CN103442807A - Catalytic system and applications thereof for manufacturing vinyl chloride by hydrochlorination of acetylene - Google Patents
Catalytic system and applications thereof for manufacturing vinyl chloride by hydrochlorination of acetylene Download PDFInfo
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- CN103442807A CN103442807A CN2011800623609A CN201180062360A CN103442807A CN 103442807 A CN103442807 A CN 103442807A CN 2011800623609 A CN2011800623609 A CN 2011800623609A CN 201180062360 A CN201180062360 A CN 201180062360A CN 103442807 A CN103442807 A CN 103442807A
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
The invention discloses a catalytic system comprising a) at least one N-alkylated imidazole and b) optionally at least one compound of at least one metal selected from Pd, Pt, Hg, Ru and Os. The invention also discloses an application of the catalytic system for a hydrochlorination reaction of acetylene with hydrogen chloride.
Description
The present invention relates to a kind of catalysis system, this catalysis system is useful especially in a kind of method for the manufacture of the hydrochlorination by acetylene vinyl chloride.The invention still further relates to this method.
Manufacture by reacting between acetylene and hydrogen chloride that vinyl chloride carries out normally in gas phase, in a kind of fixed bed reactors, when a kind of heterogeneous solid catalyst based on being loaded with mercury chloride exists.Mainly due to toxicity, at present to mercury content with minimizing or the catalysis system of compound containing mercury is more and more not interested.
Develop multiple different catalyst, be intended to replace the catalyst in current gas phase process.
For example, when, uncensored Japanese patent application 52/136104 has been described a kind of fixed catalytic bed existence be comprised of the noble metal halide be deposited on active carbon in gas phase acetylene is carried out to the method for hydrochlorinate.Yet up to now, this type of is intended to still be significantly shorter than for the life-span of the alternative catalyst of gas phase process the life-span of the catalyst based on mercury compound.
In addition, in document, there are some acetylene to be carried out to the example of hydrochlorinate under a kind of existence of liquid catalyst medium.
Deutsche Bundespatent 709.000 has been described a kind of method for preparing vinyl halide by the hydrohalide salt melt that at high temperature makes acetylene contact the organic base that contains a kind of standard catalyst.Amine of aliphatic, aromatic or heterocycle and composition thereof is considered as organic base.
Inventor's certificate SU237116 has described the stannous chloride that uses a kind of 46wt% of containing and from the aqueous peracid solution of the hydrochloride of a kind of methylamine, dimethylamine or the trimethylamine of 14wt% to 16wt%.
European patent application book EP-A-0340416 has disclosed a kind of at the temperature higher than environment temperature, acetylene the reaction at palladium compound with hydrogen chloride when catalyst exists in the solvent be comprised of aliphatic or alicyclic acid amides and has prepared the method for vinyl chloride.Although it allows to obtain high output, yet this method also has some obvious shortcomings: it has shown this liquid catalyst system under reaction condition and has degenerated gradually, thereby form the black product with carbonaceous outward appearance.In addition, under the existence of hydrogen chloride, acid amides is converted into a kind of hydrochloride, and its fusing point is normally far above environment temperature.For example, the 1-METHYLPYRROLIDONE hydrochloride only is only liquid at 80 ° more than C.In fact, this may cause serious implementation issue, the reunion of these problems and reactor down periods catalytic media or the block dependency of pipeline on the coldest point at facility.So, whole reactor and respond medium therein mobile pipeline must remain on constantly the temperature higher than the hydrochloride fusing point.
Due to the hydrochlorination system of describing in European patent application EP 0519548-A1 and EP0525843-A1, as if these different problems are resolved, and these systems comprise at least one group VIII metallic compound and or a kind of amine hydrochlorate (its fusing point is less than or equal to 25 ° of C) or a kind of a kind of organic solvent that comprises the fatty amine hydrochloride (its fusing point is higher than 25 ° of C) more than 8 carbon atoms and be selected from aliphatic, alicyclic and aromatic hydro carbons and composition thereof.However, described antigravity system wherein, especially wherein the group VIII metallic compound is the system of platinum chloride (II) or palladium bichloride (II), when consider aspect the hydrochlorination by acetylene is produced the productivity ratio of vinyl chloride and long-term stability aspect they make it possible to realize performance the time, not be entirely satisfactory.
