CN102336631B - Method for preparing chloroethylene by acetylene method and prolonging service life of gold-containing catalyst - Google Patents
Method for preparing chloroethylene by acetylene method and prolonging service life of gold-containing catalyst Download PDFInfo
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- CN102336631B CN102336631B CN2011101996529A CN201110199652A CN102336631B CN 102336631 B CN102336631 B CN 102336631B CN 2011101996529 A CN2011101996529 A CN 2011101996529A CN 201110199652 A CN201110199652 A CN 201110199652A CN 102336631 B CN102336631 B CN 102336631B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing chloroethylene by an acetylene method and prolonging the service life of a gold-containing catalyst. The method comprises the following steps of: (1) loading the gold-containing catalyst in a reactor; (2) introducing hydrogen chloride and acetylene into the reactor, performing hydrochlorination for 1 to 500 hours, and stopping introducing raw gases when the conversion rate of the acetylene declines; (3) introducing the regenerated gas of the catalyst into the reactor, and stopping introducing the regenerated gas of the catalyst at the temperature of between 120 and 160 DEG C under the pressure of 0 to 0.4MPa in 5 to 90 minutes; and (4) repeating the steps (2)-(3) till the conversion rate of the acetylene does not obviously decline. The gold-containing catalyst with low load is used for acetylene hydrochlorination, and in-situ continuous regeneration of the gold-containing catalyst is realized by unsteady operation, so that the service life of the gold-containing catalyst is prolonged on the basis of relatively high acetylene selectivity and selectivity.
Description
Technical field
The present invention relates to a kind of prolongation and prepare the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life.
Background technology
Pvc material, is widely used in the every profession and trade field in many-sided excellent performance such as physicals, chemical stability due to it, is purposes one of general-purpose plastics the most widely in the world.Polyvinyl chloride (PVC) is polymerized by vinyl chloride monomer (vinyl chloride, VCM).The industrial process of vinyl chloride monomer mainly contains process for oxychlorination of ethylene and acetylene calcium carbide route.Advantage in developed countries such as Great Britain and Americas due to petroleum industry, mainly with process for oxychlorination of ethylene, produce vinylchlorid, and the output of production of vinyl chloride by calcium carbide method is only tens percent of whole world ultimate production.But along with the world petroleum resource reserves reduce gradually, crude oil price is constantly high in recent years, the acetylene calcium carbide route that the coal of take is raw material obtains the increasing concern of investigators.Because China is the country that prospective oil is less, coal resources are relatively abundant, so calcium carbide route becomes one of main method of China PVC production.
Current industrial calcium carbide route acetylene hydrochlorination technique is mainly on the catalyzer that active ingredient, gac are carrier, to adopt acetylene and HCl that gas-solid occurs to be summed into and react generation vinylchlorid take mercury chloride.Principal reaction is as follows:
C
2H
2+HCl→CH
2＝CHCl+124.8kJ/mol
Its commercial catalysts, since the forties in 20th century, has adopted HgCl always
2/ activated-carbon catalyst, this heterogeneous catalytic reaction requires at high temperature to carry out (170～180 ℃).Due to HgCl
2vapour pressure is high, and in reaction process, catalyzer easily distils and causes inactivation, and the mercury chloride of loss can cause murder by poisoning to biological and environment.Mercury chloride catalyzing acetylene method is produced the main deficiency of process for vinyl chloride: after the catalyzer more renewed in 1, producing, the palpus maintenance is 7～20 days, and impact is produced; 2, due to mercury ion be physical adsorption on the inwall of activated carbon duct, thermostability is very poor, sublimation is fast, generally produces the mercury catalyst that 1 ton of vinylchlorid will consume 1.4～1.7kg, Production Life is short; 3, because running off, mercury enters atmosphere, contaminate environment.Therefore, the non-mercury acetylene hydrochlorination reaction of environment-friendly type is all the innovation of calcium carbide process PVC industrial technology and Green Sustainable problem demanding prompt solution with the selection of catalyst development, novel catalyst carrier.
