CN1068244C - Chromium-based fluorination catalyst, production method thereof, and fluorination method - Google Patents
Chromium-based fluorination catalyst, production method thereof, and fluorination method Download PDFInfo
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- CN1068244C CN1068244C CN94119527A CN94119527A CN1068244C CN 1068244 C CN1068244 C CN 1068244C CN 94119527 A CN94119527 A CN 94119527A CN 94119527 A CN94119527 A CN 94119527A CN 1068244 C CN1068244 C CN 1068244C
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- 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
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Abstract
In order to manufacture hydrogen-containing hydrocarbon in high yield and provide a catalyst used for the purpose and a preparation method thereof, the present invention provides a chromium base fluorinating catalyst containing Cr, Ga, O and F to be used as basic composition elements, wherein the atomic ratio of Ga to Cr is from 0.001 to 0.15. The catalyst is prepared after an oxide or hydroxide is fluorinated, so HF can be in contact with halogenated hydrocarbon in a gas phase under the existence of the catalyst.
Description
Make that those do not conform to chlorine, the hydrofluorocarbon that therefore can not damage the ozone layer is when (being called " HFC " later on), comprising difluoromethane (being called " HFC-32 " later on), 1,1,1,2-HFC-134a (being called " HFC-134a " later on) and pentafluoroethane are when (being called " HFC-125 " later on), the present invention relates to a kind of improved fluorination catalyst that is used for making HFC with high yield, the preparation method of this fluorination catalyst, and utilize this catalyst in gas phase, to be in contact with one another the method for making HFC effectively by making hydrogen fluoride and halogenated hydrocarbons.
A representative instance of the industrially preparing process of HFC is by making hydrogeneous halogenated hydrocarbons contact the method (in a lot of situations, HF with carry out simultaneously as the addition of the unsaturated halogenated hydrocarbons of starting material with the reaction that F exchanges non-F halogen) that replaces non-F halogen with F with HF.But this is reflected at and carries out not smoothly under most of situations, and output and the catalyst system therefor of HFC are relative.
An example of the most difficult reaction is by 1-chloro-2,2, the reaction of fluoridizing synthetic HFC-134a of 2-HFC-143a (being called " HCFC-133a " later on), and this reaction obviously is the disadvantageous endothermic reaction on the thermodynamics.Therefore, this reaction is generally carried out under higher temperature having under the situation about coexisting above the HF of stoichiometric and HCFC-133a.For example, according to day disclosure special permission communique 55-27138, use air-treatment CrF
33H
2A kind of compound that O obtains is as catalyst, reacts to obtain HFC-134a under 400 ℃ temperature, and productive rate is 32%.Under high like this reaction temperature, react and to impel catalyst coking and shorten catalyst life.For preventing coking, once attempt to make oxygen in reaction gas, to coexist (day disclosure special permission communique 55-27139), but this method is unsatisfactory, because the chlorination by product increases.In order to limit the formation of chlorinated secondary product, Japan special permission communique 5-88690 discloses a kind of method of reacting in the presence of oxygen, and the CoCl by a kind of non-Cr base is used in this reaction
2/ Al
2O
3Process is fluoridized the catalyst that obtains, but this activity of such catalysts and productive rate are low.Owing to these reasons, once made test of many times so that prolong the service life of catalyst.That is to say that a day disclosure special permission communique 2-172933 illustrates, a kind of catalyst has high durability (long-life), and it contains at least a element among Al, Mg, Ca, Ba, Sr, Fe, Ni, Co and the Mn and the halide or the oxide of Cr element.It is catalyst based that EP502605 discloses the Cr of a kind of Zn of carrying.In addition, a day disclosure special permission communique 4-34694 discloses a kind of Cr of containing
2O
3Catalyst, it is by partially fluorinated and carrying Ru and Pt, and that day disclosure special permission communique 5-269382 discloses is a kind of with chromium oxide and the nickel oxide catalyst as the long service life of solvent.
But in the fluorination reaction as the hydrogeneous halogenated hydrocarbons of HFC manufacture method, catalyst can fierce coking, even above-mentioned catalyst does not have the sufficiently long life-span yet.In other words, existing before this necessary choice is difficult to take place the reaction condition of coking.Because at the ratio (being called " mol ratio " later on) of HF inlet amount and the inlet amount of organic substance hour, coking developing faster, so when using conventional fluorination catalyst, increase this mole this than the development that delays coking.But the increase of mol ratio means reduce (when space velocity keeps constant) of organic substance inlet amount, also means the decline of STY (space time yield).Therefore can infer that the prolongation of catalyst life is a cost to damage STY to a certain extent in the prior art.
