CN104936933A - Process for the hydrohalogenation of an unsaturated hydrocarbon - Google Patents
Process for the hydrohalogenation of an unsaturated hydrocarbon Download PDFInfo
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- CN104936933A CN104936933A CN201380071080.3A CN201380071080A CN104936933A CN 104936933 A CN104936933 A CN 104936933A CN 201380071080 A CN201380071080 A CN 201380071080A CN 104936933 A CN104936933 A CN 104936933A
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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
- 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
- B01J31/0292—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
-
- 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
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated 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
- 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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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Process for the hydrohalogenation of an unsaturated hydrocarbon using a catalyst comprising at least one ionic liquid (IL) and at least one metal, according to which said IL and metal are encapsulated inside a porous solid carrier.
Description
This application claims the right of priority of the European application numbers 12198097.3 submitted on December 19th, 2012, for all objects, this full content applied for is combined in this by reference.
The present invention relates to a kind of for unsaturated hydrocarbons hydrohalogenation, be preferably used for acetylene hydrochlorination to produce the method for vinylchlorid (VC).
VC is manufactured normally in the gas phase, to carry out in fixed-bed reactor, under the heterogeneous solid catalyst on carrier based on mercury chloride exists by reaction between acetylene and hydrogenchloride.Mainly due to toxicity, at present to have minimizing mercury content or the catalyst system of not compound containing mercury more and more interested.
Developed multiple different catalyzer, these catalyzer are intended to replace the catalyzer in current gas phase process.
Such as, uncensored Japanese patent application 52/136104 describes a kind of method of in the gas phase acetylene being carried out hydrochlorinate under by the fixed catalytic bed existence that the noble metal halide deposited on the activated carbon is formed.But up to now, this type of is intended to still be significantly shorter than life-span of the catalyzer based on mercury compound for the life-span of the alternative catalyzer of gas phase process.
In addition, some are had acetylene to be carried out the example of hydrochlorinate under the existence of liquid catalytic medium in document.
German Patent 709.000 describes a kind ofly prepares the method for vinyl halide by high temperature making acetylene into contact contain the hydrohalogen salt melt of the organic bases of standard catalyst.Amine of aliphatic, aromatic or heterocycle and composition thereof is considered as organic bases.
The certificate SU 237116 of contriver describes and uses a kind of aqueous peracid solution containing the hydrochloride of the cuprous chloride of 46wt% and methylamine, dimethylamine or the Trimethylamine 99 from 14wt% to 16wt%.
European patent application EP-A-0 340 416 discloses and is undertaken reacting by acetylene and hydrogenchloride under palladium compound exists as catalyzer at temperatures greater than room temperature in the solvent be made up of aliphatics or cycloaliphatic amide and prepare the method for VC.Although it allows to obtain high output, but this method has some obvious shortcomings: it has shown this Liquid catalyst systems at reaction conditions and has degenerated gradually, thus forms the black product with carbonaceous appearance.In addition, under the existence of hydrogenchloride, acid amides is converted into hydrochloride, and its fusing point is normally far above room temperature.Such as, N-Methyl pyrrolidone hydrochloride is only only liquid more than 80 DEG C.In fact, this may cause serious implementation issue, the reunion of these problems and reactor down periods catalytic media or on the coldest point of facility the blocking of pipeline relevant.So the pipeline that whole reactor and the medium that responds flow wherein must remain on the temperature higher than HCI m. p constantly.
Due to the hydrochlorination system of catalysis described in European patent application EP 0 519 548-A1 and EP 0 525 843-A1, these different problems seem to be resolved, 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 DEG C) or a kind of comprise more than 8 carbon atoms fatty amine hydrochloride (its fusing point is higher than 25 DEG C) and be selected from a kind of organic solvent of aliphatics, alicyclic and aromatic hydro carbons and composition thereof.But, catalyst system described wherein, especially wherein this group VIII metallic compound is the system of platinum chloride (II) or Palladous chloride (II), when considering that in stability in the productivity that the hydrochlorination by acetylene produces VC and long-term, they make it possible to the performance realized, be not entirely satisfactory.
WO 2008/77868 discloses a kind of hydrochlorination system of catalysis, this system comprises at least one amine hydrochlorate and at least one group VIII metallic compound, this metallic compound is selected from lower group, and this group is made up of the following: the miscellany of platinum (IV) compound and tin chloride (II), platinum (II) compound and the mixture of triphenylphosphine oxide and the mixture of palladium (II) compound and triphenylphosphine.These catalyst system show the productivity as compared to the system described in European patent application EP-A0519548 and EP-A 0525843 improvement.
With for being become by acetylene hydrochlorination another example of the relevant disclosure of the liquid catalytic medium of VC to be patent application CN 102671701, this patent application discloses multiple catalysts, these catalyzer consist of the specific support of the ionic liquid having mercury to fix by load and avoid discharging mercury, this ionic liquid by silane coupling agent-silicon ester chemically with the surface bonding of this carrier, and this mercury chloride is connected on the imidazole ring of this ionic liquid by coordinate bond.The catalytic hydrochlorination of acetylene it is said be be fixed on the ionic liquid layer on this carrier surface is carried out and allow to reach high conversion of alkyne.
Finally, patent application CN 101716528 (citing Zhiyong Yu is as contriver) discloses the catalyst system for being produced VC by the hydrochlorination of acetylene, this catalyst system comprises and has chlorine, bromine, hexafluoro-phosphate radical or tetrafluoro phosphate anion as the ionic liquid (IL) of anion-radicals in imidazoles (it is a kind of positively charged ion of aprotic), one or more in the muriate of Yi Jijin, platinum, palladium, tin, mercury, copper or rhodium.
Above-mentioned last catalyst system seems to cause relatively high selectivity and transformation efficiency, at least when it in the experimental installation be made up of the material (as glass or send Simon Rex glass (Pyrex)) of chemically inertia time.In this respect, have the publication Green Chemistry (Green Chem.) of Zhiyong Yu as one of author, 2011, the 13rd volume, clearly describes a kind of glass reactor not mentioning any etching problem by the 1495th page.In fact, glass is selected for etching problem, and is only used for the returned materials (fall backmaterial) of general experimental installation.
But the applicant notices, unexpectedly, if stand the above-mentioned hydrochlorination medium containing imidazoles, material used in the industrial plants of the method by the above-mentioned patent of a kind of amine hydrochlorate process, rapidly and be seriously corroded.And from some tests, the applicant notices that this problem seems at least to be generalized to and comprises the positively charged ion of at least one aprotic and the IL of HCl.