The solid phase non-mercury catalyst active metal component of having reported mainly concentrates on Precious Metals-Gold, palladium (Au, Pd) etc., initial Hutchings[1] the hydrochlorinate catalytic activity of having tested the metal chloride of a series of carbon loads, confirmed loading type Au in research
3+effective acetylene hydrochlorination catalyzer.Strebelle[2] to PdCl
2catalytic activity studied, its acetylene hydrochlorination yield is 57%, selectivity is 96%; Mitchenko[3,4] proved equally Pd
2+catalytic activity; Song[5] adopt pickling process to prepare PdCl
2/ coconut husk type activated-carbon catalyst.Except gold, palladium, to acetylene hydrochlorination, reaction has activity: Cu to multiple transition metal
+[6], Pt
2+[7], Rh
3+[8,9], Ir
3+[9], Ru
3+[8,9] etc.For obtaining the acetylene hydrochlorination non-mercury catalyst of high reactivity, high stability, investigators have considered the catalyzer that various metals is compound.Conte[8] studied and added Pd in Au, Ir, Rh, Pt, the metals such as Ru are studied its acetylene hydrochlorination activity; Jiang Wenwei [10] has developed a kind of PtCl of containing
2, PdCl
2or AuCl
2precious metal and BiCl
2, the base metal such as CuCl non-mercury catalyst; Japanese Patent [11] is reported in AuCl
3and PtCl
2and/or PdCl
2for catalytic active component loads on gac, in the organic solvents such as water or whiteruss, HCl, diisopropylbenzene(DIPB), Chloral Hydrate and ethylene chlorhydrin, prepare vinylchlorid.Although, along with going deep into of research, the catalytic activity that contains Au catalyst improves constantly, and even can reach industrial level, the life-span short (generally only having several hours) that contains Au catalyst is that it realizes industrialized bottleneck problem always.Nkosi[12] the research supported Au catalysts that shows inactivation can use HCl regeneration, and he carries out in-situ regeneration by add NO in material mixed gas to inactivation Au catalyzer again subsequently, can make the catalyzer activity recovery.In addition, Conte[13 in 2008] also proved also can only have for the regeneration of decaying catalyst<1% active ingredient loss of chloroazotic acid, the catalyst selectivity after regeneration can reach more than 99.9%.Although investigators find the Au catalyzer of inactivation and can be reproduced, but regenerative process complexity, and the catalyzer after regeneration is inactivation again very soon, can't realize cyclic regeneration, so hydrochlorination is to solve containing the industrialized key of Au catalyst containing the regeneration of Au catalyst.
Reference:
[1]Hutchings?G.Vapor?phase?hydrochlorination?of?acetylene-Correlation?of?catalyticn?activity?of?supported?metal?chloride?catalysts.J?Catal，1985，96：292-295
[2]Strebelle?M，Devos?A.US?Patent，5254777，1993-10-19
[3]Mitchenko?S?A，Krasnyakova?T?V，Zhikharev?I?V.Kinetics?and?mechanism?of?catalyic?acetylene?hydrochlorination?with?gaseous?HCl?on?the?surface?of?mechanically?activated?K
2PdCl
4.Kinetika?i?Kataliz，2009，50：734-740
[4]Mitchenko?S?A，Krasnyakova?T?V，Zhikharev?I?V.Effect?of?mechanicochemical?treatment?on?the?activity?of?K2PdCl4?in?the?heterogeneous?catalytic?hydrochlorination?of?acetylene.Theor?Exp?Chem，2010，46：32-38
[5]Song?Q?L，Wang?S?J，Shen?B?X，Zhao?J?G.Palladium-based?catalysts?for?the?hydrochlorination?of?acetylene：Reasons?for?deactivation?and?its?regeneration.Pet?Sci?Technol，2010，28：1825-1833
[6]Wang?S?J，Shen?B?x，Song?Q?L.Kinetics?of?acetylene?hydrochlorination?over?bimetallic?Au-Cu/C?catalyst.Catal?Lett，2010，134：102-109
[7]Mitchenko?S?A，Krasnyakova?T?V，Mitchenko?R?S，Korduban?A?N.Acetylene?catalytic?hydrochlorination?over?powder?catalyst?prepared?by?pre-milling?of?K
2PtCl
4?salt.J?Mol?Catal?A：Chem，2007，275：101-108
[8]Conte?M，Carley?A?F，Attard?G，Herzing?A?A，KieLy?C?J，Hutchings?G?J.Hydrochlorination?of?acetylene?using?supported?bimetallic?Au-based?catalysts.J?Catal，2008，257：190-198
[9]Nkosi?B，Conville?N?J，Hutchings?G?J.Vapour?Phase?Hydrochlorination?of?Acetylene?with?Group?VIII?and?IB?Metal?Chloride?Catalysts.Appl?Catal，1988，43：33-39
[10] Jiang Wenwei, Yang Qin, sieve a kind of reed mentioned in ancient books, Jingjing LI. Chinese patent, 101249451,2008-8-27.
