CN1820845A - Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane - Google Patents
Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane Download PDFInfo
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- CN1820845A CN1820845A CN 200610059052 CN200610059052A CN1820845A CN 1820845 A CN1820845 A CN 1820845A CN 200610059052 CN200610059052 CN 200610059052 CN 200610059052 A CN200610059052 A CN 200610059052A CN 1820845 A CN1820845 A CN 1820845A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title abstract 2
- 239000011651 chromium Substances 0.000 title description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 14
- 229910052804 chromium Inorganic materials 0.000 title description 14
- 150000002505 iron Chemical class 0.000 title description 2
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003682 fluorination reaction Methods 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011701 zinc Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960002415 trichloroethylene Drugs 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides the formula of 1, 1, 1, 2-tetrafluoro ethane preparing catalyst. The catalyst consists of Cr element, Fe element, O element, F element and one or several metal elements selected from Co, Mg, Zn, Mg and Ni. The catalyst is prepared through co-precipitation to obtain catalyst precursor, roasting, and fluorination to obtain fluoride. The catalyst has service life meeting the requirement of industrial production and raised activity. Owing to the multiple metal base to inhibit the creation of crystal, the Cr-base catalyst can maintain the amorphous state with high activity.
Description
Technical field
The present invention relates to a kind of high activity, long-life fluorination catalyst, relate in particular to preparation 1,1,1, the catalyst of 2-HFC-134a.This catalyst adopts the coprecipitation method preparation, is mainly used in halogenated hydrocarbons and hydrofluoric exchange reaction.
Background technology
1,1,1, the ODP value of 2-HFC-134a (R134a) is zero, it is the active compound that is used for CFC cold-producing medium harmful on the alternative environment, be among R22 a kind of, long-term substitute, destroy under the increasingly serious situation of ozone layer problem in the atmosphere at the hydrogen chlorocarbon, green refrigerant will progressively replace the CFC cold-producing medium.
The most general method is to be reacted by trichloro-ethylene and hydrogen fluoride gas in the R134a production method.This reaction has two stages, and first stage is that trichloro-ethylene and hydrogen fluoride reaction generate trifluoro monochlorethane (R133a), and second stage is that trifluoro monochlorethane and hydrogen fluoride reaction change into R134a.Its conversion ratio of first stage can be more than 90%; In second stage, life of catalyst and activity can not be taken into account simultaneously.Used catalyst major part is a chromium-based catalysts now.Special also has, as Chinese patent application 92108336 reported with R133a be raw material in the presence of catalyst with potassium fluoride prepared in reaction R134a, wherein used catalyst molecule formula is R
fSO
2The compound of M, wherein R
fBe X (CF
2)
[2Y+2]OCF
2CF
2Or X (CF2)
2z, wherein X is F, Cl, or I, and Y=0-6, Z=1-6, M are F, Cl or OH.This catalyst is must add aqueous solvent in liquid-phase catalyst and the course of reaction, has increased the corrosion of equipment.Chromium-based catalysts is a solid catalyst, can effectively avoid the generation of large quantity of moisture in the course of reaction, reduces the equipment corrosion degree.Though chromium-based catalysts itself is active good, its easy charing coking, activity of such catalysts and life-span can not be taken into account simultaneously.Add many auxiliary substances in the existing R134a method for preparing catalyst, suppressed the chromium-based catalysts coking.
Adopt zinc to promote the Cr of its co-precipitation in the Chinese patent application 00819402
2O
3/ AL
2O
3The catalyst method, it uses NH
4OH, NaOH or KOH make the hydroxide that alkali co-precipitation from corresponding trivalent metal salting liquid goes out chromium and aluminum metal.Imperial Chemical Industries adopt a kind of fluoridation catalyst that is used for that contains chromium in the patent application 92101187 of China, it is characterized in that being that catalyst contains a certain amount of active zinc or compound of zinc of improving.Ausimont S.P.A. prepares R134a in the presence of the patent application 90104695 of China proposes to be stated from Cr 2 O 3 catalyst on the alchlor.Point out in a series of reports that the auxiliary compounds that adds in the chromium-based catalysts has improved the yield of R134a in varying degrees, the decline that has slowed down catalyst activity, but in industrial production, this activity of such catalysts and life-span are all undesirable.But can know that therefrom the auxiliary compounds effect of adding in the chromium-based catalysts mainly is to suppress Cr
2O
3The generation of crystal formation, Cr
2O
3Under amorphous or the amorphous crystalline state of essence, has higher initial activity.The nearest development of chromium-based catalysts is an amount of interpolation " accelerative activator " bivalent metal oxide.Propose a kind of high active long-acting fluorating catalyst in the Chinese patent application 01141970, it is made up of many Metal Substrate and fluorine, and the general formula of its structure is CrX
0.005-0.5Y
0.005-0.3O
0.1-1.0F
1.0-3.0X is Mn, Co or Zn in the formula; Y is Mg or Ni.Measurement the specific area is at 65m in embodiment
2About/g, pore volume is about 0.19ml/g.Catalyst life is long in this patent, but its activity is on the low side.