Therefore; patent application (WO 2012/113778) object of the applicant be a kind of IL that uses of protection as the method for catalyzer for unsaturated hydrocarbons (preferred acetylene) hydrohalogenation, and the method at least in part the material by the halogenated acid of tolerance in the form of dissociating make or carry out in the equipment that covers.
The applicant has been found that unexpectedly now, and catalyst according to the invention significantly reduces the above-mentioned etching problem in the unsaturated hydrocarbons hydrohalogenation process using a kind of IL catalyzer mentioned.
Therefore, the present invention relates to a kind of method for unsaturated hydrocarbons hydrohalogenation, the method uses the catalyzer comprising at least one ionic liquid (IL) and at least one metal, and according to the method, IL and metal are encapsulated in the inside of porous solid carrier.
Any unsaturated hydrocarbons can use in the method according to the invention.Preferably, it is gaseous state at hydrohalogenation temperature.
By unsaturated hydrocarbons be meant to a kind of by carbon and hydrogen form and there is at least one component that is two and/or triple bond between two C atoms; Example is acetylene, ethene and analogue.
Acetylene gives good result and is particularly preferred within the framework of the invention.
In a preferred embodiment of the present invention, this hydrohalogenation is hydrochlorination.When this unsaturated hydrocarbons is acetylene, this embodiment makes us interested especially.
Therefore, according to method of the present invention preferably a kind of for acetylene hydrochlorination to produce the method for VC.
In this manual, term " acetylene " it must be understood that as a kind of acetylene source, and it can be or " pure " acetylene (as commercially available) or comprise the mixture of acetylene that these mixtures can comprise other components except acetylene.
Other components of this kind can be the by products of acetylene synthesis, and such as ethene or other unsaturated hydrocarbons, gas, as N
2, CO
2, H
2, CO, H
2o ...
Acetylene is the partial combustion by methane, the oxicracking by hydrocarbon source, by electric arc coal stove, manufactured by plasma coal stove or as in the ethylene stream of the cracking from hydrocarbon by product occur.
Another kind of method for the manufacture of acetylene is the hydrolysis of carbide of calcium
CaC
2+2H
2O→Ca(OH)
2+C
2H
2
From CaO or CaCO
3caC is manufactured with C
2require the extremely high temperature of about 2000 DEG C, force and use electric furnace or analogue.
When use comprises the mixture of acetylene and ethene, they can directly in statu quo use, that is, without the need to component is separated, because the reactivity of acetylene compared with ethene should make the hydrochlorinate of acetylene to be first wherein separated obtained VC and to use ethene subsequently.Can by this ethylene chlorination to produce 1,2-ethylene dichloride (DCE), for the manufacture of the integrated processes of VC.The pyrolysis of DCE can produce hydrogenchloride, first to react for this carrying out with acetylene.
Alternately, because this kind of hydrogenchloride produced from DCE pyrolysis comprises a small amount of acetylene usually, before hydrogenchloride is recycled to the method, this acetylene is hydrogenated usually, and this type of acetylene can stand according to method of the present invention.
Therefore, foundation is according to a variant of the present invention, preferred hydrochlorinate method according to the present invention is carried out after DCE pyrolysis in the method from ethylene production DCE and VC, as a kind of replacement scheme of the Acetylene hydrogenation sometimes used in a kind of like this method.
In a first sub-variant, catalyzer of the present invention is placed on the quenching device inside for these pyrolysis gas of quenching or downstream.
In a second sub-variant, catalyzer of the present invention is placed on for being separated in the tubing string of HCl from VC and other compositions of quenching gas.
In a 3rd sub-variant, catalyzer of the present invention is placed on the effluent that the tubing string for being separated HCl from VC and other compositions of quenching gas adopts.Any position below the feed point that this effluent takes from this tubing string or more, more than this feed point excellent.This effluent can obtain from the vapor phase circulated this tubing string or from liquid phase or from this two-phase.Preferably, this effluent obtains from this vapor phase.In the downstream of this pyrolysis any this reacted gas of applicable position recirculation (that is, acetylene wherein has been converted into the gas of VC).The recirculation position be applicable to is such as the quenching place of this tubing string, charging place or this tubing string itself.
In a 4th sub-variant, top portion catalyzer of the present invention being placed at this tubing string from stream on, preferably after the appropriate heat treatment and/or pressure treatment of described stream.
In these variants, this catalyzer preferably honeycomb type and preferably there is multiple large passage to avoid described passage to be blocked by tar.
Statement " being encapsulated in the inside of porous solid carrier " it must be understood that as referring to that this ionic liquid and this metal are both physically mainly restricted in this porous solid carrier in the context of the present invention; In other words, they mainly in the cage be made up of this porous solid carrier/their main phases to be limited securely/to be retained in this porous solid carrier-gel nanoporous but advantageously without any chamical binding.
For word " mainly ", according to the present invention, it refers to substantially all ionic liquids and metal all in this porous solid carrier, but the sub-fraction not getting rid of them may be present on the outside surface of this porous solid carrier, but under any circumstance advantageously without any chamical binding.
This porous solid carrier preferably includes silicon-dioxide or aluminum oxide.More preferably, this porous solid carrier comprises silicon-dioxide and even more preferably: it forms primarily of silicon-dioxide.
What prepare advantageously by following steps according to the catalyzer used in the inventive method:
The precursor of this porous solid carrier is mixed with alcohol and obtains its mixture;
Heat this kind of mixture and then add described IL and metal to it, being preferably pre-mixed;
Once obtain clarification and uniform liquid mixture, in this kind of mixture, add acid and allow it to condense; And
The mixture of this condensation aging is to obtain this catalyzer preferably in powder type.
Consider that the method allows this ionic liquid and this metal physically to be limited/be packaged in this porous solid carrier-gel matrix, the method can be named as sol-gel method.
In another embodiment, this catalyzer can also be prepared by following steps:
According to the program Kaolinite Preparation of Catalyst (A) disclosed in the patent application EP 2617698 (its content combines in this application by reference) of the applicant's name, described catalyzer comprises solid carrier, metal and ionic liquid;
Catalyzer (A) is mixed with solution (B) to obtain slurry (C), in this solution (B), this ionic liquid is preferably insoluble, and described solution (B) comprises precursor and the alcohol of porous solid carrier;
In this slurry (C), add acid and allow it to condense; And
The mixture of this condensation aging is to obtain this catalyzer preferably in powder type.
The precursor of this porous solid carrier can be selected among obtainable precursor.
