CN116789516A - Method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step - Google Patents
Method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005336 cracking Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 80
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 31
- 229910052731 fluorine Inorganic materials 0.000 claims description 31
- 239000011737 fluorine Substances 0.000 claims description 31
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 23
- 229910017768 LaF 3 Inorganic materials 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims 1
- 229960003750 ethyl chloride Drugs 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 37
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003507 refrigerant Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- BAMUEXIPKSRTBS-UHFFFAOYSA-N 1,1-dichloro-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Cl)Cl BAMUEXIPKSRTBS-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000006555 catalytic reaction Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000005070 sampling Methods 0.000 description 13
- 238000007873 sieving Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 9
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GVVUPGXFVJLPDE-OWOJBTEDSA-N (e)-1,3,3,3-tetrachloroprop-1-ene Chemical compound Cl\C=C\C(Cl)(Cl)Cl GVVUPGXFVJLPDE-OWOJBTEDSA-N 0.000 description 1
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane, which comprises the step of loading a catalyst into a nickel tube fixed bed reactor. Firstly, N is used at 300-400 DEG C 2 Pretreating the catalyst. And introducing tetrafluoro dichloroethane and methane raw gas, setting the flow ratio of tetrafluoro dichloroethane to methane to be 1:1-10, and setting the temperature of the catalyst bed to be 350-550 ℃. The invention adopts the tetrafluoro dichloroethane with high GWP, high ODP value and long atmospheric life and CH which is also greenhouse gas for the first time 4 As a raw material, it is converted into a new generation of automobile refrigerant HFO-1234yf as a resource. The invention has the advantages of simple process and environment protection, and the prepared catalyst has the advantages of simple preparation method, extremely high catalytic activity and selectivity.
Description
Technical Field
The invention relates to a new route for synthesizing 2, 3-tetrafluoropropene, in particular to a method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step.
Background
2, 3-tetrafluoropropene with the molecular formula of CF 3 CFCH 2 Abbreviated as HFO-1234yf or R1234yf, is a fourth generation environmentally friendly refrigerant, with an ODP value of 0, having an extremely low GWP value (about 4), far lower than the 1, 2-tetrafluoroethane (HFC-134 a, gwp=1300) currently used on a large scale in the refrigerant field. The atmospheric life cycle of HFO-1234yf is only 11 days. Studies have shown that 2, 3-tetrafluoropropene is finally oxidatively degraded in the atmosphere to low-toxicity, harmless trifluoroacetic acid (TFA). HFO-1234yf can be used as a carrier liquid for bactericides, foam blowing agents, aerosol propellants, and circulating working fluids and fire extinguishing agents in addition to refrigerants.
The traditional synthesis methods of HFO-1234yf are mainly based on raw materials, namely halogenated alkane elimination reaction and halogenated olefin addition reaction. The most typical synthesis method is to hydrogenate halogenated olefin in two steps and then remove HF to prepare HFO-1234yf, or directly adopt halogenated olefin to add with HF and then remove HCl to prepare HFO-1234yf. For example, 1,2, 3-tetrachloropropene is used as a raw material, after addition with HF, 2-chloro-3, 3-trifluoropropene (HCFO-1233 xf) is produced, 2-chloro-1, 2-tetrafluoropropane (HCFC-244 bb) is produced, and finally HCl is removed to produce HFO-1234yf. And hexafluoropropylene is used as a raw material, and HFO-1234yf is obtained by two-step hydrogenation and HF removal. Since liquid phase fluorination is mostly used industrially, a large amount of caustic alkali is required, and serious environmental pollution is caused.
Methane and tetrafluorodichloroethane (CFC-114) are both listed as major greenhouse gases by the Kyoto protocol. Since tetrafluorodichloroethane (CFC-114) is a chlorine atom, its emissions lead to ozone depletion in the stratosphere and an increase in the greenhouse effect. Both the Montreal protocol and the Kyoto protocol encourage efficient treatment of these fluorine-containing gases. The main treatment methods of CFC-114 are high temperature incineration treatment and plasma technology treatment. However, high-temperature treatment has huge energy consumption and high cost, and the incinerated products HF and HCl can also corrode equipment and cause environmental pollution and the like. The plasma technology treatment can generate extremely toxic substances in the treatment process, and has high equipment requirement and large cost investment. The resource treatment of the fluorochloroalkane is the most beneficial way to convert the fluorochloroalkane into a product with high added value.