[11]Okuda?N，Ueha?Y，Okura?K，Hisagai?Y.JP?Patent，5213610A，1993-08-24
[12]Nkosi?B，Conville?N?J，Hutchings?G?J.Hydrochlorination?of?actylene?using?gold?catalysts：A?study?of?catalyst?deactivation.J?Catal，1991，128：366-377
[13]Conte?M，Carley?A?F，Hutchings?G?J.Reactivation?of?a?carbon-supported?gold?catalyst?for?the?hydrochlorination?of?acetylene.Catal?Lett，2008，124：165-167
Summary of the invention
The objective of the invention is to provide for the deficiencies in the prior art a kind of prolongation to prepare the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life.
Technical scheme of the present invention is summarized as follows:
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, it is characterized in that comprising the steps:
(1) in reactor, load containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene be in molar ratio 1.05～1.20: 1 ratio, air speed is 12～360mlml
cat -1h
-1condition under pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, carries out hydrochlorination 1～500h, or conversion of alkyne stops passing into described unstripped gas while starting to descend;
(3) catalyst regeneration gas be take to air speed as 12～360mlml
cat -1h
-1pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, and the time is 5～90min, stops passing into catalyst regeneration gas;
(4) repeating step (2)-(3), until conversion of alkyne obviously descends.
The second extends the method for preparing vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprises the steps:
(1) in reactor, load containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene be in molar ratio 1.05～1.20: 1 ratio, air speed is 12～360mlml
cat -1h
-1condition under pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, carries out hydrochlorination 1h～conversion of alkyne while starting to descend, and catalyst regeneration gas be take to air speed as 12～360mlml
cat -1h
-1pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, and the time is 5～90min, stops passing into catalyst regeneration gas;
(3) repeating step (2) is until obviously decline of conversion of alkyne.
The preferred fixed-bed reactor of reactor, can also select fluidized-bed reactor or moving-burden bed reactor.
Described catalyst regeneration gas is chlorine, hydrogenchloride, ammonium chloride.
The described Au catalyst that contains includes gold element, lanthanum element, cobalt element, help catalytic metal element and the carrier with porous microstructure, described lanthanum element, cobalt element, to help the mol ratio of catalytic metal element and gold element be 1～10: 1～10: 0～10: 1, gold accounts for 0.3%～2% of described catalyst quality, and in described catalyzer, to take gold trichloride or nitric acid gold be source to gold element; Described cobalt element is that to take the muriate of cobalt or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES be source; It is source that described lanthanum element be take Lanthanum trichloride or lanthanum nitrate, and the described preparation method containing Au catalyst is:
(1) calculate: down payment accounts for containing Au catalyst quality 0.3%～2%, at lanthanum element, cobalt element, to help the mol ratio of catalytic metal element and gold element be 1～10: 1～10: during 0～10: 1 ratio, calculate to adopt the required gold trichloride of equi-volume impregnating or nitric acid gold, cobalt muriate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Lanthanum trichloride or lanthanum nitrate, help catalytic metal element muriate or/and nitrate and there is the quality of carrier of porous microstructure and the volume of chloroazotic acid taken or measured;
(2) preparation dipping mother liquor: by muriate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Lanthanum trichloride or the lanthanum nitrate of described gold trichloride or nitric acid gold, cobalt, help the muriate of catalytic metal element or/and nitrate is dissolved in described chloroazotic acid, be mixed with the dipping mother liquor of homogeneous;
(3) add the carrier with porous microstructure in described dipping mother liquor; Maybe will flood mother liquor and pour into and fill in the container with porous microstructure carrier, carry out incipient impregnation, make to flood the described carrier with porous microstructure of the complete submergence of mother liquor, flood under 25～90 ℃ 0.5～16 hour; 80～180 ℃ of lower ageings 8～24 hours, obtain catalyst precursor;
(4) by described catalyst precursor 120～160 ℃, activate 0.5～3 hour in hydrogenchloride, make a kind of acetylene method prepare vinylchlorid containing Au catalyst.
Described help catalytic metal element be help catalytic metal element muriate or/and nitrate be the source, described help catalytic metal element be potassium, sodium, bismuth, iron, nickel, copper and zinc metallic element at least one.