When this porous solid carrier is silicon-dioxide, this precursor is advantageously selected from corresponding to formula Si (O-R
1) (O-R
2) (O-R
3) (O-R
4) compound, wherein R
1, R
2, R
3and R
4be identical or different, preferably saturated alkyl chain, these alkyl chains comprise from 1 to 8 carbon atom, preferably from 1 to 4 carbon atom and more preferably from 1 to 3 carbon atom.Preferably when this porous solid carrier is silicon-dioxide, this precursor is selected from corresponding to formula Si (O-R
1) (O-R
2) (O-R
3) (O-R
4) compound, wherein R
1, R
2, R
3and R
4all ethyl (tetraethoxy ortho-silicate).
When this porous solid carrier is aluminum oxide, this precursor is preferably selected from has formula Al (OR)
3aluminium alkoxide, wherein R is three identical or different, preferably identical alkyl.
Any alcohol can be selected for the catalyzer be prepared according to using in the inventive method.Preferred alcohol comprises from 1 to 8 carbon atom, preferably saturated alcohol.Preferred alcohol comprises from 1 to 6 carbon atom, preferably saturated alcohol.Most preferred alcohol comprises from 1 to 4 carbon atom, preferably saturated alcohol.Ethanol gives very good result.
The mixture of the precursor and this alcohol that heat this porous solid carrier can carry out at any temperature being suitable for the component existed.Advantageously, heat and to be included at the temperature between 40 DEG C and 75 DEG C, preferably between 50 DEG C and 70 DEG C and more preferably to carry out at 60 DEG C.
Acid to be added is had to be considered to select among any compound of Bronsted acid.The example of the acid that can enumerate is HF, HBr, HI, HCl, H
2sO
3, H
2sO
4, HNO
2, HNO
3, H
2cO
3, H
3pO
3, H
3pO
4and the ammonium salt of their correspondences and acetic acid.Preferably, this acid is HCl or NH
4f.
Aging condensed mixture can carry out at any temperature required for the catalyzer of acquisition in applicable form.Advantageously, to be thisly agingly included at the temperature between 40 DEG C and 80 DEG C, preferably between 50 DEG C and 70 DEG C and more preferably to carry out at 60 DEG C.
According to the content of the unsaturated hydrocarbons (preferred acetylene) in this unsaturated hydrocarbons (preferred acetylene) source, this hydrohalogenation (preferred hydrochlorinate) reaction can advantageously be carried out under from-30 DEG C to the temperature within the scope of 230 DEG C.Because this catalyst system has the trend of degeneration, higher temperature is not recommended.
In the method according to the invention,
-when this unsaturated hydrocarbons (preferred acetylene) source has unsaturated hydrocarbons (preferred acetylene) content being equal to or greater than 10%, this hydrohalogenation (preferred hydrochlorinate) reaction is advantageously carried out at the temperature of 40 DEG C to 200 DEG C;
-when this unsaturated hydrocarbons (preferred acetylene) source unsaturated hydrocarbons (preferred acetylene) content lower than 10% time, carry out at the temperature of this hydrohalogenation (preferred hydrochlorinate) reaction advantageously between-30 DEG C and 200 DEG C.
When this unsaturated hydrocarbons (preferred acetylene) source has unsaturated hydrocarbons (preferred acetylene) content being equal to or greater than 10%, favourable temperature of reaction (temperature of the best compromise between the stability being that is provided in productivity, productive rate and this catalytic media) is more than or equal to 40 DEG C.Then, to be more than or equal at the temperature at the temperature of 50 DEG C, being particularly preferably more than or equal to 80 DEG C and to obtain best result under particularly preferably being the temperature being more than or equal to 110 DEG C most.Advantageously, this temperature of reaction is no more than 200 DEG C.In some cases, the temperature of reaction being no more than 170 DEG C has proved favourable, or not even more than 130 DEG C.Observe lower corrosion speed and coke generation at a lower temperature, but, higher transformation efficiency can be observed at a higher temperature.
In the method according to the invention,
-when this unsaturated hydrocarbons (preferred acetylene) source has unsaturated hydrocarbons (preferred acetylene) content being equal to or greater than 10%, this hydrohalogenation (preferred hydrochlorinate) reaction advantageously lower than 10MPa, be preferably lower than 5MPa, more preferably lower than the pressure of 2.5MPa under carry out;
-when this unsaturated hydrocarbons (preferred acetylene) source unsaturated hydrocarbons (preferred acetylene) content lower than 10% time, this hydrohalogenation (preferred hydrochlorinate) reaction advantageously lower than 5MPa, be preferably lower than 2.5MPa and more preferably lower than the pressure of 1MPa under carry out.
But this pressure advantageously higher than 5Pa, preferably higher than 8Pa and more preferably higher than 10Pa.
The hydrohalogenation (preferred hydrochlorinate) of this unsaturated hydrocarbons (preferred acetylene) can gas phase or with liquid phase, preferably carry out with gas phase.The hydrohalogenation (preferred hydrochlorinate) of this unsaturated hydrocarbons (preferred acetylene) is advantageous by making the acetylene of these gaseous reactants-preferably and hydrogenchloride-carry out with this catalyst exposure in any applicable reactor.
This hydrohalogenation (preferred hydrochlorinate) reaction can be carried out routinely in the equipment of the gas of any promotion on solid material or liquid comes into contact.This kind equipment is air flow bed, pneumatic transport, swirler, fluidized-bed, vibrating bed, fixed bed, moving-bed, bubbling bed, spouted bed or any combination.
In first embodiment, this reaction is carried out in fixed bed and/or pre-assembled structure, and wherein the outside surface of this catalyzer and volume ratio (S/V) are advantageously less than or equal to 610
4m
-1, be preferably lower than or equal 310
4m
-1, more preferably less than or equal to 210
4m
-1and advantageously greater than or equal to 10m
-1, preferably greater than or equal to 20m
-1and more preferably greater than or equal to 25m
-1, described method comprises with advantageously greater than or equal to 0.005m/s, preferably greater than or equal to 0.008m/s, 0.01m/s, more preferably greater than or equal to 0.02m/s and advantageously less than or equal to 20m/s, be preferably lower than or equal 15m/s, total linear velocity more preferably less than or equal to 12m/s adds at least this unsaturated hydrocarbons (preferred acetylene) and this hydrohalogenation (preferred hydrochlorinate) reactant (reactive) continuously to the reaction zone comprising this catalyzer, both in gaseous form, and the pressure drop wherein striding across this reaction zone is advantageously less than or equal to 50kPa/m, be preferably lower than or equal 40kPa/m and more preferably less than or equal to 35kPa/m.
