be react under the condition of 1.17, vinylchlorid space-time yield reaches 122gh
-1l
-1, the selectivity of reaction reaches about 90%.As employing PtCl
2make catalyzer, under similarity condition, vinylchlorid space-time yield reaches 270gh
-1l
-1, the selectivity of reaction is 100%.Japanese Patent (JP, clear 52-136103,1977.11.14) is reported, adopts activated carbon supported gold trichloride and platinum chloride (or Palladous chloride) to be catalyzer, catalyzing acetylene hydrochlorination preparing chloroethylene under liquid-phase condition.With water or whiteruss, clorafin, hexachlorobutadiene, pentaline, diisopropylbenzene(DIPB), the organic solvent such as Chloral Hydrate or ethylene chlorhydrin is respectively as solvent or suspension agent.Platinum ratio is 0.1 ~ 10.Temperature 82 ~ 157 DEG C, air speed 150h
-1, HCl/C
2h
2react under=condition l.2, catalyst life reaches as high as 700 hours, and transformation efficiency about 60%, selectivity is greater than 99.9%.Dichloride content is less than 0.1%.This catalyst system does not have solid polymer to generate, but acetylene can decompose generation black carbon compound, and cause the waste of raw material, improve production cost, and catalyzer is expensive, the black carbon compound of generation can affect the life-span of catalyzer.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of homogeneous phase without the method for mercury catalytic production vinylchlorid.
Realizing technical solution of the present invention is:
Homogeneous phase is without a method for mercury catalytic production vinylchlorid, and the method take acetylene as carbon source, and hydrogenchloride is that chlorine source passes in proportion and is equipped with in the container of homogeneous catalyst, catalyzer effect next step produce vinylchlorid; PdCl selected by described homogeneous catalyst
2, AuCl
3, FeCl
3, ZnCl
2and CuCl
2in one or more be catalyzer, with NH
4cl, NaCl, KCl, BaCl
2, MgCl
2, CaCl
2in one or more be promotor.
Further, described homogeneous catalyst is dissolved in o-Nitrochlorobenzene, ortho-chlorotolu'ene or orthodichlorobenzene solvent, forms homogeneous catalysis system, catalyst P dCl in homogeneous catalysis system
2, AuCl
3, FeCl
3, ZnCl
2and CuCl
2content be: 0.05 ~ 10wt%, promotor NH
4cl, NaCl, KCl, BaCl
2, MgCl
2, CaCl
2content be 0.01 ~ 1wt%.
Further, acetylene and hydrogenchloride mole is 1:1.0 ~ 1.2.
Further, temperature of reaction system is 80 ~ 170 DEG C.
Further, reaction system pressure is normal pressure ~ 0.3MPa.
Final reacting product of the present invention obtains vinylchlorid and acetylene gas mixture after alkali liquor absorption.Reaction product is separated into and is refrigerated to less than-14 DEG C, and vinylchlorid is freezing is liquid, and acetylene is gas, through gas-liquid separation.
Compared with prior art, its remarkable advantage is in the present invention: homogeneous phase of the present invention can reach 97% without conversion of alkyne in the method for mercury catalytic production vinylchlorid, and vinylchlorid selectivity reaches as high as 96%, more than catalyst life 3000h.Produce vinylchlorid according to above-mentioned steps, technique is simple, catalyst levels is few, duration of service is long.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention, but the present invention is not limited to these embodiments.
Embodiment 1
By 2gCuCl
2add in 198g ortho-chlorotolu'ene, stir at 40 DEG C, obtain homogeneous catalyst.By acetylene and hydrogen chloride gas with mol ratio 1:1.2 mixing, 110 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 200h
-1, conversion of alkyne is 2.0%, and vinylchlorid selectivity is 79.4%, catalyst life 200h.
Embodiment 2
By 1gFeCl
3and 1gBaCl
2add in 198g ortho-chlorotolu'ene, stir at 40 DEG C, obtain liquid-phase catalyst.By acetylene and hydrogen chloride gas with mol ratio 1:1 mixing, 110 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 200h
-1, conversion of alkyne is 4.4%, and vinylchlorid selectivity is 65.7%, catalyst life 500h.
Embodiment 3
By 0.4gPdCl
2add in 199.6g orthodichlorobenzene, stir at 40 DEG C, obtain liquid-phase catalyst.By acetylene and hydrogen chloride gas with mol ratio 1:1.2 mixing, 130 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 100h
-1, conversion of alkyne is 96.9%, and vinylchlorid selectivity is 88.6%, catalyst life 3500h.
Embodiment 4
By 0.2gPdCl
2and 0.2gBaCl
2add in 199.6g orthodichlorobenzene, stir at 40 DEG C, obtain liquid-phase catalyst.By acetylene and hydrogen chloride gas with mol ratio 1:1.2 mixing, 110 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 100h
-1, conversion of alkyne is 22.7%, and vinylchlorid selectivity is 70.0%, catalyst life 3000h.
Embodiment 5
By 0.2gPdCl
2and 0.2gNH
4cl adds in 199.6g orthodichlorobenzene, stirs, obtain liquid-phase catalyst at 40 DEG C.By acetylene and hydrogen chloride gas with mol ratio 1:1.2 mixing, 130 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 100h
-1, conversion of alkyne is 11.5%, and vinylchlorid selectivity is 97%, catalyst life 3400h.