WO2008/77868 has disclosed a kind of hydrochlorination system of catalysis, comprise at least one amine hydrochlorate and at least one group VIII metallic compound, this metallic compound is selected from lower group, and this group comprises: the compound of the compound of a kind of platinum (IV) and the mixture of stannic chloride (II), a kind of platinum (II) and the mixture of triphenylphosphine oxide and the compound of a kind of palladium (II) and the mixture of triphenylphosphine.These catalysis systems show and compare a kind of improved productivity ratio with European patent application EP-A0519548 with the system of describing in EP-A0525843.
Finally, patent application CN101716528 has disclosed the catalysis system of producing vinyl chloride for the hydrochlorination by acetylene, this catalysis system comprise there is chlorine, the ion of bromine, hexafluoro-phosphate radical or tetrafluoro phosphate radical is as one or more in the chloride of the ionic liquid based on imidazoles of anion and gold, platinum, palladium, tin, mercury, copper or rhodium.
Above-mentioned catalysis system shows the shortcoming that requires a kind of amine hydrochlorate or a kind of ionic liquid to combine with a kind of metallic compound.
Therefore, an object of the present invention is to provide a kind of catalysis system, specifically for hydrochlorination and, more specifically for the hydrochlorination of acetylene, this catalysis system is simple as far as possible and cheap, has allowed extraordinary performance.Another object of the present invention is a kind of method that the hydrochlorination synthesizing chloroethylene of acetylene is provided under the existence of this catalysis system, and this catalysis system is not degraded and enabled to realize the extraordinary productivity ratio towards vinyl chloride under reaction condition.Unlike the system based on mercury compound, the advantage that catalysis system according to the present invention has is there is no the toxicity problem relevant to these compounds, and has avoided the evaporation of slaine in facility.
Therefore the present invention relates to a kind of catalysis system, a kind of catalysis system of the hydrochlorination for acetylene more specifically, as defined in claim 10.
According to the preferred embodiment of catalysis system of the present invention, in the claim that is subordinated to claim 10 and in hereinafter describing in more detail, propose.
Another aspect of the present invention relates to a kind of method of manufacturing vinyl chloride under the existence of defined a kind of catalysis system as claim 1 and in being subordinated to the claim of claim 1 and in the explanation of more describing in detail hereinafter by the hydrochlorination of acetylene.
According to catalysis system of the present invention, comprise
A) the alkylating imidazoles of at least one N-and
B) at least one compound of at least one metal optionally.
Catalysis system, comprise
A) the alkylating imidazoles of at least one N-and
B) at least one is selected from least one compound of the metal of Pd, Pt, Hg, Ru and Os, and these antigravity systems are novel and have provided good result in framework of the present invention, if when especially this metal is Pd.
Statement " comprising " is interpreted as in this manual referring to except the alkylating imidazoles of at least one N-and optionally at least one compound of at least one metal, according to catalysis system of the present invention, can also comprises that the catalysis characteristics on this catalysis system is with or without one or more other components of impact.In this one or more other component, can mention one or more ionic liquids, for example it is added so that influential and/or allow the reduced viscosity of this catalysis system to the catalysis characteristics of this catalysis system.
Preferably, catalysis system according to the present invention mainly consists of the following
A) the alkylating imidazoles of at least one N-and
B) at least one compound of at least one metal optionally.
Statement " mainly by ... form " be interpreted as in this manual referring to except the alkylating imidazoles of at least one N-and optionally at least one compound of at least one metal, can also comprise that according to catalysis system of the present invention the catalysis characteristics to this catalysis system does not have influential one or more other components (preferably with a small amount of); In other words, in the course of reaction of using this catalysis system, this reaction is not had to catalytic action.In this one or more other component, can mention one or more ionic liquids, for example they are added to reduce the viscosity of this catalysis system.
More preferably, catalysis system according to the present invention mainly consists of the following
A) the alkylating imidazoles of at least one N-and
B) at least one compound of at least one metal optionally.