Equipment for the first such embodiment can be any combination of random fixed bed, regular fixed bed, catalysis structured packing, honeycomb structure and analogue or these equipment.
In second embodiment, this reaction is carried out in fluidization flow, and wherein the outside surface of this catalyzer and volume ratio (S/V) are advantageously less than or equal to 10
5m
-1, be preferably lower than or equal 810
4m
-1, more preferably less than or equal to 510
4m
-1and greater than or equal to 100m
-1, preferably greater than or equal to 200m
-1and more preferably greater than or equal to 250m
-1, described method comprises with advantageously greater than or equal to 0.15m/s, preferably greater than or equal to 0.25m/s, more preferably greater than or equal to 0.4m/s and advantageously less than or equal to 6m/s, be preferably lower than or equal 4m/s, total linear velocity more preferably less than or equal to 3m/s adds at least this unsaturated hydrocarbons (preferred acetylene) and this hydrohalogenation (preferred hydrochlorinate) reactant continuously to the reaction zone comprising this catalyzer, both in gaseous form, and the pressure drop wherein striding across this reaction zone is advantageously less than or equal to 100kPa/m, more preferably less than or equal to 60kPa/m.
Allow the equipment carrying out fluidization flow can be any combination of fluidized-bed, moving-bed, vibrating bed, spouted bed, bubbling bed and analogue or these equipment.
In the 3rd embodiment, this reaction is carried out in entrained flow, and wherein the outside surface of this catalyzer and volume ratio (S/V) are advantageously less than or equal to 210
6m
-1, be preferably lower than or equal 1.210
6m
-1, more preferably less than or equal to 610
5m
-1and advantageously greater than or equal to 100m
-1, preferably greater than or equal to 200m
-1, more preferably greater than or equal to 250m
-1, described method comprises with advantageously greater than or equal to 0.25m/s, preferably greater than or equal to 0.4m/s, more preferably greater than or equal to 0.5m/s and advantageously less than or equal to 20m/s, be preferably lower than or equal 15m/s, total linear velocity more preferably less than or equal to 12m/s adds at least this unsaturated hydrocarbons (preferred acetylene) and this hydrohalogenation (preferred hydrochlorinate) reactant continuously to the reaction zone comprising this catalyzer, both in gaseous form, the pressure drop wherein striding across this reaction zone is advantageously less than or equal to 50kPa/m, be preferably lower than or equal 20kPa/m and more preferably less than or equal to 5kPa/m.
Allow the equipment carrying out entrained flow can be any combination of pneumatic transport, air flow bed, circulation bed, swirler and analogue or these equipment.
In the present invention, fixed bed and fluidized-bed are preferred, and fixed bed is most preferred.
Granules of catalyst is intended to refer to the solids component (such as powder, extrudate, spherolite etc.) of catalyzer, polynuclear plane, the microreactor of catalysis and structured packing (as
deng).Catalyzer can be body catalyst or loaded catalyst.
These granules of catalyst can be assembled with minor structure, such as polynuclear plane, the microreactor of catalysis, structured packing element and analogue; Single particle can also be orderly mode such as assemble in bed; Or single particle can operate generally in fluidized-bed, air flow bed, vibrating bed, moving-bed, spouted bed, bubbling bed or analogue.
When these granules of catalyst are assembled with minor structure, the outer volume of this catalyzer can, from the average geometric outside dimension of catalyzer minor structure, use classical surface and cubature formula to calculate.This catalyst surface can from the average geometric Size calculation of the outside dimension of macroscopic elements and interior dimensions.If do not have shape can be used for limiting for these granules of catalyst, they can be considered to spheroid, and geometry outside dimension is the diameter of equivalent sphere.
When these granules of catalyst are such as assembled in an orderly way in the fixed bed of various geometrical shape, this outer volume can, from the average geometric outside dimension of this catalytic bed, use classical surface and cubature formula to calculate.This catalyst surface can from the average geometric Size calculation of the outside dimension of these particles and interior dimensions.If do not have shape can be used for limiting for these granules of catalyst, they can be considered to spheroid, and geometry outside dimension is the diameter of equivalent sphere.
When these granules of catalyst such as operate generally in fluidized-bed, air flow bed, vibrating bed, moving-bed, spouted bed, bubbling bed or analogue, this outer volume can, from the average geometric outside dimension of the catalyzer of wishing when static, use classical surface and cubature formula to calculate.This catalyst surface can from the average geometric Size calculation of the outside dimension of these desired independent granules of catalyst and interior dimensions.If do not have shape can be used for limiting for these granules of catalyst, they can be considered to spheroid, and geometry outside dimension is the diameter of equivalent sphere.
In the method according to the invention, granules of catalyst can show any shape.This granules of catalyst is generally in the form being selected from lower group, and this group is made up of the following: ring, bead, spherolite, tablet, extrudate, pellet, crushing, saddle, small pieces, the structured packing of polynuclear plane, dipping and their any mixture.
When this catalyzer is the form in bead, these beads are considered to spheroid, and geometry outside dimension is the diameter of equivalent sphere.
When this catalyzer is the form of cylindrical particle (such as spherolite, extrudate), these granules of catalyst are considered to right cylinder, and geometry outside dimension is median size and average particle length.Can be on average geometric mean, arithmetical mean or logarithmic mean.Such as arithmetical mean is especially easily.
When these granules of catalyst do not have simple geometric shape, as when such as having small pieces, saddle, the extrudate of crushing of different shapes (star, etc.), they are considered to spheroid and geometry outside dimension is the diameter of equivalent sphere.
When these granules of catalyst are in the form of cylinder ring, these granules of catalyst are considered to hollow right cylinder and the geometrical dimension cylindrical mean diameter (internal diameter and external diameter) that is these, and these cylindrical mean lengths.
When this catalyzer is the form in the polynuclear plane with cylindrical channel, geometrical dimension is mean length and the diameter of these passages.
Those are only some examples about the geometry outside dimension that how can limit these granules of catalyst needed for the outside surface calculating catalyzer/volume ratio.How those of ordinary skill in the art obtains those sizes of any catalyst shape by easily understanding, comprise this above shape do not disclosed.
Can by any means, such as pass through the vision to independent granules of catalyst or microscopic measurement, measurement subsequently for the particle (such as more than 100) of the reliable enough large quantity of statistics is averaged, or from by such as screening, the size-grade distribution of sedimentation (naturally or be forced to) method or light scattering method, obtain the value of the feature outside dimension of these granules of catalyst.