Therefore, if can obtain a kind ofly than the more difficult generation coking of conventional catalyst with catalyst than the long life is arranged, then not only can prolong life of catalyst, but also might under lower mol ratio, react, thereby expection can improve productive rate.
Based on above-mentioned background, the purpose of this invention is to provide a kind of in making HFC the fluorination catalyst in service life, and use above-mentioned catalyst in gas phase, to contact the method for making HFC effectively with HF by the halogenated hydrocarbons that 1-4 carbon atom arranged.
The inventor has carried out conscientious research so that address the above problem, and find that (wherein the atomic ratio of Ga and Cr is in 0.0001 to 0.15 the scope as the catalyst of the element of basic composition for a kind of Ga of containing, Cr, O and F, preferred 0.001 to 0.1, preferred especially 0.003 to 0.05) life-span is than conventional (Cr base fluorating catalyst significant prolongation.So finished the present invention.
Therefore, the invention provides:
(1) a kind of catalyst that contains Ga, Cr, O and F as catalyst basic composition element, wherein Ga to the atomic ratio of Cr in 0.0001 to 0.15 scope, preferred 0.001 to 0.1, preferred especially 0.003 to 0.05;
(2) manufacture method of catalyst (1) comprising the catalyst precarsor that contains Cr element and Ga element is contacted with fluorine, hydrogen fluoride or hydrofluorocarbons, is carried out fluorination treatment; With
(3) a kind of method of fluorination of halogenated hydrocarbon comprises halogenated hydrocarbons is contacted with HF in the presence of catalyst (1).
Though chromium-based fluorination catalyst of the present invention contains a large amount of (in the magnitude of % weight) alkali metal as the component outside Ga, Cr, O and the F and not really desirable, can contain other element of a few percent in the catalyst.Specifically, can contain according to the atomic ratio from 0.001 to 0.5 of Cr, preferred from 0.003 to 0.2 at least a element that is selected from the 8th, 9,10,11 and 12 families (new IUPAC nomenclature), comprising Co, Ni, Cu, Zn, Cd etc., expect that these elements play a part to improve active as promoter or co-catalyst.
The compound (for example oxide and hydroxide) that catalyst of the present invention can contain Ga and Cr prepares as catalyst precarsor, with HF, F
2Or fluorine-containing halogenated hydrocarbons is fluoridized this catalyst precarsor in the molecule, thus with fluorine partly replace O and OH, the compound that contains Ga and Cr can be carried on the carrier, the suitable carriers example comprises activated carbon, aluminium oxide, aluminum fluoride, magnesium fluoride etc.
Can utilize any known method as the method for preparing catalyst precarsor, the method for for example kneading, infusion process and its precipitation method; Can use the starting material of any material, as long as they can have been bought on commercial scale as the preparation catalyst precarsor.In above-mentioned method, infusion process and its precipitation method are preferable methods, because they can be introduced Ga among the Cr with high degree of dispersion.Wherein, coprecipitation is more preferred, because it can optionally control the dispersity of Ga.Therefore, the example of a method for optimizing of preparation catalyst precarsor may further comprise the steps: the solution that is dissolved with Ga salt and Cr salt is formed with the precipitating reagent reaction precipitates, to precipitation filter, wash, drying and calcination (embodiment of coprecipitation); Perhaps following steps: with the solution impregnation chromium oxide or the chromium hydroxide of Ga compound, dry and calcination (embodiment of infusion process).When using carrier, can prepare catalyst precarsor with the solution impregnating carrier that is dissolved with Ga and Cr compound, drying and calcination then.
The embodiment of the more preferably method of preparation catalyst precarsor comprises following method: (particularly trivalent hydroxide) adds a kind of precipitating reagent (alkali) in advance in the chromium hydroxide slurry, Ga and Cr salt that its quantity is enough at least neutralize and will adds afterwards, the mixed solution that slowly adds Ga and Cr salt then is with product separation, washing, drying and the calcination that forms; And following method: side by side or alternately drip solution and a kind of precipitating reagent that is dissolved with Ga and Cr salt, so that the formation slurry is controlled reaction solution simultaneously, make that the pH of solution is 6 to 12, preferably 6.5 to 10, then with product filtration, washing, drying and calcination.