The Preparation of catalysts process generally has the precipitation method, infusion process, blending method, thermal decomposition method etc.China's application number is once to have mentioned in 01141970 the patent using the immersion process for preparing catalyst, the content of active component chromium generally lower (＜10%).Activity is restricted, and space-time yield is low.Showa Denko K. K has reported Cr during heat-treat condition is to catalyst in the chromium-based catalysts preparation process in the patent application 94115127 of China
2O
3The crystalline form influence is very big, needs at H
2Exist following 350 ℃ of-500 ℃ of roastings to prepare Cr
2O
3Precursor as catalyst.Patent application 01140970 has adopted catalyst precarsor at 200 ℃ of-400 ℃ of low-temperature bakes, feeds N in the activation processing process
2, H
2Mist.This method has suppressed the sintering phenomenon of catalyst effectively.These two catalyst all adopt hydrogen as protection gas, increase the danger of producing in the production process.
Preparation of catalysts of the present invention adopts coprecipitation, and at 100 ℃ of-200 ℃ of left and right sides low temperature dryings, about 300 ℃-400 ℃ are carried out roasting under inert gas N2 protection.Raw material after the roasting can obtain catalyst precarsor (form with oxide exists) through compression moulding again.
Summary of the invention
The present invention is in order to solve the chromium-based catalysts life-span when satisfying industrial requirements, to improve the difficult problem of activity of such catalysts.On the basis that the present invention is based on the Preparation of catalysts process is determined, the composition of catalyst a large amount of experiments have been carried out.Selected element mainly is to choose from alkali earth metal and transition metal.
The present invention is a kind of preparation 1,1,1, the catalyst of 2-HFC-134a, and its general structure is as follows:
CrX
AFe
BO
CF
D
X is selected from Co in the formula, Mn, Zn, Mg, one or more among the Ni;
A＝0.001-0.6，
B＝0.001-0.5，
C＝1.0-2，
D＝1.0-4.0。
Preferably, X is selected from Co, Mn and/or Zn.Preferred, X is selected from Co.Preferred, X is selected from Mn.Preferred, X is selected from Zn.
Preferably, A=0.01-0.4.Preferably, B=0.01-0.3.Preferably, C=1.0-1.5.Preferably, D=2.0-3.0.
The present invention also comprises 1,1,1, the method for the catalyst of 2-HFC-134a, take by weighing the chromic salts of 1mol accurately, (X is selected from Co to the X salt of A mol, Mn, Zn, Mg, a kind of among the Ni) and the ferrous salt (salt can be nitrate, sulfate or chloride) of B mol be dissolved in water, water is pure water.Adding alkaline solution (NaOH, KOH or NH
4OH solution), keep between the PH=7-10.Filter, dry, carry out low-temperature bake in 330 ℃ of-380 ℃ of scopes at 100 ℃-200 ℃.Feed inert gas N in the roasting process
2, the raw material extrusion modling after the roasting can make catalyst precarsor.Each component in the catalyst precarsor mainly is that the form with oxide exists.
After catalyst precarsor prepares, in the nickel pipe of the φ 26*2.9 that packs into, at inert gas N
2Protection feed down a certain amount of hydrogen fluoride gas and fluoridize.
The present invention has added novel metal base iron under satisfying the situation of industrial requirement substantially in the life-span, because the adding of ferro element all has significant improvement specific area, pore volume, the aperture of catalyst, has improved activity of such catalysts greatly.The growth that suppresses crystal formation that is added in of other auxiliary elements has played decisive role.Through evaluation test in 500 hours, be converted in the reaction of R134a at R133a, the R134a conversion ratio is all more than 30%.And after adding the ferrous metal element, the specific surface area of catalyst of being prepared, pore volume all increase to some extent, have increased the contact area of reactive material at catalyst surface accordingly, have improved yield, the increase in aperture has also effectively reduced the probability that produces micropore sintered phenomenon, has improved space-time yield.
Description of drawings
Fig. 1 is for carrying out the productive rate of R134a of life test with the reaction time variation diagram to embodiment one.X represents the reaction time among the figure, and Y represents the productive rate of R134a.This reaction be R133a and hydrogen fluoride in 350 ℃ of-370 ℃ of scopes, flow-control is at 3-5: the result who carries out life test under 1 situation.
