CN107417487A - Method for hydrohalogenation alkynes and for manufacturing chlorination alkene by the hydrochlorination of alkynes - Google Patents

Method for hydrohalogenation alkynes and for manufacturing chlorination alkene by the hydrochlorination of alkynes Download PDF

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CN107417487A
CN107417487A CN201710107802.6A CN201710107802A CN107417487A CN 107417487 A CN107417487 A CN 107417487A CN 201710107802 A CN201710107802 A CN 201710107802A CN 107417487 A CN107417487 A CN 107417487A
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imidazoles
catalyzing
ionic liquid
butyl
catalyst system
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米歇尔·施特雷贝勒
克里斯蒂安·弗兰克
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Solvay SA
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    • 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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0278—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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0278—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
    • B01J31/0281—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 the nitrogen being a ring member
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0278—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
    • B01J31/0281—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 the nitrogen being a ring member
    • B01J31/0282—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 the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0278—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
    • B01J31/0281—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 the nitrogen being a ring member
    • B01J31/0284—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 the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0287—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 atoms other than nitrogen as cationic centre
    • B01J31/0288—Phosphorus
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • 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
    • B01J31/0298—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 the ionic liquids being characterised by the counter-anions
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention relates to a kind of method for hydrohalogenation alkynes and for manufacturing chlorination alkene by the hydrochlorination of alkynes.Specifically, the present invention relates to the method that vinyl chloride is manufactured for the hydrohalogenation alkynes in the presence of a kind of catalyst system and catalyzing and by the hydrochlorination of acetylene, the catalyst system and catalyzing includes at least one ionic liquid, the ionic liquid includes at least one non-protonated cation, according to this method, methods described is carried out made of the halogenated acid existing for being resistant in the form of dissociation and more specifically HCl material or in the equipment of covering.

Description

For hydrohalogenation alkynes and for manufacturing chlorination by the hydrochlorination of alkynes The method of alkene
The application be the applying date on 2 21st, 2012, Application No. 201280010264.4, entitled " be used for The Chinese invention patent application of hydrohalogenation alkynes and the method for manufacturing chlorination alkene by the hydrochlorination of alkynes " Divisional application.
Technical field
It is used for hydrohalogenation alkynes and for manufacturing chlorination alkene by the hydrochlorination of alkynes the present invention relates to a kind of Method.In particular it relates to for the hydrohalogenation alkynes in the presence of a kind of catalyst system and catalyzing and the hydrogen chlorine that passes through acetylene Change reaction to manufacture the method for vinyl chloride, the catalyst system and catalyzing includes at least one ionic liquid, and the ionic liquid includes at least one Kind non-protonated cation, according to this method, methods described is in the halogenated acid as existing for being resistant in the form of dissociation and more Specifically carried out made of HCl material or in the equipment of covering.
Background technology
It is typically in the gas phase, in a kind of fixed bed reactors to manufacture vinyl chloride by the reaction between acetylene and hydrogen chloride In, based on being loaded with what is carried out in the presence of a kind of heterogeneous solid catalyst of mercury chloride.The reason for mainly due to toxicity, It is more and more interested in mercury content or not compound containing mercury the catalyst system and catalyzing with reduction at present.
A variety of different catalyst are developed, it is intended to substitute the catalyst in current gas phase process.
For example, uncensored Japanese patent application 52/136104 is described by depositing noble metal on the activated carbon Halide composition it is fixed catalytic bed in the presence of in the gas phase by acetylene carry out hydrogen chloride a kind of method.But so far, Such life-span for being intended to the alternative catalyst for gas phase process is still far shorter than the catalyst based on mercury compound Life-span.
In addition, there are a kind of some examples that acetylene is carried out to hydrogen chloride in the presence of liquid catalytic medium in document.
Deutsche Bundespatent 709.000 describes a kind of by making acetylene into contact contain a kind of having for standard catalyst at high temperature The hydrohalide salt melt of machine alkali and the method for preparing vinyl halide.Aliphatic, aromatic or heterocycle amine And its mixture is considered as organic base.
The certificate SU 237116 of inventor describe using a kind of stannous chloride containing 46wt% and from 14wt% to The aqueous peracid solution of the hydrochloride of a kind of 16wt% methylamine, dimethylamine or trimethylamine.
European Patent Application EP-A-0 340 416 is disclosed at temperatures greater than room temperature by aliphatic or alicyclic ring Acetylene and hydrogen chloride are reacted in the presence of palladium compound is as catalyst in the solvent of race's acid amides composition and prepare chloroethene A kind of method of alkene.Although it allows to obtain high yield, however, this method has the shortcomings that some are obvious：It is rendered Go out this Liquid catalyst systems at reaction conditions gradually to degenerate, so as to form the black product with carbonaceous appearance.In addition, In the presence of hydrogen chloride, acid amides is converted into a kind of hydrochloride, and its fusing point is typically to be far above room temperature.For example, N- methyl Pyrrolidones hydrochloride is only only liquid more than 80 DEG C.In fact, this may cause serious implementation issue, these problems with The reunion of reactor down periods catalytic media or on the most cold point of facility the blocking of pipeline it is related.Then, whole reactor And the pipeline that also reaction medium flows wherein have to be continuously maintained in the temperature higher than HCI m. p.
Due to the hydrogen chlorine of the catalysis described in the 548-A1 of european patent application EP 0 519 and the 843-A1 of EP 0 525 Change reaction system, the problem of these are different seems to be resolved, and these systems include the metallization of at least one group VIII Compound and/or a kind of amine hydrochlorate (its fusing point is less than or equal to 25 DEG C) or a kind of fat comprising more than 8 carbon atoms Amine hydrochlorate (its fusing point is higher than 25 DEG C) and one kind selected from aliphatic, alicyclic and aromatic hydro carbons and its mixture have Solvent.However, described catalyst system wherein, especially wherein group VIII metallic compound is platinum chloride (II) Or the system of palladium bichloride (II), when in view of in terms of the productivity ratio of vinyl chloride is produced by the hydrochlorination of acetylene and long-term Stability in terms of they make it possible to realize performance when, be not entirely satisfactory.
WO 2008/77868 discloses a kind of hydrochlorination system of catalysis, including at least one amine hydrochlorate and extremely A kind of few group VIII metallic compound, the metallic compound are selected from the group, and the group is made up of the following：A kind of platinum (IV) The mixture of compound and stannic chloride (II), a kind of compound of platinum (II) and the mixture and one kind of triphenylphosphine oxide The compound of palladium (II) and the mixture of triphenylphosphine.These catalyst system and catalyzings are shown and european patent application EP-A 0519548 A kind of improved productivity ratio is compared with the system described in EP-A 0525843.
Finally, patent application CN 101716528 (quoting Zhiyong Yu as inventor) is disclosed for passing through acetylene Hydrochlorination production vinyl chloride catalyst system and catalyzing, the catalyst system and catalyzing include there are chlorine, bromine, hexafluoro-phosphate radical or four fluorophosphoric acid The ion of root is as anion base in imidazolesThe ionic liquid of (it is a kind of non-protonated cation), Yi Jijin, platinum, Palladium, tin, mercury, copper or rhodium chloride in one or more.
Above-mentioned last catalyst system and catalyzing seems to cause high selectivity and high conversion, at least when it is used for by chemically lazy When in experimental facilities made of the material (as glass or sending Simon Rex (Pyrex) glass) of property.In this respect, there is Zhiyong Publication Green Chemistry (Green Chem.) of the Yu as one of author, 2011, volume 13, page 1495, is expressly recited A kind of glass reactor for not referring to any etching problem.In fact, glass is not selected for etching problem, and It is only used for the returned materials (fall back material) of general experimental facilities.
The content of the invention
However, applicant noted that unexpectedly, if be subjected to above-mentioned containing imidazolesHydrochlorination be situated between Matter, the material used in the industrial plants that the method for above-mentioned patent is handled with a kind of amine hydrochlorate, rapidly and seriously by Corrosion.And from some experiments, applicant have noted that this problem seems to be generalized to comprising at least one non-protonated The ionic liquid of cation and HCl.
