CN103304368A - Preparation method of 1,1,1,2-tetrafluoroethane, and preparation method of catalyst of 1,1,1,2-tetrafluoroethane - Google Patents
Preparation method of 1,1,1,2-tetrafluoroethane, and preparation method of catalyst of 1,1,1,2-tetrafluoroethane Download PDFInfo
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Abstract
The invention discloses a method for preparing 1,1,1,2-tetrafluoroethane through treating 2-chloro-1,1,1-trifluoroethane as a raw material, and a special fluorination catalyst therefor. The fluorination catalyst is composed of a first active component and/or a second active component, wherein the first active component comprises Cr and Mg; and the second active component is one of VB metal elements, VIB metal elements except Cr, IIB metal elements or IIIA metal elements, or is a combination comprising two or more thereof. The fluorination catalyst has the advantages of conversion rate and selectivity guarantee, and high stability.
Description
Technical field
The present invention relates to the preparation method of a kind of hydrogen fluorohydrocarbon and catalyzer thereof, be specifically related to the preparation method of HFA 134a and chromium Mg catalyst thereof.
Background technology
HFA 134a is called again R134a, HFC-134a, is that an ODP value is 0 ODS substitute, is used as widely refrigeration agent, in order to substitute the refrigeration agent R22 of depletion.
Have multiplely about the HFA 134a syntheti c route, divide by raw material to mainly contain trieline route, zellon route, trichloroethane route and chloroform route, divide by technique to mainly contain liquid-phase fluorination technique and vapor phase flaorination process.
(1) trieline route
The patent WO9008755 of Du Pont discloses with trieline and hydrofluoric acid and has reacted in the presence of catalyzer, generate R133a, R134a and other organic by-products, catalyzer is a certain amount of cobalt of load or chromium metallic compound above aluminum fluoride, partially fluorinated aluminum oxide or the gac etc.
Imperial Chemical Industries EP0449617 discloses and adopted trieline is raw material prepares R134a through two steps method, the reaction of trieline and hydrofluoric acid generated R133a when the method was included in the first reaction zone, make R133a and hydrofluoric acid reaction generate R134a at the second reactor, whole products from the R134a reaction zone is joined the R134a reaction zone with required additional trieline, separate R134a and hydrogenchloride from the circulation product flow, the catalyzer that adopts is the chromic oxide of chromic oxide and zinc or nickel promotion.
When the large CN1055534 of King Company discloses the gas dilution that adopts reactionlessness, trieline and hydrofluoric acid gas phase fluorination obtain R134a and R133a, temperature of reaction is easy to control, when adopting 1, when the gas that 1,1-Halothane and hydrogen fluoride reaction produce is used as diluent gas, can be with 1, the generation of 1-difluoroethylene does not affect the carrying out of reaction always in very low level.The catalyzer that reaction is adopted is chromic oxide.
Clear and electrician CN1082019 has reported the method that R134a is produced in trieline and hydrofluoric acid reaction, and equipment and the efficient of producing R134a has been simplified and improved to the method.Clear and electrician's patent JP8108073 discloses the chromium-based catalysts of a kind of Cr of containing, Ga, O and F, can be used for the gas phase fluorination of R133a, generates R134a.
(2) the 2-chloro-1,1,1 ,-Halothane (R133a) route
The catalyzer that dust Loew atropic CN1077945 discloses take chromium as main ingredient exists lower, method by gas phase R133a and hydrofluoric acid continuous production R134a, allow from reactor airflow distillation out, so that being separated in the top and being what to contain that reaction produces almost all is the stream of the R134a of hydrogenchloride and at least 90%, isolate the stream of at least 90% unconverted reactant in the bottom, and bottom fraction is direct cycled to reactor without any purification process.