Be used as the Ga and the Cr compound of starting material in the time of can suitably using nitrate, chloride and sulfate as the preparation catalyst precarsor.Wherein, nitrate and chloride are particularly preferred for coprecipitation and infusion process respectively.The preferred embodiment of precipitating reagent is ammonia, NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus, ammonium carbonate and carbonic hydroammonium.Wherein particularly preferably be ammonia.
When molded shape is desirable catalyst shape, before or after above-mentioned calcination, carry out molded compressing tablet, perhaps before drying, carry out compression moulding.
Dry preferred in 80-130 ℃ scope (particularly 90-120 ℃) in air or inert gas (as N
2) carried out at least 30 minutes in the atmosphere, but also can adopt other drying means, for example vacuum drying.
Calcination is carried out in 300 to 600 ℃, preferred 350-500 ℃ temperature range, but calcination atmosphere need not be selected according to used preparation method.In other words, when chromium compound (as chromium hydroxide, chromium oxide etc.) under about high temperature more than 350 ℃ with O
2During contact, specific area takes place sharply to descend, and it can burn and burn up in the situation of active carbon.Therefore, when using chromium compound,, to contain O being not less than to be exposed under 350 ℃ the temperature scarcely perhaps when use active carbon during as carrier as the solvent of catalyst precarsor and without carrier
2In the atmosphere of 1000 handkerchiefs (absolute pressure), and preferably at inert gas (as N
2, Ar etc.) or reducibility gas atmosphere in carry out calcination." reducing atmosphere " used herein is meant wherein to contain a kind ofly has the gas of reducing power (as H
2, CO, NO etc.) atmosphere, it can comprise other inert gas and moisture.Can contain a kind of oxidizing gas that concentration can not cause any safety problem, for example O
2, but preferably do not contain.
When using aluminium oxide or various metal fluoride as carrier, calcination can (normally in air) be carried out in oxygen-containing atmosphere, even because these carriers at O
2Also has the effect that stops specific area to descend in the atmosphere.But described in day disclosure special permission communique 5-92141, Cr can scatter when problem was after the calcination precursor fluoridized.Therefore, when stating carrier in the use, calcination is also carried out in the atmosphere of inert gas or reducibility gas.Or, in case after the calcination of in inert gas, carrying out, preferably further in reducibility gas atmosphere, carry out calcination.
Another kind of preferable methods is to arrange a step of heat treatment in reducing atmosphere in sintering process.In other words, when using chromium compound, after drying steps, in the atmosphere of reducibility gas, directly carry out calcination as the key component of catalyst precarsor or when using active carbon as carrier.Or, in case in inert gas, carry out preferably further in reducibility gas atmosphere, carrying out after the calcination.When using aluminium oxide and various metal fluoride as carrier, directly in the atmosphere of reducibility gas, carrying out calcination behind the drying steps, or, in case after the calcination in oxygen-containing atmosphere, preferably further calcination in the atmosphere of reducibility gas.
When heat treatment is when carrying out in reducing atmosphere as mentioned above, the quantity of the Cr that scatters when before reaction catalyst precarsor being fluoridized can reduce, and catalytic activity can improve.In addition, can expect that also other effect is arranged.Heat treatment temperature should be at 350-500 ℃, preferably from 370-460 ℃, preferably from 370-450 ℃.Used all kinds of reducibility gas are H
2, Co, NO etc.But H
2More suitable, because its easy processing.The concentration of reducibility gas is from the 0.1-100% volume, if necessary, and the water of no more than 20% volume that can coexist in the gas or be no more than 99.9% inert gas.But, consider O from security standpoint
2Concentration must limit to such an extent that be lower than 0.1% volume.Gas flow rate is preferably 10-1000h by gas hourly space velocity
-1(changing into standard state) is pressed onto 10kg/cm from atmosphere
2Pressure limit be to grasp easily.Heat treatment time is at least 30 minutes, preferably from 1 to 10 hour.
Heat treated catalyst precarsor had better not at high temperature be exposed to O in reducibility gas atmosphere
2Pressure is at least in the atmosphere of 1000 handkerchiefs (absolute pressure).Therefore, after with the calcination of precursor in reducibility gas atmosphere, should not contain O again
2Atmosphere (as air) in calcination.In addition, intrasystem atmosphere will be replaced by air when taking out precursor after the calcination in finishing reducibility gas atmosphere, and will avoid O this moment
2Introduce the operation that temperature is higher than 200 ℃ reaction system.In other words, should discharge atmosphere pressures by little by little air being introduced in preferred system's (being preferably lower than 120 ℃) under 150 ℃, so that increase intrasystem O gradually
2Concentration.