The applicant and then discovery, unexpectedly, as the HCl using tolerance dissociation, (i.e. tolerance is dissociated into active proton With the HCl in chlorine anion) material when, this problem almost disappears.This is quite unexpected, because being situated between in the reaction There is no water (but it is known that HCl dissociation is promoted by the presence of water) in matter and because using a kind of amine salt In hydrochlorate, previous hydrochlorination, HCl presence seems not cause etching problem.In fact, the problem of same, is with institute Some halogenated acids and occur, so not only with hydrogen chloride, and sent out with hydrogen iodide, with hydrogen fluoride and with hydrogen bromide It is raw.Such acid can be used for a kind of hydrogenization of alkynes, the alkynes be a kind of compound wherein two carbon by one three Key connection.It can be mentioned that acetylene, propine (also referred to as allylene), 2-butyne dicarboxylic ester, 1,4- in such alkynes Butylene glycol, together with the third acetylene compound.
Present invention is accordingly directed to one kind to be used for a kind of alkynes of hydrohalogenation (preferably acetylene) in the presence of a kind of catalyst system and catalyzing Method, the catalyst system and catalyzing include at least one ionic liquid, and the ionic liquid includes at least one non-protonated cation, root According to this method, methods described be at least in part the halogenated acid as existing for being resistant in the form of dissociation and be by selected from metal, Polymer, ceramics, refractory material, (dipping) graphite and enamel material made of or the equipment of covering in carry out.
The preferred embodiment of the present invention is related to anti-by the hydrogen chloride of acetylene in the presence of a kind of catalyst system and catalyzing A kind of method of vinyl chloride should be manufactured, the catalyst system and catalyzing includes at least one ionic liquid, the ionic liquid includes at least one The non-protonated cation of kind, according to this method, methods described is at least in part in the HCl as existing for being resistant in the form of dissociation And be made of the material selected from metal, polymer, ceramics, refractory material, (dipping) graphite and enamel or cover Equipment in carry out.
Term " at least in part carry out " mean the equipment, at least the reaction carried out wherein and with it is anti- Answer medium contact part, be by above-mentioned resistant material one of made of.
Term " being resistant to halogenated acid existing in the form of dissociation (HCl) " is meant in a normal industrial application life-span mistake In journey (several years, at least typically 10 years), involved material can be used for the part of the equipment, without being replaced or Repair.
In the present invention, term " acetylene " is understood as acetylene or the mixture comprising acetylene, and these mixtures remove second Other components, such as ethene or other unsaturated hydro carbons can also be included outside alkynes, these hydro carbons can be the pair of acetylene synthesis Product.The source of such mixture of different unsaturated compounds can be the mixture in any known source, because they It can be obtained during the known synthetic method for acetylene.The mixture for including the acetylene less than 50% can be used. However, it is preferred that term " acetylene " refers to the mixture comprising at least 90% acetylene and more preferably 100% acetylene.
Acetylene is mainly by the part burning manufacture of methane or the pair being used as in the Ethylene vapor from hydrocarbon cracking Product occurs.
Another method for manufacturing acetylene is the hydrolysis of calcium carbide
CaC2+2H2O→Ca(OH)2+C2H2
This requires about 2000 DEG C of extremely high temperature, so that electric furnace or the like must be used.
Mixture comprising acetylene and ethene can be used directly as it is, i.e. without component is separated, because second Reactivity of the alkynes compared with ethene causes the hydrogen chloride of acetylene acts on can separate obtained vinyl chloride first and then make Carried out with ethene.Can be by the ethylene chlorination to produce 1,2- dichloroethanes, so as to for a kind of manufacture VCM Integrated processes.The pyrolysis of 1,2- dichloroethanes can produce hydrogen chloride, for first reaction carried out with acetylene.According to this hair Bright hydrochlorination advantageously can be from room temperature to carrying out at a temperature of in the range of 220 DEG C.At higher temperatures, should Catalyst system and catalyzing has a kind of trend of degraded.Preferable reaction temperature, that is to say, that productivity ratio, yield and catalytic media are provided It is best between stability to trade off, it is greater than or equal to about 40 DEG C.At a temperature of greater than or equal to about 50 DEG C, it is particularly preferred Be greater than or equal to about 80 DEG C at a temperature of and most particularly preferably obtained at a temperature of greater than or equal to about 120 DEG C Obtain best result.Preferably, the reaction temperature is no more than about 200 DEG C.About 40 DEG C to about 200 DEG C of a reaction temperature is most It is particularly preferred.In some cases, the reaction temperature no more than 170 DEG C has turned out to be favourable.
According to the hydrochlorination of the present invention advantageously in environmental pressure or compatible with for handling the security legislation of acetylene Higher pressure under carry out.Generally, the pressure will be no more than 5MPa, preferably its dividing the acetylene no more than 2.5Mpa Pressure.
According to the hydrochlorination of acetylene of the present invention advantageously in any suitable reactor by by gaseous reactant (acetylene and hydrogen chloride) is contacted and carried out with the catalyst system and catalyzing.
Routinely it can be carried out according to the hydrochlorination of the present invention in the equipment that any promotion solution-air exchanges, should Equipment is such as plate tower, overflow-type packed column or overflow-type non-filling post.Another of this method can make gas phase and liquid There is the embodiment of good mass exchange between phase including the use of counter-current reactor, optionally sparged packed-bed type, the liquid Catalyst system and catalyzing inversely flows through the filler in the air-flow of reactant.
In the method according to the invention, the hydrogen chloride and the mol ratio of acetylene being introduced into reactor be beneficially greater than or Equal to about 0.5.Preferably, this ratio is greater than or equal to about 0.8.Advantageously, this mol ratio is less than or equal to about 3.It is excellent Selection of land, the hydrogen chloride and the mol ratio of acetylene being introduced into reactor are less than or equal to about 1.5.
When hydrogen chloride and acetylene be with the mol ratio of about 0.5 to about 3 in use, having been obtained for good knot Fruit.
Acetylene and hydrogen chloride can contact in the reactor, or preferably be mixed before reactor is introduced.
In order to increase the value of the acetylene of dissolving in the liquid phase, it is thus also possible to use a kind of method, only will in the method Acetylene is introduced into reactor in a gaseous form, and it is with the chlorination being present in the form of hydrochloride in liquid phase in the reactor Hydrogen reacts.The chlorination Hydrogen Energy introduces in any form：Dilution it is gaseous, pure or be dissolved in solvent to be extracted In, such as a kind of insoluble amine, it is advantageous that carry out the drying process of a centre afterwards.
The catalyst system and catalyzing according to used in the present invention includes at least one ionic liquid, and the ionic liquid includes at least one Non-protonated cation and at least one anion.
Ionic liquid is mainly the salt in liquid condition, and common liq (such as water and gasoline) is mainly by electricity Property molecule form.Ionic liquid is advantageously made up of ion.
Generally it is considered that it is any melting and Undec salt will generally produce a kind of ionic liquid.However, many salt Melt at high temperature, the high temperature is far above the temperature used in catalysis process.For the purposes of the present invention, term ionic liquid It is a kind of system of liquid at a temperature of should referring to used in the method using the catalyst system and catalyzing.
For the purposes of the present invention, preferable ionic liquid is under 150 DEG C or lower temperature, more preferably at 100 DEG C Or under lower temperature, even more preferably under 80 DEG C or lower temperature be liquid those.Most preferably in room temperature or Even below room temperature when the ionic liquid in liquid condition.Furthermore it is preferred that ionic liquid be that there is low-down vapour pressure It is and low-down flammable and show those of good electric conductivity.
The ionic liquid of reaction medium is advantageously used for preferably for the product and intermediate formed in the reaction With a kind of solvent power.
In this manual, statement " at least one ionic liquid " is understood to refer to a kind of or more than one ionic liquid Body.
Preferably, the catalyst system and catalyzing is mainly made up of a kind of ionic liquid as defined above.