Statement " by ... form " be interpreted as in this manual referring to this catalysis system only by the alkylating imidazoles of at least one N-and optionally at least one compound of at least one metal form.
Catalysis system according to the present invention comprises the alkylating imidazoles of at least one N-as component a).
In this manual, statement " the alkylating imidazoles of at least one N-" is interpreted as referring to a kind of or more than the alkylating imidazoles of a kind of N-.
Preferably, this catalysis system comprises the alkylating imidazoles of a kind of N-.
At the remainder of this paper, it is a kind of or more than the alkylating imidazoles of a kind of N-, except as otherwise noted that the statement " the alkylating imidazoles of N-" of using with odd number or plural form is interpreted as meaning.
The alkylating imidazoles of N-according to the present invention advantageously defines by following chemical formula (I)
Radicals R wherein
1, R
2, R
3and R
4hydrogen or that can optionally replace, saturated or undersaturated C independently of one another can respectively do for oneself
1-C
18(preferred C
1-C
14, more preferably C
1-C
12, C most preferably
1-C
10and C especially most preferably
1-C
8) alkyl group.
The example of the alkylating imidazoles of N-is 1-methylimidazole, 1-ethyl imidazol(e), 1-propyl imidazole, 1-butyl imidazole, 1-amyl group imidazoles, 1-hexyl imidazoles, 1-heptyl imidazoles, 1-octyl group imidazoles, 1-nonyl imidazoles, 1-decyl imidazoles, 1-methyl-2-octyl group imidazoles, 1-Ethyl-2-Methyl imidazoles, 1-butyl-glyoxal ethyline, 1-hexyl-glyoxal ethyline and 1-decyl-glyoxal ethyline.
Preferably, the alkylating imidazoles of this N-is to be selected from: 1-methylimidazole, 1-ethyl imidazol(e), 1-butyl imidazole, 1-hexyl imidazoles, 1-octyl group imidazoles, 1-decyl imidazoles, 1-methyl-2-octyl group imidazoles, 1-Ethyl-2-Methyl imidazoles, 1-butyl-glyoxal ethyline, 1-hexyl-glyoxal ethyline and 1-decyl-glyoxal ethyline.
More preferably, the alkylating imidazoles of this N-is to be selected from those that use in working example hereinafter, i.e. 1-methylimidazole, 1-ethyl imidazol(e) and 1-butyl imidazole.The alkylating imidazoles of most preferred those N-be for example from
commercially available.
For the manufacture of the method for suitable alkylating imidazoles, be that those of ordinary skill is known and therefore there is no need to be described in detail at this.
Catalysis system according to the present invention comprises that at least one compound of at least one metal optionally is as components b).
In this manual, as used herein, statement " at least one compound of at least one metal " comprises the compound of the mixture of different compounds of a kind of single metallic compound of metal and metal of the same race or different metal or comprises the mixture of the compound of two kinds of metals defined above,, according to catalysis system of the present invention, can comprise more than a kind of metal as defined above (correspondingly, metallic compound).
Preferably, this catalysis system comprises a kind of compound of at least one metal, and more preferably, a kind of a kind of compound of metal.
At the remainder of this paper, it is a kind of or more than a kind of compound and a kind of or more than a kind of metal, except as otherwise noted that the statement " compound " of using with odd number or plural form and " metal " are interpreted as meaning accordingly.
In this manual, statement " comprising optionally at least one compound " is interpreted as referring to that this kind of compound exists or do not exist in this catalysis system.
According to first embodiment according to the present invention, according to catalysis system of the present invention, do not comprise components b), i.e. at least one compound of at least one metal.
Definition defined above and preference are equally applicable to this first embodiment.
According to second embodiment according to the present invention, catalysis system according to the present invention advantageously comprises:
A) the alkylating imidazoles of at least one N-and
B) at least one compound of at least one metal.
Definition defined above and preference are equally applicable to this second embodiment.
Optionally comprise that according to catalysis system of the present invention at least one compound of at least one metal is as components b).
