CN1083038A

CN1083038A - Vapor phase flaorination process

Info

Publication number: CN1083038A
Application number: CN 93107464
Authority: CN
Inventors: 马修·赫米斯·莱尔
Original assignee: AlliedSignal Inc
Current assignee: Honeywell International Inc
Priority date: 1992-06-17
Filing date: 1993-06-17
Publication date: 1994-03-02
Also published as: WO1993025507A1; MX9303208A

Abstract

The present invention relates to a kind of vapor phase flaorination process, specifically, it is at transistion metal compound---in the presence of the chromium compound catalyst, no more than three carbon atoms of gas phase fluorination contain halocarbon, wherein at least one is not that the halogen of fluorine is replaced by fluorine.This catalyzer comprises a kind of chromium cpd and at least a transistion metal compound that is selected from the cohort of being made up of oxide compound, fluorochemical, oxyfluoride and the acid salt of Ni, Pd and Pt.

Description

Vapor phase flaorination process

The present invention relates to a kind of vapor phase flaorination process, specifically, it is in the presence of transistion metal compound-chromium compound catalyst, no more than three carbon atoms of gas phase fluorination contain halocarbon, wherein at least one is not that the halogen of fluorine is replaced by fluorine.

Japanese patent application No. 323,688/1988(publication number 172,933/1990) disclosed a kind of halogenide of at least a element in being selected from the group of forming by Al, Mg, Ca, Ba, Sr, Fe, Ni, Co, Mn and Cr or oxide compound catalyzer in the presence of, fluoridize 1-chloro-2,2, the method for 2-Halothane (HCFC-133a).

The PCT application number WO 89/1034 that transfers Eve Deng Ke discloses and a kind ofly contains at least a metal that is selected from Ni, Co, Fe, Mg, Cr, Cu and the Ag group, and is loaded in the fluorination catalyst on the activated alumina.This activated alumina is the key ingredient of the catalyzer that goes through.This catalyzer can be used as the usefulness that some halohydrocarbon is fluoridized (comprising HCFC-133a, peroxide ethene, trieline and methylene dichloride) catalysis.These are example application of single-metal reforming catalyst, and demonstrate its consistence active and other prior art.

U.S. Patent number 4,814,522 have disclosed to be selected from catalyzer and have comprised single chromated oxide or itself and one or more Rh ^O, Ru ^O, Ir ^O, Pd ^O, Pt ^O, Ag ^OThe oxide compound of phosphorous oxides, Si oxide, boron oxide compound or aluminium, magnesium, zinc, iron, rhodium, nickel, palladium, cobalt, platinum, caesium, silver, copper, lead, bismuth, iridium, manganese, barium, tin, lanthanum, calcium, ruthenium, zirconium, vanadium, molybdenum or tungsten or halid composition exist down, are exchanged the method for the chlorine or bromine atom of another kind of perhalogenation hydrocarbon by a kind of a kind of fluorine atom of perhalogenation alkene.This method does not adopt HF.

Be used in aliphatic halo ethane fluorizated chromium-based catalysts, when HCFC-133a fluoridized to HFC-134a, work-ing life was short, can not be accepted (refer under high pressure use, the recovery of HCl at this moment is very effective and easy).In order to prolong catalyst life, usually fluoridize and under low pressure, operate.Yet, under low pressure, need additionally freezingly to pay product to reclaim HCl.Additional freezing requirement has also increased the cost of process unit.British Patent No. 2,030,981 and Japanese patent application No. 19775-6464(publication number 82206/1976) disclosed air or O ₂Import fluorination reactor to prolong catalyst life.Air or O ₂Make the oxidation of some product behind the importing reactor, produce ill effect, reduced the yield of fluorinated product.In addition, owing to imported air or O ₂, improved the temperature of fluoridation, may increase the loss of product.

The present invention relates to a kind of vapor phase flaorination process, this technology comprises exists down the catalyzer with three or the halon (wherein at least a is not the halogen of fluorine) that is less than three carbon atoms and transistion metal compound of anhydrous HF, the oxide compound, halogenide and the oxyhalogenide that contain chromium cpd and at least a Ni of being selected from, Pd and Pt and acid salt group, carrying out gas-phase reaction in being higher than under 200 ℃ the temperature, is not that the described halogen of fluorine is replaced by fluorine to produce wherein at least one.