In this paper remainder, the statement used with singular or plural form " ionic liquid " is understood to mean that one kind Or more than one ionic liquid, unless otherwise indicated.
In this manual, statement " at least one non-protonated cation " is understood to refer to a kind of or more than one Non-protonated cation.
Preferably, the ionic liquid includes a kind of non-protonated cation.
In this paper remainder, the statement used with singular or plural form " non-protonated cation " is interpreted as A kind of or more than one non-protonated cation is represented, unless otherwise indicated.
As used herein, the non-protonated cation of term, should refer in the cation for the purposes of the present invention just The cation of one or more free hydrogen atoms is not carried on one or more atoms assigned by electric charge.
Advantageously, the non-protonated cation is to be selected from
- quaternary ammonium cation, can be by formula [NR1R2R3R]+Represent,
-Cation, can be by formula [NR1R2R3R]+Represent,
- the cation including five or hexa-member heterocycle, the heterocycle have at least one nitrogen-atoms, advantageously one or two nitrogen Atom.
Preferred cationic including five or hexa-member heterocycle is
- there is the imidazoles for leading to formula (I)Cation
- there is the pyridine for leading to formula (II)Cation, and
- there is the pyrrolidines for leading to formula (III)Cation
Wherein group R and R1To R9Hydrogen, optionally substituted saturation or undersaturated can be respectively independently of one another C1-C18Alkyl group (preferably optionally substituted saturation or undersaturated C1-C16Alkyl group and more preferably can optionally it substitute Saturation or undersaturated C1-C14Alkyl group), wherein carbochain is not by the optionally substituted saturation of oxygen atoms or The C of saturation2-C18Alkyl group or optionally substituted C6-C12Aromatic yl group, precondition are the positive charge distribution of cation It is not hydrogen to arrive the group entrained by one or more atoms thereon.
Preferably, the non-protonated cation is to be selected from：Quaternary ammonium cation,Cation, imidazolesCation, pyridineCation and pyrrolidinesCation.
It is highly preferred that the non-protonated cation is to be selected from：Cation, imidazolesCation, pyridineCation And pyrrolidinesCation.
Most preferably, the non-protonated cation is to be selected from：Cation and imidazolesCation.
The example of quaternary ammonium cation is tributyl-methyl phosphonium ammonium, butyl trimethyl ammonium, octyl trimethyl ammonium, tetramethyl-ammonium, four Ethyl ammonium, tetrabutylammonium, methyl trioctylammonium, 2- hydroxyethyls trimethyl ammonium and diethylmethyl (2- methoxy ethyls) Ammonium.
The example of cation is triisobutyl methylTributyl-methyl phosphoniumEthyl tributylThe tetrabutylFour Octyl groupTributyl myristylThe decyl of three hexyl fourAnd benzyltriphenyl phosphonium
ImidazolesThe example of cation is 1,3- methylimidazoles1- ethyl-3-methylimidazoles1- butyl -3- first Base imidazoles1- amyl group -3- methylimidazoles1- hexyl -3- methylimidazoles1- decyl -3- methylimidazoles1- dodecanes Base -3- methylimidazoles1- myristyl -3- methylimidazoles1- cetyl -3- methylimidazoles1- (2- hydroxyl second Base) -3- methylimidazoles1- pi-allyl -3- methylimidazoles1- benzyl -3- methylimidazoles1- phenyl propyl -3- methyl Imidazoles1,3- diethyl imidazoliums1- butyl -3- ethyl imidazol(e)s1- methyl -3- propyl imidazoles1- methyl -3- octyl groups Imidazoles1- methyl -3- octadecyl imidazoles1,3- dibutyl -2-methylimidazole1,3- didecyls -2-methylimidazole1- (2- hydroxyethyls) -3- methylimidazoles1- ethyl -2,3- methylimidazoles1- propyl group -2,3- methylimidazoles1- butyl -2,3- methylimidazoles1- butyl -3,4- methylimidazoles1- hexyl -2,3- methylimidazoles1- Cetyl -2,3- methylimidazoles1,2,3- tri-methylimidazoliums1,3,4- tri-methylimidazoliums1- butyl -3- ethyls Imidazoles1,3- dibutyl imidazoles1- methyl -3- octylimidazoles1- butyl -3,4,5- tri-methylimidazoliumsAnd 1,3, 4,5- tetramethyl imidazoles
PyridineThe example of cation is 1- picolines1- ethylpyridines1- propyIpyridines1- butyl-pyridiniums1- hexyl pyridines1- octylpyridiniums1,2- lutidines2- ethyl -1- picolines1- butyl -2- first Yl pyridines1- butyl -3- picolines1- butyl -4- picolines1- hexyl -3- picolines1- hexyls- 4- picolines1- butyl -2- ethylpyridines1- butyl -3-ethylpyridine4- methyl isophthalic acids-octylpyridinium1- fourths Base -2- ethyl -6- picolines2- ethyl -1,6- lutidines1- butyl -3,4- lutidinesAnd 1- Butyl -3,5- lutidines
PyrrolidinesThe example of cation is 1,1- dimethyl pyrrolidines1- ethyl -1- crassitudes1- second Base -3- crassitudes1- butyl -1- crassitudes1- hexyl -1- crassitudes1- octyl group -1- methyl pyrroles Cough up alkane1- butyl -1- ethyl pyrrolidinesAnd 1- methyl isophthalic acids-propyl pyrrole alkane
In this manual, statement " at least one anion " is understood to refer to a kind of or more than one anion.
Preferably, the ionic liquid includes a kind of anion.
In this paper remainder, the statement used with singular or plural form " anion " be understood to mean that it is a kind of or More than one anion, unless otherwise indicated.
As anion, however, it would be possible to use all anion.The anion [Y] is preferably chosen from：
The group being made up of the halide with below formula and the anion of halogen and so-called false halide：
Cl-、Br-、BF4 -、PF6 -、Al2Cl4 -、Al2Cl7 -、FeCl4 -、BCl4 -、SbF6 -、AsF6 -、ZnCl3 -、
SnCl3 -、CF3SO3 -、(CF3SO3)2N-、CF3CO2 -、CCl3CO2 -、CN-、SCN-And OCN-,
The group being made up of the sulfate radical with below general formula, inferior sulfate radical and sulfonate radical：SO4 2-、HSO4 -、SO3 2-、HSO3 -、 RaOSO3 -、RaSO3 -,
The group being made up of the phosphate radical class with below general formula：
PO4 3-、HPO4 2-、H2PO4 -、RaPO4 2-、HRaPO4 -、RaRbPO4 -,
The group being made up of the phosphonate radical with below general formula and phosphinic acids root：
RaHPO3 -、RaRbPO2 -、RaRbPO3 -、
The group being made up of the orthophosphite with below general formula：
PO3 3-、HPO3 2-、H2PO3 -、RaPO3 2-、RaHPO3 -、RaRbPO3 -,
The group being made up of the phosphinate with below general formula and phosphinate：
RaRbPO2 -、RaHPO2 -、RaRbPO-、RaHPO-,
The group being made up of the carboxylate radical with below general formula：RaCOO-,
The group being made up of the borate (borates) with below general formula：
BO3 3-、HBO3 2-、H2BO3 -、RaRbBO3 -、RaHBO3 -、RaBO3 2-,
The group being made up of the borate (boronates) with below general formula：
RaBO2 2-、RaRbBO-,
The group being made up of the carbonate with below general formula and carbonic ester：
HCO3 -、CO3 2-、RaCO3 -,
The group being made up of the silicate with below general formula and esters of silicon acis：
SiO4 4-、HSiO4 3-、H2SiO42-、H3SiO4 -、RaSiO4 3-、RaRbSiO4 2-、RaRbRcSiO4 -、HRaSiO4 2-、 H2RaSiO4 -、HRaRbSiO4 -,
The group being made up of the alkyl silane with below general formula and aryl-silane salt：
RaSiO3 3-、RaRbSiO3 2-、RaRbRcSiO-、RaRbRcSiO3 -、RaRbRcSiO2 -、RaRbSiO3 2-,
The group being made up of the carboxylic acid imide root with below general formula, double (sulfonyl) imines roots and sulphonyl imine root：
The group being made up of the alkoxy with below general formula and aryloxy group：RaO-,
And by complicated metal ion such as Fe (CN)6 3-、Fe(CN)6 4-、MnO4 -、Fe(CO)4 -The group of composition,
And wherein group Ra, Rb, Rc is to be respectively independently of one another：C1-C18- alkyl；Wherein carbochain may be by one Or multiple phosphorus, oxygen and/or sulphur atom and/or the C of the imine group interruption of one or more substitutions2-C18- alkyl；C6-C12- virtue Base；C5-C12- cycloalkyl；Or one five or the phosphorous of six rings, the heterocycle of oxygen and/or sulphur or two of which are formed together A kind of undersaturated, saturation or aromatic ring, the ring may be by one or more phosphorus, oxygen and/or sulphur atom and/or one Individual or multiple substituted imine groups interruptions, these groups mentioned in it may each by functional group, as aryl, alkyl, Aryloxy group, alkoxy, halogen, hetero atom and/or heterocyclic substituted.