This metal is any metal.This metal advantageously is selected from Pd, Pt, Au, Hg, Ru, Os, Ru, Rh and Ir.Preferably, this metal is to be selected from Pd, Pt, Au, Hg, Ru and Os.
According to catalysis system of the present invention, therefore preferably include
A) the alkylating imidazoles of at least one N-and
B) at least one is selected from least one compound of the metal of Pd, Pt, Au, Hg, Ru and Os.
Although when this metal be selected from above-mentioned those the time obtained good result, when this metal is to have obtained extraordinary result while being selected from Pd, Ru, Au and Os, when this metal be while being selected from Pd, Ru and Au, obtained particularly preferred result and when this metal be to have obtained more particularly preferred result while being selected from Pd and Ru.When being Pd, this metal obtained the most significant result.
Preferred Pt (IV) or Pt (II) or Pd (II) compound be in the preparation process according to catalysis system of the present invention, can change into mentioned metal muriatic those.Therefore, can use chloride, nitrate, acetate, carbonate or the oxide of platinum (IV), platinum (II) or palladium (II).And the chloride of these metals and acetate are preferred.
In the chlorine-based compound of platinum (IV), can mention platinum chloride (IV) and chloroplatinic acid or its esters, for example Na
2ptCl
6, K
2ptCl
6or Li
2ptCl
6.
In the chlorine-based compound of platinum (II), can mention the chloroplatinite (platinochlorides) of platinum chloride (II) and alkali or alkaline-earth metal, for example Na
2(PtCl
4), K
2(PtCl
4), Li
2(PtCl
4) and (NH
4)
2(PtCl
4).
In the chlorine-based compound of palladium (II), can mention the chloropalladite (palladochlorides) of palladium bichloride (II) and alkali or alkaline-earth metal, for example, as Na
2(PdCl
4), K
2(PdCl
4), Li
2(PdCl
4) and (NH
4)
2(PdCl
4).
Particularly preferably be PtCl
4, PtCl
2, PdCl
2and palladium (II) is chosen as respectively the compound of platinum (IV), platinum (II) and palladium (II).PtCl
2, PdCl
2and palladium (II) is most preferred.
In the compound of Au, Au
3+compound is preferred, and same in the situation that Pd and Pt, and it is preferred can being converted into muriatic those compounds.AuCl
3most preferred.
The suitable compound of Ru and Os be chemical valence be 3 those and can be converted into again muriatic those compounds or these chlorides itself are particularly preferred.RuCl
3and OsCl
3respectively most preferred.
Among the suitable compound of Hg, can mention HgCl
2.
In the catalysis system according to this second embodiment, the content of metallic compound means advantageously to be more than or equal to about 1mmol/l and to be less than or equal to about 1000mmol/l with mM number of every liter of alkylating imidazoles of N-.In the catalysis system according to this second embodiment, the content of metallic compound advantageously is more than or equal to about 1mmol/l, preferably greater than or equal to about 5mmol/l and particularly preferably be more than or equal to about 10mmol/l.In this catalysis system, the content of metallic compound advantageously is less than or equal to about 1000mmol/l, preferably be less than or equal to about 800mmol/l, particularly preferably be less than or equal to about 600mmol/l, more particularly preferably be less than or equal to about 500mmol/l, and the most particularly preferably be less than or equal to about 400mmol/l.Although not enforceable, yet all metallic compounds that preferably this catalysis system comprises are all the forms in dissolving.
In general, according to the catalysis system of the second embodiment, when using in hydrochlorination together with hydrogen chloride, be dissolve or be dispersed in the alkylating imidazoles of N-and then with hydrogen chloride, make that this solution is saturated to be prepared by the metallic compound by desirable amount.Yet, also likely at first that the alkylating imidazoles of this N-is saturated with hydrogen chloride, then this metallic compound is introduced in the alkylating imidazoles of this N-afterwards.The amount of the metallic compound usually, used is to make in catalysis system all forms in dissolving of metallic compounds.Yet, also likely use a kind of metallic compound, at least a portion that its value or the character had make this compound is present in this catalysis system with the form of the solid that disperses, and not unfavorable to the present invention.