In the above-described embodiments, total linear velocity is interpreted as the linear velocity of the total gas feed referring to the reaction zone containing catalyzer.
Total linear velocity is obtained divided by the cross section in described district by the flow of total gas feed of the reaction zone containing catalyzer.
Total gas feed can be measured by any means, as such as via aperture, Venturi meter, nozzle, spinner-type flowmeter, Pitot tube, calorimetric, turbine, eddy current, electromagnetism, Doppler effect, ultrasonic, hot or coriolis flowmeter (Coriolisflow meter).
The cross section of described reaction zone is interpreted as the average cross section of the length referred to along described reaction zone.Described reaction zone can be level or vertical.
Stride across this pressure drop containing the reaction zone of catalyzer to be interpreted as referring to dynamic pressure drop, comprise the pressure drop that correspondence is connected to the fluid means in this district.
Pressure drop can be measured by any means, such as, pressure reduction (Dp) counts (differential pressure (Dp) cell), pressure warning unit (such as U-tube manometer, cup type pressure warning unit, Bourdon pressure gage (bourdon manometer), pirani gage (Piranni manometer), vacuumionization gauge, diaphragm gauge, piezoelectric pressure meter) and their any combination to picture.Preferred means are selected from lower group, and this group is made up of the following: Dp meter, U-tube manometer, Bourdon pressure gage, diaphragm gauge, piezoelectric pressure meter and their any combination.Preferred means are selected from lower group, and this group is made up of the following: Dp meter, diaphragm gauge, piezoelectric pressure meter and their any combination.
Embodiment described above (can combine) allows to obtain the residence time usually, thus makes it possible to obtain high transformation efficiency and ensure that the good dispersion of these reactants at this catalytic inner.
In the method according to the invention,
-when this unsaturated hydrocarbons (preferred acetylene) source has unsaturated hydrocarbons (preferred acetylene) content being equal to or greater than 10%, the mol ratio of this hydrohalogenation thing (preferred hydrogenchloride) and this unsaturated hydrocarbons (preferred acetylene) is advantageously more than or equal to 0.5, be advantageously less than or equal to 3 preferably greater than or equal to 0.8, be preferably less than or equal to 1.5;
-when the content of the unsaturated hydrocarbons (preferred acetylene) in this unsaturated hydrocarbons (preferred acetylene) source be lower than 10% time, this hydrohalogenation thing (preferred hydrogenchloride) and the mol ratio of this unsaturated hydrocarbons (preferred acetylene) be advantageously more than or equal to 1000, be less than or equal to 100000 preferably greater than or equal to 5000, be preferably less than or equal to 50000 and be more preferably less than or equal 20000.
This unsaturated hydrocarbons (preferred acetylene) can be made to contact in the reactor with this hydrohalogenation thing (preferred hydrogenchloride) or, preferably, introducing this reactor before mix.
Catalyzer used according to the invention comprises at least one ionic liquid (at least in procedure of the present invention, namely, the liquid of ion characteristic is shown) in the hydrohalogenation process of unsaturated hydrocarbons, therefore at least one positively charged ion and at least one negatively charged ion is comprised, and in one embodiment, comprise positively charged ion and at least one negatively charged ion of at least one aprotic.
Ionic liquid is mainly in the salt of liquid state, and common liq (such as water and gasoline) is mainly by electroneutral molecular composition.Ionic liquid is advantageously made up of ion.It should be noted that in framework of the present invention, imidazoles self is not ionic liquid, but in the method for the present invention of hydrohalogenation relating to unsaturated hydrocarbons, they can by becoming ionic liquid with the reaction of hydrohalogenation thing (such as HCl).
Can think that any salt melting (in Undec situation) will produce ionic liquid usually generally.But much salt at high temperature melts, this high temperature is far above the temperature used in catalysis process.For the purposes of the present invention, term ionic liquid should refer to and use the system for liquid at the temperature used in the method for this catalyst system.
For the purposes of the present invention, preferred ionic liquid be under 150 DEG C or lower temperature, more preferably under 100 DEG C or lower temperature, be even more preferably those of liquid under 80 DEG C or lower temperature.In addition, preferred ionic liquid has low-down vapour pressure and low-down combustibility and shows those of good electroconductibility.
This ionic liquid being advantageously used for reaction medium preferably has solvent power for these reactants (unsaturated hydrocarbons and hydrohalogenation thing are such as acetylene and HCl) but the product (as VC) preferably formed in the reaction (and finally these intermediates) is soluble in this ionic liquid.
In this manual, state " at least one ionic liquid " to be interpreted as referring to one or more than a kind of ionic liquid.
Preferably, this catalyzer comprises only a kind of as ionic liquid defined above.
At remainder herein, the statement " ionic liquid " used with odd number or plural form is interpreted as representing one or more than a kind of ionic liquid, except as otherwise noted.
In this manual, stating " positively charged ion of at least one aprotic " is interpreted as referring to a kind of or more than a kind of positively charged ion of aprotic.
Preferably, this ionic liquid comprises a kind of positively charged ion of aprotic.
At remainder herein, the statement " positively charged ion of aprotic " used with odd number or plural form is interpreted as representing a kind of or more than a kind of positively charged ion of aprotic, except as otherwise noted.
As used herein, the positively charged ion of term aprotic, should refer to the positively charged ion not carrying one or more free hydrogen atom on the one or more atoms assigned by this cationic positive charge for purposes of the present invention.
Advantageously, the positively charged ion of this aprotic is selected from
-quaternary ammonium cation, can by general formula [NR
1r
2r
3r]
+represent,
-phosphonium cations, can by general formula [PR
1r
2r
3r]
+represent,
-comprising the positively charged ion of five or hexa-member heterocycle, this heterocycle has at least one nitrogen-atoms, advantageously one or two nitrogen-atoms.
Comprise five or the preferred cationic of hexa-member heterocycle be
-there is the glyoxaline cation of general formula (I)
-there is the pyridylium of general formula (II), and
-there is the tetramethyleneimine positively charged ion of general formula (III)
Wherein radicals R and R
1to R
9can (its condition is the cationic positive charge group entrained by one or more atoms be assigned on it is not hydrogen) be hydrogen, the optional saturated or undersaturated C replaced separately independently of one another
1-C
18alkyl (the preferably optional saturated or undersaturated C replaced
1-C
16alkyl and the more preferably optional saturated or undersaturated C replaced
1-C
14alkyl), wherein carbochain is by the saturated of the optional replacement of an oxygen atoms or undersaturated C
2-C
18alkyl or the optional C replaced
6-C
12aryl.