Give preferably Ra, Rb, Rc and be respectively hydrogen, methyl, ethyl, normal-butyl, 2- ethoxys, 2- cyanogen independently of one another Ethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxy carbonyl) ethyl, 2- (n-butoxycarbonyl) ethyls and chlorine.
This or these ion is preferably chosen among the following：Chlorion, bromide ion, iodide ion, trifluoromethanesulfonic acid Root, tosylate, tetrafluoro ethylsulfonic acid root, double-trifluoromethane sulfonic acid acid imide root, tetrachloro high ferro acid group, tetrafluoroborate, Tetrafluoro phosphate radical and hexafluoro-phosphate radical.
Method for manufacturing suitable ionic liquid is known to those of ordinary skill and therefore It is not necessary to herein It is described in detail.
Catalyst according to the invention system can be used for liquid phase or be deposited over solid carrier such as silica, aluminum oxide, silicon On aluminium stone, cordierite, mullite or activated carbon (only listing several suitable carrier materials), the up to pore volume of carrier and can With the limiting value of surface area.The carrier can have any shape, including but not limited to honeycomb for examples of such carriers material Shape thing and extrudate or the like.
When the catalyst system and catalyzing is in the liquid phase in use, can be by it with a kind of organic solvent diluting.In being included in basis The selection of the property of organic solvent in the catalyst system and catalyzing of the present invention particularly depends on claimed below：It is relative at reaction conditions It is inert for reactant, it easily mixes or be not easy to mix with ionic liquid；And depending on following is intended to：It and this Kind of ionic liquid forms a kind of medium, and the viscosity of the medium is less than the viscosity during ionic liquid individualism.
However, it is preferred that the ionic liquid is used as a kind of solvent, so that without using other solvent.
In the first preferred embodiment of the present invention, the catalysis system is mainly made up of at least one ionic liquid, should Ionic liquid includes at least one non-protonated cation and at least one anion selected from chlorion and methanesulfonate.
Statement " mainly by ... form " be understood to refer to remove in this manual defined at least one ionic liquid Outside body, it can also be included according to the catalyst system and catalyzing of the present invention and not have influential one kind or more on the catalysis characteristics of the catalyst system and catalyzing The other component of kind (preferably with a small amount of)；In other words, the reaction is not catalyzed in the course of reaction using the catalyst system and catalyzing Effect.In this one or more other component, it can be mentioned that in addition to this kind of or different kinds of ions liquid defined above One or more ionic liquids, such as add them into reduce the viscosity of the catalyst system and catalyzing.
Mainly it is made up of according to the catalyst system and catalyzing of the first embodiment of the present invention at least one ionic liquid, the ionic liquid Including at least one non-protonated cation and at least one anion selected from chlorion and methanesulfonate, wherein for Preference for non-protonated cation is listed above.
Preferably, the ionic liquid is to be selected from：Quaternary ammonium chloride (quaternary ammonium chlorides), first sulphur Sour quaternary ammonium (quaternary ammonium methanesulfonates), chlorinationMethanesulfonic acidImidazolitm chlorideFirst sulphur Imidazole acidPyridinium chlorideMethanesulfonic acid pyridineChlorination pyrrolidinesAnd methanesulfonic acid pyrrolidines
It is highly preferred that the ionic liquid is to be selected from：ChlorinationMethanesulfonic acidImidazolitm chlorideMethanesulfonic acid imidazolesChlorine Change pyridineMethanesulfonic acid pyridineChlorination pyrrolidinesAnd methanesulfonic acid pyrrolidines
It is highly preferred that the ionic liquid is to be selected from chlorinationMethanesulfonic acidImidazolitm chlorideAnd methanesulfonic acid imidazoles
Particularly preferred ionic liquid is to be selected from 1- butyl -3- methylimidazolium chloridesThe decyl chlorination of three hexyl four1- Ethyl -3- methylmethanesulfonate imidazoles1- methyl -3- octyl group imidazolitm chlorides1- ethyl -3- methylimidazolium chloridesAnd 1- Benzyl -3- methylimidazolium chlorides
Particularly preferred ionic liquid is from liquid electrolyte technology company (Iolitec GmbH) or from BASF share Company (BASF SE) it is commercially available those.
In second preferred embodiment of the method according to the invention, the catalyst system and catalyzing includes：
A) imidazoles of at least one N- alkylations and/or corresponding imidazolesAnd
B) at least one compound of optionally at least one metal.
Statement " comprising " is understood to refer to except the imidazoles and/or corresponding of at least one N- alkylations in this manual ImidazolesAnd outside at least one compound of optionally at least one metal, may according to the catalyst system and catalyzing of the present invention One or more other components of influence are with or without comprising the catalysis characteristics on the catalyst system and catalyzing.It is one or more another at this In outer component, it can be mentioned that one or more ionic liquids, such as be added into so as to the catalysis characteristics to the catalyst system and catalyzing Have an impact and/or allow the viscosity of the catalyst system and catalyzing to reduce.
Preferably, mainly it is made up of according to the catalyst system and catalyzing of the present invention the following
A) imidazoles of at least one N- alkylations and/or corresponding imidazolesAnd
B) at least one compound of optionally at least one metal.
Statement " mainly by ... form " has with the above for identical meanings defined in the first embodiment of the present invention.
Statement " the imidazoles and/or corresponding imidazoles of at least one N- alkylations" be understood to refer to one kind or be more than The imidazoles and/or corresponding imidazoles of a kind of N- alkylations
Preferably, the catalyst system and catalyzing of the second embodiment of the present invention includes a kind of imidazoles and/or corresponding of N- alkylations Imidazoles
In this paper remainder, the statement used with the singular or plural form " imidazoles of N- alkylations and/or corresponding Imidazoles" it is understood to mean that the imidazoles of a kind of or more than one N- alkylations and/or corresponding imidazolesUnless otherwise Explanation.
The imidazoles of N- alkylations according to the second embodiment of the present invention is advantageously defined by below formula (I)
Wherein group R1、R2、R3And R4Hydrogen or an optionally substituted saturation or insatiable hunger can be respectively independently of one another The C of sum1-C18(preferably C1-C14, more preferably C1-C12, most preferably C1-C10And particularly most preferably C1-C8) alkyl group.
The example of the imidazoles of N- alkylations is 1- methylimidazoles, 1- ethyl imidazol(e)s, 1- propyl imidazoles, 1- butyl imidazoles, 1- Amyl group imidazoles, 1- hexyl imidazoliums, 1- heptyl imidazoles, 1- octylimidazoles, 1- nonyls imidazoles, 1- decyls imidazoles, 1- methyl -2- octyl groups Imidazoles, 1- Ethyl-2-Methyls imidazoles, 1- butyl -2-methylimidazole, 1- hexyls -2-methylimidazole and 1- decyl -2- methyl miaows Azoles.