Catalyst precarsor can prepare with above-mentioned any method or known before this any method, but the atomic ratio of Ga and Cr (be called later on " Ga/Cr " than) must remain in 0.0001 to 0.15 the scope, preferably from 0.001 to 0.1, preferably 0.003 to 0.05.If Ga/Cr than less than above-mentioned scope, then can not reach the effect that prevents coking, and if Ga/Cr is bigger than too, then reaction speed undesirably reduces.The ratio of the situation of mediating method by regulating the powder that will mix, in the situation of infusion process and coprecipitation by control Ga and/or the concentration of Cr compound solution and the composition of solution, realize control easily to the Ga/Cr ratio.
Fluorination catalyst of the present invention also needs O and F as the basic composition element.Though the OK range of O and F content becomes with the preparation method of Ga/Cr ratio and catalyst precarsor, every kind of component must account for 0.3% of total catalyst weight at least.Preferred O content range is a 1-25% weight, and preferred F content is from 15% to 45% weight.In order to make catalyst contain O and F, the compound that will contain Ga and Cr is used HF, F as described above
2Or the halogenated hydrocarbon gas that contains F in the molecule is fluoridized.Wherein, consider from the cost angle, best with the method that HF fluoridizes.
The temperature of fluoridizing before the catalyst precarsor reaction is from 300 to 500 ℃, especially preferably from 300 to 450 ℃.The concentration of fluorization agent (for example HF) can from 0.1 to 100% volume, but the most handy inert gas is (as N in case of necessity
2) with the fluorization agent dilution, (being called " △ T " later on) is at most 50 ℃ because the temperature that heat release causes raises so that make.Suitable gas flow rate is 10 to 10000h by GHSV
-1, pressure limit is to be pressed onto 20kg/cm from atmosphere
2G.
A preferred embodiment of catalyst precarsor fluorination process is to infeed HF and N under atmospheric pressure and 300-400 ℃
2Thereby, make HF concentration become the 5-30% volume, begin then to fluoridize.Focus pass precursor stacking bed after, HF concentration and pressure are brought up at least 90% volume and 2-10kg/cm respectively
2G will note the heat release situation simultaneously, proceeds to handle, up at least no longer heat release under final condition.
The calcination of above-mentioned catalyst precarsor and fluoridize and can carry out in same reactor as long as reactor is to be made by inconel (Inconel) or hastelloy (Hastelloy), and can be operated easily.
Contain Ga, Cr, O and F fluorination catalyst, can be used for the reaction that halogenated hydrocarbons is fluoridized by HF as basic composition element and the preparation of available aforesaid way, and effective especially for the fluorination reaction of hydrogeneous halogenated hydrocarbons.In other words, compare with fluorination catalyst (as fluorine chromium oxide) commonly used, the more difficult generation of coking, and also catalyst life is longer.
" hydrogeneous halogenated hydrocarbons " speech used among the present invention is represented at C
1To C
4Mainly contain those halogenated hydrocarbons of H in the molecule, instantiation comprises CHCl
3, CH
2Cl
2, CH
2FCl, CH
3Cl, C
2HCl
3, C
2H
2Cl
2, C
2H
3Cl, C
2HCl
5, C
2HFCl
4, C
2HF
2Cl
3, C
2HF
3Cl
2, C
2HF
4Cl, C
2H
2Cl
4, C
2H
2FCl
3, C
2H
2F
2Cl
2, C
2H
2F
3Cl, C
2H
3Cl
3, C
2H
3FCl
2, C
2H
3F
2Cl, C
2H
4Cl
2, C
2H
4FCl, C
2H
5Cl, C
3H
2F
4Cl
2And C
3HF
4Cl
3In addition, the Cl in the above-mentioned hydrocarbon can be replaced wholly or in part by Br.Wherein, fluorination catalyst of the present invention is for CH
2Cl
2, CH
2FCl (HCFC-31), CHCl=CCl
2(trichloro-ethylene), CF
3CH
2Cl (HCFC-133a), CCl
2=CCl
2(perchloroethylene), CF
3CHCl
2(HCFC-123), CF
3The fluorination reaction of CHFCl (HCFC-124) etc. is effective, and these reactions are considered to synthetic CH
2F
2(HFC-32), CH
2FCF
3(HFC-134a) and CF
3CHF
2(HFC-125) approach, above-claimed cpd is as not having the HFC of potential destruction coming into one's own day by day in recent years to ozone layer.