Preferably, the positively charged ion of this aprotic is selected from: quaternary ammonium cation, phosphonium cation, glyoxaline cation, pyridylium and tetramethyleneimine positively charged ion.
More preferably, the positively charged ion of this aprotic is selected from: phosphonium cation, glyoxaline cation, pyridylium and tetramethyleneimine positively charged ion.
Most preferably, the positively charged ion of this aprotic is selected from: phosphonium cation and glyoxaline cation.Especially the latter is preferred, and more properly: dialkylimidazolium cation, and even more preferably: 1,3-dialkylimidazolium cation.
The example of quaternary ammonium cation is tributyl-methyl phosphonium ammonium, butyl trimethyl ammonium, octyl trimethyl ammonium, tetramethyl-ammonium, tetraethyl ammonium, TBuA, methyl trioctylammonium, 2-hydroxyethyl trimethyl ammonium and diethylmethyl (2-methoxy ethyl) ammonium.
The example of phosphonium cation is triisobutyl Jia Ji Phosphonium, tributyl Jia Ji Phosphonium, ethyl San Ding Ji Phosphonium, 4-butyl-phosphonium, Si Xin Ji Phosphonium, tributyl Shi tetra-Wan Ji Phosphonium, three hexyl Shi tetra-Wan Phosphonium and Bian base triphenyl phosphonium.
The example of glyoxaline cation is 1,3-methylimidazole, 1-ethyl-3-methylimidazole, 1-butyl-3-Methylimidazole, 1-amyl group-3-Methylimidazole, 1-hexyl-3-Methylimidazole, 1-decyl-3-Methylimidazole, 1-dodecyl-3-Methylimidazole, 1-tetradecyl-3-Methylimidazole, 1-hexadecyl-3-Methylimidazole, 1-(2-hydroxyethyl)-3-Methylimidazole, 1-allyl group-3-Methylimidazole, 1-benzyl-3-Methylimidazole, 1-phenyl propyl-3-Methylimidazole, 1,3-diethyl imidazolium, 1-butyl-3-ethyl imidazol(e), 1-methyl-3-propyl imidazole, 1-methyl-3-octylimidazole, 1-methyl-3-octadecyl imidazoles, 1,3-dibutyl-glyoxal ethyline, 1,3-didecyl-glyoxal ethyline, 1-(2-hydroxyethyl)-3-Methylimidazole, 1-ethyl-2,3-methylimidazole, 1-propyl group-2,3-methylimidazole, 1-butyl-2,3-methylimidazole, 1-butyl-3,4-methylimidazole, 1-hexyl-2,3-methylimidazole, 1-hexadecyl-2,3-methylimidazole, 1,2,3-tri-methylimidazolium, 1,3,4-tri-methylimidazolium, 1-butyl-3-ethyl imidazol(e), 1,3-dibutyl imidazoles, 1-methyl-3-octylimidazole, 1-butyl-3,4,5-tri-methylimidazolium and 1,3,4,5-tetramethyl-imidazoles.
The example of pyridylium is 1-picoline, 1-ethylpyridine, 1-propyIpyridine, 1-butyl-pyridinium, 1-hexyl pyridine, 1-octylpyridinium, 1, 2-lutidine, 2-ethyl-1-picoline, 1-butyl-2-picoline, 1-butyl-3-picoline, 1-butyl-4-picoline, 1-hexyl-3-picoline, 1-hexyl-4-picoline, 1-butyl-2-ethylpyridine, 1-butyl-3-ethylpyridine, 4-methyl isophthalic acid-octylpyridinium, 1-butyl-2-ethyl-6-picoline, 2-ethyl-1, 6-lutidine, 1-butyl-3, 4-lutidine and 1-butyl-3, 5-lutidine.
The cationic example of tetramethyleneimine is 1,1-dimethyl pyrrolidine, 1-ethyl-1-crassitude, 1-ethyl-3-crassitude, 1-butyl-1-crassitude, 1-hexyl-1-crassitude, 1-octyl group-1-crassitude, 1-butyl-1-ethyl pyrrolidine and 1-methyl isophthalic acid-propyl pyrrole alkane.
In another embodiment, this positively charged ion can be a kind of protonated positively charged ion, as glyoxaline cation, and the alkylating glyoxaline cation of preferred N-.Preferably, the alkylating imidazoles of this N-is defined by formula (IV):
Wherein radicals R
1, R
2, R
3and R
4can be hydrogen or optional replace, saturated or undersaturated C independently of one another separately
1-C
18alkyl.
More preferably, the alkylating imidazoles of this N-is selected from: 1-Methylimidazole, 1-ethyl imidazol(e), 1-butyl imidazole, 1-hexyl imidazolium, 1-octylimidazole, 1-decyl imidazoles, 1-methyl-2-octylimidazole, 1-Ethyl-2-Methyl imidazoles, 1-butyl-glyoxal ethyline, 1-hexyl-glyoxal ethyline and 1-decyl-glyoxal ethyline.The alkylating imidazoles of N-being selected from 1-Methylimidazole, 1-ethyl imidazol(e) and 1-butyl imidazole is even preferred.
In this manual, state " at least one negatively charged ion " to be interpreted as referring to one or more than a kind of negatively charged ion.
Preferably, this ionic liquid comprises a kind of negatively charged ion.
At remainder herein, the statement " negatively charged ion " used with odd number or plural form is interpreted as representing one or more than a kind of negatively charged ion, except as otherwise noted.
As negatively charged ion, all negatively charged ion may be used in principle.This negatively charged ion is preferably selected from:
The group be made up of with halogen-containing negatively charged ion and so-called false halogen ion halogen ion,
The group be made up of sulfate radical, inferior sulfate radical and sulfonate radical,
The group be made up of phosphate radical,
The group be made up of phosphonate radical and phospho acid root,
The group be made up of orthophosphite,
The group be made up of phosphonous acid root and phosphinous acid root,
The group be made up of carboxylate radical,
The group be made up of borate (borate),
The group be made up of borate (boronate),
The group be made up of carbonate and carbonic ether,
The group be made up of silicate and silicon ester,
The group be made up of the salt of alkyl silane and aryl-silane,
The group be made up of carboxylic imide root, two (alkylsulfonyl) imide root and alkylsulfonyl imide root, the group be made up of alkoxyl group (alkoxide) and aryloxy (aryloxide).