Preferably, the imidazoles of N- alkylations is to be selected from：1- methylimidazoles, 1- ethyl imidazol(e)s, 1- butyl imidazoles, 1- hexyls Imidazoles, 1- octylimidazoles, 1- decyls imidazoles, 1- methyl -2- octylimidazoles, 1- Ethyl-2-Methyls imidazoles, 1- butyl -2- methyl Imidazoles, 1- hexyls -2-methylimidazole and 1- decyls -2-methylimidazole.
It is highly preferred that the imidazoles of N- alkylations is to be selected from：1- methylimidazoles, 1- ethyl imidazol(e)s and 1- butyl imidazoles. The imidazoles of most preferred those N- alkylations is for example from aldrichIt is commercially available.
Method for manufacturing the imidazoles being suitably alkylated is known to those of ordinary skill and is therefore not necessarily to It is described in detail herein.
Catalyst system and catalyzing according to the second embodiment of the present invention includes at least one chemical combination of optionally at least a kind of metal Thing is as component b).
Statement " at least one compound of at least one metal " as used herein includes a kind of single metal of metal Compound, and the mixture of the different compounds of same metal, or the compound of different metal or include defined above two The mixture of the compound of kind of metal, i.e. catalyst system and catalyzing according to the second embodiment of the present invention may include it is more than one such as The metal of upper definition or correspondingly metallic compound.
Preferably, the catalyst system and catalyzing includes a kind of compound of at least one metal, and a kind of it is highly preferred that metal A kind of compound.
The statement " compound " used with singular or plural form and " metal " are interpreted as accordingly representing a kind of or more In a kind of compound and one kind or more than one metal, unless otherwise indicated.
Statement " including optionally at least one compound " is understood to refer to such a compound in the catalyst system and catalyzing Existence or non-existence.
According to the first sub- embodiment, catalyst system and catalyzing according to the second embodiment of the present invention advantageously includes component a) i.e. extremely The imidazoles and/or corresponding imidazoles of a kind of few N- alkylationsIn other words, the catalyst system and catalyzing does not include component b) advantageously i.e. At least one compound of at least one metal.
According to the second sub- embodiment, the catalyst system and catalyzing advantageously includes
A) imidazoles of at least one N- alkylations and/or corresponding imidazolesAnd
B) at least one compound of at least one metal.
In the second embodiment of the present invention, the metal can be any metal.The metal be advantageously selected from Pd, Pt, Au, Hg, Ru, Os, Ru, Rh and Ir.Preferably, the metal is to be selected from Pd, Pt, Au, Hg, Ru and Os.
Therefore catalyst system and catalyzing according to the second embodiment of the present invention preferably comprises
A) imidazoles of at least one N- alkylations and/or corresponding imidazolesAnd
B) at least one compound of at least one metal selected from Pd, Pt, Au, Hg, Ru and Os.
Although when the metal be selected from it is above-mentioned those when obtain good result, when the metal be selected from Pd, Extraordinary result is obtained when Ru, Au and Os, particularly preferred result is obtained simultaneously when the metal is and is selected from Pd, Ru and Au And obtain particularly good result when the metal is and is selected from Pd and Ru.Most significant knot is obtained when the metal is Pd Fruit.
Preferable Pt (IV) or Pt (II) or Pd (II) compound are the preparation process in the catalyst system and catalyzing according to the present invention In can change into mentioned metal chloride those.Therefore, it is possible to use the chlorine of platinum (IV), platinum (II) or palladium (II) Compound, nitrate, acetate, carbonate or oxide.And the chloride and acetate of these metals are preferable.
In platinum (IV) chlorine-based compound, it can be mentioned that platinum chloride (IV) and chloroplatinic acid or its esters, such as Na2PtCl6、K2PtCl6Or Li2PtCl6。
In platinum (II) chlorine-based compound, it can be mentioned that platinum chloride (II) and the chloroplatinite of alkali or alkaline-earth metal (platinochlorides), such as Na2(PtCl4)、K2(PtCl4)、Li2(PtCl4) and (NH4)2(PtCl4)。
In palladium (II) chlorine-based compound, it can be mentioned that palladium bichloride (II) and the chloropalladite of alkali or alkaline-earth metal (palladochlorides), such as Na2(PdCl4)、K2(PdCl4)、Li2(PdCl4) and (NH4)2(PdCl4)。
It is particularly preferred that PtCl4、PtCl2、PdCl2Platinum (IV), platinum (II) and palladium are chosen as respectively with palladium (II) (II) compound.PtCl2、PdCl2It is most preferred with palladium (II).
In Au compound, Au3+Compound is preferable, and equally in the case of Pd and Pt, can be converted It is preferable for those compounds of chloride.AuCl3It is most preferred.
Ru and Os suitable compound is those that chemical valence is 3 and can be converted into chloride again Those compounds or these chlorides are particularly preferred in itself.RuCl3And OsCl3It is most preferred respectively.
Among Hg suitable compound, it can be mentioned that HgCl2。
In the catalyst system and catalyzing according to the second sub- embodiment, imidazoles that the content of metallic compound is alkylated with every liter of N- And/or corresponding imidazolesMM number represent advantageously greater than or equal to about 1mmol/l and less than or equal to about 1000mmol/l.In the catalyst system and catalyzing according to second embodiment, the content of metallic compound is beneficially greater than or waited In about 1mmol/l, especially preferred greater than or equal to preferably greater than or equal to about 5mmol/l and about 10mmol/l.In the catalysis In system the content of metallic compound advantageously less than or equal to about 1000mmol/l, preferably less than or equal to about 800mmol/ L, about 600mmol/l is particularly preferably less than or equal to, is particularly preferably less than or equal to about 500mmol/l and be most especially excellent Choosing is less than or equal to about 400mmol/l.It is although not enforceable, in those cases it may however be preferred to be included in all in the catalyst system and catalyzing Metallic compound is at the form of dissolving.
In general, it is by the way that the metallic compound of desired value is molten according to the catalyst system and catalyzing of the second sub- embodiment Solve or be dispersed in the imidazoles of N- alkylations and/or corresponding imidazolesIn and then this solution is satisfied with hydrogen chloride With and prepare.However, it is also possible to first by the N- imidazoles being alkylated and/or corresponding imidazolesWith hydrogen chloride saturation, Followed by by the metallic compound introduce the N- alkylation imidazoles and/or corresponding imidazolesIn.Generally, it is used The value of metallic compound is such that in the catalyst system and catalyzing whole metallic compounds all in the form of dissolving.However, also have A kind of metallic compound may be used, its value or possessed property cause at least a portion of this compound with scattered The form of solid is present in the catalyst system and catalyzing, without unfavorable to the present invention.
In the 3rd preferred embodiment of the present invention, the catalyst system and catalyzing includes a kind of mixture of the following：
A) at least one compound of at least one metal selected from one of palladium, platinum and osmium；And
B) at least one ionic liquid of at least one non-protonated cation and at least one anion is included；
The mixture is selected from the group of following mixture, including
When the metal is palladium,
Palladium (II) and 1- butyl -3- methylimidazolium chloridesOr 1- ethyl -3- methylimidazolium chlorides
Palladium bichloride (II), copper chloride and 1- butyl -3- methylimidazolium chlorides
Palladium bichloride (II), stannous chloride and 1- butyl -3- methylimidazolium chlorides
Palladium bichloride (II) and 1- ethyl -3- methylimidazolium chlorides1- methyl -3- octyl group imidazolitm chlorides1- benzyls- 3- methylimidazolium chloridesThe decyl chlorination of three hexyl fourOr 1- butyl -4- picolinesDouble (trifluoromethyl sulfonyls) is sub- Aminate,
Palladium bichloride (II), palladium (II) and 1- butyl -4- picolinesDouble (trifluoromethyl sulfonyl) imidizations Thing；
When the metal is platinum,
Platinum chloride (II) and 1- butyl -3- methylimidazolium chlorides1- butyl -3- methyl tetrachloro high ferro imidazole acids 1- ethyl -3- methylimidazolium chlorides1- ethyl -3- methylmethane sulfonic acid imidazoles1- ethyl -3- methyl tetrafluoro ethylsulfonic acids Imidazoles1- methyl -3- octyl group imidazolitm chlorides1- methyl -3- octyl group trifluoromethanesulfonic acid imidazolesOr the decyl chloride of three hexyl four Change
Platinum chloride (IV) and 1- ethyl -3- methyl trifluoro methanesulfonic acid imidazolesOr the decyl of three hexyl fourDouble (fluoroforms Base sulfonyl) imines compound,
The sour potassium of chlordene platinum (IV) and 1- ethyl -3- methyl trifluoro methanesulfonic acid imidazolesAnd
When the metal is osmium,
Osmium chloride (III) and 1- butyl -3- methylimidazolium chlorides1- ethyl -3- methyl tetrafluoro ethylsulfonic acid imidazoles1- methyl -3- octyl group imidazolitm chloridesOr the decyl chlorination of three hexyl four
It is as defined above to state "comprising".