Catalyzer for using has following report:
(1) the Chinese patent CN177522 of Ao Simengtuo company discloses the catalyzer of relevant R134a preparation, namely based on armorphous Cr (III) compound and a kind of metallic compound that is selected from Mg, Ca, Sr, Ba, Ti and Zr, be carried on aluminum fluoride or the fluorination catalyst of the aluminum oxide fluoridized;
(2) Xi'an Inst. of Modern Chemistry's Chinese patent CN1145275, CN1153160 have reported respectively the catalyzer of halohydrocarbon gas phase fluorination and preparation method and the technological problems of R134a, and the fluorination catalyst of reporting is: adopt silica containing γ-Al
2O
3Fluoridize at 150 ~ 300 ℃ with anhydrous hydrogen fluoride and nitrogen mixture and pure anhydrous hydrogen fluoride, removal is as the silicon-dioxide of pore-forming material, make the active aluminum fluoride of bigger serface, catalyzer with its load chromium, cobalt, magnesium, can be used as trieline and be raw material through the R133a intermediate, two step gas phase fluorination are produced the catalyzer of R134a;
(3) people such as Loustaunau (Catalysis Letters (2010), 138 (3-4) 215-223) have reported that chromium-based catalysts take zinc doping as catalysts for gas phase fluorination, can be converted into R133a R134a;
(4) PCT of Ineos company patent application WO 2010026383, WO 2010026382 disclose a kind of method of relevant R134a preparation, be fluorination catalyst and the method for preparing hydrofluoric ether, the catalyzer that adopts is a kind of novel chromium-containing catalyst, comprises to promote active a certain amount of zinc;
(5) people (ndian Journal of Chemistry, Section A:Inorganic, Bio-inorganic, Physical, the Theoretical ﹠amp such as He Jun; Analytical Chemistry (2009), 48A (4) 489-497) has reported take the CrOx-Y2O3 catalyzer as fluorination catalyst, carry out 2-chloro-1,1, the fluoridizing of 1-Halothane, CrFx, CrOxFy or Cr (OH) xFy is the activity site of fluoridation.The people CN 101041132 such as He Jun have reported the Cr/Y catalyzer, are used for the R133a fluoridation and prepare R134a;
(6) Dong Hongtao etc. (organic fluorine industry (2007), (3) 13-15) have reported the R133a of Cr-Zn-Al catalyst and the method that the hydrofluoric acid fluoridation prepares R134a, temperature of reaction is 350～370 ℃;
(7) the people WO 2007149660 such as Bertelo has reported a kind of preparation method who fluoridizes with chromium-based catalysts, and the transformation efficiency that R133a fluoridizes preparation R134a is 10%;
(8) the Chinese patent CN of Eastern Mountain, Shandong chemical company 1820845 has reported preparation 1, the prescription of 1,1,2-Tetrafluoroethane, this catalyzer is comprised of chromium, iron, oxygen, fluorine and a kind of metallic element, and this metallic element is selected from one or more in cobalt, manganese, zinc, the magnesium nickel.Effectively suppressed the generation of crystal formation, guaranteed that chromium-based catalysts keeps highly active amorphous state;
(9) people such as Dmitriev has reported under the catalysis of chromium and magnesium fluoride catalyzer (median size of catalyzer is 0.125-0.315mm) at Russ P RU 2243961, under 140～190 ℃, be 4.5s duration of contact, trieline is raw material, the selectivity that generates R134a with the hydrofluoric acid gas phase fluorination is 99.9%, and productive rate is 97.9%;
(10) people (the Catalysis Letters (1996) such as Lu Jian, 41 (3,4), 221-224) having investigated CrF3/AlF3 is the situation that catalyzer prepares R134a, when trieline is raw material, it is 260 ℃ that the best is fluoridized temperature, and when R133a was raw material, it was 350 ℃ that the best is fluoridized temperature.
Summary of the invention
The object of the present invention is to provide a kind of with 2-chloro-1,1,1,-Halothane (R133a) is for raw material prepares 1,1, and 1, the method of 2-Tetrafluoroethane (R134a) and professional catalyzer, 2-chloro-1,1,1,-Halothane and hydrofluoric acid under certain reaction conditions with hydrofluoric acid generation gas phase fluorination, obtain 1,1 with higher selectivity and transformation efficiency, the method of 1,2-Tetrafluoroethane.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of with 2-chloro-1,1,1 ,-Halothane is the method that raw material prepares HFA 134a, under the fluorination catalyst effect, and 2-chloro-1,1,1 ,-Halothane and hydrofluoric acid generation gas phase fluorination prepare HFA 134a.