Fluorination reaction can be taked such as reaction methods such as fixed bed, fluid bed, moving beds, but in general, the mol ratio of HF and halogenated hydrocarbons is 0.5 to 20, and temperature is 200 to 400 ℃, and pressure is that atmospheric pressure is to 20kg/cm
2G, SV are 50 to 100,000h
-1Because in fluorination catalyst of the present invention, be not easy to take place coking, so HF can be more less than the situation of using conventional fluorination catalyst with the mol ratio of halogenated hydrocarbons.Therefore, not only life of catalyst can improve, and high STY value also can improve, thereby can improve output.
Embodiment
With reference to embodiment and comparative examples the present invention is made specific explanations below, but the present invention is not subjected to the restriction of these explanations natch.In addition, Ga/Cr is than each the element atomic ratio that contains in the catalyst of representing to record with chemical analysis, and the mol ratio among the reaction embodiment is then represented the mol ratio of HF and halogenated hydrocarbons.SV is the numerical value that changes into standard state, and pressure is gauge pressure.(Preparation of Catalyst embodiment 1).
With 0.92g Ga (NO
3)
3NH
218.9% weight) and 10gCr (NO O (Ga content:
3)
39H
2O is dissolved in the aqueous solution that obtains containing Ga and Cr in the 240g pure water.
Then, by Cr (NO
3)
3Add ammoniacal liquor (NH again in solution and the chromium hydroxide slurry that makes after ammoniacal liquor mixes
3).In this way the pH of slurry (Cr content in the slurry=1.4% weight) being adjusted to after 9, in about 20 minutes, the above-mentioned aqueous solution that contains Ga and Cr dropwise is added in this slurry of 840g, so that make the hydroxide slurry that contains Ga and Cr.With formed slurry by filtration, fully wash with pure water, drying is 12 hours under 110 ℃.The solid of gained is levigate, mix with graphite, use the tablet press machine granulation subsequently.
Particle is packed in the calcination pipe, at H
2Obtained catalyst precarsor in 4 hours in 400 ℃ of following calcinations in the air-flow.The precursor of gained is packed in the reaction tube of being made by Inconel, using N earlier
2In the 20% volume HF air-flow of dilution under 350 ℃ and atmospheric pressure, cutting off N then
2Supply is descended in the HF of 100% volume air-flow, at last pressure is elevated to 5kg/cm
2G carries out fluorination treatment again in the HF of 100% volume air-flow.The composition of handling the back particle is listed as follows:
Ga：0.79,Cr：58.6,O：19.1,F：19.5
Analysis result shows that the Ga/Cr ratio is 0.01.(Preparation of Catalyst embodiment 2)
With Cr (NO
3)
3Solution mixes under fully stirring with ammoniacal liquor, makes the chromium hydroxide slurry, with slurry by filtration.Leach thing and fully wash with pure water, following dry 12 hours at 110 ℃ then.The solid of gained is levigate, in the levigate thing that 50 grams obtain like this, slowly splash into GaCl
3The aqueous solution is (by 0.43g GaCl
2Be dissolved in the 25g pure water and prepare).With wetting like this powder under 110 ℃ dry again 12 hours, mix with graphite then, use the comminutor granulation subsequently.Then according to carrying out fluorination treatment with the same way as for preparing among the embodiment 1.Particulate component after handling like this is listed as follows:
Ga：0.39,Cr：57.5,O：18.0,F：21.0
Analysis result shows that the Ga/Cr ratio is 0.005.(the Preparation of Catalyst embodiment 1 of contrast)
According to the step of preparation embodiment 1, but do not add Ga (NO in the aqueous solution in dropwise being added to the chromium hydroxide slurry
3)
3NH
2O makes the catalyst precarsor that does not contain Ga.According to preparation among the embodiment 1 identical mode formed catalyst precarsor is carried out fluorination treatment.The composition of the particle after the processing is listed as follows:
Cr：58.9,O：18.5,F：20.6
(the Preparation of Catalyst embodiment 2 of contrast)
According to the step of preparation embodiment 1, but add 18.4g Ga (NO in the aqueous solution in dropwise being added to the chromium hydroxide slurry
3)
3NH
2O makes the very big catalyst precarsor of Ga addition.According to the mode identical formed catalyst precarsor is carried out fluorination treatment with preparation embodiment 1.The composition of the particle after the processing is listed as follows.
