CN1078172A - fluorination catalyst and fluorination process - Google Patents

fluorination catalyst and fluorination process Download PDF

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CN1078172A
CN1078172A CN93103175A CN93103175A CN1078172A CN 1078172 A CN1078172 A CN 1078172A CN 93103175 A CN93103175 A CN 93103175A CN 93103175 A CN93103175 A CN 93103175A CN 1078172 A CN1078172 A CN 1078172A
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catalyst
zinc
hfc
chloro
iron
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CN1050776C (en
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J·D·斯科特
M·J·沃特森
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A kind of chromium-free fluorination catalyst, it comprises the zinc of the activity promotion amount that is loaded on aluminium oxide, halo aluminium oxide or the zirconyl oxyhalides alumina supporter.And in the presence of this catalyst, by hydrocarbon or halogenated hydrocarbons and hydrogen fluoride are produced fluorinated hydrocarbons in gas-phase reaction Application of Catalyst.

Description

Fluorination catalyst and fluorination process
The invention relates to improved fluorination catalyst, and by means of hydrocarbon and halogenated hydrocarbon and hydrofluoric catalytic reaction and the method for producing fluorinated hydrocarbons.The present invention is particularly about the aluminium oxide that promotes, the aluminium oxide or the zirconyl oxyhalides Al catalysts of halogenation, and is about by 1-chloro-2,2 in a specific embodiments, 2-HFC-134a and hydrofluoric catalytic reaction and produce 1,1,1, the method for 2-HFC-134a.
It is known to produce fluorinated hydrocarbons by means of hydrocarbon and halogenated hydrocarbon and hydrofluoric gas phase catalytic fluorination, and said fluorinated hydrocarbons also can contain the halogen atom beyond the defluorination; And existing a large amount of catalyst is proposed to be used in this method.Comprise or based on the catalyst of chromium, particularly chromium oxide through being usually used in these known methods.And, advise that also by the metal with some active promotion amount, for example zinc, nickel, cobalt and manganese mix in this catalyst, to promote the activity of these chromium-containing catalysts.
Therefore, the chromium oxide of chromium oxide or halogenation for example can be used for as GB1, and 307, trichloro-ethylene described in 224 and hydrofluoric gas-phase reaction are to produce 1-chloro-2,2,2-HFC-143a, and as GB1,1-chloro-2,2 described in 589,924,2-trichloroethanes and hydrofluoric gas-phase reaction are to produce 1,1,1, the 2-HFC-134a.To 1-fluoro-2,2,2, the fluorination of-HFC-143a can be used said identical catalyst for CDF.GB1,589,924 have described by means of with CDF impurity and hydrogen fluoride reaction and from 1,1,1, remove this impurity in the 2-HFC-134a.
These catalyst also can be included in the chromium on metal oxide, halogenation oxide or the oxo fluoride carrier, carrier is aluminium oxide or magnesia for example, and when using this catalyst in fluorination process, this chromium can be converted into chromium oxide, halogenation chromium oxide or fluorine chromium oxide.Have found that when not having chromium, these carriers self only show very faint catalytic activity, some carrier has demonstrated tangible activity behind the zinc that mixes active promotion amount.
According to the present invention, a kind of chromium-free fluorination catalyst is provided, it comprises the zinc of active promotion amount or is loaded in aluminium oxide, the compound of the zinc on halogenation aluminium oxide or the oxo aluminum halide carrier.
According to the present invention, a kind of production method of fluorinated hydrocarbons also is provided, this method is included in the fluorination catalyst that defines in the preceding paragraph and exists to descend in gas phase with hydrocarbon or halogenated hydrocarbons and hydrogen fluoride reaction.
Mixing in the catalyst consumption of zinc is to determine like this, when zinc promoter is mixed aluminium oxide, halo aluminium oxide or oxo aluminum halide, will cause the promotion of their activity.This consumption is very important, and this is because when comparing with the catalyst activity of the zinc promoter of mixing optimised quantity, the zinc promoter of mixing too many amount will cause the minimizing of catalyst activity, rather than increase.Therefore, have only when zinc promoter to exist, could produce best activity and promote with correct amount.