Can be used to liquid phase or be deposited over solid carrier as on silica, aluminium oxide, cimita, cordierite, mullite or active carbon (only listing several suitable carrier materials), up to the pore volume of carrier and the limiting value of useable surface area according to the antigravity system of the first and second embodiments of the present invention.This carrier can have any shape for the examples of such carriers material, includes but not limited to cellular thing and extrudate or analog.
When this catalysis system is used in liquid phase, it can be used to a kind of organic solvent diluting.So be included according to the selection of the character of the organic solvent in catalysis system of the present invention and especially depend on following requirement: it under reaction condition, for reactant, be inertia, it easily mixes with the alkylating imidazoles of N-; And depend on following hope: it and the alkylating imidazoles of this N-form a kind of medium, the viscosity of the viscosity of this medium during lower than the alkylating imidazoles individualism of this N-.
Yet preferably,, the alkylating imidazoles of this N-self serves as a kind of solvent, thereby make, other solvent needn't be arranged.
Can be for any reaction for alkynes according to catalysis system of the present invention, that is, two carbon are by the compounds of a triple bond connection.Can mention acetylene, propine (also referred to as allylene), dimethyl butyn, Isosorbide-5-Nitrae-butylene glycol in this type of alkynes, together with the propine compounds.This reaction can be hydrohalogenation, particularly hydrochlorinate effect (carrying out with hydrogen chloride), hydrogen iodination (carrying out with hydrogen iodide), hydrofluorination (carrying out with hydrogen fluoride) or hydrobromination (carrying out with hydrogen bromide), or with reacting that phosphoric acid carries out.
Catalysis system according to the present invention is useful especially for the hydrochlorinate effect of acetylene.
In the present invention, it is acetylene or the mixture that comprises acetylene that term " acetylene " is interpreted as, and these mixtures can also comprise other components except acetylene, for example ethene or other unsaturated hydro carbons, and these hydro carbons can be the synthetic accessory substances of acetylene.The source of this type of mixture of different unsaturated compounds can be the mixture in any source, as they can obtain in the process of the known synthetic method for acetylene.Can use the mixture that comprises the acetylene that is less than 50%.Yet preferably, term " acetylene " refers to the acetylene that comprises at least 90% and the more preferably mixture of 100% acetylene.
Acetylene is mainly that the partial combustion by methane is manufactured or as occurring from the accessory substance in the ethene steam of hydrocarbon cracking.
Another kind of method for the manufacture of acetylene is the hydrolysis of calcium carbide
CaC
2+2H
2O→Ca(OH)
2+C
2H
2
This requires the extremely high temperature of about 2000 ° of C, thereby make, must use electric furnace or analog.
The mixture that comprises acetylene and ethene can directly in statu quo be used, that is, and and without component is separated, because the reactivity that acetylene is compared with ethene makes the hydrochlorinate effect of acetylene can at first separate obtained vinyl chloride and uses ethene subsequently and carry out.Can be by this ethylene chlorination to produce 1,2-dichloroethanes, thereby for a kind of integrated processes of manufacturing VCM.The pyrolysis of 1,2-dichloroethanes can produce hydrogen chloride, for this carrying out with acetylene, first reacts.
Therefore, the invention still further relates to a kind of for by acetylene, with react (the hydrochlorinate effect) of hydrogen chloride, manufacturing the method for vinyl chloride under the existence according to a kind of catalysis system of the present invention.
The above method that is applicable to vinyl chloride constructed in accordance for the defined definition of catalysis system according to the present invention and preference.
The method according to this invention advantageously can be carried out the temperature in the scope from room temperature to 220 ° C.Under higher temperature, this catalysis system has a kind of trend of degraded.Preferred reaction temperature, that is to say best trading off between the stability that productivity ratio, output and catalytic media are provided, and is to be more than or equal to approximately 40 ° of C.Being more than or equal at the temperature of about 50 ° of C, more particularly preferably be at the temperature that is more than or equal to about 80 ° of C and particularly preferably be most at the temperature that is being more than or equal to about 120 ° of C and obtained best result.Preferably, this reaction temperature is no more than approximately 200 ° of C.Approximately 40 ° of C are the most particularly preferred to the about reaction temperature of 200 ° of C.In some cases, the reaction temperature that is no more than 170 ° of C proves favourable.