The described carrier with porous microstructure is gac, silicon-dioxide, silicon carbide or molecular sieve.
The muriate of described cobalt is CoCl
26H
2o, Co (NH
3)
6cl
36H
2o or CoCl
3.
Containing Au catalyst, can also be to include gold element, help catalytic metal element and there is the carrier of porous microstructure; Described gold element take golden halogenide or the gold complex compound be source, gold accounts for containing 0.05～2% of Au catalyst weight; The described catalytic metal element that helps is potassium, barium, copper, zinc, nickel, bismuth, calcium, lithium or caesium, and the described catalytic metal element that helps be take its muriate, acetate or vitriol as source; The described carrier with porous microstructure is gac, molecular sieve or silica gel; Described muriate, acetate or the vitriol of catalytic metal element of helping accounts for described 0.1～5% of the Au catalyst weight that contains, by pickling process, prepared by the described Au catalyst that contains.
Method advantage of the present invention is: use low charge capacity to carry out the acetylene hydrochlorination reaction containing Au catalyst, by unstable state, operate, realize the original position cyclic regeneration containing Au catalyst, thereby, in higher acetylene selectivity with optionally on basis, extend the work-ing life that contains Au catalyst.
Embodiment
Describe the present invention in detail below by embodiment.But the present invention is confined to this never in any form, this catalyzer also can be used for fluidized-bed, moving-burden bed reactor.
Embodiment 1
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 1%;
By 0.2124g HAuCl
44H
2o is dissolved in the 12ml chloroazotic acid, according to the Co/Au mol ratio, is to add CoCl at 1: 1
26H
2o, La/Au mol ratio are to add LaCl at 2: 1
3, the Cu/Au mol ratio is to add CuCl at 2: 1
2, and stir, treat that solid all dissolves to obtain the dipping mother liquor; The 10g absorbent charcoal carrier is poured in the dipping mother liquor made, dipping after 16 hours under 25 ℃, 140 ℃ of lower ageings 8 hours, take out cooling standbyly, obtains catalyst precursor; In 120 ℃ of lower hydrogenchloride, activation obtains AuCl in 3 hours
3the catalyzer that charge capacity is 1%.
Embodiment 2
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 0.3%;
By 0.0630g HAuCl
44H
2o is dissolved in the 15ml chloroazotic acid, according to the Co/Au mol ratio, is to add Co (NO at 2: 1
3)
2, the La/Au mol ratio is to add La (NO at 1: 1
3)
3, the Ni/Au mol ratio is to add Ni (NO at 2: 1
3)
2, and stir, treat that solid all dissolves to obtain the dipping mother liquor; Self-control molecular sieve carrier in 10g laboratory is poured in the dipping mother liquor made, and dipping after 0.5 hour under 90 ℃, 120 ℃ of lower ageings 12 hours, take out cooling standbyly, obtains catalyst precursor; Within 0.5 hour, obtain AuCl 140 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 0.3%.
Embodiment 3
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 2%;
By 0.4247g HAuCl
44H
2o is dissolved in the 14ml chloroazotic acid, according to the Co/Au mol ratio, is to add CoCl at 10: 1
3(by the literature method preparation), La/Au mol ratio are to add La (NO at 2: 1
3)
3, the Na/Au mol ratio is to add NaCl at 2: 1, and stirs, treat that solid all dissolves to obtain the dipping mother liquor; The dipping mother liquor made is poured into and filled 10g SiO
2in the container of carrier, under 70 ℃, dipping, after 12 hours, 90 ℃ of lower ageings 16 hours, takes out cooling standbyly, obtains catalyst precursor; Within 1 hour, obtain AuCl 140 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 2%.
Embodiment 4
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 1%;
By 0.2124g HAuCl
44H
2o is dissolved in the 12ml chloroazotic acid, according to the Co/Au mol ratio, is to add Co (NH at 2: 1
3)
6cl
36H
2o, La/Au mol ratio are to add LaCl at 1: 1
3,, and stir, treat that solid all dissolves to obtain the dipping mother liquor; The 10g absorbent charcoal carrier is poured in the dipping mother liquor made, under 70 ℃, dipping, after 14 hours, 140 ℃ of lower ageings 12 hours, takes out cooling standbyly, obtains catalyst precursor; Within 0.5 hour, obtain AuCl 140 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 1%.
