CN101735005A - Improvement of catalytic method - Google Patents

Improvement of catalytic method Download PDF

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Publication number
CN101735005A
CN101735005A CN200810177896A CN200810177896A CN101735005A CN 101735005 A CN101735005 A CN 101735005A CN 200810177896 A CN200810177896 A CN 200810177896A CN 200810177896 A CN200810177896 A CN 200810177896A CN 101735005 A CN101735005 A CN 101735005A
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China
Prior art keywords
gold
catalyzer
carbon
deposited
grain
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Pending
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CN200810177896A
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Chinese (zh)
Inventor
N·A·卡西
P·约翰斯顿
M·L·斯米德特
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority to CN200810177896A priority Critical patent/CN101735005A/en
Priority to PCT/GB2009/051522 priority patent/WO2010055341A2/en
Priority to CN2009801544999A priority patent/CN102282112A/en
Publication of CN101735005A publication Critical patent/CN101735005A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B01J35/391—
    • B01J35/393—
    • B01J35/397—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/06—Vinyl chloride
    • B01J35/30—
    • B01J35/40—
    • B01J35/617—
    • B01J35/618—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation

Abstract

The invention relates to an improvement on a catalytic method, and discloses a catalyst, comprising gold nanoparticles carried on a carbon carrier. The catalyst is basically non-toxic, and is active for the reaction of acetylene and hydrogen chloride to form a vinyl chloride monomer (VCM).