The method according to this invention is advantageously carried out under environmental pressure or the more high pressure compatible with the security legislation that is used for processing acetylene.Usually, this pressure will be no more than 5MPa, and preferably it will be no more than the dividing potential drop of the acetylene of 2.5Mpa.
According to the method for the preparing vinyl chloride by hydrochlorination by acetylene of the present invention, advantageously by being contacted with this catalysis system, gaseous reactant (acetylene and hydrogen chloride) undertaken in any suitable reactor.
The method according to this invention can be routinely be carried out in the equipment of any promotion solution-air exchange, and this equipment is for example plate tower, overflow-type packed column or the non-packed column of overflow-type.The another one of this method can make to have between gas phase and liquid phase the embodiment of good mass exchange to comprise the use counter-current reactor, the packed bed type of optionally spraying, the reverse air-flow in reactant of liquid catalyst system and flow through this filler.
In the method according to the invention, add the mol ratio of hydrogen chloride in reactor and acetylene advantageously to be more than or equal to approximately 0.5.Preferably, this ratio is more than or equal to approximately 0.8.Advantageously, this mol ratio is less than or equal to approximately 3.Preferably, adding the mol ratio of hydrogen chloride in reactor and acetylene is to be less than or equal to approximately 1.5.
When hydrogen chloride and acetylene are from approximately 0.5 when using about 3 mol ratio, obtained good result.
Acetylene can contact with hydrogen chloride in reactor, or preferably before introducing reactor, is mixed.
In order to increase the amount that is dissolved in the acetylene in liquid phase, also likely use a kind of method, only acetylene is introduced in reactor with gaseous form in the method, in this reactor, it reacts with the hydrogen chloride existed with the form of hydrochloride in liquid phase.The chlorination Hydrogen Energy is introduced in any form: the gaseous state of dilution, pure or be dissolved in and remain in the solvent of extraction, a kind of insoluble amine for example, carry out the drying process of an intermediate after advantageously.
Advantageously can be in the method according to the invention for the manufacture of vinyl chloride according to catalysis system of the present invention.
Therefore the invention still further relates to catalysis system according to the present invention does in order to manufacture the purposes of vinyl chloride for the catalytic hydrochlorinate of acetylene.
Catalysis system according to the present invention provides at conversion ratio, selectively and therefore also have extraordinary performance aspect improved productivity ratio, and it is characterized by long-term stability.Avoid the use mercury compound, according to catalysis system of the present invention, there is in addition the toxicity problem relevant to these compounds.
Following example is intended to illustrate the present invention, but is not intended to limit its scope.The example meaned by letter C is comparison example and other examples have been described according to catalysis system of the present invention.
General program for working example:
The corresponding solution of the catalysis system that 30ml is comprised as described below and prepare adds an inner volume, and to be 45ml send in the Simon Rex reactor, this reactor is equipped with heat to transmit dual chuck of oil circulation therein and, for introducing device reactant, that consist of a sintered glass nozzle, this nozzle is intended to guarantee the dispersion of gas in liquid medium.This reactor is remained at the temperature of 150 ° of C.
Reactant acetylene and HCl are introduced with the amount (measuring under 0 ° of C and atmospheric pressure) of 10Nl/h and 12Nl/h with the mol ratio of 1:1.2.
The form of the alkylating imidazoles of N-when receiving used.When existing in this catalysis system, pointed metallic compound is dissolved in the alkylating imidazoles of the N-used with necessary amount.Except indicating in addition, the amount of metal is the ionic liquid of 22.6mmol/l.
The effluent that leaves this reactor is analyzed with regard to the conversion ratio of acetylene.Selectively be 100% in all experiments, that is, except desirable product vinyl chloride, do not have accessory substance.Therefore, can directly calculate productivity ratio by the conversion ratio of acetylene.
The alkylating imidazoles of N-of testing and indicating in the table of having summed up the catalysis system of testing is the following:
IM1 1-methylimidazole
IM2 1-butyl imidazole
IM3 1-ethyl imidazol(e)
The result of these experiments provides and/or shows in Fig. 1 and 2 in following table, these figure demonstrated conversion of alkyne (%) over time (the x axle show in hour time).The numbering of next-door neighbour's curve is corresponding to the numbering of example.