The specific embodiment
Embodiment one: Cr: Co: Fe=1: (be A=0.2, B=0.1) at 0.2: 0.1
The Preparation of catalysts process:
Take by weighing the chromic salts of 1mol soluble in water accurately, the cobalt salt of 0.2mol and the ferrous salt of 0.1mol (salt can be nitrate, sulfate or chloride) are dissolved in water, and water is pure water.Adding alkaline solution (NaOH, KOH or NH
4OH solution), keep between the PH=7-10.Filter, dry, carry out low-temperature bake in 330 ℃ of-380 ℃ of scopes at 100 ℃-200 ℃.Feed inert gas N in the roasting process
2, the raw material extrusion modling after the roasting can make catalyst precarsor.Each component in the catalyst precarsor mainly is that the form with oxide exists.
After catalyst precarsor prepares, in the nickel pipe of the φ 26*2.9 that packs into, at inert gas N
2Protection feed down a certain amount of hydrogen fluoride gas and fluoridize.
The mensuration of catalyst precarsor
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (10 -10m) | Most probable radius (10 -10m) |
| 0.32 | 197.6 | 18.34 | 12.17 |
Catalyst activity
| Temperature ℃ | Flow-control (HF: R133a) | R134a productive rate % |
| 280 | 3-5∶1 | 17.21 |
| 300 | 1-3∶1 | 12.34 |
| 350 | 3-5∶1 | 42.34 |
| 350 | 1-3∶1 | 30.01 |
Embodiment two: Cr: Co: Fe=1: (be A=0.1, B=0.1) at 0.1: 0.1
The preparation method is with embodiment one
The mensuration of catalyst precarsor
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (10 -10m) | Most probable radius (10 -10m) |
| 0.27 | 204 | 20.24 | 7.63 |
Catalyst activity
| Temperature ℃ | Flow-control (HF: R133a) | R134a productive rate % |
| 280 | 3-5∶1 | 15.34 |
| 280 | 1-3∶1 | 11.46 |
| 350 | 3-5∶1 | 32.27 |
| 350 | 1-3∶1 | 25.14 |
Embodiment three: Cr: Zn: Fe=1: (be A=0.1, B=0.04) at 0.1: 0.04
The preparation method is with embodiment one
The mensuration of catalyst precarsor
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (10 -10m) | Most probable radius (10 -10m) |
| 0.15 | 143.2 | 17.64 | 7.65 |
Catalyst activity
| Temperature ℃ | Flow-control (HF: R133a) | R134a productive rate % |
| 280 | 3-5∶1 | 14.72 |
| 300 | 3-5∶1 | 21.45 |
| 350 | 3-5∶1 | 29.62 |
| 350 | 1-3∶1 | 23.47 |
Embodiment four: Cr: Mg: Fe=1: (be A=0.4, B=0.02) at 0.4: 0.02
The preparation method is with embodiment one
The mensuration of catalyst precarsor
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (10 -10m) | Most probable radius (10 -10m) |
| 0.24 | 204.7 | 15.34 | 7.62 |
Catalyst activity
| Temperature ℃ | Flow-control (HF: R133a) | R134a productive rate % |
| 280 | 1-3∶1 | 10.24 |
| 280 | 3-5∶1 | 12.20 |
| 350 | 3-5∶1 | 13.26 |
| 350 | 3-5∶1 | 14.24 |
| 350 | 1-3∶1 | 12.62 |
Embodiment five: Cr: Mg: Fe=1: (be A=0.4, B=0.3) at 0.4: 0.3
The preparation method is with embodiment one
The mensuration of catalyst precarsor
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (10 -10m) | Most probable radius (10 -10m) |
| 0.3 | 124 | 17.35 | 7.29 |
Catalyst activity
| Temperature ℃ | Flow-control (HF: R133a) | R134a productive rate % |
| 350 | 3-5∶1 | 5.24 |
Embodiment six: Cr: Zn: Fe=1: (be A=0.2, B=0.1) at 0.2: 0.1
The preparation method is with embodiment one
The mensuration of catalyst precarsor
| Pore volume (ml/g) | Specific area (m 2/g) | Average pore radius (10 -10m) | Most probable radius (10 -10m) |
| 0.32 | 256 | 17.3 | 20.03 |
Catalyst activity
| Temperature ℃ | Flow-control (HF: R133a) | R134a productive rate % |
| 350 | 1-3∶1 | 20.14 |
| 350 | 3-5∶1 | 32.56 |
Embodiment seven: Cr: Mn: Fe=1: (be A=0.02, B=0.001) at 0.02: 0.001
Embodiment eight: Cr: Ni: Fe=1: (be A=0.6, B=0.15) at 0.6: 0.15
Embodiment nine: Cr: Mn: Fe=1: (be A=0.35, B=0.2) at 0.35: 0.2
Embodiment ten: Cr: Ni: Fe=1: (be A=0.6, B=0.6) at 0.6: 0.6
Embodiment 11: the catalyst life test
According to the embodiment situation, embodiment one is carried out life test.As Figure of description Fig. 1:
X represents the reaction time among the figure, and Y represents the productive rate of R134a.This reaction be R133a and hydrogen fluoride in 350 ℃ of-370 ℃ of scopes, flow-control is at 3-5: the result who carries out life test under 1 situation.Tested 500 hours, still more than 30%, activity of such catalysts is better for catalyst activity.After catalyst activity reduction, can carry out activating and regenerating to this catalyst.This catalyst satisfies industrial requirement substantially, can be used for industrial production.