Fluorination catalyst of the present invention is the catalyzer take chromium, magnesium as main ingredient, namely take chromium metal, magnesium as the basis, can add other compositions, can certainly not add other compositions, only contains two kinds of metallic elements of chromium and magnesium.Fluorination catalyst of the present invention is comprised of the first active ingredient and/or the second active ingredient, wherein:
The first active ingredient is chromium and magnesium;
The second active ingredient is one or more combinations in group vib metallic element, IIB family metallic element or the IIIA family metallic element that is selected from outside VB family metallic element, the dechromisation.
Above-mentioned VB family metallic element is preferably niobium or tantalum, and described group vib metallic element is preferably molybdenum, and described IIB family metallic element is preferably zinc, and described IIIA family metallic element is preferably aluminium or indium.
The preparation method of fluorination catalyst presoma of the present invention comprises blending method and coprecipitation method.When preparing with coprecipitation method, the introducing of chromium base can be the solubility chromic salts such as chromium chloride, chromium nitrate, chromium sulphate, potassium chromium sulfate, the introducing of magnesium base can be the solubility magnesium salts such as magnesium chloride, magnesium nitrate, sal epsom, the introducing of other components is also introduced by the form of its soluble salt, such as zinc chloride, indium chloride, aluminum nitrate etc.
When preparing the fluorination catalyst presoma with coprecipitation method, may further comprise the steps: with soluble metallic salt or soluble metal salt brine solution and precipitation agent reaction, through stir, precipitation and filtering, and drying becomes catalyst precursor with roasting, wherein:
Described soluble metallic salt is soluble salt, the soluble salt of IIB family metallic element and the soluble salt of IIIA family metallic element of the outer group vib metallic element of soluble salt, the dechromisation of solubility chromic salts, solubility magnesium salts, VB family metallic element;
Described precipitation agent is that concentration is 5%～10% ammoniacal liquor, and the pH value when soluble metallic salt or soluble metal salt brine solution and precipitation agent reaction is controlled at 7.0～10.0.
In the above-mentioned fluorination catalyst presoma preparation process, the weight of described solubility chromic salts is preferably and accounts for 5～60% of soluble metallic salt gross weight, and more preferably 10～50%; The weight of described solubility magnesium salts is preferably and accounts for 40～95% of soluble metallic salt gross weight, and more preferably 50～90%; The gross weight of the soluble salt of the soluble salt of the group vib metallic element that the soluble salt of described VB family metallic element, dechromisation are outer, the soluble salt of IIB family metallic element and IIIA family metallic element is preferably and accounts for 0～20% of soluble metallic salt gross weight, and more preferably 0～10%.
When above-mentioned coprecipitation method prepares the fluorination catalyst presoma, it is 8% ammoniacal liquor that described precipitation agent is preferably concentration, pH value when soluble metallic salt or soluble metal salt brine solution and precipitation agent reaction preferably is controlled at 7.5～9.5, and the concentration of described soluble metal salt brine solution is preferably 10%～30%.
When preparing the fluorination catalyst presoma with blending method, the introducing of chromium base can be the soluble chromium compounds such as chromium hydroxide, chromic oxide, chromium fluoride, the introducing of magnesium base can be the soluble magnesium compounds such as magnesium fluoride, magnesium oxide, other active ingredients can add with the form of oxide compound or fluorochemical, such as zinc oxide, zinc fluoride etc.Working method comprises ball milling, kneading or pugging.The weight of described solubility chromic salts is preferably and accounts for 5～60% of soluble metallic salt gross weight, and more preferably 10～50%; The weight of described solubility magnesium salts is preferably and accounts for 40～95% of soluble metallic salt gross weight, and more preferably 50～90%; The gross weight of the soluble salt of the soluble salt of the group vib metallic element that the soluble salt of described VB family metallic element, dechromisation are outer, the soluble salt of IIB family metallic element and IIIA family metallic element is preferably and accounts for 0～20% of soluble metallic salt gross weight, and more preferably 0～10%.