Described catalyzer comprises the transistion metal compound in oxide compound, halide brine oxide compound and the acid salt group of at least a Ni of being selected from, Pd, Pt, and the compound of chromium.The amount that this transition metal is loaded on the chromium cpd is about 0.1-49 atom % with respect to total metal (transition metal and chromium) amount, preferably between about 0.1-15 atom %, and the amount that chromium is loaded on the transistion metal compound is about 0.1-49 atom % with respect to total amount of metal, preferably between 0.1-15 atom %.

Catalyzer described here uses with other component (or binding agent or carrier), the atomic ratio of transition metal/chromium that catalystic material is contained is between about 10: 1 to about 1: 10, preferably, transition metal between about 2: 1 and 1: 2, is preferably about 1: 1 to the atomic ratio of chromium.Be used for catalyzer term herein, comprise adopt carrierization, non-carrierization or with a kind of suitable binding agent blended catalystic material.

Can use any chromium cpd, but chromic oxide, C ₂O ₃With chromium fluoride be preferable.Can adopt the chromium in the chromium cpd of any oxidation state, but the Cr(III) be the most stable for preferable.In addition, chromic oxide, Cr ₂O ₃TCrF ₃Be preferable chromium cpd, and chromic oxide and Cr ₂O ₃Best chromium cpd.

Cr ₂O ₃Can adopt any known technology to make, for example :) by heating Cr(OH ₃Or by heating the chromic oxide gel that from the aqueous solution, is settled out behind the alkali by adding; The mixture of chromic oxide gel (by heating urea and the Cr(III) salt by the heating hydration produces, and passes through CrO ₃With alcohol or the reaction of other stable reductive agent; By the suitable carbon compound of oxidation, such as: chromium+oxalic acid or chromium acetate; The chromium compounds of perhaps thermolysis higher oxidation state is for example: (NH ₄) ₂Cr ₂O ₇Or CrO ₃）

Used transition metal is selected from element Ni, Pd and Pt.Preferable transistion metal compound is selected from oxide compound, oxyhydroxide, halogenide, oxyhalogenation thing and the acid salt of metal.Better transistion metal compound is the Ni base.Solubility Ni salt and NiCl ₂Transistion metal compound for the best.

Transistion metal compound can mix with chromium compounds with any method in the known technology, such as: be deposited on the chromium cpd surface, with the chromium cpd coextraction, with the chromium cpd co-precipitation, mix with the chromium of other form, be dispersed in the whole chromium cpd or form a kind of compound of isodigeranyl metal with chromium.The amount that can be added to the binding agent in the catalystic material is any amount that catalyzer is bonded together, and its value can be up to 50% of catalyst weight.This catalyzer also can or can directly put on this metal on the support of the catalyst by any known technology continuously or side by side by transistion metal compound and chromium cpd or co-precipitation formation.Suitable carriers is stable or form a kind of stable carrier with HF reaction in HF, and they comprise (but not being to limit) Al ₂O ₃, AlF ₃, the Al oxyfluoride, Al hydroxyfluoride and carbon.Carrier contains the catalyzer of 50% weight at least.Preferably, this catalystic material contains total carrier and the catalytic amount until about 15% atomic wts.In order to improve prepared catalyst activity and stability, after transistion metal compound deposition or deposition, can this catalyzer of roasting.

Though catalyzer of the present invention can be got any shape, Powdered is not preferable, because little powder is enough to by reactor or causes big pressure drop, in addition, catalyzer of the present invention is preferably suitable to be configured as.Catalyzer can with existing any Technology (such as: extrude or compressing tablet) be prepared into shape arbitrarily, also can be shaped as bulk, spherical or shape that other is suitable.

Catalyzer can be dried before use.The catalyzer of making can in reactor, make anhydrous HF this above catalyzer by carrying out pre-treatment.This anhydrous HF will be fluoridized the part catalystic material, and may fluorinated support (if using carrier).The definite structure of this catalyst surface and composition may be very complicated under reaction conditions.This catalyzer is according to starting raw material, can exist with the mixture of oxide compound, halogenide, oxyhalogenide, acid salt and/or other compound of chromium and transition metal, regardless of this catalyzer authentic material in use, the term of catalyzer comprises oxide compound, halogenide, oxyhalogenide, hydroxyhalide and/or acid salt and their derivative.