Claims (10)
1. one kind prepares 1,1,1, the catalyst of 2-HFC-134a, and its general structure is as follows:
CrX
AFe
BO
CF
D
X is selected from Co in the formula, Mn, Zn, Mg, one or more among the Ni;
A＝0.001-0.6，
B＝0.001-0.5，
C＝1.0-2，
D＝1.0-4.0。
2. preparation 1,1,1 as claimed in claim 1, the catalyst of 2-HFC-134a is characterized in that X is selected from Co, Mn and/or Zn.
3. preparation 1,1,1 as claimed in claim 1, the catalyst of 2-HFC-134a is characterized in that X is selected from Co.
4. preparation 1,1,1 as claimed in claim 1, the catalyst of 2-HFC-134a is characterized in that X is selected from Mn.
5. preparation 1,1,1 as claimed in claim 1, the catalyst of 2-HFC-134a is characterized in that X is selected from Zn.
6. as each described preparation 1,1,1 of claim 1 to 5, the catalyst of 2-HFC-134a is characterized in that, A=0.01-0.4.
7. as each described preparation 1,1,1 of claim 1 to 5, the catalyst of 2-HFC-134a is characterized in that, B=0.01-0.3.
8. as each described preparation 1,1,1 of claim 1 to 5, the catalyst of 2-HFC-134a, C=1.0-1.5.
9. as each described preparation 1,1,1 of claim 1 to 5, the catalyst of 2-HFC-134a is characterized in that, D=2.0-3.0.
As claim 1 to 5 each described 1,1,1, the Preparation of catalysts method of 2-HFC-134a is characterized in that, take by weighing the chromic salts of 1mol accurately, (X is selected from Co to the X salt of A mol, Mn, Zn, Mg, a kind of among the Ni) and the ferrous salt (salt can be nitrate, sulfate or chloride) of B mol be dissolved in water; Adding alkaline solution again keeps between the PH=7-10; Filter, dry, carry out low-temperature bake, the raw material extrusion modling after the roasting in 330 ℃ of-380 ℃ of scopes at 100 ℃-200 ℃; Feeding a certain amount of hydrogen fluoride gas then fluoridizes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100590521A CN1308072C (en) | 2005-09-30 | 2006-02-28 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510104260.4 | 2005-09-30 | ||
| CN200510104260 | 2005-09-30 | ||
| CNB2006100590521A CN1308072C (en) | 2005-09-30 | 2006-02-28 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1820845A true CN1820845A (en) | 2006-08-23 |
| CN1308072C CN1308072C (en) | 2007-04-04 |
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ID=36922510
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|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN1308072C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304368A (en) * | 2012-03-07 | 2013-09-18 | 中化蓝天集团有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane, and preparation method of catalyst of 1,1,1,2-tetrafluoroethane |
| CN105344349A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Solid fluorinated catalyst and preparation method thereof |
| CN105936515A (en) * | 2015-12-30 | 2016-09-14 | 衢州学院 | Synthesis method of 1,1,1,2- tetrafluoroethane catalyst precursor and catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2764980B2 (en) * | 1988-12-28 | 1998-06-11 | 旭硝子株式会社 | Perchlorethylene fluorination method |
| GB9104775D0 (en) * | 1991-03-07 | 1991-04-17 | Ici Plc | Fluorination catalyst and process |
| CN1169620C (en) * | 2001-09-26 | 2004-10-06 | 西安金珠近代化工有限责任公司 | High active long-acting fluorating catalyst and its producing method |
| CN100372607C (en) * | 2004-12-23 | 2008-03-05 | 西安近代化学研究所 | Florination catalyst, its manufacturing method and use |
-
2006
- 2006-02-28 CN CNB2006100590521A patent/CN1308072C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304368A (en) * | 2012-03-07 | 2013-09-18 | 中化蓝天集团有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane, and preparation method of catalyst of 1,1,1,2-tetrafluoroethane |
| CN105344349A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Solid fluorinated catalyst and preparation method thereof |
| CN105936515A (en) * | 2015-12-30 | 2016-09-14 | 衢州学院 | Synthesis method of 1,1,1,2- tetrafluoroethane catalyst precursor and catalyst |
| CN105936515B (en) * | 2015-12-30 | 2017-10-24 | 衢州学院 | A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as |
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| CN1308072C (en) | 2007-04-04 |
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