Description

The improvement of catalysis process
Technical field
The present invention relates to a kind of improvement of catalysis process and the improvement of this method catalyst system therefor.More specifically, it relates to a kind of method and catalyzer that is prepared vinyl chloride monomer (" VCM ") by acetylene.
Background technology
At present one of method that prepare VCM in the prior art be in the presence of cupric chloride with ethene, hydrogenchloride and combination with oxygen to form Ethylene Dichloride, this Ethylene Dichloride at high temperature is decomposed with formation VCM and HCl.From the original method that twentieth century begins in early days, adopt the acetylene (acetylene) that makes by carbide of calcium by mercuri catalyzer and HCl reaction.This original method is still used in China, can obtain cheap acetylene by the carbide of calcium that obtains via the abundant in coal resource in China.Although this original method fund and running cost are low, beyond China, are eliminated in a large number, then tended to described ethylene process.
The mercury catalyst that uses in the original method normally is loaded in the mercury chloride of the 8-10% on the gac, and this catalyzer is highly toxic.This toxicity has problems because of processing at the production period and the catalyst loading of described catalyzer with during removing catalyzer after the cycle of operation.The cycle of operation can be continuously 6 months time usually.In use in the passivation of mercury catalyst and the reactor because distillation or the HgCl that causes of volatilization 2Loss may be an important problem.Compare with ethylene process, use the acetylene method of mercuri catalyzer to need lower facility investment; If a kind of not volatile and catalyzer that toxicity is little can the replacement for mercury catalyzer, and do not need existing installation design to carry out great equipment to change, this will have remarkable advantages.
Existed recommendation to be used for a large amount of academic researches and the publication of a kind of auri catalyzer of acetylene-HCl reaction, described auri catalyzer is to the most activated catalyzer of this reaction.Although it is said higher golden load on carbon (＞1wt%) can weaken passivation, passivation still can take place in Au catalyst.Other of Au catalyst passivation observe found, all passivation can be taken place under high temperature and the low temperature, and low-temperature passivation looks like by coking and cause, it may be the result of vinylchlorid and acetylene surface reaction.
Japanese Patent JP522136104, Denki Kagaku Kogyo KK, 1977 have instructed to adopt and have loaded on the carbon support and golden halogenide platinum halogenide or the combination of palladium halogenide as being used for the catalyzer that VCM produces.Wherein do not describe this Preparation of catalysts, the commercial applications of described method or catalyzer does not realize yet.
We are interpreted as that with prior art prior art shows metallic gold (Au 0) be inactive as catalyzer.
Particularly in China, still need a kind of catalysis process that can be used for preparing by acetylene in new or the existing installation VCM, described catalysis process use is a kind of can to resist passivation, or compare at least with mercury catalyst and can not have the worse life-span, and have the desirably catalyzer of longer acceptable life, and described catalyzer almost there is not or do not have toxicity.
Summary of the invention
Therefore, the invention provides the method for a kind of acetylene and HCl reaction, described method comprises makes reactant by loading on the catalyzer on the carbon support, and described catalyst pack containing metal gold grain is suitably gold nano grain.
The present invention also provides a kind of auri catalyzer that is applied to the inventive method, and this catalyst pack carbon-containing carrier and metallic gold particle are suitably gold nano grain.
Description of drawings
Fig. 1 has shown the EPMA image that is stated from three kinds of catalyst samples on the carbon extruded stock among embodiment 1a and the 1b.
Fig. 2 illustrates the contrast of mercury catalyst and Au catalyst among the embodiment 2.
Fig. 3 illustrates the contrast of the conversion of alkyne of the prepared catalyzer of embodiment 1a and 1b.
Fig. 4 and Fig. 5 have shown among the embodiment 2 through using the SEM Photomicrograph of two width of cloth different amplification of back catalyzer of the present invention in 25 days; Fig. 4 shows that reaction forms the SEM Photomicrograph of a large amount of nanotubes on the sample after 25 days; Fig. 5 is presented at the SEM Photomicrograph of the opening end of the gold grain of nanotube ends and a nanotube.
Fig. 6 illustrates the sample image of the used catalyzer of the present invention that takes out from the tubular reactor middle part among the embodiment 2.
Fig. 7 illustrates embodiment 1c and the prepared conversion of alkyne result who is stated from the catalyst sample on the silicon-dioxide of 1d.
Embodiment