Embodiment 5
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 1%;
By 0.2124g HAuCl
44H
2o is dissolved in the 14ml chloroazotic acid, according to the Co/Au mol ratio, is to add Co (NH at 2: 1
3)
6cl
36H
2o, La/Au mol ratio are to add La (NO at 10: 1
3)
3, the Bi/Au mol ratio is to add Bi (NO at 4: 1
3)
2, and stir, treat that solid all dissolves to obtain the dipping mother liquor; The 10g Carboround is poured in the dipping mother liquor made, under 80 ℃, dipping, after 10 hours, 180 ℃ of lower ageings 10 hours, takes out cooling standbyly, obtains catalyst precursor; Within 0.5 hour, obtain AuCl 160 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 1%.
Embodiment 6
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 1%;
By 0.2124g HAuCl
44H
2o is dissolved in the 12ml chloroazotic acid, according to the Co/Au mol ratio, is to add CoCl at 2: 1
26H
2o, La/Au mol ratio are to add LaCl at 1: 1
3, the K/Au mol ratio is to add KCl at 1: 1, and stirs, treat that solid all dissolves to obtain the dipping mother liquor; 10g MCM-41 type molecular sieve carrier is poured in the dipping mother liquor made, and under 60 ℃, dipping, after 14 hours, 80 ℃ of lower ageings 24 hours, takes out cooling standbyly, obtains catalyst precursor; Within 0.5 hour, obtain AuCl 120 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 1%.
Embodiment 7
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 1%;
By 0.2578g HAu (NO
3)
43H
2o is dissolved in the 12ml chloroazotic acid, according to the Co/Au mol ratio, is to add Co (NH at 2: 1
3)
6cl
36H
2o, La/Au mol ratio are to add LaCl at 1: 1
3, the Zn/Au mol ratio is to add Zn (NO at 2: 1
3)
2, the Fe/Au mol ratio is to add FeCl at 2: 1
3and stir, treat that solid all dissolves to obtain the dipping mother liquor; The 10g absorbent charcoal carrier is poured in the dipping mother liquor made, under 70 ℃, dipping, after 14 hours, 140 ℃ of lower ageings 12 hours, takes out cooling standbyly, obtains catalyst precursor; Within 0.5 hour, obtain AuCl 140 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 1%.
Embodiment 8
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
As calculated: gold account for acetylene method prepare vinylchlorid when the Au catalyst quality 1%;
By 0.2124g HAuCl
44H
2o is dissolved in the 12ml chloroazotic acid, according to the Co/Au mol ratio, is to add Co (NH at 2: 1
3)
6cl
36H
2o, La/Au mol ratio are to add LaCl at 1: 1
3,, and stir, treat that solid all dissolves to obtain the dipping mother liquor; The 10g absorbent charcoal carrier is poured in the dipping mother liquor made, under 70 ℃, dipping, after 14 hours, 140 ℃ of lower ageings 12 hours, takes out cooling standbyly, obtains catalyst precursor; Within 0.5 hour, obtain AuCl 140 ℃ of lower hydrogenchloride activation
3the catalyzer that charge capacity is 1%.
Embodiment 9
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 5 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.05: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 160 ℃, gauge pressure is 0MPa, carries out hydrochlorination 500h, stops passing into described unstripped gas:
(3) by catalyst regeneration gas NH
4cl is 36mlml in air speed
cat -1h
-1pass in fixed-bed reactor, at 160 ℃, gauge pressure is 0MPa, and the time is 15min, stops passing into NH
4cl:
(4) repeating step (2)-(3), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.8%, the selectivity of vinylchlorid is greater than 99.9%, conversion of alkyne (reaction the has been carried out 3800 hours) stopped reaction that obviously descends, now, catalyst life reaches 3800 hours.
Embodiment 10
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 6 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.10: 1 in molar ratio, air speed is 360mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 120 ℃, gauge pressure is 0.4MPa, carries out hydrochlorination 1h, stops passing into described unstripped gas:
(3) by catalyst regeneration gas HCl, in air speed, be 360mlml
cat -1h
-1pass in fixed-bed reactor, at 160 ℃, gauge pressure is 0.2MPa, and the time is 90min, stops passing into HCl:
(4) repeating step (2)-(3), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 99.1%, and the selectivity of vinylchlorid is greater than 99.9%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 5000 hours.