Table 1 – example 1 to 14
| Example number | Ionic liquid | Metallic compound | Result |
| 1 | IM1 | / | Fig. 1 |
| 2 | IM2 | / | Fig. 1 |
| 3 | IM3 | / | Fig. 1 |
| 4 | IM1 | PdCl 2 | Fig. 2 |
| 5 | IM2 | PdCl 2 | Fig. 2 |
| 6 * | IM2 | PtCl 2 | Fig. 2 |
| 7 | IM2 | AuCl 3 | Fig. 2 |
| 8 | IM3 | PdCl 2 | Fig. 2 |
| 9 * | IM3 | PtCl 2 | Fig. 2 |
| 10 | IM3 | AuCl 3 | Fig. 2 |
| 11 | IM3 | RuCl 3 | Fig. 2 |
| 12 | IM3 | OsCl 3 | Fig. 2 |
| 13 | IM3 | Pd(OAc) 2 | Fig. 2 |
| 14 # | IM3 | HgCl 2 | Fig. 2 |
*: in experimentation, the amount of metal increases to 67.8mmol/l by 22.6
#: the amount of metal is 354mmol/l
The result of these experiments shows, uses and has obtained extraordinary conversion ratio according to the catalysis system of example 1 to 14.
Claims (14)
- Under the existence of catalysis system by the method for manufacturing vinyl chloride of reacting of acetylene and hydrogen chloride, described catalysis system comprisesA) the alkylating imidazoles of at least one N-andB) optional at least one compound of at least one metal.
- 2. method according to claim 1, the alkylating imidazoles of wherein said N-is defined by following chemical formula (I):
Radicals R wherein 1, R 2, R 3and R 4hydrogen or optional replace, saturated or undersaturated C independently of one another can respectively do for oneself 1-C 18alkyl group. - 3. method according to claim 2, the alkylating imidazoles of wherein said N-is selected from: 1-methylimidazole, 1-ethyl imidazol(e), 1-butyl imidazole, 1-hexyl imidazoles, 1-octyl group imidazoles, 1-decyl imidazoles, 1-methyl-2-octyl group imidazoles, 1-Ethyl-2-Methyl imidazoles, 1-butyl-glyoxal ethyline, 1-hexyl-glyoxal ethyline and 1-decyl-glyoxal ethyline.
- 4. method according to claim 3, the alkylating imidazoles of wherein said N-is selected from: 1-methylimidazole, 1-ethyl imidazol(e) and 1-butyl imidazole.
- 5. method according to claim 1, do not comprise metallic compound.
- 6. method according to claim 1, compriseA) the alkylating imidazoles of at least one N-andB) at least one compound of at least one metal.
- 7. method according to claim 6, wherein said metal is selected from Pd, Pt, Au, Hg, Ru and Os.
- 8. method according to claim 7, wherein said metal is Pd.
- 9. method according to claim 1, wherein said reaction is to carry out under the temperature from room temperature to 220 ° C.
- 10. catalysis system, it comprisesA) the alkylating imidazoles of at least one N-andB) at least one is selected from least one compound of the metal of Pd, Pt, Hg, Ru and Os.
- 11. catalysis system according to claim 10, the alkylating imidazoles of wherein said N-is defined by following chemical formula (I):
Radicals R wherein 1, R 2, R 3and R 4hydrogen or optional replace, saturated or undersaturated C independently of one another can respectively do for oneself 1-C 18alkyl group. - 12. catalysis system according to claim 11, the alkylating imidazoles of wherein said N-is selected from: 1-methylimidazole, 1-ethyl imidazol(e), 1-butyl imidazole, 1-hexyl imidazoles, 1-octyl group imidazoles, 1-decyl imidazoles, 1-methyl-2-octyl group imidazoles, 1-Ethyl-2-Methyl imidazoles, 1-butyl-glyoxal ethyline, 1-hexyl-glyoxal ethyline and 1-decyl-glyoxal ethyline.