This or these ion is preferably selected among following item: chlorion, bromide anion, iodide ion, trifluoromethanesulfonic acid root (trifluoromethayl sulfonic acid root), tosylate, tetrafluoro ethylsulfonic acid root, two-trifluoromethyl sulfonyl imide root, tetrachloro high ferro acid group, tetrafluoroborate, tetrafluoro phosphate radical and hexafluoro-phosphate radical.
Most preferred IL is the salt of imidazoles halogenation and muriate or rather.Particularly preferably be 1-butyl-3-methylimidazolium chloride (BMIMCl), owing to being easily purchased.
Method for the manufacture of suitable ionic liquid is that those of ordinary skill is known and so there is no necessary to be described in detail at this, especially because in them some and especially BMIMCl be commercially available.
Catalyzer used according to the invention also comprises at least one metal.
In this manual, state " at least one metal " to be interpreted as referring to one or more than a kind of metal.Preferably, this catalyzer comprises only a kind of metal.
This metal can be any metal.This metal is advantageously selected from Pd, Pt, Au, Hg, Ru, Os, Ru, Rh and Ir.Preferably, this metal is selected from Pd, Pt, Au, Hg, Ru and Os.
Although when this metal be selected from above enumerate those time obtain good result, obtain extraordinary result when this metal is selected from Pd, Ru, Au and Os, obtain extraordinary especially result when this metal is selected from Pd, Ru and Au and obtain particularly extraordinary result when this metal is selected from Pd and Ru.The most significant result is obtained when this metal is Pd.
The metal content of catalyst according to the invention, is preferably equal to or higher than 0.25wt% (gross weight based on catalyzer), preferably higher than 0.5wt%.It is generally equal to or lower than 10wt%, preferably lower than 5wt%.
Statement as used herein " metal " comprises metallic compound, that is, a kind of single metallic compound of metal and the mixture of different compounds of same metal or the compound of different metal mixture or comprise the compound of two kinds of metals as hereinbefore defined.
Preferably, this catalyzer is a kind of compound from least one metal, and more preferably obtains from a kind of a kind of compound of metal.
This metallic compound can have any character; But, its normally a kind of salt, more preferably halogenide and even more preferably muriate.
In the chlorine-based compound of palladium (II), the chloro-palladite (palladochloride) of Palladous chloride (II) and basic metal or alkaline-earth metal can be mentioned, such as, as Na
2(PdCl
4), K
2(PdCl
4), Li
2(PdCl
4) and (NH
4)
2(PdCl
4).Palladous chloride (II) give good result.
All embodiments described above allow to obtain the low-down corrosion rate on material; these materials can in the normal industrial lifetimes (several years; typically at least 10 years) in process under design pressure or using the form of bulk or protective layer used in industrial equipments as, thus allow these equipment to resist the corrosion of reaction medium.This protective layer by the material identical with providing that material of the mechanical resistance of these equipment or can be made from another kind of material.
The halogenated acid (preferred HCl) of tolerance in the form of dissociating, can or be metal, fluorinated polymer, pottery, (dipping) graphite, enamel and silicon carbide using the form of bulk or the example of material that uses as protective layer.
The example of the material that can use as protective layer (being made up of the material being different from that material providing mechanical resistance) is: metal, such as Nb, Ta; Metal alloy, such as
enamel, such as
fluorinated polymer, as PTFE, PFA, MFA, PVDF ...
For metal, corrosion permits degree (or the amount of the corrosion allowed before must replacing about part) to be normally less than 5mm, the corrosion degree of permitting being less than 3mm is preferred, and the corrosion degree of permitting being less than 2mm is preferred and the corrosion degree of permitting being less than 1.8mm is particularly preferred.For metal, corrosion permits degree normally higher than 0.01mm, preferably higher than 0.03mm and more preferably higher than 0.05mm.
For on-metallic protective coating, the thickness of this layer is normally greater than 0.1mm, is preferably greater than 0.3mm, more preferably greater than 0.5mm.Usually, the thickness of this protective layer is lower than 20mm, preferably lower than 15mm and more preferably less than 10mm.
These equipment can be made up of one list material or bi-material layers.When these equipment are bi-material layers, this supporting body material does not contact with reaction medium and provides mechanical resistance usually.This supporting body material can be metal or plastics.The example of supporting body material is carbon steel, stainless steel, fiberglass reinforced polyester, polyethylene, polypropylene, PVC ..., carbon steel is preferred.The supporting body material of mechanical resistance is provided usually to stand the corrosion of outside atmosphere.Preferably, this supporting body material also has the protective layer of an antagonism external corrosion.Exterior cover sheets can be the additional thickness of same material, or enamelled coating.When this protective layer is additional thickness, it is normally higher than 0.1mm, and preferably higher than 0.3mm, and more preferably higher than 0.5mm, it is normally lower than 5mm simultaneously, preferably lower than 3mm, more preferably less than 2.5mm.
Following instance is intended to the present invention is described, but is not intended to limit its scope.
Example 1 (according to the present invention)
At 100 DEG C, BMIMCl (1.4g) was melted 5 minutes periods.Then, under agitation PdCl was added 45 minutes periods
2(0.097g).
Tetraethoxy ortho-silicate (TEOS, 10mL) and the mixture of ethanol (7mL) are heated to 60 DEG C and then will contain the PdCl of BMIMCl
2mixture transfers to this immediately containing in the solution of TEOS.
Clarify in formation and after uniform liquid mixture, add hydrochloric acid (5M, 5mL) and this mixture that condenses gradually.
At 60 DEG C after aging 12h, the dry solid material 3h that generates and then grind to obtain thin powder at 150 DEG C in a vacuum.
Hydrochlorination carries out in the glass reactor with 10mm diameter, and this glass reactor is equipped with fritted glass disk in bottom, to obtain the good dispersion of the gaseous reactant be made up of acetylene and hydrochloric acid.
Granules of catalyst is arranged to the fixed bed being placed on this reactor bottom.
The thermal control of this system is obtained by double wall reactor, and this reactor has deep fat adjustment and maintains desired temperature, and this temperature is controlled by the thermocouple sheath be placed in this reactor self.
With the catalyzer of 1.543g and the C of 5NL/ hour at 150 DEG C
2h
2the C of 24.6% is caused with the hydrochlorination of the gas flow rate of the HCl of 6NL/ hour
2h
2transformation efficiency, and the selectivity being greater than 99.8%, produced the productivity (representing with g VC/g catalyzer/h) of 2.036 after 22 hours.