After above-mentioned coprecipitation method or blending method prepare the fluorination catalyst presoma, need before use through activation treatment, first under 300～380 ℃ of temperature and N
2Roasting is 4～7 hours in the air-flow, then fluoridizes through HF, is down to room temperature for subsequent use.
Of the present invention with 2-chloro-1,1,1 ,-Halothane is that raw material prepares in the HFA 134a technique, feed hydrogen fluoric acid and 2-chloro-1,1,1, and the mole proportioning of-Halothane is 1～20:1, is preferably 4～15; 1; The gas phase fluorination temperature is 260～320 ℃, is preferably 270～300 ℃; Be 10～35s duration of contact, is preferably 11～25s; Reaction velocity is 0.03～0.09s
-1, 0.04～0.06 s more preferably
-1
HFA 134a preparation technology of the present invention has compared to existing technology catalyzer and is guaranteeing transformation efficiency, optionally having simultaneously an advantage of high stability.
Embodiment
Come the present invention is further specified below in conjunction with specific embodiment, but do not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained all alternativess, improvement project and the equivalents that may comprise in claims scope.
Catalyzer Preparation Example 1
With 45% chromium nitrate, 55% magnesium nitrate is made into the aqueous solution of 15% concentration, carry out parallel-flow precipitation take constant PH as 9.0 with the ammoniacal liquor of 8% concentration, filtration drying obtains preparing stand-by chromium-magnesium compound, interpolation 1%(weight) pugging behind the ZnO, again through extrusion molding, catalyzer calcination device is put in 120 ℃ of lower oven dry, adopts the mode of temperature programming to control Heating temperature, at first in atmosphere of inert gases, be warming up to 380 ℃, constant temperature is approximately behind the 6h, and cooling is down to 240 ℃ to temperature, pass into hydrofluoric acid, adopt temperature programming to 380 ℃, be cooled to room temperature, make catalyzer for subsequent use.
Catalyzer Preparation Example 2
Be made into the solution of 15% concentration with 45% chromium nitrate, 55% magnesium nitrate, the ammoniacal liquor of 8% concentration is dripped in mixing solutions, when the pH of solution value is 8.7, stop to drip, after continuing to stir 2h, filter, wash, with the filter cake extrusion moulding that obtains, oven dry is put into activated reactor with resulting catalyst precursor, activates; In atmosphere of inert gases, temperature programming control activation temperature, during to 400 ℃, cooling to 200 ℃, passes into hydrofluoric acid, and be warming up to 360 ℃ and obtain catalyzer, cooling, for subsequent use.
Fluoridation embodiment 1
In gas phase fluorination nickel based metal reactor, put into the catalyzer 700g according to catalyzer Preparation Example 1 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 290 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 7.2:1, be 15s duration of contact, and air speed is 0.067s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 29.2%, R134a is 97.26%, and after 600h was carried out in reaction, reaction raw materials transformation efficiency and R134a selectivity did not have to descend substantially.
Fluoridation embodiment 2
In gas phase fluorination nickel based metal reactor, put into the catalyzer 700g according to catalyzer Preparation Example 1 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 300 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 7.4:1, be 14s duration of contact, and air speed is 0.07s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 32.9%, R134a is 93.79%, and after 560h was carried out in reaction, reaction raw materials transformation efficiency and R134a selectivity did not have to descend substantially.
Fluoridation embodiment 3
In gas phase fluorination nickel based metal reactor, put into the catalyzer 600g according to catalyzer Preparation Example 1 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 280 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 6.5:1, be 20s duration of contact, and air speed is 0.05s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 28.0%, R134a is 98.55%, and after 600h was carried out in reaction, reaction raw materials transformation efficiency and R134a selectivity did not have to descend substantially.
Fluoridation embodiment 4
In gas phase fluorination nickel based metal reactor, put into the catalyzer 500g according to catalyzer Preparation Example 2 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 300 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 8.15:1, be 13.01s duration of contact, and air speed is 0.077s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 29.98%, R134a is 96.06%, and after 300h was carried out in reaction, reaction raw materials transformation efficiency and R134a selectivity did not have to descend substantially.