Be impregnated in the catalyst and will depend on the surface area of employed underlying carrier, particularly carrier, and depend on the employed method of this improved catalyst of preparation with the zinc promotion dosage of obtaining the remarkable activity promotion.Yet for any specific carrier and method for preparing catalyst, the optimum amount of zinc promoter can be determined by simple normal experiment.Generally speaking, the consumption of zinc will be that about 0.5%-of catalyst weight is about 30% usually, preferably about 1.5%-about 25%.
The optimum amount that mixes zinc depends on the surface area of catalyst, and particularly the worksheet area of " the worksheet area of catalyst " catalyst is a surface area of also using the measured catalyst in hydrogen fluoride preliminary treatment (as mentioned below) back in Preparation of Catalyst; Or if catalyst carries out preliminary treatment without hydrogen fluoride, the worksheet area of catalyst is the surface area after catalyst is used to use hydrofluoric gas phase fluorination so, and the worksheet area of catalyst can be about 10 to about 100m 2/ g is normally at the about 50m of about 10- 2/ g.When being about 50m according to surface area 2The about 400m of/g- 2When the aluminium oxide of/g prepares this catalyst, after preparation and preliminary treatment, will obtain the catalyst of worksheet area in the range of definition, this catalyst can be about 50m according to surface area 2The about 250m of/g- 2/ g, preferably about 150m 2/ g to 250m 2The raw alumina of/g prepares.
As mentioned above, the amount of mixing promoter in the catalyst also depends on the Preparation of catalysts method that is adopted.The live part that it is believed that catalyst is to contain the surface of being located in the cationic carrier of zinc promoter on aluminium oxide, halo aluminium oxide or the zirconyl oxyhalides aluminium lattice, and the amount of so just lip-deep zinc promoter has been determined activity of such catalysts.For the catalyst that makes by dipping, the active facilitation of per unit weight zinc promoter is usually above the catalyst at non-surperficial position zinc-bearing accelerator by the additive method preparation.
As an example, by under the situation of the zinc that mixes of dipping on the alumina support, the surface area of the aluminium oxide that the preparation catalyst uses is 180m 2/ g, when the consumption of zinc is that about 0.5%-of catalyst weight is about 10%, it is about 6% to be preferably about 0.5%-, and it is about 4% to be more preferred from about 1.5%-,, will produce best active facilitation at particularly at about 1.5%-about 3.5% o'clock.Be less than the zinc deficiency of 0.5% weight so that catalyst produces significant facilitation, and more than the zinc of about 8% weight, then the active facilitation that provides in the zinc of above-mentioned optimum range is compared, and can not produce the remarkable increase of catalyst activity.As a comparison, under the situation of the catalyst by prepared by co-precipitation, wherein, a large amount of zinc is impregnated in non-surperficial position, and the consumption of zinc is that about 3%-of catalyst weight is about 30%, and it is about 25% to be preferably about 4%-, particularly about 5%-about 15%.
Zinc promoter can compound form mix in the catalyst, said compound is for for example at least at the halide that to a certain degree depends on employed catalyst preparation process, oxyhalide, oxide or hydroxide.For by impregnated alumina, during the occasion of halo aluminium oxide or zirconyl oxyhalides alumina supporter, this compound is water soluble salt preferably in Preparation of catalysts, halide for example, and nitrate or acetate, and use with its aqueous solution.The promoter of hydroxide and aluminium can carry out co-precipitation, convert oxide subsequently to, with the preparation catalyst.The mixing of insoluble zinc compound and basic catalyst and mill a kind of Preparation of catalysts method also is provided comprises based on the Preparation of catalysts method of zirconyl oxyhalides aluminium: promoter compound is added to the hydration aluminum fluoride, and calcine this mixture.
Above-mentioned any method or other method all can be used to prepare zinc of the present invention and promote catalyst.
Fluorination catalyst will stand the hydrogen fluoride and the pre-fluorination treatment of inert diluent not necessarily usually before being used for the catalyst of fluorination reaction.Common preliminary treatment comprise with catalyst with hydrogen fluoride or hydrogen fluoride with heat in 250 ℃-450 ℃ under air mixture contacts.Therefore, can believe that the work catalyst is that partially fluorinated zinc is loaded on the aluminium oxide of fluoridizing or on the fluorine alumina at least.