Chinese CN 103691430a developed a conversion route for hydrodechlorination of tetrafluorodichloroethane to mainly tetrafluorochloroethane and tetrafluoroethane. The reaction product is still a fluorine-containing gas which largely destroys the ozone layer and causes the greenhouse effect, and cannot form a novel green-friendly refrigerant with high added value.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step from the viewpoint of protecting environment, the method adopts the removed harmful tetrafluorodichloroethane and methane as raw materials to synthesize the 2, 3-tetrafluoropropene refrigerant with high added value, changes waste into valuable, reduces the production cost of the 2, 3-tetrafluoropropene while protecting the environment, and has the advantages of simple process, high reaction selectivity of the used catalyst, high conversion rate and good stability.
The method adopts a gas-solid phase catalytic means of a fixed bed reactor to prepare the HFO-1234yf with high added value by coupling CFC-114 and methane through co-pyrolysis in one step. The specific reaction is as shown in formulas (1) - (4). The route converts the CFC-114 with low added value into HFO-1234yf with high added value for the first time, and has good industrial application prospect and extremely high environmental protection value. The invention relates to a method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane, which comprises the steps of adding a catalyst into a fixed bed reactor, heating to a catalytic reaction temperature, and introducing tetrafluorodichloroethane and methane under normal pressure to react to prepare 2, 3-tetrafluoropropene; the product was detected on-line by GC-MS and the conversion and target product selectivity were calculated.
CH 4 →CH 3 ·+H (1)
CF 3 CFCl 2 →CF 3 CFCl·+Cl (2)
CF 3 CFCl·+CH 3 ·→CF 3 CFClCH 3 (3)
CF 3 CFClCH 3 →CF 3 CFCH 2 +HCl (4)
The method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step comprises the steps of taking lanthanum fluoride doped with O element as a catalyst, loading the catalyst into a nickel tube reactor, heating to a pretreatment temperature, and introducing N 2 The catalyst is pretreated by gas, then heated to catalytic cracking temperature and introduced into tetrafluorodichloroethane to carry out co-cracking reaction with methane, so as to prepare 2, 3-tetrafluoropropene.
Further, the preparation method of the catalyst comprises the steps of reacting a lanthanum source and a fluorine source as raw materials to generate lanthanum fluoride LaF 3 Then at O 2 Roasting for 2-6 h at 350-450 ℃ in the atmosphere to obtain the lanthanum fluoride catalyst doped with O element, which is named as catalyst LaOF.
Further, the lanthanum source is La (NO 3 ) 3 、La 2 O 3 、La 2 (CO 3 ) 3 、La 2 (SO 4 ) 3 、LaCl 3 At least one of the fluorine sources is NH 4 HF 2 HF solution, CHClF 2 And one of PVDF.
Further, adopting a precipitation method to prepare lanthanum fluoride LaF 3 When the fluorine source is NH 4 HF 2 Or HF solution, the preparation process is as follows: stirring lanthanum source and fluorine source in deionized water, stirring at 60-120deg.C for 4-12 hr, and reacting to obtain LaF 3 Precipitating, centrifuging, washing, and drying to obtain lanthanum fluoride LaF 3 。
Further, adopting a precipitation method to prepare lanthanum fluoride LaF 3 When the fluorine source is PVDF, the preparation process is as follows: adding lanthanum source and fluorine source into N, N-dimethylformamide solvent, stirring under water bath heating to form transparent colloid, and blowing at 115-130deg.CDrying in a drying oven to obtain lanthanum fluoride LaF 3 。
Further, preparing lanthanum fluoride LaF by adopting a ball milling method 3 When the fluorine source is NH 4 HF 2 Or PVDF, the preparation process is as follows: placing a lanthanum source and a fluorine source into a ball milling tank according to a mass ratio of 1:2.5-5, and performing ball milling under the conditions of a ball milling rotating speed of 120-180r/min and a ball milling time of 2-4h to obtain lanthanum fluoride LaF 3 。
Further, the lanthanum fluoride LaF is prepared by adopting a gas phase calcination method 3 When the fluorine source is CHClF 2 The preparation process comprises the following steps: placing a lanthanum source into a tube furnace, introducing a gas-phase fluorine source, and roasting at 500-700 ℃ for 2-8h to obtain lanthanum fluoride LaF 3 。
Further, the temperature of the co-cleavage reaction is 350 to 550 ℃, preferably 380 to 470 ℃.
Further, the feeding volume flow ratio of the tetrafluoro dichloroethane to the methane is 1: 1-10, preferably the ratio of the volume flow of the materials is 1:3 to 5; the feeding volume flow of the tetrafluoro dichloroethane is 10-90 mL/min, preferably 30-70 mL, based on the catalyst loading of 2 mL; the space velocity of the whole reaction is 600h -1 ～29700h -1 Preferably 3600h -1 ～12600h -1 。
Further, with N 2 The catalyst is pretreated at the temperature of 200-500 ℃ for 2-10 h, preferably 300-400 ℃ and 4-8 h.