Ga：12.4,Cr：46.5,O：16.7,F：21.4
Analysis result shows that the Ga/Cr ratio is 0.2.(Preparation of Catalyst embodiment 3)
Prepare catalyst according to the mode identical with preparation embodiment 1, but will prepare particle molded among the embodiment 1 in nitrogen flows in 400 ℃ of following calcinations.The Ga/Cr ratio that analysis result is determined is 0.01.(Preparation of Catalyst embodiment 4)
Will be by 75g Cr (NO
3)
39H
2O and 0.69g Ga (NO
3)
3NH
2O is dissolved in the solution that is made in the 200ml pure water and the ammoniacal liquor of 28% weight dropwise was added in the 1l container that the 100ml pure water wherein is housed in about 20 minutes, controls the flowing velocity of two kinds of aqueous solution simultaneously, makes the pH of reaction solution be in 7.5 to 8.5 the scope.With formed slurry by filtration, fully wash with pure water, following dry 12 hours at 110 ℃ then.Step according to preparation embodiment 1 prepares catalyst subsequently.The Ga/Cr ratio of being determined by analysis result is 0.01.(Preparation of Catalyst embodiment 5)
With 110g CrCl
36H
2O and 0.58g GaCl
3After being dissolved in the 78g pure water, the activated alumina of 100g is immersed in the solution so that absorb the solution of quantity sufficient.Then aluminium oxide was descended dry 12 hours at 120 ℃, in the calcination pipe of the glass system of packing into.Earlier in air stream in 350 ℃ of following calcinations 3 hours, then at H
2In the air-flow in 400 ℃ of following calcinations 4 hours.Formed precursor is packed in the reaction tube with the Inconel system, using N earlier
2Under 350 ℃ and atmospheric pressure, cutting off N then in the air-flow that contains 20% volume HF of dilution
2Supply is descended in the HF of 100% volume air-flow, is risen to 3kg/cm at pressure again
2In the HF of 100% volume air-flow, carry out fluorination treatment under the G.
The Ga/Cr ratio of being determined by analysis result is 0.008.(Preparation of Catalyst embodiment 6)
Step according to preparation embodiment 1 prepares catalyst, but the aqueous solution that contains Ga and Cr that uses in preparation embodiment 1 adds 2.97g Zn (NO in addition
3)
26H
2O is mixed with the aqueous solution that contains Ga, Cr and Zn.
The Ga/Cr ratio of being determined by analysis result is 0.01, and the Zn/Cr ratio is 0.04.(reaction embodiment 1)
Levigate and the classification with the catalyst for preparing among the Preparation of Catalyst embodiment is packed the particle of 2.5ml particle diameter between 0.71mm and 1mm in the reaction tube of Inconel system into.Under following activity rating condition, carry out the fluorination reaction of HCFC-133a then, measure the HFC-134a productive rate.Subsequently reaction condition is changed over the following condition (being called " accelerated degradation condition " later on) that to degrade, product was kept 15 hours.But the HFC-134a productive rate keeps about 11% steady state value.Subsequently reaction condition is changed back to once more above-mentioned activity rating condition, measure the active degree that descends.Table 1 has been listed the HFC-134a productive rate of accelerated degradation front and back and the ratio of the productive rate before and after the accelerated degradation.
The activity rating condition:
Temperature: 320 ℃,
Pressure: atmospheric pressure,
The HF/HCFC-133a mol ratio: 8,
SV：1,500h
-1
The accelerated degradation condition:
Temperature: 360 ℃,
Pressure: atmospheric pressure,
The HF/HCFC-133a mol ratio: 1,
SV:2,000h
-1(reaction embodiment 2)
Method according to reaction embodiment 1 is measured the activity decline degree that causes owing to accelerated degradation, but is to use the catalyst of preparation among the Preparation of Catalyst embodiment 2.The results are shown in the table 1.(the reaction embodiment 1 of contrast)
Measure because the activity that accelerated degradation causes reduces degree according to the method for reaction embodiment 1, but be to use preparation in the Preparation of Catalyst embodiment 1 of contrast catalyst, the results are shown in the table 1.(the reaction embodiment 2 of contrast)
Measure because the activity that accelerated degradation causes reduces degree according to the method for reaction embodiment 1, but be to use the catalyst of preparation in the Preparation of Catalyst embodiment 1 of contrast.The results are shown in the table 1.