For for the use of fixed bed or fluid bed, the ball that catalyst can appropriate size or the form of particle are used.It can by in air in about 300 ℃-Yue 500 ℃ temperature heat and periodically regeneration or reactivation.Air can mix use with inert gas such as nitrogen, or mixes use with hydrogen fluoride, and hydrogen fluoride will produce heat from the processing procedure of catalyst, and it can be directly used in the gas phase fluorination processing.
Substantially (do not promote) aluminium oxide, the activity of halo aluminium oxide or zirconyl oxyhalides Al catalysts increases by mixing promoter.By this catalyst, by 1-chloro-2,2,2-HFC-143a and hydrogen fluoride production 1,1,1, the selectivity of the catalytic reaction of 2-HFC-134a at least can be the same high with the catalyst that uses corresponding not promotion, usually will be greater than 85%.
Talk about if desired, this catalyst can contain one or more metals in addition that dezincifies, for example, and nickel, copper, manganese, cobalt and iron; Particularly iron, cobalt and copper.This is because the existence of one or more these metals can strengthen the recovery extent that makes catalyst activity by the regeneration of catalyst.When particularly preferred zinc loaded, we Chang Youxuan uses only zinc, or is mainly zinc at least, only contained a small amount of other metal, for example was less than 2.0% weight, preferably was less than 1.5% weight, particularly was less than other metal of 1.0% weight.Yet, this catalyst contains much more relatively zinc and loads, for example, and for example in the occasion of the catalyst that makes by dipping, the zinc useful load will be greater than about 3%, be preferably greater than about 4%, particularly greater than about 5%, beyond the dezincification, we especially preferably mix a spot of iron, for example to can be about 0.1%-of catalyst weight about 2% for the incorporation of iron, and preferably about 0.1%-is about 1.5%, better about 0.5%-about 1.5%.Be preferably about 80: 1 to 2: 1, more preferably about 16: 1 to about 2: 1 based on the zinc of catalyst percent by weight and the ratio of iron.Preferred this ratio is irrelevant with the absolute magnitude of zinc in catalyst and iron.
Therefore, though the absolute magnitude of zinc and iron can be higher, for example with respect to catalyst weight at least 6%, preferred at least 10% zinc, and about 0.2-is about 12%, and the iron of preferably about 0.4-about 4.5% is for the catalyst that for example makes by coprecipitation method, to cause a large amount of and zinc and iron are impregnated in the outer surface portions of catalyst, but the relative quantity that is based on the zinc of weight percent of catalyst and iron is still preferably in the above-mentioned scope that provides.
The application of catalyst in fluorination process that is further characterized in that promotion of the present invention, fluorination process comprises that hydrocarbon or halogenated hydrocarbons and hydrogen fluoride react in gas phase.
Alkene (unsaturated hydrocarbons), particularly alkenyl halide, for example preferred C that contains a chlorine atom at least 1-4Alkenyl halide can fluoridize; The object lesson that can fluoridize is by 1-chloro-2,2, and the 2-HFC-143a produces 1,1,1, and the 2-HFC-134a is produced 1-chloro-2,2 by trifluoro-ethylene, 2-HFC-143a and with 1-chloro-2, and the 2-difluoroethylene converts 1-chlorine 2,2 to, the 2-HFC-143a.The example of the fluorination reaction that other this catalyst is suitable for is that perchloroethylene and hydrogen fluoride are produced dichlorotrifluoroethane (123) in gas-phase reaction, one chloro-tetrafluoroethane (124) and/or pentafluoroethane (125), produce trichorotrifluoroethane (113) in gas-phase reaction, a dichlorotetra-fluoroethane (114/114a) and/or a chloropentafluoroethane (115) with perchloroethylene and chlorine and hydrogen fluoride.
When using chromium oxide or halo chromium oxide as catalyst, employed fluorination conditions can be known spendable those conditions; For example, depend on the specific fluorination reaction of being carried out, can be with atmospheric pressure or super-atmospheric pressure, the temperature of hydrogen fluoride and 180 ℃ to 500 ℃.