The catalyzer of making be applicable to fluoridize contain no more than 3 carbon atoms and wherein at least one halogen be not the halohydrocarbon of fluorine, this at least one be not that the halogen of fluorine is replaced by fluorine.Suitable halohydrocarbon is saturated or unsaturated, and is that part is halogenated or perhalogeno.Preferable halohydrocarbon comprises methylene dichloride, CCl ₂CCl ₂(PCE), CHCl ₂CF ₃, (HCFC-123), CHClFCF ₃(HCFC-124), CHClCCl ₂(TCE) and CH ₂ClCF ₃(HCFC-133a).Better halohydrocarbon is selected from 1-chloro-2,2,2-Halothane (HCFC-133a), CCl ₂CCl ₂And CHClCCl ₂

Fluoridation anticorrosive material such as: carry out in the reactor of Inconel(nickel alloys) system.Catalyzer is placed in the reactor, and by rights such as: reactor is placed on process furnace, salt bath or sand-bath internal heating to temperature of reaction.This temperature of reaction depends on by the specific halohydrocarbon of fluorizated, and preferable between 200 ℃-550 ℃.Yet,, help catalyzer and catalytic activity does not descend when the temperature of fluoridation during greater than about 300 ℃ high temperature.In addition, do not need to add air or oxygen.For example, to 1-chloro-2,2, it is between 325 ℃-450 ℃ that the 2-Halothane is carried out the fluorizated preferred temperature.

Do not need to add oxygen and air.But in fluoridation, can add a spot of oxygen or air, to improve life of catalyst of the present invention.The amount that oxygen or air add preferably at 0.01-10 mole % oxygen or air/1mol by the fluorizated halohydrocarbon.

This reaction can be carried out to superatmospheric any pressure being lower than normal atmosphere.Yet a major advantage of catalyzer of the present invention is their catalytic life.In addition, catalyzer of the present invention can use under up to about 300Psi pressure.

In order to guarantee preferable yield, and the corrosion that prevents equipment configuration, fluoridize under anhydrous condition and carry out.In the time may existing up to 10000ppm water in industrial reactor, the water that exists with such quantity causes equipment to produce unacceptable high corrosion.In addition, under industrial condition, water content preferably is less than 6000ppm approximately, and best for being lower than about 2000ppm.In the preferable water content of laboratory scale for being less than about 300ppm.Catalyzer can not with any gas of catalyst reaction in heat drying, and preferable gas is N ₂Yet, the anhydrous N of mobile of the catalyzer in reactor ₂/ HF carries out pre-treatment by beds.

With HF and halohydrocarbon with pump to guarantee suitable duration of contact, preferably between second, pump into reactor about the speed of 1-40 between second best about 0.1-100.

Effluent is removed from reactor, and isolates required fluorination of halogenated hydrocarbon with any traditional method from effluent.All in an embodiment percentage number averages are represented with molecular fraction.

Embodiment 1

Be used in and contain 6.18 gram NiCl in 150 ml deionized water ₂6H ₂The Cr of the 1.6mm(1/16 ") of solution impregnation 50.0 grams of O ₂O ₃Extrudate prepares catalyzer.After two hours, remove and anhydrate,, obtain containing the catalyzer of 3.6%Ni samples dried.

In the reactor (0.3 inch internal diameter, the long pipe of 25 inch) of Inconel(nickel alloys), load the 18.0cc catalyzer and put into sand-bath.With reactor be heated to 400 ℃ about 4 hours.Nitrogen gas stream is passed through beds.In 200psi(1.38 * 10 ³Kpa) make nitrogen bubble pass through HF under.Then, catalyzer stands N ₂/ HF air-flow 3.5 hours.

After the pre-treatment, with HF: 1,1, the 1-trifluoro-chloroethane be the charging of 5: 1 mol ratios with enough rate pump feeding reactors, thereby when 400 ℃ and 200psi, keep 10 second duration of contact.By online gas chromatographic analysis reaction effluent, it the results are shown in the table 1.Listed the fluorizated HCFC-133a of institute percentage ratio in the conversion process (fluorizated HCFC-133a mol number/enter HCFC-133a mol number).Selectivity is the percentage ratio of the HCFC-133a mol number of fluorinated product mol number/conversion.HFC-134a(CF ₃CFH ₂) be required product.