- 13. catalysis system according to claim 12, the alkylating imidazoles of wherein said N-is selected from: 1-methylimidazole, 1-ethyl imidazol(e), 1-butyl imidazole.
- 14. catalysis system according to claim 10, wherein said metal is Pd.
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| PCT/EP2011/072775 WO2012084643A2 (en) | 2010-12-22 | 2011-12-14 | Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene |
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| CN103920511A (en) * | 2014-04-10 | 2014-07-16 | 新疆中泰化学股份有限公司 | Catalyst for preparing vinyl chloride by acetylene hydrochlorination and preparation method thereof |
| CN107486224A (en) * | 2017-08-29 | 2017-12-19 | 贵州重力科技环保有限公司 | A kind of ultralow solid mercury catalyst of high catalytic conversion and preparation method thereof |
| CN109647523B (en) * | 2018-12-25 | 2021-10-29 | 南开大学 | Preparation method and use method of metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in fixed bed |
| CN112007696B (en) * | 2020-09-23 | 2021-08-27 | 中国科学院大连化学物理研究所 | Gold-silver nanocluster catalyst for acetylene hydrochlorination |
| CN112973800A (en) * | 2021-03-01 | 2021-06-18 | 内蒙古大学 | Preparation method and application of nitrogen modified ruthenium-based catalyst |
| CN115608415B (en) * | 2021-07-16 | 2024-04-16 | 中国科学院大连化学物理研究所 | Supported catalyst, preparation and application thereof |
| CN113549116B (en) * | 2021-08-18 | 2022-11-08 | 河北美邦工程科技股份有限公司 | Preparation method and application of metal chelating imidazole catalyst |
| CN116393168A (en) * | 2023-04-06 | 2023-07-07 | 厦门中科易工化学科技有限公司 | Catalyst for preparing chloromethane, application of catalyst and preparation method of chloromethane |
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| CN101716528A (en) * | 2009-10-30 | 2010-06-02 | 于志勇 | Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof |
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| DE709000C (en) | 1936-03-01 | 1941-08-02 | Chem Fab Von Heyden Akt Ges | Process for the preparation of vinyl halides |
| JPS52136104A (en) | 1976-05-08 | 1977-11-14 | Denki Kagaku Kogyo Kk | Preparation of vinyl chloride |
| DE3824634A1 (en) | 1988-04-30 | 1989-11-09 | Huels Chemische Werke Ag | METHOD FOR PRODUCING VINYL CHLORIDE BY REACTIVATING ACETYLENE WITH HYDROCHLORINE |
| JPH0369680A (en) * | 1989-08-03 | 1991-03-26 | Achilles Corp | Synthetic resin sheet and production thereof |
| BE1004983A3 (en) | 1991-06-20 | 1993-03-09 | Solvay | CATALYST SYSTEM AND METHOD hydrochlorination CHLORIDE PRODUCTION START IN VINYL CHLORIDE ACETYLENE AND HYDROGEN IN THE PRESENCE OF THIS SYSTEM CATALYST. |
| BE1004984A3 (en) | 1991-06-20 | 1993-03-09 | Solvay | CATALYST SYSTEM AND METHOD hydrochlorination CHLORIDE PRODUCTION START IN VINYL CHLORIDE ACETYLENE AND HYDROGEN IN THE PRESENCE OF THIS SYSTEM CATALYST. |
| JP3564838B2 (en) * | 1995-12-19 | 2004-09-15 | 宇部興産株式会社 | Method for producing cycloalkanol and cycloalkanone |
| FR2910350B1 (en) | 2006-12-22 | 2009-01-30 | Solvay | CATALYTIC HYDROCHLORIZATION SYSTEM AND PROCESS FOR PRODUCING VINYL CHLORIDE FROM ACETYLENE AND HYDROGEN CHLORIDE IN THE PRESENCE OF THIS CATALYTIC SYSTEM |
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| CN104086351A (en) * | 2014-06-30 | 2014-10-08 | 浙江大学 | Method for preparing vinyl chloride by taking azacyclo-protonic acid ionic liquid as medium through acetylene hydrochlorination |
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