Yet the aluminium oxide that the activity that the catalyst of promotion increases makes reaction can use ratio not promote under inefficent loss reaches under the low significantly temperature of the required temperature of same activity and carries out.For example, when using the aluminium oxide that does not promote, use 360 ℃ of relatively-high temperatures or higher, under atmospheric pressure, by 1-chloro-2,2, the 2-HFC-143a generates 1,1,1, the productive rate of 2-HFC-134a only is 0.5%, and uses aluminium oxide that zinc promotes just to be enough to the reaction efficiency that reaches bigger at for example 280 ℃ low temperature.If in other words reaction temperature is identical, for example be 300 ℃, when using the catalyst that promotes, need the time of contact shorter.
The preferred concrete example of the inventive method is 1,1,1, the preparation method of 2-tetrafluoroethene, this method comprises: in the presence of the catalyst of promotion of the present invention, with 1-chloro-2,2,2-HFC-143a and hydrogen fluoride gas phase are reacted, and this method can be carried out in about 280 ℃-500 ℃ under atmospheric pressure or super-atmospheric pressure.
This method can be the step in two-step method or the three-step approach, and for example, it can be to produce 1,1 by trichloro-ethylene, 1, in second step of the method for 2-HFC-134a, the first step is trichloro-ethylene and the gas phase fluorination of hydrogen fluoride in the presence of fluorination catalyst, to produce 1-chloro-2,2,2-HFC-143a.The catalyst of promotion of the present invention can be used for the first step and second step of this two-step method.The reaction condition commonly used of the first step is atmospheric pressure or super-atmospheric pressure and about 180 ℃-Yue 400 ℃ temperature.
By 1-chloro-2,2, the 2-HFC-143a produces 1,1,1, and the 2-HFC-134a contains poisonous impurity 1-chloro-2 with generation, the product stream of 2-difluoroethylene.This impurity can for example react it and hydrogen fluoride and remove in gas phase under 150 ℃-270 ℃ by be lower than about 270 ℃ in the presence of fluorination catalyst.The catalyst of promotion of the present invention can be used for this reaction.So the invention provides by the trifluoro-ethylene preparation does not have 1-chloro-2 substantially, 1,1,1 of 2-difluoroethylene, three one-step preparing methods of 2-HFC-134a, wherein the catalyst that promotes is used in a step or two steps or the reaction of per step.
Above-mentioned prepares 1,1,1 by trichloro-ethylene, and the particularly preferred concrete example of the two-step preparation of 2-HFC-134a comprises following steps:
(A) with 1-chloro-2,2,2-HFC-143a and carbon hydrogen fluoride mixture and fluorination catalyst contact in first reaction zone in about 280 ℃-Yue 450 ℃, contain 1,1,1 with formation, the product of 2-HFC-134a and hydrogen chloride and unreacting material.
(B) second reaction zone that the product and the trichloro-ethylene of step (A) are delivered to the fluorinated catalyst, the temperature in this district is about 180 ℃ to about 400 ℃, but is lower than the temperature in the step (A), contains 1-chloro-2 with formation, 2, the 2-HFC-143a, 1,1,1, the 2-HFC-134a, hydrogen chloride and unreacted trichloro-ethylene and hydrofluoric product
(C) product of treatment step (B), with from 1-chloro-2,2, the 2-HFC-143a is isolated hydrogen chloride and 1,1,1 in unreacted hydrogen fluoride and the unreacted trichloro-ethylene, the 2-HFC-134a,
(D) with the 1-chloro-2,2 that obtains in the step (C), 2-HFC-143a and hydrogen fluoride are delivered to the said first reaction zone step (A) together, and wherein, chromium-free fluorination catalyst is used in a step (A) and a step (B) at least as the aforementioned.
In the step (A) of preferred concrete example, use the hydrogen fluoride that is at least stoichiometric amount usually, consumption is every mole of 1-chloro-2,2 usually, 2-HFC-143a 1-10 mole, preferred 1-6 mole.Therefore, remove 1,1,1,2-HFC-134a, hydrogen chloride and beyond product, this reactions steps contains unreacted hydrogen fluoride usually.The preferable reaction temperature that is used for this step of this method is 325 ℃-385 ℃, and be 1-100 the time of contact under the 5-20 bar pressure, preferred 5-30 second.