Preferably, catalyst system and catalyzing according to the third embodiment of the invention is mainly by least oneization of at least one metal The mixture of compound and at least one ionic liquid as defined above forms.
For first and/or second embodiment, statement " mainly by ... form " and " at least one of at least one metal Compound " is also as defined above.
According to the third embodiment of the invention catalyst system and catalyzing includes at least one gold selected from one of palladium, platinum and osmium At least one compound of category is as component a).
In the description of the third embodiment of the present invention, statement " at least one compound of at least one metal " includes one The single metallic compound of kind of metal, and the mixture of the different compounds of same metal, or the compound of different metal or The mixture of compound including two kinds of metals defined above, i.e. the catalyst system and catalyzing may include more than one as defined above Metal (correspondingly, metallic compound).
In the description of the third embodiment of the present invention, statement " a kind of metal selected from one of palladium, platinum and osmium " should be managed Solve to refer to that one kind in the metal is palladium, platinum or osmium.
The statement " compound " used with singular or plural form and " metal " are interpreted as accordingly representing a kind of or more In a kind of compound and one kind or more than one metal, unless otherwise indicated.
According to the third embodiment of the invention the first sub- embodiment, the catalysis system include a kind of mixing a) and b) Thing, the mixture are selected from the group of following mixture, comprising
Palladium (II) and 1- butyl -3- methylimidazolium chloridesOr 1- ethyl -3- methylimidazolium chlorides
Palladium bichloride (II), copper chloride and 1- butyl -3- methylimidazolium chlorides
Palladium bichloride (II), stannous chloride and 1- butyl -3- methylimidazolium chlorides
Palladium bichloride (II) and 1- ethyl -3- methylimidazolium chlorides1- methyl -3- octyl group imidazolitm chlorides1- benzyls- 3- methylimidazolium chloridesThe decyl chlorination of three hexyl fourOr 1- butyl -4- picolinesDouble (trifluoromethyl sulfonyls) is sub- Aminate.
According to the third embodiment of the invention the second sub- embodiment, the catalyst system and catalyzing include a kind of mixing a) and b) Thing, the mixture are selected from the group of following mixture, comprising
Platinum chloride (II) and 1- butyl -3- methylimidazolium chlorides1- butyl -3- methyl tetrachloro high ferro imidazole acids 1- ethyl -3- methylimidazolium chlorides1- ethyl -3- methylmethane sulfonic acid imidazoles1- ethyl -3- methyl tetrafluoro ethylsulfonic acids Imidazoles1- methyl -3- octyl group imidazolitm chlorides1- methyl -3- octyl group trifluoromethanesulfonic acid imidazolesOr the decyl chloride of three hexyl four Change
Platinum chloride (IV) and 1- ethyl -3- methyl trifluoro methanesulfonic acid imidazolesOr the decyl of three hexyl fourDouble (fluoroforms Base sulfonyl) imines compound,
The sour potassium of chlordene platinum (IV) and 1- ethyl -3- methyl trifluoro methanesulfonic acid imidazoles
According to the third embodiment of the invention the second sub- embodiment, the catalyst system and catalyzing include a kind of mixing a) and b) Thing, the mixture are selected from the group of following mixture, comprising
Osmium chloride (III) and 1- butyl -3- methylimidazolium chlorides1- ethyl -3- methyl tetrafluoro ethylsulfonic acid imidazoles1- methyl -3- octyl group imidazolitm chloridesOr the decyl chlorination of three hexyl four
Although had been obtained for well using the catalyst system and catalyzing of three sub- embodiments according to the third embodiment of the invention Result, but obtain extraordinary result with according to first and according to the catalyst system and catalyzing of the second sub- embodiment, and use Particularly preferred result is obtained according to the catalyst system and catalyzing of the first sub- embodiment.
At least one gold selected from one of palladium, platinum or osmium in catalyst system and catalyzing according to the third embodiment of the invention The content of the compound of category is advantageously more than or equal to 1mmol/l with a mM number expression for every liter of ionic liquid and is less than Or equal to 1000mmol/l.The content of compound as defined above is advantageously more than or equal to 1mmol/l, is preferably greater than or waits In 5mmol/l and especially preferred greater than or equal to 10mmol/l.The content of compound as defined above be advantageously less than or Equal to 1000mmol/l and preferably lower than or equal to 900mmol/l.
The content of the compound of palladium, platinum or osmium in catalyst system and catalyzing according to the third embodiment of the invention is often to lift away from A mM number expression for sub- liquid is advantageously more than or equal to 1mmol/l and is less than or equal to 1000mmol/l.As above it is fixed Justice compound content advantageously be more than or equal to 1mmol/l, preferably greater than or equal to 5mmol/l and particularly preferably More than or equal to 10mmol/l.The content of compound as defined above is advantageously less than or equal to 1000mmol/l, preferably small In or equal to 500mmol/l, particularly preferably less than or equal to 200mmol/l, particularly be preferably lower than or equal to 100mmol/l, And most it is particularly preferably less than or equal to 50mmol/l.
It is although not enforceable, in those cases it may however be preferred to which that it is all place to be included in all metallic compounds in the catalyst system and catalyzing In the form of dissolving.
In general, catalyst system and catalyzing according to the third embodiment of the invention is by by the metallization of desired value Compound is dissolved or dispersed in ionic liquid and then makes this solution saturation with hydrogen chloride and prepare.Can however, also having Can first by the ionic liquid with hydrogen chloride saturation, followed by the metallic compound is introduced into the ionic liquid.Generally, institute The value of the metallic compound used is such that in catalyst system and catalyzing whole metallic compounds all in the form of dissolving.However, It is also possible to using a kind of metallic compound, its value or possessed property cause at least a portion of this compound with point The form of scattered solid is present in the catalyst system and catalyzing, without unfavorable to the present invention.
According to the 4th preferred embodiment of the present invention, the catalyst system and catalyzing is such as to be carried in patent application CN101716528 Go out claim and the system (its content is hereby incorporated by reference in the present invention) described, i.e., a kind of catalyst system and catalyzing, the catalytic body System is comprising the ion with chlorine, bromine, hexafluoro-phosphate radical or tetrafluoro phosphate radical as anion based on imidazolesIonic liquid, And gold, platinum, palladium, tin, mercury, copper or rhodium chloride in one or more.
As described above, the method according to this invention is at least in part in the HCl as existing for being resistant in the form of dissociation Carried out made of material or in the equipment of covering, the material is：From metal, polymer, ceramics, refractory material, (dipping ) graphite and enamel.
It is not intended to theory to be limited, applicants believe that although the method for the present invention is usual in the absence of water Carry out, but the reaction medium is that so highly polar (ion) is dissociated into active proton and chlorine so that it promotes HCl Ion, it result in the corrosion that greatly accelerates of the material as stainless steel.
Therefore, as the appropriate material in the framework that can be used for the present invention, it can be mentioned that metal and nonmetallic materials Both.
These materials can be used in block or in the form of coating, but should be the HCl of tolerance dissociation.