Table 1

The transformation efficiency selectivity

Time CF ₃CClH ₂CF ₃CFH ₂CF ₃CH ₃CF ₃CHFCl

10 hours 39.1% 82.5% 16.2% 0.8%

20 hours 33.3% 83.6% 14.5% 1.4%

30 hours 41.4% 79.0% 19.9% 1.0%

40 hours 38.6% 78.1% 20.7% 1.1%

50 hours 26.8% 80.9% 17.3% 1.6%

60 hours 21.8% 84.1% 13.8% 1.7%

Average 33.5% 81.4% 17.1% 1.3%

This transformation efficiency keeps high transformation efficiency in 60 hours (show transformation efficiency be 21.8%) preceding entire reaction.At whole fluorination reaction process CF ₃CFH ₂Keep high selectivity.

Embodiment 2

The NiCr catalyzer of carrierization is by containing 4.22 gram NiCl ₂6H ₂O and 2.00 gram CrO ₃The aqueous solution (3.8 milliliters) and 19 ml methanol solution enter jointly that on the partially fluorinated alumina balls of 32.69 grams (3 mm dia) prepares.Excessive liquid is in 70 ℃ of evaporations, and with solid in 125 ℃ of dryings 16 hours.The catalyzer that obtains contains 3%Ni and 3%Cr(Ni/Cr mol ratio is 0.9).

Internal diameter is that 0.6 inch (1.5 centimetres) and length are to load the 20.00cc catalyzer in the nickel chromium iron reactor of 25 inch (63.5 centimetres), and reactor is placed sand-bath.Reactor is heated to 375 ℃ (about 4 hours), and kept again 6 hours.Nitrogen is passed through on this catalyzer with the speed that 450cc/ divides.Cool the temperature to 200 ℃, and make nitrogen bubbling under normal atmosphere pass through HF.Make temperature rise to 350 ℃ after 1 hour.With HF/N ₂Air communication was crossed catalyzer 4 hours.

With 4: 1(HF:1,1,1-trifluoro-chloroethane) when 50psi and 550 ℃ to be enough to assurance table 2 rate pump feeding reactor of listed duration of contact.To be enough to guarantee oxygen: 1,1, the mol ratio of 1-trifluoro-chloroethane is that the speed of 0.015 ratio adds air.The gas chromatographic analysis reaction effluent of communications and liaison machine, it the results are shown in the table 2.

Table 2

10.1 seconds 4.5 seconds 2.2 seconds duration of contact

CF ₃CClH ₂Transformation efficiency 21.8% 16.2% 10.9%

CF ₃CFH ₂Selectivity 97.3% 95.5% 92.8%

CF ₃CFH ₂Productive rate 8.0 16.6 21.3

(1b/h.cu.ft.)

Even under the duration of contact of the weak point of being recommended on the industrial-scale production, CF ₃CFH ₂Transformation efficiency and productive rate be still high.

Embodiment 3

Press the NiCr/AlF of embodiment 2 preparations ₃Catalyzer is loaded in the nickel chromium iron reactor, and in 400 ℃ of dryings 4 hours, handles 4 hours in the time of 400 ℃ with HF then, and be cooled to 290 ℃.Make HF and CCl ₂CCl ₂Under the condition shown in table the first hurdle,, after 130 hours, be warming up to 310 ℃ by reactor.Reaction product selectivity and productive rate under two kinds of temperature have been listed in the table 3.

Table 3

CHC under two kinds of temperature ₂CF ₂Shown selectivity is good.

Embodiment 4-6

The NiCr/AlF that will in embodiment 2, prepare ₃Catalyzer is loaded in the nickel chromium iron reactor, and the dry and heating with the method for embodiment 2.The organic compound that is listed in the table 4 is passed through catalyzer with the condition that is listed in the table 4.

Table 4

The primary product table is in following table 5.

Table 5

Organic compound	Primary product
		CHClFCF ₃	CHClFCF ₃+CHF ₂CF ₃
CHClCCl ₂	CH ₂ClCF ₃
		CH ₂Cl ₂	CH ₂F ₂

The comparative example 1

Except not adding the Ni, will be at the Cr of embodiment 1 ₂O ₃Stand the identical water treatment in order to the catalyzer of dipping embodiment 1, adopt identical reaction conditions simultaneously, it the results are shown in the table 6.