HFC-134a productive rate comparative catalyst accelerated degradation preacceleration degraded back productivity ratio before and after table 1 accelerated degradation
The preparation embodiment 2 12.4 9.2 0.74 of preparation embodiment 1 23.8 10.3 0.43 contrasts of productive rate (%) productive rate * (%) preparation embodiment 1 24.1 16.9 0.70 preparation embodiment 2 21.0 16.2 0.77 contrasts
In last table, productive rate is represented the productive rate of HFC-134a, and productivity ratio is represented the ratio of the productive rate before and after the accelerated degradation.
Can be understood by The above results, contain the situation of the catalyst that adds Ga therein, even when catalyst exposure also very difficult generation coking under the reaction condition that degraded takes place probably, therefore, the active degree that descends is little.Reaction embodiment 2 by contrast also can understand, if the Ga that adds amount is too big, activity of such catalysts undesirably descends.(reaction embodiment 3 to 6)
The degree that the activity that causes owing to accelerated degradation according to the same way as mensuration with reaction embodiment 1 descends, but be to use the catalyst that after Preparation of Catalyst embodiment 3 reaches, prepares.Table 2 has been listed the ratio of the HFC-134a productive rate before and after the accelerated degradation.
The ratio catalyst production of the HFC-134a productive rate before and after table 2 accelerated degradation is than preparation embodiment 3 0.71 preparation embodiment 4 0.77 preparation embodiment 5 0.63 preparation embodiment 6 0.70
In last table, productive rate is represented the productive rate of HFC-134a, and productivity ratio is represented the ratio of the productive rate before and after the accelerated degradation.(reaction embodiment 7)
According to reaction embodiment 1, use the catalyst of preparation among the Preparation of Catalyst embodiment 1 to carry out the fluorination reaction of HCFC-123 under the following conditions, measure the active degree that descends.Activity rating condition: temperature: 320 ℃, pressure: atmospheric pressure, the HF/HCFC-133a mol ratio: 4, SV:1,000h
-1Accelerated degradation condition: temperature: 370 ℃, pressure: atmospheric pressure, the HF/HCFC-133a mol ratio: 1, SV:1,000h
-1The ratio of the productive rate of the HFC-125 before and after the accelerated degradation is 0.48.
As mentioned above, because the long service life of fluorination catalyst of the present invention, so it can produce hydrofluorocarbon with high yield.
Claims (11)
1. chromium-based fluorination catalyst that contains chromium, gallium, oxygen and fluorine as the basic composition element, wherein the atomic ratio of gallium and chromium is a benchmark with the catalyst gross weight in 0.001 to 0.15 scope, oxygen content is that 1-25% weight and fluorine content are 15-45% weight.
2. according to a kind of chromium-based fluorination catalyst of claim 1, wherein the atomic ratio of gallium and chromium is in 0.003 to 0.05 scope.
3. according to a kind of chromium-based fluorination catalyst of claim 1, wherein also contain at least a element that is selected from chromium, nickel, zinc and cadmium, the atomic ratio of described element and chromium is in 0.001 to 0.5 scope.
4. method of making the chromium-based fluorination catalyst of claim 1, comprising the catalyst precarsor that contains chromium element and gallium element is contacted with fluorine gas, hydrogen fluoride or hydrofluorocarbons, carry out fluorination treatment to obtain this catalyst, wherein said catalyst precarsor is by coprecipitation or immersion process for preparing.
5. according to a kind of method of claim 4, wherein catalyst precarsor is a kind of oxide and/or hydroxide.
6. according to a kind of method of claim 4, its uses in containing the atmosphere of reducibility gas catalyst precarsor heat treated under 350-500 ℃ temperature.
7. a kind of method of claim 6, reducibility gas wherein is a hydrogen.
8. the method for a fluorination of halogenated hydrocarbon, it is characterized in that, hydrogen fluoride and halogenated hydrocarbons are contacted in the presence of the chromium-based fluorination catalyst of aforesaid right requirement 1 in gas phase, and wherein the mol ratio of HF and described halogenated hydrocarbon is 0.5-20, and temperature is that 200-400 ℃ and pressure are atmospheric pressure-20kg/cm
2G.
9. a kind of method according to Claim 8, halogenated hydrocarbons wherein is hydrogeneous halogenated hydrocarbons.