In step (B), every mole of trichloro-ethylene often uses 10-100, the hydrogen fluoride of preferred 15-60 mole.Therefore, the product in this step also will contain unreacted hydrogen fluoride.Can be with 1 to 100 second, the time of contact of preferred 5-30 second, temperature is generally 220 ℃ to 350 ℃, and pressure often clings to for 5-20.
The method according to this invention comprises preferred concrete example, preferably continued operation, yet, in actual applications, the one-tenth activation of catalyst.The periodic regeneration of essential catalyst or reactivation interrupt the continued operation of this method possibly.In this method operating period, can be to catalyst supply air to the deactivation of anticatalyst, and reduce the frequency that interrupts this method owing to catalyst regeneration or reactivation.
To further illustrate the present invention by following example, but limit the present invention anything but.
Embodiment 1-7
With the 4.79g diameter is that 0.5-1.4mm, surface area are 180m 2The particulate alumina of/g (being provided by Harshaw Ltd) adds in zinc chloride (0.21g) aqueous solution in 10ml distilled water, and stirs to guarantee that solid is by the solution complete wetting.Then by direct heating with this mixture drying, and the solid that generates sieved, to be given in the final catalyst granules that the particle diameter that contains about 2.0%w/w zinc on the aluminium oxide is 0.5-1.4mm.Repeat above-mentioned steps, only be to use the liquor zinci chloridi that increases concentration, in final catalyst, contain high final catalyst to 6.6%w/w zinc to produce.Use the atmospheric pressure microreactor to measure the activity of fluoridizing of aluminium oxide that zinc promotes.The 2g catalyst is packed in the microreactor of 1/4 inch diameter, and be controlled under the HF air-flow in 300 ℃ 1 hour, be heated to 350 ℃ then, and further be controlled at air/HF(ratio 1: 20) under the air-flow about 15 hours.
Then, be the 1-chloro-2,2 of 1.0: 3.5 mixing with the mole feed molar ratio, 2-HFC-143a (133a) and HF contacted for 2 seconds to the microreactor feed at 300 ℃.
In order to compare, also tested the not accelerating oxidation aluminium of the aluminium oxide that is used for preparing promotion.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 1, and shows, zinc is added in the aluminium oxide, and for 1,1,1, the yield of 2-HFC-134a (134a) increases useful effect.
During at the about 3%w/w of about 2%-, the activity of the aluminium oxide catalyst of zinc dipping reaches the peak at zinc content.
Table 1
Embodiment 8
Is 180m with the 4.39g particle diameter for the 0.5-1.4mm surface area 2The particulate alumina of/g (being provided by Harshaw Ltd) adds to Nickel dichloride hexahydrate (II) in 5ml distilled water (0.41g) and in the aqueous solution of zinc chloride (0.21g), and stirs to guarantee that solid is by the solution complete wetting.Then by this mixture of direct drying, and the solid that generates being sieved, is the final catalyst granules of 0.5-1.4mm with the particle diameter that obtains containing about 2.0%w/w zinc and about 2%w/w nickel on aluminium oxide.
According to the step of embodiment 1-7, under atmospheric pressure this catalyst of 2g is tested.
In order to compare, also to measuring according to the activity of such catalysts that on aluminium oxide, contains 2% and 3.8% weight nickel of aforesaid nickel chloride (II) aqueous solution preparation.The atom of 3.8% nickel on the aluminium oxide catalyst load with the catalyst that contains 2% zinc and 2% nickel on identical.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 2, and show that compare with aluminium oxide is only arranged, zinc/nickel is added to aluminium oxide beneficial effect, however, compare with independent interpolation zinc, the interpolation effect of zinc/nickel is poor, even also poorer than the effect of adding nickel separately.