Table 6

The transformation efficiency selectivity

Time CF ₃CClH ₂CF ₃CFH ₂CF ₃CH ₃CF ₃CHFCl

10 hours 20.2% 88,3% 10.3% 1.3%

20 hours 13.4% 88.6% 9.9% 1.4%

30 hours 7.3% 88.1% 10.4% 1.3%

40 hours 4.62% 87.2% 10.8% 1.6%

50 hours 3.2% 86,4% 11.1% 1.9%

60 hours 2.6% 86.3% 11.4% 1.8%

Average 8.6% 87.4% 10.6% 1.6%

Its transformation efficiency very low for the present invention (embodiment 1) catalyzer shown 1/4, and descended sharp at 30 hours.The HCFC-133a transformation efficiency descends in time and shows that life of catalyst is short.

The comparative example 2

A kind of being carried on contains the Ni catalyzer on the gama-alumina extrudate, by with containing 4.94 gram NiCl ₂6H ₂The aqueous solution dipping 40 gram aluminum oxide of O prepare.Remove and to anhydrate, and in 145 ℃ with dry 16 hours of catalyzer.Catalyzer is pressed the method pre-treatment of embodiment 1, and initial 20 hours is 400 ℃ of operations down.Latter stage in test is raised to 425 ℃ with temperature then.It the results are shown in the table 7.

Table 7

The transformation efficiency selectivity

Time CF ₃CClH ₂CF ₃CFH ₂CF ₃CH ₃CF ₃CHFCl

10 hours 3.4% 90.6% 1.7% 3.9%

20 hours 3.2% 92.4% 1.6% 2.1%

30 hours 6.9% 95.6% 1.5% 0.7%

40 hours 7.6% 96.0% 1.3% 1/2%

50 hours 7.3% 96.4% 1.2% 0.8%

60 hours 6.6% 96.5% 1.2% 0.6%

Average 7.1% 96.1% 1.3% 0.8%

(400°)

Average 7.1% 96.1% 1.3% 0.8%

(425°)

The average conversion of NiCr catalyzer of the present invention is 33.5%, and the average selectivity of HFC-134a is 81.4% in initial 60 hours.So the transformation efficiency of catalyzer of the present invention is 10 times of the catalyzer of single nickel on aluminum oxide, and than block Cr ₂O ₃The transformation efficiency Senior Three doubly.

Contrast the result of these embodiment, embodiment 1 is loaded with Cr ₂O ₃The Ni catalyzer, under identical temperature with Comparative Examples 1 only use Cr ₂O ₃Comparing, the former has the transformation efficiency of the HCFC-133a of longer life-span and Geng Gao.At last, the result of Comparative Examples 2 shows that being carried on the Ni catalyzer that on the aluminum oxide and does not contain Cr demonstrates than the much lower HCFC-133(a of Ni catalyzer on chromic oxide) CF ₃CClH ₂Transformation efficiency.So, owing to have synergistic effect between Ni and the chromium compounds, be better than single chromium cpd as fluoridation catalyst with containing the two catalyzer of Ni and chromium cpd, also be better than being carried on the Ni compound catalyst that does not have on the chromium cpd matrix.

Comparative example 3-9

Following embodiment has compared the Mg CrAl that is disclosed among the JA 322,688, Fe-Cr, and four kinds of catalyzer of MnCr and NiCr select the MgCrAl-oxide compound to be because it has shown the best catalytic activity of the catalyzer of JA 322,688 preparations.Select the FeCr-oxide compound to be because it is the unique hybrid metal metal catalyst that contains Cr and transition metal for preparing by JA 323,688.Selecting the MnCr-oxide compound is to be used as contrast (though it is not to prepare according to JA 323,688), and it also is by the hybrid metal metal catalyst that contains Cr and transition metal.MgCrAl-oxide compound and eCr-oxide catalyst are to prepare according to the embodiment that provides among the JA 323,688.The method preparation that MnCr-oxide compound and NiCr-oxide compound are disclosed to approach JA 323,688 as far as possible, and its difference has been described.

The comparative example 3

" MgCrAl-oxide compound " catalyzer: this catalyzer is pressed the method preparation that JA 323,688 is disclosed fully.With 1100 gram Al(NO ₃) ₃9H ₂O and 40 gram Mg(NO ₃) ₂6H ₂O is dissolved in the 2.5 liter water, under agitation, adds 2000 gram 28%NH ₄OH.This mixture is added in the hot water of 80 ℃ of 4 liters.With the sedimentation and filtration that produces, use deionized water wash, and in 125 ℃ of dryings 16 hours.The exsiccant catalyzer was baked 5 hours in 450 ℃.Dry rear catalyst becomes " piece " shape, use be the block of about 5mm size.Its mol ratio is Al/cr=9.4, mg/Cr=0.5.