Catalyzer of the present invention can be thought to comprise the nuclear with containing metal gold and contain Au 3+The gold grain of shell.Described shell needs not to be complete, but preferred described particle all or nearly all exposed surface all have Au 3+The surface; If for example the part surface of metallic gold by carbocyclic ring around, then described " shell " can be only be expanded on exposed particle surface.The higher oxidation state gold material that is present in the described shell needn't only be Au 3+, for example Au can also be arranged 1+This oxidation state material can be stable by halogenide.Metallic gold (Au 0) needn't be the oxidation state of only depositing in the nuclear.
Do not wish to be limited to any theory, think nuclear in metallic gold and the Au in the shell 3+Might play the effect of redox couple, perhaps metallic gold plays the effect of electron trap (electron sink) in the reaction of expectation.
When catalyzer when being fresh, gold grain is distributed on the surface of carbon support ideally.After using for some time, gold grain can load on the carbon fine-fibered (fibrils) especially.Described carbon fine-fibered can be a carbon nanotube.
Catalyzer of the present invention never was observed in the past or was described.What the observation post that causes passivation with former Au catalyst coking was different is, we believe carbon fine-fibered in the present invention so that its mode that keeps active and be exposed to reactant is carried the catalytic gold particle, rather than active Au catalyst particle is buried under coke type material.
Catalyzer of the present invention can be by the Preparation of Activated Carbon of high surface area, and described gac preferred surface is long-pending greater than 800m 2/ g, for example surface-area is 1300m 2The carbon extruded stock of/g.Can use other carbon support in addition, comprise carbon Powdered or particulate state or other form.The commercially available acquisition of these materials.If contain the impurity as the potential catalyst poisonous substance in the described carbon, for example S, As, Fe can adopt mode of washing, for example preferably adopt hydrochloric acid to carry out pickling.Have been found that if necessary it is in 3% the hydrochloric acid that carbon is dispersed in concentration, make it boiling, drain, and be effective with distilled water or deionized water wash.
Catalyzer can adopt multiple method for preparing catalyst preparation well known in the art, for example just wet impregnation method (incipient wetness), sedimentation, the precipitator method and combination thereof.Can be with described gold by golden precursor such as HAuCl 4XH 2The O or the aqueous solution are applied on the carbon; perhaps by metallic gold or other precursor are dissolved in the mixture of nitric acid and hydrochloric acid; then this solution is added in carbon granule or the extruded stock so that it is applied on the carbon, vice versa, and the mixture of wherein said nitric acid and hydrochloric acid is commonly referred to " chloroazotic acid ".Observed when using wang aqueous solution, carbon is transformed into gold, just is transformed into dun/black then in several seconds, when adopting just wet impregnation method to deposit, observes NO xSmog generates.The preferred at present wang aqueous solution that uses.Though we do not wish to be limited to any theory, think gold at first as golden salt sedimentation, and this salt be reduced to metallic gold by gac, when being exposed to wang aqueous solution, itself or maintain the original state or form and comprise Au 3+Shell.
Initial stage test the gold grain that is adopted as us, usually preferred 100% gold basically, but the also reactive activity catalyzer of paying close attention to of expection alloy and/or mixture.Possible alloy and/or mixture can comprise copper and/or silver, and they also can show as effective higher oxidation state surface mass.
The present invention now will be described with reference to following examples.
Embodiment 1a-1d---Preparation of catalysts
Embodiment 1a 1%Au/C extruded stock: under 150 gram scales, prepare:
By mixing 25 milliliters of HNO 3(69%) and 50 milliliters of HCl (37%) preparation wang aqueous solution.It is joined the HAuCl that 83ml contains 1.50gAu 4In the aqueous solution.Carbon extruded stock (0.8 millimeter of 150 gram-diameter, commercially available by Norit) is adopted just wet this solution soaking of impregnation method.After leaving standstill, wash this material twice, then whole night 105 ℃ of following dryings.
Embodiment 1b 1%Au/C extruded stock prepares under 150 gram scales:
By mixing 25 milliliters of HNO 3(69%) and 50 milliliters of HCl (37%) preparation wang aqueous solution.It is joined the HAuCl that 83ml contains 1.50gAu 4The aqueous solution.Carbon extruded stock (150 gram-with embodiment 1a) is adopted just wet this solution soaking of impregnation method.After leaving standstill, 105 ℃ of following dryings whole night with this material.
The method of embodiment 1a also is used to prepare the Au catalyst on the carbon extruded stock that is loaded in 3 millimeters of diameters.