Table 2
Figure 931031753_IMG2
Embodiment 9
Is 180m with the 4.39g particle diameter for the 0.5-1.4mm surface area 2The particulate alumina of/g (Harshaw Ltd provides) adds to cobalt chloride hexahydrate (II) in 5ml distilled water (0.404g) and in the aqueous solution of zinc chloride (0.21g), and stirs to guarantee that solid is by the solution complete wetting.Then by direct heating with this mixture drying, and the solid that obtains sieved contain 2.0%w/w zinc on the aluminium oxide and the 2%w/w cobalt button directly is the final catalyst granules of 0.5-1.4mm to be given in.
Step according to embodiment 1-7 is under atmospheric pressure tested this catalyst of 2g.
For relatively, also to measuring according to the activity of such catalysts that on aluminium oxide, contains 2%3.8% weight cobalt of cobalt chloride (II) aqueous solution preparation of crossing as mentioned above.The atom of 3.8% cobalt on the aluminium oxide catalyst load with the catalyst that contains 2% zinc and 2% cobalt on identical.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 3, and show that compare with aluminium oxide is only arranged, zinc/cobalt is added to aluminium oxide beneficial effect, however, compare with independent interpolation zinc, the interpolation effect of zinc/cobalt is poor, even also poorer than the effect of adding cobalt separately.
Table 3
Figure 931031753_IMG3
Embodiment 10
Is 1.80m with the 4.43g particle diameter for the 0.5-1.4mm surface area 2The particulate alumina of/g (Harshaw Ltd provides) adds to four hydration manganese chlorides (II) in the 5ml distilled water (0.36g) and in the aqueous solution of zinc chloride (0.21g), and stirs to guarantee the solid solution complete wetting.Then by direct heating with this mixture drying, and the solid that obtains sieved contain 2.0%w/w zinc on the aluminium oxide and 2%w/w manganese particle diameter is the final catalyst granules of 0.5-1.4mm to be given in.
According to the step of embodiment 1-7, under atmospheric pressure this catalyst of 2g is tested.
In order to compare, also to measuring according to the activity of such catalysts that on aluminium oxide, contains 2% and 3.68% weight manganese of aforesaid manganese chloride (II) aqueous solution preparation.The atom of 3.68% manganese on the aluminium oxide catalyst load with the catalyst that contains 2% zinc and 2% manganese on identical.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 4, and show that compare with aluminium oxide is only arranged, zinc/manganese is added to aluminium oxide beneficial effect, however, compare with independent interpolation zinc, the interpolation effect of zinc/manganese is poor, even also poorer than the effect of adding manganese separately.
Table 4
Figure 931031753_IMG4
Embodiment 11-20
Is 180m with the 4.30g particle diameter for the 0.5-1.4mm surface area 2The particulate alumina of/g (Harshaw Ltd provides) adds to iron chloride (III) in 10ml distilled water (0.07g) and in the aqueous solution of zinc chloride (0.63g), and stirs to guarantee that solid is by the solution complete wetting.Then by direct heating with this mixture drying, and the solid that obtains sieved contain 6.0%w/w zinc on the aluminium oxide and 0.5%w/w iron, particle diameter are the final catalyst granules of 0.5-1.4mm to be given in.Except the iron chloride (III) and liquor zinci chloridi that use variable concentrations, repeat above-mentioned steps, to provide the zinc of listing in table 5 and the final catalyst of iron loading.
Under atmospheric pressure getting each 2g of these catalysis according to the step of embodiment 1-7 tests.
In order to compare, also to measuring according to the activity of such catalysts that on aluminium oxide, contains 2% weight iron of iron chloride (III) aqueous solution preparation as mentioned above.The atom of 6%w/w zinc and 0.5%w/w iron loads the atom equal to go up at aluminium oxide catalyst (embodiment 7) 6.6%w/w zinc and loads on aluminium oxide, for compare also the activity of such catalysts of embodiment 7 and embodiment 3,5 and 6 is listed in below.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 5, and shows, with independent iron or separately the interpolation of zinc compare, high relatively zinc load and zinc than iron ratio greater than 2: 1 times, zinc/iron adds to aluminium oxide beneficial effect.
Table 5
Embodiment 21-25
Following embodiment shows, with test button that zinc is used in combination in, have zinc only and provided than the catalyst that on aluminium oxide catalyst, contains the bigger activity of 6.6% weight zinc with the sample of iron.