Fluoridation embodiment 5
In gas phase fluorination nickel based metal reactor, put into the catalyzer 500g according to catalyzer Preparation Example 2 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 290 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 6.25:1, be 14.59s duration of contact, and air speed is 0.069s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 29.16%, R134a is 96.72%, and after 300h was carried out in reaction, reaction raw materials transformation efficiency and R134a selectivity did not have to descend substantially.
Fluoridation embodiment 6
In gas phase fluorination nickel based metal reactor, put into the catalyzer 470g according to catalyzer Preparation Example 2 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 290 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 5.53:1, be 20.47s duration of contact, and air speed is 0.049s
-1Reaction product is through after washing alkali cleaning, carry out gas chromatographic detection, the transformation efficiency of R133a is 28.44%, the selectivity of R134a is 96.09%, and after reaction was carried out 90 days, reaction raw materials transformation efficiency and R134a selectivity did not have to descend substantially, the transformation efficiency of R133a is that the selectivity of 23.37%, R134a is 96.45%.
Fluoridation embodiment 7: fluoridation behind the catalyst regeneration
Behind the catalyzer pressure coking and deactivation after the fluoridation embodiment 6 reaction end, passing into oxygen regenerates, then proceed fluoridation, operation is with fluoridation embodiment 6,290 ℃ of fluorination reaction temperature, the mole proportioning of hydrofluoric acid and R133a is 6.84:1, and be 18.69s duration of contact, and air speed is 0.053s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 29.39%, R134a is 97.14%, and after 90h was carried out in reaction, the transformation efficiency of R133a was that the selectivity of 24.02%, R134a is 99.47%.Namely by behind the catalyst regeneration, transformation efficiency and selectivity all increase.
Fluoridation comparative example 1
In gas phase fluorination nickel based metal reactor, put into the catalyzer 600g according to catalyzer Preparation Example 1 preparation gained, be warming up to 220 ℃ under the atmosphere of inert gases, then pass into hydrofluoric acid, be warming up to 340 ℃ of temperature of reaction, pass into raw material R133a and hydrofluoric acid with certain speed, the mole proportioning of hydrofluoric acid and R133a is 6.42:1, be 21.39s duration of contact, and air speed is 0.047s
-1, reaction product is carried out gas chromatographic detection through after washing alkali cleaning, and the transformation efficiency of R133a is that the selectivity of 32.1%, R134a is 80.15%.
Claims (9)
1. one kind with 2-chloro-1,1,1,-Halothane is that raw material prepares 1,1,1, the method of 2-Tetrafluoroethane is characterized in that under the fluorination catalyst effect 2-chloro-1,1,1 ,-Halothane and hydrofluoric acid generation gas phase fluorination prepare 1,1,1,2-Tetrafluoroethane, described fluorination catalyst is comprised of the first active ingredient and/or the second active ingredient, wherein:
The first active ingredient is chromium and magnesium;
The second active ingredient is one or more combinations in group vib metallic element, IIB family metallic element or the IIIA family metallic element that is selected from outside VB family metallic element, the dechromisation;
Hydrofluoric acid and 2-chloro-1,1,1, the mole proportioning of-Halothane is 1 ~ 20:1, and the gas phase fluorination temperature is 260 ~ 320 ℃, and be 10 ~ 35s duration of contact, and reaction velocity is 0.03 ~ 0.09s
-1
According to claimed in claim 1 with 2-chloro-1,1,1 ,-Halothane is that raw material prepares 1,1,1, the method of 2-Tetrafluoroethane is characterized in that described VB family metallic element is niobium or tantalum, and described group vib metallic element is molybdenum, described IIB family metallic element is zinc, and described IIIA family metallic element is aluminium or indium.
3. the preparation method of a fluorination catalyst claimed in claim 1, the preparation method who it is characterized in that described fluorination catalyst presoma is coprecipitation method, may further comprise the steps: with soluble metallic salt or soluble metal salt brine solution and precipitation agent reaction, through stirring, precipitate and filtering, and drying becomes catalyst precursor with roasting, wherein:
Described soluble metallic salt is soluble salt, the soluble salt of IIB family metallic element and the soluble salt of IIIA family metallic element of the outer group vib metallic element of soluble salt, the dechromisation of solubility chromic salts, solubility magnesium salts, VB family metallic element;
Described precipitation agent is that concentration is 5%～10% ammoniacal liquor, and the pH value when soluble metallic salt or soluble metal salt brine solution and precipitation agent reaction is controlled at 7.0～10.0.