Compared with the prior art, the invention has the following maximum advantages:
1) The invention adopts three methods of precipitation method, mechanical ball milling method and gas phase calcination method to prepare LaF 3 Catalysts, especially in O 2 The LaOF catalyst is formed by medium calcination, and the intervention of O atoms improves the sintering resistance and carbonization resistance of the catalyst; while also deriving more defects to promote the conversion of methane to methyl. The catalyst has the advantages of short preparation period, simple method, high reproducibility, stable catalyst performance and higher activity and selectivity.
2) The invention initiates a route for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step. The invention has the advantages that the method is used for synthesizing the fourth generation refrigerant HFO-1234yf in one step, does not need multistage reaction in the process, is simple and quick, and simultaneously reduces the industrial energy consumption and the large-scale use of caustic alkali.
Drawings
FIG. 1 shows a catalyst LaOF, laF according to example 4 of the present invention 3 (N 2 ) Schematic of catalyst activity and selectivity to other catalysts.
Detailed Description
The invention will be further described with reference to specific examples and drawings, to which, however, the scope of the invention is not limited. The technical proposal and the invention concept are equivalent to or changed in accordance with the invention, and the invention is covered in the protection scope of the invention.
Example 1
Weigh 6.48gLa (NO) 3 ) 3 Dissolve in 30mL deionized water and transfer to a round bottom flask and transfer 6.24. 6.24gNH 4 HF 2 After dissolving in 30mL of deionized water, the solution was slowly added dropwise thereto, and treated in an oil bath for 4 hours at 60 ℃. Will obtain LaF 3 The precipitate was centrifuged, washed, dried, and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst is first charged in N 2 Pretreating in atmosphere at 350deg.C, N 2 The flow is 10mL/min, the pretreatment time is 2h, and then the mixed gas of the tetrafluoro dichloroethane and the methane is introduced, wherein the gas volume flow ratio is 1:1, and the tetrafluoro dichloroethane is 10mL/min. The reaction pressure is normal pressure and the space velocity is 600h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 55%, the selectivity of the target product 2, 3-tetrafluoropropene is 88%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
The catalyst LaOF of the invention is introduced with N before being applied to catalytic reaction 2 The pretreatment is performed by heating to remove impurities such as physically adsorbed water on the surface of the catalyst, and nitrogen is used as a diluent gas, so that the service life of the catalyst can be prolonged, and sintering is avoided. If not let in N 2 Pretreatment is carried out, the introduction of tetrafluoro dichloroethane and methane raw gas is directly carried out, and through a catalytic experiment, the sintering and carbon deposition of the catalyst can be accelerated, the conversion rate of the catalyst is easy to be reduced, and the service life of the catalyst is also reduced.
Example 2
Weigh 6.48gLa (NO) 3 ) 3 Dissolve in 30mL deionized water and transfer to a round bottom flask and transfer 6.24. 6.24gNH 4 HF 2 Dissolving in 30mL deionized water, slowly dripping, and treating in oil bath for 4h at 60deg.C. Will obtain LaF 3 The precipitate was centrifuged, washed, dried, and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 500 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 4h, and the temperature is raised to the reaction temperature of the catalyst of 550 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:10, and the tetrafluoro-dichloroethane is 90mL/min. The reaction pressure is normal pressure and the airspeed is 29700h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours for sampling analysis, the conversion rate of the tetrafluorodichloroethane is 50%, the selectivity of the target product 2, 3-tetrafluoropropene is 87%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 3
Weigh 6.48gLa (NO) 3 ) 3 Dissolve in 30mL deionized water and transfer to a round bottom flask and transfer 6.24. 6.24gNH 4 HF 2 Dissolving in 30mL deionized water, slowly dripping, and treating in oil bath for 4h at 60deg.C. Will beObtaining LaF 3 The precipitate was centrifuged, washed, dried, and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 300 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 4h, and the temperature is raised to the reaction temperature of the catalyst of 380 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:3, and the tetrafluoro-dichloroethane is 30mL/min. The reaction pressure is normal pressure and the airspeed is 3600h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 66%, the selectivity of the target product 2, 3-tetrafluoropropene is 87%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 4
Weigh 6.5gLa 2 O 3 18.2 and 18.2gNH 4 HF 2 After mixing, the mixture is equally divided into two ball milling tanks, and the ball-to-material ratio is 4:1. the ball milling rotating speed is 150r/min, the ball milling time is 3h, and the catalyst is collected after the ball milling is finished. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst is first charged in N 2 Pretreating in atmosphere at 400 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 8h, and the temperature is raised to 470 ℃ of the catalyst reaction temperature. And introducing a mixed gas of tetrafluoro-dichloroethane and methane, wherein the gas volume flow ratio is 1:5, and the tetrafluoro-dichloroethane is 70mL/min. The reaction pressure is 12600h under normal pressure -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 70%, the selectivity of the target product 2, 3-tetrafluoropropene is 85%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
The catalyst LaOF, laF of example 4 of the invention 3 (N 2 ) Catalyst and SrF 2 Comparison of conversion of tetrafluorodichloroethane in catalytic co-cracking reaction of tetrafluorodichloroethane and methane and selectivity of target product 2, 3-tetrafluoropropene. As shown in FIG. 1, the conversion rate of the catalyst LaOF in the embodiment 4 of the invention is steadily increased in 15 hours before the catalytic reaction, the conversion rate is stabilized after the catalytic reaction is carried out for 15 hours after the active site is fully exposed, the catalytic early stage is the induction period of the catalyst, and the conversion rate is gradually stable and unchanged in the later stage.