Embodiment 11
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 7 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0.4MPa, carries out hydrochlorination, stops passing into described unstripped gas when conversion of alkyne starts to descend:
(3) by catalyst regeneration gas Cl
2in air speed, be 360mlml
cat -1h
-1pass in fixed-bed reactor, at 140 ℃, gauge pressure is 0.4MPa, and the time is 30min, stops passing into Cl
2:
(4) repeating step (2)-(3), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.2%, and the selectivity of vinylchlorid is greater than 98.9%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 4200 hours.
Embodiment 12
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 8 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0MPa, carries out hydrochlorination 10h, stops passing into described unstripped gas:
(3) by catalyst regeneration gas Cl
2in air speed, be 36mlml
cat -1h
-1pass in fixed-bed reactor, at 140 ℃, gauge pressure is 0MPa, and the time is 30min, stops passing into Cl
2:
(4) repeating step (2)-(3), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.2%, and the selectivity of vinylchlorid is greater than 99.6%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 5200 hours.
Embodiment 13
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load prepared by 3g (Chinese patent CN102029189A embodiment 3) in fixed-bed reactor containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0MPa, carries out hydrochlorination 10h, stops passing into described unstripped gas:
(3) by catalyst regeneration gas Cl
2in air speed, be 36mlml
cat -1h
-1pass in fixed-bed reactor, at 140 ℃, gauge pressure is 0MPa, and the time is 30min, stops passing into Cl
2:
(4) repeating step (2)-(3), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 97.8%, and the selectivity of vinylchlorid is greater than 99.2%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 4100 hours.
Embodiment 14
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 5 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.05: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 160 ℃, gauge pressure is 0MPa, carries out hydrochlorination 500h, by catalyst regeneration gas NH
4cl be take air speed as 36mlml
cat -1h
-1pass in described reactor, at 160 ℃, gauge pressure is 0MPa, and the time is 15min, stops passing into catalyst regeneration gas NH
4cl;
(3) repeating step (2) analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.5%, and the selectivity of vinylchlorid is greater than 99.7%, conversion of alkyne (reaction the has been carried out 4000 hours) stopped reaction that obviously descends, now, catalyst life reaches 4000 hours.
Embodiment 15
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 6 preparations in fixed-bed reactor;
(1) just unstripped gas hydrogenchloride and acetylene are the ratio of 1.10: 1 in molar ratio, and air speed is 360mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 120 ℃, gauge pressure is 0.4MPa, carries out hydrochlorination 1h, and catalyst regeneration gas HCl be take to air speed as 360mlml
cat -1h
-1pass in fixed-bed reactor, at 160 ℃, gauge pressure is 0.2MPa, and the time is 90min, stops passing into catalyst regeneration gas HCl;
(2) repeating step (2), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 99.7%, and the selectivity of vinylchlorid is greater than 99.9%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 5100 hours.
Embodiment 16
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 7 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0.4MPa, carries out hydrochlorination to conversion of alkyne while starting to descend, by catalyst regeneration gas Cl
2take air speed as 360mlml
cat -1h
-1pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0.4MPa, and the time is 30min, stops passing into catalyst regeneration gas Cl
2;
(3) repeating step (2), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.9%, and the selectivity of vinylchlorid is greater than 99.2%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 4800 hours.
Embodiment 17
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load the Au catalyst that contains of 3g embodiment 8 preparations in fixed-bed reactor;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0MPa, carries out hydrochlorination 10h, by catalyst regeneration gas Cl
2take air speed as 36mlml
cat -1h
-1pass in described reactor, at 140 ℃, gauge pressure is 0MPa, and the time is 30min, stops passing into catalyst regeneration gas Cl
2;
(3) repeating step (2), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 99.6%, and the selectivity of vinylchlorid is greater than 99.6%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 5200 hours.
Embodiment 18
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(2) load prepared by 3g (Chinese patent CN102029189A embodiment 9) in fixed-bed reactor containing Au catalyst;
(3) just unstripped gas hydrogenchloride and acetylene are the ratio of 1.10: 1 in molar ratio, and air speed is 360mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 120 ℃, gauge pressure is 0.4MPa, carries out hydrochlorination 1h, and catalyst regeneration gas HCl be take to air speed as 360mlml
cat -1h
-1pass in fixed-bed reactor, at 160 ℃, gauge pressure is 0.2MPa, and the time is 90min, stops passing into catalyst regeneration gas HCl;
(4) repeating step (2), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.7%, and the selectivity of vinylchlorid is greater than 99.2%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 4000 hours.