4. according to the preparation method of fluorination catalyst claimed in claim 3, the weight that it is characterized in that described solubility chromic salts accounts for 5～60% of soluble metallic salt gross weight, the weight of described solubility magnesium salts accounts for 40～95% of soluble metallic salt gross weight, and the gross weight of the soluble salt of the soluble salt of the group vib metallic element that the soluble salt of described VB family metallic element, dechromisation are outer, the soluble salt of IIB family metallic element and IIIA family metallic element accounts for 0～20% of soluble metallic salt gross weight.
5. according to the preparation method of fluorination catalyst claimed in claim 4, it is characterized in that the weight of described solubility chromic salts accounts for the 10-50% of soluble metallic salt gross weight, the weight of described solubility magnesium salts accounts for 50～90% of soluble metallic salt gross weight, and the gross weight of the soluble salt of the soluble salt of the group vib metallic element that the soluble salt of described VB family metallic element, dechromisation are outer, the soluble salt of IIB family metallic element and IIIA family metallic element accounts for 0～10% of soluble metallic salt gross weight.
6. according to the preparation method of fluorination catalyst claimed in claim 3, it is characterized in that described precipitation agent is that concentration is 8% ammoniacal liquor, pH value when soluble metallic salt or soluble metal salt brine solution and precipitation agent reaction is controlled at 7.5～9.5, and the concentration of described soluble metal salt brine solution is 10%～30%.
7. according to the preparation method of fluorination catalyst claimed in claim 3, it is characterized in that the before use activated processing of described catalyst precursor, first under 300～380 ℃ of temperature and N
2Roasting is 4～7 hours in the air-flow, then fluoridizes through HF, is down to room temperature for subsequent use.
According to claimed in claim 1 with 2-chloro-1,1,1,-Halothane is that raw material prepares 1,1,1, the method of 2-Tetrafluoroethane, it is characterized in that described hydrofluoric acid and 2-chloro-1,1,1, the mole proportioning of-Halothane is 4 ~ 15:1, the gas phase fluorination temperature is 270 ~ 300 ℃, and be 11 ~ 25s duration of contact, and reaction velocity is 0.04 ~ 0.06 s
-1
9. the preparation method of a fluorination catalyst claimed in claim 1 is characterized in that the preparation method of described fluorination catalyst is blending method, comprises ball milling, kneading or pugging.
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| CN106824232A (en) * | 2017-01-22 | 2017-06-13 | 北京宇极科技发展有限公司 | High price chromium-based catalysts, Preparation method and use |
| CN107376952A (en) * | 2017-06-09 | 2017-11-24 | 浙江三美化工股份有限公司 | A kind of preparation method of HFC-134a catalyst |
| CN107570181A (en) * | 2017-08-07 | 2018-01-12 | 乳源东阳光氟有限公司 | A kind of preparation method of fluorination catalyst |
| CN107597135A (en) * | 2017-08-07 | 2018-01-19 | 乳源东阳光氟有限公司 | A kind of preparation method of fluorination catalyst |
| CN109046335A (en) * | 2018-07-09 | 2018-12-21 | 浙江巨化技术中心有限公司 | A kind of preparation method synthesizing 1,1,2,2- tetrafluoroethane catalyst |
| CN109675592A (en) * | 2018-12-26 | 2019-04-26 | 乳源东阳光氟有限公司 | A kind of compound fluorination catalyst of metal oxide/C and its preparation method and application |
| CN112642449A (en) * | 2020-12-21 | 2021-04-13 | 江苏三美化工有限公司 | Catalyst for gas phase fluorination of 1,1,1, 2-tetrafluoroethane and preparation method thereof |
| CN114644544A (en) * | 2020-12-17 | 2022-06-21 | 陕西中化蓝天化工新材料有限公司 | Preparation method of fluoroalkane |
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