Among these metal materials, it can be mentioned that tantalum and tantalum alloy, zirconium and zircaloy, titanium and titanium alloy, platinum and " platinum " The metal of race, silver and closed with minimum for silver-colored rhotanium, gold and electrum and plation, the molybdenum and molybdenum of 30% gold medal Gold, nickel-molybdenum alloy, NI-CR-MO alloys, monel, copper alloy (silicon bronze), copper tantalum and copper-niobium alloys, the tin antimony containing 5% antimony Alloy, tin-nickel alloy, niobium and niobium tantalum alloy.
In these metals of the platinum family, it can be mentioned that rhodium, iridium, ruthenium, palladium and osmium.
Among these metal materials, gold and tantalum are preferable.Tantalum, platinum and niobium even give good at up to 150 DEG C Good result, zirconium, silver and Ti-Pd alloys are corroded severely at this temperature.Especially tantalum and tantalum-base alloy (are included and are more than 50% tantalum) it is preferable metal within the framework of the invention.
Specific tolerance HCl alloy can also be used, such as：7 grades of titaniums, B races, alloy 400th, 904L levels stainless steel and super austenitic stainless steel or C races.
Among these nonmetallic materials, it can be mentioned that high density polyethylene (HDPE)；Fluoroelastomer based elastomeric；Based on poly- third Alkene, fluoropolymer (as：Polytetrafluoroethylene (PTFE)：PTFE；Fluorinated ethylene propylene (FEP)：FEP；Perfluoro alkoxy：PFA MFA；Polychlorostyrene trifluoro second Alkene：PCTFE；Polyvinylidene fluoride：PVDF；Polyvinyl fluoride：PVF；Polyethylene tetrafluoroethene：ETFE；Polyethylene CTFE： ECTFE thermoplastic)；ABS (acrylonitrile-butadiene-styrene (ABS)) copolymer；Acrylonitrile (40%)-vinyl chloride (60%) Copolymer；Polysulfones；Polyphenylene (PPH) polymer is as polyphenylene sulfide and PPSU；Based on polyester resin, phenolic resin, furans The glass resin laminated material of resin, epoxy resin and vinylester resin；Ceramics based on aluminum oxide and corundum；Based on hafnium carbide With the cermet material of titanium nitride；Based on carborundum, silica, the aluminium silicate salt of high silica contents, zirconium silicate, zirconium oxide and Silimanite (Al2O3-SiO2) refractory material；Based on epoxy resin, Sakaphen, based on phenol-formaldehyde resin andBrauthite coating；Based on silicates, phenol-formaldehyde resin and the sulfide mixed with quartz sand Acid resistance cement；Self-curing acid resistance cement based on the phenol-formaldehyde resin mixed with graphite；The furfuryl alcohol mixed with graphite Resin；The epoxy resin mixed with carbon and the polyester resin mixed with quartz.In the case of cement, the substrate should be by one Individual extra plastic tab protection.Graphite (with polytetrafluoroethylene (PTFE) or with a kind of resin impregnating), carbon, the glass of graphite, dipping Glass, quartz, enamel, porcelain, earthenware, rustic ware and acidproof brick may also be suitable as nonmetallic materials.Carborundum, aluminum oxide (dipping) graphite gives good result.
Among the polymer/resin that these can be used, it is also possible to refer in detail below these：CPVC be (chlorination PVC)、470、XP 45, DCPD (dicyclopentadiene), vulcanie and EPDM.
Enamel is advantageously used for a kind of material of coated steel.
In these polymer, those height are suitably comprising TPO such as high density polyethylene (HDPE) (HDPE), superelevation point Son amount PE (UHMWPE) and polypropylene (PP) and especially, thermoplastic, the sulfur-containing polymer such as polysulfones based on fluoropolymer Or polysulfide, especially this kind of aromatic polymer and the graphite of graphite and dipping.
In these thermoplastics based on fluorinated polymer, those height suitably include polyvinylidene fluoride, gathered Tetrafluoroethene, PFA, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro ethylene methacrylic ether copolymer and four Viton copolymers.
These polymer can be used with solid state or strengthened with a kind of sheath (steel, hooped reinforcement is as GRP).
Among the polymer/resin that these can be used, PEEK (polyether-ether-ketone) and fluorinated polymer are preferably at least For high temperature (typically above 100 DEG C) application.As fluorinated polymer, PTFE, FEP, PFA-MFA are (in trade (brand) nameUnder sell), ETFE and ECTFE be (as in trade (brand) nameUnder sell this) give it is good Good result.For giving good result compared with cryogenic applications, polymer in detail below：PP (or polypropylene) homopolymers and CPVC (PVC of chlorination).
Among the coating that these are formed by resin, it is especially suitable for based on those of epoxy resin or phenolic resin 's.Plastic coating can apply to such as steel or GRP (glass-reinforced polyester).
Depending on condition of work and the species of equipment, for coating or manufacturing the equipment for handling method of the invention Preferred material is graphite, with polytetrafluoroethylene (PTFE) or with a kind of graphite of resin impregnating, enamel, tantalum, gold, fluoropolymer, poly- Olefines and metal alloy.
For some special parts, such as heat exchanger and pump, no matter whether impregnated graphite is, is particularly suitable. For the heat-exchange apparatus for allowing heating or the evaporation of these fluids in the method, the graphite impregnated with polytetrafluoroethylene (PTFE) is It is particularly suitable.
Enamel, tantalum, gold and perfluorinated polymers are the coating or manufacture of equipment for being highly suitable for operating at high temperature.
TPO, fluoropolymer and metal alloy are the systems for being highly suitable for the coating or the equipment to work at high temperature Make.
Especially glassed steel (sometimes referred to as " glass-lined steel ") seems to show within the framework of the invention well.Really Real, a kind of solution more less expensive than the steel with a kind of fluoridized polymer linner and enamel illustrates to be polymerize with fluoridized Thing is compared to the more preferable bonding of steel.
It is therefore preferred that this method of the present invention is to be carried out at least in part in the equipment made of glassed steel, that is, use In at least one single-piece of the equipment of the method for the present invention be made of glassed steel.
In this respect, preferable enamel is in WO 2009/043796 (its content is hereby incorporated by reference in the present invention) Those described.These enamel include silicon, oxygen and calcium, and preferably, and potassium and titanium；They most preferably have：
The calcium of-low content；And/or
The potassium of-high content；And/or
The titanium of-low content.
Embodiment
Following instance is intended to illustrate invention, but is not intended to limit its scope.
General Experimental Procedures for these examples：
Hydrochlorination is carried out in a glass reactor, and the glass reactor is equipped with a sintered glass in bottom Disk disperses to obtain the good of the gaseous reactant being made up of acetylene and hydrochloric acid.
The thermal control of the system is obtained by a double wall reactor, and there is the reactor deep fat to adjust To maintain desired temperature, the temperature is controlled by a thermocouple sheath being placed in the reactor itself.
The gas flow rate is C2H2It it is 6Nl/ hours for 5Nl/ hours and HCl.Under 150 DEG C and atmospheric pressure, for one The residence time that " empty " reactor (being only mounted with ionic liquid) calculates is 3.2 seconds.
The small sample for there are these materials to be assessed is immersed in the medium and analyzed.
At 150 DEG C after 7h, SS (stainless steel) 316L samples are kept individually hardly by Butyl-methyl imidazolitm chloride (BMIM) influence, but in the imidazolesHCl and C2H2In the presence of (hydrochlorination medium), had been observed that after 1/2h The corrosion of destructive.Zirconium and silver are applied equally to, the latter is even completely dissolved in the medium.
On the other hand, in same reaction medium (imidazolesHCl and C2H2) in after 554h, glassed steel is kept not by shadow Ring.Also keep not or significantly not impacted under the same conditions：(0.0%), PEEK (0.0%), ECTFE (- 0.3%) and PTFE (0.0%) are after 216h；ETFE (0.0%) is after 186h；FEP (0.0%) is after 139.5h； The graphite (0.0%) impregnated with PTFE is after 210h and with a kind of graphite of resin impregnating (0.0%) after 161h；Oxygen Change aluminium (0.0%) after 210h；Niobium (- 0.6%) is after 164h；Tantalum (0.0%) is after 142h；Platinum (- 0.1%) is after 158.5h And carborundum (0.0%) is after 180.5h；The weight of these numerical monitors in () after the soak period of instruction becomes Change.