Embodiment 19
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load prepared by 3g (CN101947465A embodiment 2) in fixed-bed reactor containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0.4MPa, carries out hydrochlorination to conversion of alkyne while starting to descend, by catalyst regeneration gas Cl
2take air speed as 360mlml
cat -1h
-1pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0.4MPa, and the time is 30min, stops passing into catalyst regeneration gas Cl
2;
(3) repeating step (2), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 98.2%, and the selectivity of vinylchlorid is greater than 99.6%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 4500 hours.
Embodiment 20
A kind of prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, comprise the steps:
(1) load prepared by 3g (CN101947465A embodiment 6) in fixed-bed reactor containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.15: 1 in molar ratio, air speed is 36mlml
cat -1h
-1condition under pass in described fixed-bed reactor, at 140 ℃, gauge pressure is 0MPa, carries out hydrochlorination 10h, by catalyst regeneration gas Cl
2take air speed as 36mlml
cat -1h
-1pass in described reactor, at 140 ℃, gauge pressure is 0MPa, and the time is 30min, stops passing into catalyst regeneration gas Cl
2;
(3) repeating step (2), analytical reaction tail gas, the transformation efficiency that obtains acetylene can reach 99.7%, and the selectivity of vinylchlorid is greater than 99.2%, the conversion of alkyne stopped reaction that obviously descends, catalyst life reaches 4200 hours.
Experiment showed, and adopt fluidized-bed reactor or moving-burden bed reactor also can complete the present invention, but the parameter of reaction to be done suitable adjustment.
Claims (6)
1. a prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, it is characterized in that comprising the steps:
(1) in reactor, load containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.05～1.20:1 in molar ratio, air speed is 12～360mlml
cat -1h
-1condition under pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, carries out hydrochlorination 1～500h, or conversion of alkyne stops passing into described unstripped gas while starting to descend;
(3) catalyst regeneration gas be take to air speed as 12～360mlml
cat -1h
-1pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, and the time is 5～90min, stops passing into catalyst regeneration gas;
(4) repeating step (2)-(3), until conversion of alkyne obviously descends;
The described Au catalyst that contains includes gold element, lanthanum element, cobalt element, help catalytic metal element and the carrier with porous microstructure, described lanthanum element, cobalt element, to help the mol ratio of catalytic metal element and gold element be 1～10:1～10:0～10:1, gold accounts for 0.3%～2% of described catalyst quality, and in described catalyzer, to take gold trichloride or nitric acid gold be source to gold element; Described cobalt element is that to take the muriate of cobalt or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES be source; It is source that described lanthanum element be take Lanthanum trichloride or lanthanum nitrate, and the described preparation method containing Au catalyst is:
(1) calculate: down payment accounts for containing Au catalyst quality 0.3%～2%, at lanthanum element, cobalt element, while helping the ratio that the mol ratio of catalytic metal element and gold element is 1～10:1～10:0～10:1, calculate to adopt the required gold trichloride of equi-volume impregnating or nitric acid gold, cobalt muriate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Lanthanum trichloride or lanthanum nitrate, help catalytic metal element muriate or/and nitrate and there is the quality of carrier of porous microstructure and the volume of chloroazotic acid taken or measured;
(2) preparation dipping mother liquor: by muriate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Lanthanum trichloride or the lanthanum nitrate of described gold trichloride or nitric acid gold, cobalt, help the muriate of catalytic metal element or/and nitrate is dissolved in described chloroazotic acid, be mixed with the dipping mother liquor of homogeneous;
(3) add the carrier with porous microstructure in described dipping mother liquor; Maybe will flood mother liquor and pour into and fill in the container with porous microstructure carrier, carry out incipient impregnation, make to flood the described carrier with porous microstructure of the complete submergence of mother liquor, flood under 25～90 ℃ 0.5～16 hour; 80～180 ℃ of lower ageings 8～24 hours, obtain catalyst precursor;
(4) by described catalyst precursor 120～160 ℃, activate 0.5～3 hour in hydrogenchloride, make a kind of acetylene method prepare vinylchlorid containing Au catalyst; Described help catalytic metal element be help catalytic metal element muriate or/and nitrate be the source, described help catalytic metal element be potassium, sodium, bismuth, iron, nickel, copper and zinc metallic element at least one.