Fig. 1 in the accompanying drawing has shown the EPMA figure of three kinds of carbon extruded stocks, about 5.5 millimeters of these three kinds of carbon extruded stock thickness have the sedimentary gold nano grain of method of the present invention (machine of employing is a JEOL modelJXA-8500F field emitted electron probe-microanalyser) of employing.Golden watch reveals and obviously is deposited on a layer thickness and is approximately on 100 microns the skin layer.Preferred most of gold is with the highest 200 microns, and more preferably the layer form of the highest 100 micron thickness is deposited on the carbon support.
Embodiment 1c (comparative example) 1%Au/SiO 2 Spherical material prepares under 50 gram scales:
By mixing 25 milliliters of HNO 3(69%), 75 milliliters of HCl (37%) and 25 ml waters prepare chloroazotic acid storage liquid.One five equilibrium sample (22 milliliters) is joined the HAuCl that 30ml contains 0.50gAu 4In the aqueous solution.With silica sphere (50 gram-280m 2/ g, diameter 1.1-2.4 millimeter) just wet this solution soaking of impregnation method of employing.After leaving standstill, dry this material obtains a kind of yellow product.
Embodiment 1d (comparative example) 1%Au/SiO 2 Spherical material prepares under 50 gram scales:
The HAuCl that will contain 0.50gAu 4Solution with water is diluted to 50 milliliters, and is used for adopting just wet impregnation method to soak silica sphere (50 grams-with embodiment 1c).After leaving standstill, dry this material obtains a kind of yellow product.
Studies show that in embodiment 1a and 1b, gold is for having the form of nanoparticles of metallic gold nuclear; But in embodiment 1c and 1d, it is as the HAuCl on the silica spheres 4Exist.That is, in embodiment 1c and 1d, HAuCl 4Simple absorption on described carrier only deposits as Au 3+Gold, do not observe metallic gold or gold grain.
Embodiment 2---the preparation of VCM
With the catalyst loading of 5.05 grams as embodiment 1b preparation in the glass reactor of 2 centimetres of diameters, 4 centimetres of degree of depth.With this glass reactor with the chuck parcel that is filled with the heated oil that flows, to cause and to keep reaction.In pre-treatment and step of reaction, thermopair is placed on the middle part of described bed and top with monitor temperature.Thereby following temperature is meant the temperature at catalyst bed middle part.
At first, catalyzer is following dry 30 minutes in 100 ℃ in stream of nitrogen gas (100 ml/min).At this moment, nitrogen is changed into hci gas flow (116 ml/min) and observe and continue several minutes thermopositive reaction.After heat release weakened, temperature rose to 180 ℃, and continued hydrogenchloride and handled 1 hour.At this moment, use purging with nitrogen gas reactor 15 minutes, temperature drops to 90 ℃.Make reactant gases (hydrogenchloride and acetylene) pass through catalyst bed then with 1: 1 nominal mol ratio.Enter before the reactor, make gas process gas mixer and preheat the unit, it is made up of a heated beam that granulated glass sphere is housed.For fear of heat release excessive (＞180 ℃), careful raising air-flow and oil bath temperature all reach the peak flow rate of 114 ml/min up to hydrogenchloride and acetylene.Typically it needs 45 minutes, then by improve the oil outer temperature with the temperature maintenance at described bed middle part the temperature that requires (typically being 180 ℃).Result (Fig. 2) demonstration initial activity and passivation rate and the commercially available mercuric chleride catalyst (10%HgCl that under similar condition, tests 2) (fs inactive catalyst) approaching.Active sharply rising that shows at figure middle part caused by postrun flow velocity adjustment whole night.
The comparison diagram of the conversion of alkyne of embodiment 1a and embodiment 1b catalyzer is shown among Fig. 3.Compare with the catalyzer of embodiment 1a, do not adopt the catalyst activity of embodiment 1b of last water-washing step bigger, and through the test phase post-passivation obviously still less.
After using through 25 days as described in the embodiment 2, the catalyst according to the invention sample that obtains by the reactor upstream portion by scanning electron microscopy study.Fig. 4 and Fig. 5 have shown two width of cloth SEM Photomicrographs of different amplification.The surface presents a large amount of carbon fine-fibereds; Fig. 5 shows that these are carbon nanotubes, and they are carrying the metallic gold nano particle at its end.
Further image (Fig. 6) is from the sample of the used catalyzer of tubular reactor middle part taking-up, show to begin to form carbon nanotube, and be epontic from carbon support.
Additional experiment among Fig. 7 shows, uses the golden sample catalyst on the silicon-dioxide for preparing among embodiment 1c and the 1d, and acetylene is converted to the transformation efficiency of VCM obviously than using Au catalyst low (being lower than 4%) on the carbon.In addition, the catalyzer that is deposited on the silicon-dioxide in use shows lasting passivation phenomenon.