Example 2 (according to the present invention)
The PdCl2 of BMIMCl and 0.024g of 2.0g is used to repeat example 1 for the preparation of this catalyzer.
At identical conditions, the amount except catalyzer is except 2.7g, carries out hydrochlorination.
This C
2h
2transformation efficiency is 17.10%, and this selectivity is greater than 99.8%, produces the productivity (representing with g VC/g catalyzer/h) of 0.809 after 167 hours.
Example 3 (according to the present invention)
At 100 DEG C, BMIMCl (5.7g) was melted 5 minutes periods.Then, under agitation PdCl was added 45 minutes periods
2(0.39g).
Tetraethoxy ortho-silicate (TEOS, 40mL) and the mixture of ethanol (28mL) are heated to 60 DEG C and then will contain the PdCl of BMIMCl
2mixture transfers to this immediately containing in the solution of TEOS.
Clarify in formation and after uniform liquid mixture, add hydrochloric acid (20M, 5mL) and this mixture that condenses gradually.
At 60 DEG C after aging 12h, the dry solid material 3h that generates and then grind to obtain thin powder at 150 DEG C in a vacuum.
A certain amount of live catalyst of use as described after this carries out corrosion experiment.First, the zirconium plate of 1.5+/-0.2mm is inserted an inside reactor.Then, this catalyzer is added in the mode of allow the total surface covering this plate at least 75%.Then, at the C of 5NL/h
2h
2with at 150 DEG C, start this reaction under the HCl flow velocity of 6NL/h and stop after 2 hr.This plate is reclaimed and then sent for analysis.Wherein according to ASTM G1, these results that 1999 versions obtain.Measured corrosion is 330 μm/year.
Be combined in this patent, patent application and the disclosure content of publication and the afoul degree of the description of the application by reference if any to term may be caused unclear, then this explanation should be preferential.
Claims (15)
1., for the method for unsaturated hydrocarbons hydrohalogenation, the method uses the catalyzer comprising at least one ionic liquid (IL) and at least one metal, and according to the method, IL and metal are encapsulated in the inside of porous solid carrier.
2. the method according to last claim, wherein this porous solid carrier comprises silicon-dioxide or aluminum oxide.
3. the method according to any one of the preceding claims, wherein this porous solid carrier comprises silicon-dioxide.
4. the method according to any one of the preceding claims, wherein this catalyzer is prepared by following steps:
The precursor of this porous solid carrier is mixed with alcohol and obtains its mixture;
Heat this kind of mixture and then add described IL and metal to it;
Once obtain clarification and uniform liquid mixture, in this kind of mixture, add acid and allow it to condense; And
The mixture of this condensation aging is to obtain this catalyzer preferably in powder type.
5. the method according to last claim, wherein this alcohol is ethanol.
6. the method according to any one of the preceding claims, wherein:
-when this unsaturated hydrocarbons source has the unsaturated hydrocarbons content being equal to or greater than 10%, this hydrohalogenation is carried out at the temperature of 40 DEG C to 200 DEG C
-when this unsaturated hydrocarbons source unsaturated hydrocarbons content lower than 10% time, carry out at the temperature of this hydrohalogenation between-30 DEG C and 200 DEG C.
7. the method according to any one of the preceding claims, wherein:
-when this unsaturated hydrocarbons source has the unsaturated hydrocarbons content being equal to or greater than 10%, this hydrohalogenation is carried out under lower than the pressure of 10Mpa,
-when this unsaturated hydrocarbons source unsaturated hydrocarbons content lower than 10% time, this hydrohalogenation is carried out under lower than the pressure of 5Mpa.
8. the method according to any one of the preceding claims, wherein this reaction is carried out in fixed bed and/or pre-assembled structure, and wherein the outside surface of this catalyzer and volume ratio (S/V) are less than or equal to 610
4m
-1and higher than 10m
-1described method comprises adding at least this unsaturated hydrocarbons and this hydrohalogenation thing greater than or equal to 0.005m/s and less than or equal to total linear velocity of 20m/s continuously to the reaction zone comprising this catalyzer, both in gaseous form, and the pressure drop wherein striding across this reaction zone less than or equal to 50kPa/m.
9. method according to any one of claim 1 to 7, wherein this reaction is carried out in fluidization flow, and wherein the outside surface of this catalyzer and volume ratio (S/V) are less than or equal to 10
5m
-1and higher than 100m
-1described method comprises adding at least this unsaturated hydrocarbons and this hydrohalogenation thing greater than or equal to 0.15m/s and less than or equal to total linear velocity of 6m/s continuously to the reaction zone comprising this catalyzer, both in gaseous form, and the pressure drop wherein striding across this reaction zone less than or equal to 100kPa/m.
10. method according to any one of claim 1 to 7, wherein this reaction is carried out in entrained flow, and wherein the outside surface of this catalyzer and volume ratio (S/V) are less than or equal to 210
6m
-1and higher than 100m
-1described method comprises adding at least this unsaturated hydrocarbons and this hydrohalogenation thing greater than or equal to 0.25m/s and less than or equal to total linear velocity of 20m/s continuously to the reaction zone comprising this catalyzer, both in gaseous form, and the pressure drop wherein striding across this reaction zone less than or equal to 50kPa/m.
11. methods according to any one of the preceding claims, wherein:
-when this unsaturated hydrocarbons source has the unsaturated hydrocarbons content being equal to or greater than 10%, the mol ratio of this hydrohalogenation thing and this unsaturated hydrocarbons is more than or equal to 0.5 and is less than or equal to 3;
-when this unsaturated hydrocarbons source unsaturated hydrocarbons content lower than 10% time, the mol ratio of this hydrohalogenation thing muriate and this unsaturated hydrocarbons is more than or equal to 1000 and is less than or equal to 100000.
12. methods according to any one of the preceding claims, wherein this IL is 1-butyl-3-methylimidazolium chloride (BMIMCl).
13. methods according to any one of the preceding claims, wherein this metal is Pd.
14. methods according to any one of the preceding claims, described method be a kind of for acetylene hydrochlorination to produce the method for vinylchlorid.
15. according to last claim method, described method is carried out after the pyrolysis of 1,2-ethylene dichloride in the method from ethylene production 1,2-ethylene dichloride and vinylchlorid.
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| PCT/EP2013/077064 WO2014095982A1 (en) | 2012-12-19 | 2013-12-18 | Process for the hydrohalogenation of an unsaturated hydrocarbon |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2014095982A1 (en) | 2014-06-26 |
| EA029427B1 (en) | 2018-03-30 |
| EA201591183A1 (en) | 2015-12-30 |
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