Except that the solution that adds to aluminium oxide is as described below, prepare catalyst according to the described method of previous embodiment 1-12:
Embodiment 21: identical with embodiment 12.
Embodiment 22:4.07g aluminium oxide adds to the ZnCl in 10ml water 2(0.63g) and CoCl 2In the aqueous solution of hexahydrate (0.3g).
Embodiment 23:4.07g aluminium oxide adds to the ZnCl in 10ml water 2(0.63) and NiCl 2In the aqueous solution of six directions thing (0.3g).
Embodiment 24:4.04g aluminium oxide adds to the ZnCl in 10ml water 2(0.63g) and Mn(CH 3CO 2) 2In the aqueous solution of tetrahydrate (0.34g).
Embodiment 25:4.17g aluminium oxide adds to the ZnCl in 10ml water 2(0.63g) and CuCl 2In the aqueous solution of dihydrate (0.2g).
According to the step of embodiment 1-7, under atmospheric pressure, get each 2g of these catalyst and test.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 6, and the result shows, adds to aluminium oxide with any other metal with zinc and compares, and zinc/iron adds to aluminium oxide beneficial effect.
Table 6
Figure 931031753_IMG6
Embodiment 26 and 27
With the 4.98g particle diameter is that (surface area is 13m for the particle aluminum fluoride of 0.5-1.4mm 2/ g) add in zinc chloride (II) aqueous solution (0.02g) of 5ml distilled water.This aluminum fluoride is by making aluminium oxide (Harshaw Ltd provides) and hydrogen fluoride in 48 hours in 340 ℃ of reactions.Stirring is to guarantee that solid is by the solution complete wetting.Then by direct heating with this mixture drying, and the solid that obtains sieved, with obtain on aluminum fluoride, containing 0.2%w/w zinc, particle diameter is the final catalyst granules of 0.5-1.4mm.Except that using zinc chloride (II) solution that increases concentration, repeat above-mentioned steps, to obtain on aluminum fluoride, containing the final catalyst of 0.5%w/w zinc.
According to the step of embodiment 1-7, under atmospheric pressure, get each 2g of these catalyst and test.
In order to compare, also the activity of the aluminum fluoride that does not promote of the aluminum fluoride catalyst that is used for preparing promotion is tested.
Result of study is with 1,1,1, and the percentage yield of 2-HFC-134a is listed in the table 7.
Table 7
Embodiment 28 and 29
In these two embodiment, below steps outlined utilize embodiment 7(embodiment 28) and embodiment 11(embodiment 29) catalyst that makes carries out.
The 0.67g catalyst is filled in the reaction tube of inconel of 1/4 inch diameter, in 300 ℃ of dryings, and by heating in the flow of hydrogen fluoride of dividing flow velocity at 20ml/ 1 hour and activate, using trichloro-ethylene subsequently is 1: 20 than hydrogen fluoride, be 1 second time of contact, under atmospheric pressure trichloro-ethylene and hydrogen fluoride added in the reactor.The activity of monitoring catalyst between 210 ℃ and 250 ℃, and the result listed in the table 8 as " original activity ".
Yet, temperature is risen to 350 ℃ turned round 3 days continuously.After this, cool the temperature to 210 ℃-250 ℃, and in the activity of this temperature range monitoring catalyst.Monitoring result is listed in the table 8 as " activity after 3 days ".Then, close trichloro-ethylene and hydrogen fluoride feed, and by heating 2 hours and regenerated catalyst in 350 ℃ in the air stream that divides at 10ml/.Then, divide with 20ml/ respectively and 1ml/ divides and forms hydrogen fluoride again and trichloro-ethylene flows, and in the activity of 210 ℃ of-250 ℃ of monitoring catalysts.Monitoring result is listed in the table 8 as " activity after the regeneration ".All results of study are all with 1-chloro-2,2 in table 8, and the percentage yield of 2-HFC-143a represents, and show, iron is added in the catalyst that zinc promotes, its regeneration is had beneficial effect.
Table 8
Figure 931031753_IMG8

Claims (19)

1, a kind of chromium-free fluorination catalyst comprises the zinc of the activity promotion amount that is loaded on aluminium oxide, halo aluminium oxide or the zirconyl oxyhalides alumina supporter.