Embodiment 6
By 0.2gPdCl
2add in 198g orthodichlorobenzene with 0.05gKCl, stir at 40 DEG C, obtain liquid-phase catalyst.By acetylene and hydrogen chloride gas with mol ratio 1:1.2 mixing, 130 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 100h
-1, conversion of alkyne is 96.0%, and vinylchlorid selectivity is 94.4%, catalyst life 3400h.
Embodiment 7
By 0.2AuCl
3add in 199.8g orthodichlorobenzene, stir at 40 DEG C, obtain liquid-phase catalyst.Acetylene and hydrogen chloride gas are passed in reactor with mol ratio 1:1.2 mixing, raised temperature 130 DEG C, pass under normal pressure and be equipped with in the reactor of liquid-phase catalyst, reaction volume air speed is 200h
-1, conversion of alkyne is 8.6%, and vinylchlorid selectivity is 23.3%, catalyst life 350h.
Claims (5)
1. homogeneous phase is without a method for mercury catalytic production vinylchlorid, it is characterized in that, the method take acetylene as carbon source, and hydrogenchloride is that chlorine source passes in proportion and is equipped with in the container of homogeneous catalyst, catalyzer effect next step produce vinylchlorid; PdCl selected by described homogeneous catalyst
2, AuCl
3, FeCl
3, ZnCl
2and CuCl
2in one or more be catalyzer, with NH
4cl, NaCl, KCl, BaCl
2, MgCl
2, CaCl
2in one or more be promotor.
2. homogeneous phase according to claim 1 is without the method for mercury catalytic production vinylchlorid, it is characterized in that, described homogeneous catalyst is dissolved in o-Nitrochlorobenzene, ortho-chlorotolu'ene or orthodichlorobenzene solvent, forms homogeneous catalysis system, catalyst P dCl in homogeneous catalysis system
2, AuCl
3, FeCl
3, ZnCl
2and CuCl
2content be: 0.05 ~ 10wt%, promotor NH
4cl, NaCl, KCl, BaCl
2, MgCl
2, CaCl
2content be 0.01 ~ 1wt%.
3. homogeneous phase according to claim 2 is without the method for mercury catalytic production vinylchlorid, it is characterized in that, acetylene and hydrogenchloride mole be 1:1.0 ~ 1.2.
4. without the method for mercury catalytic production vinylchlorid, homogeneous phase according to claim 1 is characterized in that temperature of reaction system is 80 ~ 170 DEG C.
5. homogeneous phase according to claim 1 is without the method for mercury catalytic production vinylchlorid, it is characterized in that, reaction system pressure is normal pressure ~ 0.3MPa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492869A (en) * | 2016-10-10 | 2017-03-15 | 厦门中科易工化学科技有限公司 | A kind of non-noble metal mercury-free catalyst for acetylene hydrochlorination reaction and its preparation method and application |
| CN107456989A (en) * | 2017-08-29 | 2017-12-12 | 贵州重力科技环保有限公司 | A kind of high degree of dispersion nanometer catalyst without mercury of acetylene hydrochlorination and preparation method thereof |
| CN108373400A (en) * | 2018-02-05 | 2018-08-07 | 陕西北元化工集团股份有限公司 | A kind of acetylene method VCM synthesis technique |
| CN113582809A (en) * | 2021-08-03 | 2021-11-02 | 厦门中科易工化学科技有限公司 | Method for eliminating hydrogen chloride by using organic chloride |
| CN113582812A (en) * | 2021-08-03 | 2021-11-02 | 厦门中科易工化学科技有限公司 | Method for preparing chloroethylene by liquid phase catalysis |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492869A (en) * | 2016-10-10 | 2017-03-15 | 厦门中科易工化学科技有限公司 | A kind of non-noble metal mercury-free catalyst for acetylene hydrochlorination reaction and its preparation method and application |
| CN106492869B (en) * | 2016-10-10 | 2019-03-19 | 厦门中科易工化学科技有限公司 | A kind of non-noble metal mercury-free catalyst and its preparation method and application for acetylene hydrochlorination reaction |
| CN107456989A (en) * | 2017-08-29 | 2017-12-12 | 贵州重力科技环保有限公司 | A kind of high degree of dispersion nanometer catalyst without mercury of acetylene hydrochlorination and preparation method thereof |
| CN108373400A (en) * | 2018-02-05 | 2018-08-07 | 陕西北元化工集团股份有限公司 | A kind of acetylene method VCM synthesis technique |
| CN108373400B (en) * | 2018-02-05 | 2020-06-30 | 陕西北元化工集团股份有限公司 | Acetylene method chloroethylene synthesis process |
| CN113582809A (en) * | 2021-08-03 | 2021-11-02 | 厦门中科易工化学科技有限公司 | Method for eliminating hydrogen chloride by using organic chloride |
| CN113582812A (en) * | 2021-08-03 | 2021-11-02 | 厦门中科易工化学科技有限公司 | Method for preparing chloroethylene by liquid phase catalysis |
| CN113582809B (en) * | 2021-08-03 | 2024-10-22 | 厦门中科易工化学科技有限公司 | Method for eliminating hydrogen chloride by using organic chloride |
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Application publication date: 20150923 |