The comparative example 4

" FeCr-oxide compound " catalyzer: except restraining Fe(NO with 800 ₃) ₃9H ₂O and 198 gram Cr(NO ₃) ₃9H ₂Outside the O, (Fe(NO ₃) 9H ₂O presses JA323,688 regulation, but be not outsourcing, and find that it is unsettled), this catalyzer prepares (specifically describing in JA 323,688 embodiment 5) as stated above.Its mol ratio is: Fe/Cr=4.0.

The comparative example 5

" MnCr-oxide compound " catalyzer: this catalyzer is not by JA 323,688 described method preparations, except adopting 377 gram Mn(NO ₃) ₂4H ₂O and 150 gram (Cr(NO ₃) ₃9H ₂Outside the O, adopt FeCr Preparation of catalysts method and mol ratio (4.0) to prepare the MnCr catalyzer.

The comparative example 6

" NiCr-oxide compound " catalyzer: this catalyzer neither can not synthesize as stated above by JA 323,688 described method preparations, and this is because the solubleness of Ni in ammonia solution is, usually precipitating metal oxyhydroxide.

So, with 323 gram Ni(NO ₃) ₂6H ₂O and 500 gram Cr(NO ₃) ₂9H ₂O mixes in 2.5 liter water.Approaching the method for JA 323,688 as far as possible,, and be allowed to condition under the room temperature 24 hours precipitations of ageing and separate out nickel hydroxide this mixture heating up to 80 ℃.With part Ni flush away, make last Ni/Cr ratio less than 1.As stated above that this catalyzer is dry and bake.

The comparative example 7

By each catalyzer of comparative example 3-6 preparation, with JA323, in reactor, screen under the same terms of 688 defineds.In 600 milliliters of nichrome reactors, load about 95 milliliters of catalyzer, at 375 ℃ with it's dry 8 hours make past under the condition of catalyzer with the velocity flow of 200 ml/min nitrogen gas stream.After being cooled to 200 ℃, regularly drum stream is by the cylinder of dress HF for nitrogen, and the result is with the nitrogen gas stream that contains HF (200 millis/minute) this catalyzer of pre-treatment.This process continues 4 hours, will rise to 350 ℃ in temperature during this period of time.Stop to infeed nitrogen/HF air-flow, and begin reaction.HF and HCFC-133a reactant are with 3: 1(HF: mol ratio HCFC-133a) is pre-mixed.With the speed charging of 185 ml/min and by above the catalyzer, under atmospheric pressure the speed with 4.9 ml/min makes air through premixed reactant.Each catalyzer was used for two weeks.Reaction conditions is identical to be: 30 seconds duration of contact, O ₂: the mol ratio of the mol ratio of HCFC-133a such as HF: HCFC-133a is according to JA323, described in 688.Its result (work the starting raw material % that transforms, be converted into the selectivity of 134a, productive rate and the % that is converted into 134a) is shown in Table 8.

Table 8
					350 ℃, Opsig, 30 second duration of contact, 0.02 O ₂:133a,3∶1 HF∶133a
The catalyzer of preparation	NiCr- (CE6)	MgCrAl (CE3)	MnCr- (CE5)	FeCr- (CE ₄)
					The 133a transformation efficiency	21%	16%	＞26%	12%
The 134a selectivity	93%	93%	＜59%	45%
					134a productive rate (1b/h.cu.ft)	0.7	0.5	0.6	0.2
Change into 134a	19.5%	15%	15%	5.4%

Above-mentioned numerical value is represented after all stable reaction conditions and the mean value behind the catalyzer exhibit stabilization energy.Generally transformation efficiency is high when on-test, and reduces to more stable value immediately.Thus, be better than the result after 6 months who in JA 323,688, is reported greatly in the result shown in the table 8.The MgCrAl-oxide catalyst that makes by comparative example 3 has reappeared the result (18% 133a that transforms, the selectivity of 134a is 94%, 17% to be converted to 134a) of report in JA 323,688 well.The FeCr-oxide catalyst shows than JA323, the 688 poor slightly performances of being reported (10% 133a that transforms, the selectivity of 134a is 80%, 8% to be converted to 134a).The activity that the MnCr-oxide catalyst demonstrates is between MgCrAl-oxide compound and FeCr-oxide catalyst (at no embodiment report among the JA 323,688).The NiCr-oxide catalyst demonstrates the performance better slightly than other catalyzer under the condition of this embodiment.Yet reaction causes the duration of contact of fluoridation longer with slow flow rate by beds, and this causes low productive rate again, thereby is worthless.As a result, reagent will have the more time reaction, and the difference between the multiple distinct catalyzer, dwindles and is difficult to and distinguish.Under the harsh industrialized condition that the relative mass of various catalyzer is adopted in following comparative example 8 and 9 is tangible.