2, catalyst as claimed in claim 1, wherein, the consumption of zinc is the 0.5%-30% of catalyst weight.
3, catalyst as claimed in claim 2, it is by making with water-soluble zinc salt impregnated alumina, halo aluminium oxide or zirconyl oxyhalides aluminium, and contains the zinc of 0.5% weight-10%.
4, catalyst as claimed in claim 1, it is by zinc hydroxide and aluminium hydroxide co-precipitation, converts hydroxide to oxide then and makes, wherein the content of zinc is 3% to 30% of catalyst weight.
5, catalyst as claimed in claim 1, wherein catalyst also comprises one or more metals beyond dezincifying.
6, catalyst as claimed in claim 8, wherein metal is selected from: nickel, cobalt, manganese, iron and copper.
7, catalyst as claimed in claim 6, wherein, the content of the metal beyond dezincifying is at most 2.0% of catalyst weight.
8, catalyst as claimed in claim 9, wherein metal is an iron.
9, catalyst as claimed in claim 8, wherein zinc content is at least 3% of catalyst weight.
10, as the catalyst of claim 8 or 9, wherein the percentage by weight of zinc and iron is 2: 1-80: 1.
11, catalyst as claimed in claim 3, it comprises the zinc that is at least catalyst weight 3%, and also comprises the iron of 0.1%-2%.
12, catalyst as claimed in claim 4, it also comprises iron, is 16 based on the zinc of catalyst percent by weight than the ratio of iron wherein: 1-2: 1.
13, catalyst as claimed in claim 4, it also comprises iron, wherein the zinc based on the catalyst percent by weight is 16: 1 to 2: 1 than iron ratio.
14, the production method of fluorinated hydrocarbons, it is included in the fluorination catalyst that claim 1-13 determines in each and exists down, and hydrocarbon or halogenated hydrocarbons and hydrogen fluoride are reacted in gas phase.
15, as the method for claim 14, wherein halogenated hydrocarbons comprises alkene or the alkane that contains 1-4 carbon atom and have a chlorine atom at least.
16, as the method for claim 15, wherein halogenated hydrocarbons is selected from: 1-chloro-2,2,2-HFC-143a, trichloro-ethylene, 1-chloro-2,2-difluoroethylene and perchloroethylene.
17, as the method for claim 16, it comprises step (a), with trichloro-ethylene and hydrogen fluoride reaction, produce 1-chloro-2,2 thus, the 2-HFC-143a, and step (b), the 1-chloro-2,2 that step (a) is obtained, 2-HFC-143a and hydrogen fluoride reaction are to produce 1,1,1, the 2-HFC-134a, wherein, in step (a) and at least one step (b), use as each desired catalyst of claim 1-18.
18, as the method for claim 17, it comprises the steps:
(A) first reaction zone in 280 ℃-450 ℃ with 1-chloro-2,2, the 2-HFC-143a contacts with fluorination catalyst with hydrofluoric mixture, forms to contain 1,1,1, the product of 2-HFC-134a and hydrogen chloride and unreacting material;
(B) to deliver to fluorinated catalyst, temperature be 200 ℃-400 ℃ but be lower than second reaction zone of the temperature of step (A) together with trichloro-ethylene with the product of step (A), formation contains 1-chloro-2,2, the 2-HFC-143a, 1,1,1, the 2-HFC-134a, hydrogen chloride and unreacted trichloro-ethylene and hydrofluoric product;
(C) product of treatment step (B) from 1-chloro-2,2, is isolated hydrogen chloride and 1,1,1 in 2-HFC-143a, unreacted hydrogen fluoride and the unreacted trichloro-ethylene, the 2-HFC-134a;
(D) the 1-chloro-2 that step (C) is obtained, 2,2-HFC-143a and hydrogen fluoride are delivered to said first reaction zone (steps A) together, wherein, at least a in the fluorination catalyst that uses in step (A) and step (B) is chromium-free fluorination catalyst as each requirement of claim 1-18.
19, as each desired method of claim 14-18, wherein, catalyst is in 300 ℃-500 ℃ periodically regeneration by contacting with air.
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