PP homopolymers and CPVC are tested under the same conditions, but under a lower temperature (90 DEG C) and They seem to do well and illustrate seldom weight change (accordingly -0.2%and+0.1%) after 186h.
Other polymer/resins are also tested, still under the same conditions, obtain following result：
150 DEG C/the 118h of@(+0.7%) of Derakane 470
100 DEG C/the 40.5h of@(- 0.2%) of Kera SP 30
90 DEG C/the 187h of@(+0.9%) of Covidur 883
90 DEG C/the 162h of@(+0.9%) of Vulco 2190
HB2@100 DEG C/163.5h, 90 DEG C/163.5h of (0%) HC276@(0%).
In addition, compared with the result obtained in glass reactor, some among material tested above are suitable The conversion ratio (conversion rate) is unexpectedly improved, i.e.,：PTFE, with PTFE or with a kind of phenolic resin and tantalum The graphite of dipping.

Claims (22)

1. for a kind of method of the hydrohalogenation alkynes in the presence of catalyst system and catalyzing, the catalyst system and catalyzing includes at least one ionic liquid Body, the ionic liquid include at least one non-protonated cation, and according to this method, methods described is at least partially in by as follows Carried out made of material or in the equipment of covering, the material be resistant to halogenated acid existing in the form of dissociating and selected from metal, Polymer, ceramics, refractory material, (dipping) graphite and enamel.
2. according to the method described in previous item claim, wherein the alkynes is acetylene and the halogenated acid is HCl.
3. according to the method described in previous item claim, wherein the hydrochlorination is from room temperature to 220 DEG C of scope Carried out at interior temperature.
4. the method according to any one of the preceding claims, wherein the non-protonated cation be selected from quaternary ammonium sun from Son,Cation, imidazolesCation, pyridineCation and pyrrolidinesCation.
5. the method according to any one of the preceding claims, wherein the ionic liquid is used as solvent, so that no Use other solvent.
6. the method according to any one of the preceding claims, wherein the catalyst system and catalyzing is mainly by least one ionic liquid Body forms, and the ionic liquid includes at least one non-protonated cation and at least one is selected from chlorion and methanesulfonate Anion.
7. according to the method described in previous item claim, wherein the ionic liquid is selected from chlorinationMethanesulfonic acidChlorination miaow AzolesAnd methanesulfonic acid imidazoles
8. according to the method described in previous item claim, wherein the ionic liquid is selected from 1- butyl -3- methylimidazolium chloridesThe decyl chlorination of three hexyl four1- ethyl -3- methylmethanesulfonate imidazoles1- methyl -3- octyl group imidazolitm chlorides1- second Base -3- methylimidazolium chloridesAnd 1- benzyl -3- methylimidazolium chlorides
9. method according to any one of claim 1 to 5, wherein the catalyst system and catalyzing includes：
A) imidazoles of at least one N- alkylations and/or corresponding imidazolesAnd
B) optionally, at least one compound of at least one metal.
10. according to the method described in previous item claim, wherein the imidazoles of N- alkylations is defined by below formula (I)
Wherein group R1、R2、R3And R4Hydrogen or the saturation optionally substituted or undersaturated C can be respectively independently of one another1-C18 (preferably C1-C14, more preferably C1-C12, most preferably C1-C10And particularly most preferably C1-C8) alkyl group.
11. according to the method described in previous item claim, wherein the imidazoles of N- alkylations is selected from：1- methylimidazoles, 1- Ethyl imidazol(e) and 1- butyl imidazoles.
12. the method according to any one of claim 9 to 11, wherein the catalyst system and catalyzing includes：
A) imidazoles of at least one N- alkylations and/or corresponding imidazolesAnd
B) at least one compound of at least one metal selected from Pd, Pt, Au, Hg, Ru and Os.
13. according to the method any one of Claims 1-4 5, wherein the catalyst system and catalyzing includes the mixing of the following Thing：
A) at least one compound of one of them at least one metal selected from palladium, platinum and osmium；And
B) at least one ionic liquid comprising at least one non-protonated cation and at least one anion；
The mixture is selected from the group of following mixture, and the group includes
When the metal is palladium,
Palladium (II) and 1- butyl -3- methylimidazolium chloridesOr 1- ethyl -3- methylimidazolium chlorides
Palladium bichloride (II), copper chloride and 1- butyl -3- methylimidazolium chlorides
Palladium bichloride (II), stannous chloride and 1- butyl -3- methylimidazolium chlorides
Palladium bichloride (II) and 1- ethyl -3- methylimidazolium chlorides1- methyl -3- octyl group imidazolitm chlorides1- benzyl -3- first Base imidazolitm chlorideThe decyl chlorination of three hexyl fourOr 1- butyl -4- picolinesDouble (trifluoromethyl sulfonyl) imidizations Thing,
Palladium bichloride (II), palladium (II) and 1- butyl -4- picolinesDouble (trifluoromethyl sulfonyl) imines compounds；
When the metal is platinum,
Platinum chloride (II) and 1- butyl -3- methylimidazolium chlorides1- butyl -3- methyl tetrachloro high ferro imidazole acids1- second Base -3- methylimidazolium chlorides1- ethyl -3- methylmethane sulfonic acid imidazoles1- ethyl -3- methyl tetrafluoro ethyl sulfonic acid imidazoles1- methyl -3- octyl group imidazolitm chlorides1- methyl -3- octyl group trifluoromethanesulfonic acid imidazolesOr the decyl chlorination of three hexyl four
Platinum chloride (IV) and 1- ethyl -3- methyl trifluoro methanesulfonic acid imidazolesOr the decyl of three hexyl fourDouble (trifluoromethyl sulphurs Acyl group) imines compound,
The sour potassium of chlordene platinum (IV) and 1- ethyl -3- methyl trifluoro methanesulfonic acid imidazolesAnd
When the metal is osmium,
Osmium chloride (III) and 1- butyl -3- methylimidazolium chlorides1- ethyl -3- methyl tetrafluoro ethyl sulfonic acid imidazoles1- first Base -3- octyl group imidazolitm chloridesOr the decyl chlorination of three hexyl four
14. method according to any one of claim 1 to 5, wherein the catalyst system and catalyzing include with chlorion, bromine from The ion of son, hexafluoro-phosphate radical or tetrafluoro phosphate radical is as anion based on imidazolesIonic liquid and the following in One or more：Gold, platinum, palladium, tin, mercury, the chloride of copper or rhodium.
15. the method according to any one of the preceding claims, methods described is at least in part made of glassed steel Carried out in equipment.
16. according to the method described in previous item claim, wherein the enamel includes silicon, oxygen, calcium, potassium and titanium and had：
The calcium of-low content；And/or
The potassium of-high content；And/or
The titanium of-low content.
17. the method according to any one of claim 1 to 14, methods described is at least in part by tantalum, platinum or niobium system Into or covering equipment in carry out.
18. the method according to any one of claim 1 to 14, methods described made of tantalum or is being covered at least in part Carried out in the equipment of lid.
19. the method according to any one of claim 1 to 14, methods described is at least in part by carborundum, oxidation Carried out made of aluminium or (dipping) graphite or in the equipment of covering.
20. the method according to any one of claim 1 to 14, methods described is at least in part poly- by PEEK or fluorination Carried out made of compound or in the equipment of covering.
21. the method according to any one of claim 1 to 14, methods described is at least in part by PP (or polypropylene) Carried out made of homopolymer or CPVC (PVC of chlorination) or in the equipment of covering.
22. the method according to any one of claim 1 to 14, methods described at least in part by PTFE, use PTFE Or carried out made of the graphite or tantalum of resin impregnating or in the equipment of covering.
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