10. according to a kind of method of claim 9, hydrogeneous halogenated hydrocarbons wherein is selected from carrene, chlorofluoromethane, 1-chloro-2,2,2-HFC-143a, 1,1-two chloro-2,2,2-HFC-143a and 1-chloro-1,2,2,2-HFC-134a.
11. according to a kind of method of claim 10, hydrogeneous halogenated hydrocarbons wherein is a 1-chloro-2,2, the 2-HFC-143a.
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|---|---|---|---|
| JP24791894A JP3558385B2 (en) | 1994-10-13 | 1994-10-13 | Chromium-based fluorination catalyst and fluorination method |
| CN94119527A CN1068244C (en) | 1994-10-13 | 1994-12-16 | Chromium-based fluorination catalyst, production method thereof, and fluorination method |
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| JP24791894A JP3558385B2 (en) | 1994-10-13 | 1994-10-13 | Chromium-based fluorination catalyst and fluorination method |
| CN94119527A CN1068244C (en) | 1994-10-13 | 1994-12-16 | Chromium-based fluorination catalyst, production method thereof, and fluorination method |
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| CN1068244C true CN1068244C (en) | 2001-07-11 |
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| CN (1) | CN1068244C (en) |
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| GB0507139D0 (en) | 2005-04-08 | 2005-05-18 | Ineos Fluor Holdings Ltd | Catalyst |
| US8661459B2 (en) | 2005-06-21 | 2014-02-25 | Microsoft Corporation | Content syndication platform |
| US9104773B2 (en) | 2005-06-21 | 2015-08-11 | Microsoft Technology Licensing, Llc | Finding and consuming web subscriptions in a web browser |
| US8280843B2 (en) | 2006-03-03 | 2012-10-02 | Microsoft Corporation | RSS data-processing object |
| CN100444958C (en) * | 2006-11-08 | 2008-12-24 | 浙江衢化氟化学有限公司 | Fluorination catalyst, its prepn. method and use |
| CN101412654B (en) * | 2008-07-21 | 2011-12-28 | 浙江衢化氟化学有限公司 | Preparation of 1,1-difluoroethane and fluorating catalyst |
| CN106824232B (en) * | 2017-01-22 | 2019-08-02 | 北京宇极科技发展有限公司 | High price chromium-based catalysts, Preparation method and use |
| CN107803195B (en) * | 2017-09-22 | 2020-12-22 | 乳源东阳光氟有限公司 | Activation method of fluorination catalyst |
| CN111036225B (en) * | 2019-12-17 | 2023-03-07 | 山东东岳化工有限公司 | Method for preparing high-activity pentafluoroethane chromium-based catalyst through sectional roasting and sectional fluorination |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766260A (en) * | 1987-07-07 | 1988-08-23 | E. I. Du Pont De Nemours And Company | Gas-phase fluorination process |
| CN1039013A (en) * | 1988-06-29 | 1990-01-24 | 纳幕尔杜邦公司 | Gas-phase hydrofluorination process |
| JPH02172932A (en) * | 1988-12-23 | 1990-07-04 | Asahi Glass Co Ltd | Fluorination of 1,1,2-trichloro-2,2-difluoroethane |
| CN1064628A (en) * | 1991-03-07 | 1992-09-23 | 帝国化学工业公司 | The Catalysts and its preparation method that is used for fluorination reaction |
-
1994
- 1994-10-13 JP JP24791894A patent/JP3558385B2/en not_active Expired - Lifetime
- 1994-12-16 CN CN94119527A patent/CN1068244C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4766260A (en) * | 1987-07-07 | 1988-08-23 | E. I. Du Pont De Nemours And Company | Gas-phase fluorination process |
| CN1039013A (en) * | 1988-06-29 | 1990-01-24 | 纳幕尔杜邦公司 | Gas-phase hydrofluorination process |
| JPH02172932A (en) * | 1988-12-23 | 1990-07-04 | Asahi Glass Co Ltd | Fluorination of 1,1,2-trichloro-2,2-difluoroethane |
| CN1064628A (en) * | 1991-03-07 | 1992-09-23 | 帝国化学工业公司 | The Catalysts and its preparation method that is used for fluorination reaction |
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| JP3558385B2 (en) | 2004-08-25 |
| CN1124673A (en) | 1996-06-19 |
| JPH08108073A (en) | 1996-04-30 |
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