2. a prolongation prepares the method for vinylchlorid containing the acetylene method in Au catalyst work-ing life, it is characterized in that comprising the steps:
(1) in reactor, load containing Au catalyst;
(2) by unstripped gas hydrogenchloride and acetylene, be the ratio of 1.05～1.20:1 in molar ratio, air speed is 12～360mlml
cat -1h
-1condition under pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, carries out hydrochlorination 1h～conversion of alkyne while starting to descend, and catalyst regeneration gas be take to air speed as 12～360mlml
cat -1h
-1pass in described reactor, at 120～160 ℃, gauge pressure is 0～0.4MPa, and the time is 5～90min, stops passing into catalyst regeneration gas;
(3) repeating step (2) is until obviously decline of conversion of alkyne;
The described Au catalyst that contains includes gold element, lanthanum element, cobalt element, help catalytic metal element and the carrier with porous microstructure, described lanthanum element, cobalt element, to help the mol ratio of catalytic metal element and gold element be 1～10:1～10:0～10:1, gold accounts for 0.3%～2% of described catalyst quality, and in described catalyzer, to take gold trichloride or nitric acid gold be source to gold element; Described cobalt element is that to take the muriate of cobalt or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES be source; It is source that described lanthanum element be take Lanthanum trichloride or lanthanum nitrate, and the described preparation method containing Au catalyst is:
(1) calculate: down payment accounts for containing Au catalyst quality 0.3%～2%, at lanthanum element, cobalt element, while helping the ratio that the mol ratio of catalytic metal element and gold element is 1～10:1～10:0～10:1, calculate to adopt the required gold trichloride of equi-volume impregnating or nitric acid gold, cobalt muriate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Lanthanum trichloride or lanthanum nitrate, help catalytic metal element muriate or/and nitrate and there is the quality of carrier of porous microstructure and the volume of chloroazotic acid taken or measured;
(2) preparation dipping mother liquor: by muriate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Lanthanum trichloride or the lanthanum nitrate of described gold trichloride or nitric acid gold, cobalt, help the muriate of catalytic metal element or/and nitrate is dissolved in described chloroazotic acid, be mixed with the dipping mother liquor of homogeneous;
(3) add the carrier with porous microstructure in described dipping mother liquor; Maybe will flood mother liquor and pour into and fill in the container with porous microstructure carrier, carry out incipient impregnation, make to flood the described carrier with porous microstructure of the complete submergence of mother liquor, flood under 25～90 ℃ 0.5～16 hour; 80～180 ℃ of lower ageings 8～24 hours, obtain catalyst precursor;
(4) by described catalyst precursor 120～160 ℃, activate 0.5～3 hour in hydrogenchloride, make a kind of acetylene method prepare vinylchlorid containing Au catalyst; Described help catalytic metal element be help catalytic metal element muriate or/and nitrate be the source, described help catalytic metal element be potassium, sodium, bismuth, iron, nickel, copper and zinc metallic element at least one.
3. method according to claim 1 and 2, is characterized in that described reactor is fixed-bed reactor.
4. method according to claim 1 and 2, is characterized in that described catalyst regeneration gas is chlorine, hydrogenchloride, ammonium chloride.
5. method according to claim 1 and 2, is characterized in that the described carrier with porous microstructure is gac, silicon-dioxide, silicon carbide or molecular sieve.
6. method according to claim 1 and 2, the muriate that it is characterized in that described cobalt is CoCl
26H
2o, Co (NH
3)
6cl
36H
2o or CoCl
3.
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| CN102631947B (en) * | 2012-04-01 | 2014-07-02 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Gold complex catalyst for hydrochlorinating acetylene |
| CN103623837B (en) * | 2012-08-24 | 2016-01-06 | 天津市天地创智科技发展有限公司 | The Ru-Co-Cu catalyst of acetylene hydrochlorination synthesizing chloroethylene |
| CN106215977B (en) * | 2016-07-25 | 2018-12-04 | 宁夏新龙蓝天科技股份有限公司 | A kind of synthesis vinyl chloride thereof that catalytic activity is high no mercury catalyst and preparation method thereof |
| CN111111709B (en) * | 2020-01-06 | 2023-02-28 | 山东鲁泰化学有限公司 | Acetylene hydrochlorination non-mercury catalyst taking titanium dioxide nanotube as carrier |
| CN115837277A (en) * | 2022-11-15 | 2023-03-24 | 鄂尔多斯市瀚博科技有限公司 | Regeneration method of gold catalyst in vinyl chloride production process |
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