Claims (16)

1. method that makes acetylene and HCl prepared in reaction VCM, comprise make acetylene and HCl under gas phase by containing the metallic gold particulate catalyzer that is carried on the carbon support.
2. the method for claim 1, wherein gold grain is deposited in the top layer of carbon support.
3. method as claimed in claim 2, wherein most of gold grains are deposited on thickness and are no more than in the layer of 200 μ m.
4. method as claimed in claim 3, wherein most of gold grains are deposited on thickness and are no more than in the layer of 100 μ m.
5. as each described method of claim 1-4, wherein said gold grain comprises metallic gold nuclear and contains Au 3+Partial or complete shell.
6. as each described method of claim 1-5, wherein said gold grain is carried on the carbon fine-fibered.
7. as each described method of claim 1-6, wherein said carbon support is a kind of carbon extruded stock or pellet of high surface area.
8. an auri catalyzer that is used for by acetylene VCM comprises the gold grain that is carried on the carbon support, and wherein said particle has metallic gold nuclear and comprises Au 3+The shell of species.
9. catalyzer as claimed in claim 8, wherein gold grain is deposited in the top layer of carrier.
10. catalyzer as claimed in claim 9, wherein most of gold grains are deposited on thickness and are no more than in the layer of 200 μ m.
11. catalyzer as claimed in claim 10, wherein most of gold grain deposit thickness are no more than in the layer of 100 μ m.
12. catalyzer as claimed in claim 8, wherein said gold grain is carried on the carbon fine-fibered.
13. catalyzer as claimed in claim 12, wherein said carbon fine-fibered is a carbon nanotube.
14. as each described catalyzer of claim 8-13, wherein said carbon support is the high surface area carbon extruded stock.
15. a method for preparing catalyst according to the invention comprises gold is deposited on the carbon support from wang aqueous solution, and deposition has the gold grain that the surface that comprises higher oxidation state gold species was examined and had to metallic gold.
16. method as claimed in claim 15, it does not comprise the washing step after catalyzer forms.
CN200810177896A 2008-11-14 2008-11-14 Improvement of catalytic method Pending CN101735005A (en)

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PCT/GB2009/051522 WO2010055341A2 (en) 2008-11-14 2009-11-12 Improvements in catalytic processes
CN2009801544999A CN102282112A (en) 2008-11-14 2009-11-12 Improvements in catalytic processes

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110841722A (en) * 2019-10-16 2020-02-28 鄂尔多斯市瀚博科技有限公司 Mercury-free catalyst passivation process for vinyl chloride synthesis

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201111819D0 (en) * 2011-07-11 2011-08-24 Johnson Matthey Plc Catalyst and method for its preparation
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
EA030122B1 (en) * 2013-12-13 2018-06-29 Солвей Са Method for production of vinyl chloride from acetylene and hydrogen chloride
GB201509019D0 (en) 2015-05-27 2015-07-08 Johnson Matthey Plc Process and catalyst
CN106423287A (en) * 2016-09-10 2017-02-22 新疆大学 Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination
ES2676121B1 (en) * 2016-12-15 2019-04-29 Consejo Superior Investigacion HYDROCHLORINATION REGIOSELECTIVA, STEREOSELECTIVA AND CATALYTICA OF ALQUINOS
EP4197635A1 (en) 2021-12-17 2023-06-21 Johnson Matthey Public Limited Company Gold containing catalyst, method of preparation and use

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101249451A (en) * 2008-04-10 2008-08-27 四川大学 Non-mercury catalyst for acetylene hydrochlorination and method of preparing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101249451A (en) * 2008-04-10 2008-08-27 四川大学 Non-mercury catalyst for acetylene hydrochlorination and method of preparing the same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BONGANI NKOSI等: "Hydrochlorination of Acetylene Using Carbon-Supported Gold Catalysts: A Study of Catalyst Reactivation", 《JOURNAL OF CATALYSIS》 *
DAVID THOMPSON: "New Advances in Gold Catalysis Part 1*", 《GOLD BULLETIN》 *
MARCO CONTE等: "Reactivation of a Carbon-supported Gold Catalyst for the Hydrochlorination of Acetylene", 《CATAL LETT》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110841722A (en) * 2019-10-16 2020-02-28 鄂尔多斯市瀚博科技有限公司 Mercury-free catalyst passivation process for vinyl chloride synthesis

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Application publication date: 20100616