The comparative example 8

The flow rate of 133a improves, and be outside 13 seconds duration of contact, and the fluoridation of using the MnCr-oxide catalyst to make 133a be converted into 134a is undertaken by above-mentioned.All other conditions are same as described above.The transformation efficiency of 133a reduces to 5%, and 133a is converted into the selectivity of 134a less than 78%.

The comparative example 9

Using each catalyzer (except MnCr) to carry out fluoridation is to carry out under the condition of suitability for industrialized production being suitable for.This reaction conditions is listed in first hurdle in the table 9.These conditions are that industrially scalable is required when carrying out fluoridation.It the results are shown in table 9.

The decline of the transformation efficiency of MgCrAl-oxide compound and FeCr-oxide compound obviously descend during in elevated pressures with than short contacting time (reducing to 4% and 2% from 16% and 12% respectively).Yet the transformation efficiency of NiCr-oxide compound is held constant at 21% and selectivity increases slightly.So the productive rate that the NiCr catalyzer demonstrates HFC 134a has very big raising.At least 10 times of this productive rates are to according to JA323, arbitrary catalyzer gained productive rates of 688 preparations.The activity that the NiCr catalyzer shows under industrialized condition, also more far better than the catalyst composition of the embodiment that presses JA 323,688 prepared " best ".The activity of the excellence of NiCr catalyzer under industrialized condition can not predict in 688 compositions that disclosed and the fluorination conditions at JA323.The catalyst composition with the known technology preparation of the optimum activity that demonstrates in addition contains magnesium, alkaline-earth metal, but does not contain transition metal.Therefore, both do not recognized the catalytic activity that does not yet propose NiCr catalyzer excellence among the JA 323,688.

Claims

1, a kind of flaorination process, its feature comprises that first kind has three or be less than three carbon atoms and be not the halohydrocarbon of halogen of fluorine and anhydrous HF by at least one in the presence of a kind of transistion metal compound of oxide compound, halogenide and the oxyhalogenide group of at least a Ni of being selected from, Pd and Pt and catalyzer that a kind of chromium cpd is formed, carrying out gas-phase reaction in being higher than under 200 ℃ the temperature, is not second kind of halohydrocarbon that the described halogen of fluorine is replaced by fluorine to produce wherein at least one.

2, technology as claimed in claim 1 is characterized in that described catalyzer or carrier or tackiness agent mix, and described transition metal and described chromium cpd with transition metal to the ratio of chromium atom between about 10: 1 and 1: 10.

3, technology as claimed in claim 2 is characterized in that the carrier of described catalyzer is selected from by Al ₂O ₃, AlF ₃, the group formed of fluorine alumina, aluminium hydroxide and carbon.

4, technology as claimed in claim 3 is characterized in that described chromium cpd is selected from chromic oxide, Cr ₂O ₃, CrF ₃Or fluorine chromic oxide.

5, technology as claimed in claim 4 is characterized in that described first kind of halohydrocarbon is for being selected from by methylene dichloride, CCH ₂CCl ₂, CHCl ₂CF ₃, CHClFCF ₃, CHClCCl ₂And CH ₂ClCF ₃The group of being formed.

6, technology as claimed in claim 4 is characterized in that described first kind of halohydrocarbon is CH ₂ClCF ₃, and second kind of halohydrocarbon is CF ₃CH ₂F.

7, technology as claimed in claim 4 is characterized in that described first kind of halohydrocarbon is CCl ₂CCL ₂And second kind of halohydrocarbon is CHCl ₂CF ₃

8, technology as claimed in claim 4 is characterized in that described first kind of halohydrocarbon is CHClCCl ₂, and second kind of halohydrocarbon is CH ₂ClCF ₃

9, technology as claimed in claim 1 is characterized in that the described step of introducing oxygen or air that also comprises in fluorination process.

10, technology as claimed in claim 2 is characterized in that also comprising in the described fluorination process step of introducing oxygen or air.