LaF in FIG. 1 3 (N 2 ) The catalyst preparation method is the same as that of the catalyst LaOF of example 4 of the present invention, except that "O" is used 2 Calcining under atmosphere, replacing with N 2 Calcination under atmosphere ", srF 2 Is a commercial catalyst, and the catalytic effect of the catalyst is obviously inferior to that of the catalyst LaOF.
Example 5
Weigh 6.5gLa 2 O 3 18.2 and 18.2gNH 4 HF 2 After mixing, the mixture is equally divided into two ball milling tanks, and the ball-to-material ratio is 4:1. the ball milling rotating speed is 150r/min, the ball milling time is 3h, and the catalyst is collected after the ball milling is finished. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst is first charged in N 2 Pretreating in atmosphere at 350deg.C, N 2 The flow is 10mL/min, the pretreatment time is 6h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro-dichloroethane is 50mL/min. The reaction pressure is normal pressure and space velocity is 7500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 67%, the selectivity of the target product 2, 3-tetrafluoropropene is 83%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 6
13.71g of La are weighed 2 (CO 3 ) 3 Dissolved in 60mL of deionized water and transferred to a round bottom flask, and 20mL of 40% hf solution was slowly added dropwise to form a precipitate, which was oil-bath treated for 12h at 120 ℃. Will obtain LaF 3 The precipitate was centrifuged, washed, dried, and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst is first charged in N 2 Pretreating in atmosphere at 200deg.C, N 2 The flow is 10mL/min, the pretreatment time is 10h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro-dichloroethane is 50mL/min. The reaction pressure is normal pressure and space velocity is 7500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 64%, the selectivity of the target product 2, 3-tetrafluoropropene is 88%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 7
13.71g of La are weighed 2 (CO 3 ) 3 Dissolved in 60mL of deionized water and transferred to a round bottom flask, and 20mL of 40% hf solution was slowly added dropwise to form a precipitate, which was oil-bath treated for 12h at 120 ℃. Will obtain LaF 3 The precipitate was centrifuged, washed, dried, and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreatment under atmosphereAt a temperature of 350 ℃, N 2 The flow is 10mL/min, the pretreatment time is 10h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro-dichloroethane is 90mL/min. The reaction pressure is normal pressure and space velocity is 13500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 54%, the selectivity of the target product 2, 3-tetrafluoropropene is 87%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 8
13.71g of La are weighed 2 (CO 3 ) 3 Dissolved in 60mL of deionized water and transferred to a round bottom flask, and 20mL of 40% hf solution was slowly added dropwise to form a precipitate, which was oil-bath treated for 12h at 120 ℃. Will obtain LaF 3 The precipitate was centrifuged, washed, dried, and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 350deg.C, N 2 The flow is 10mL/min, the pretreatment time is 10h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro-dichloroethane is 90mL/min. The reaction pressure is normal pressure and the space velocity is 13500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 58%, the selectivity of the target product 2, 3-tetrafluoropropene is 84%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 9
11.36g of La are weighed out 2 (SO 4 ) 3 Placing in a quartz porcelain boat, transferring into a tube furnace, and taking CHClF as gas phase fluorine source 2 The flow rate of the gas-phase fluorine source is controlled to be 40mL/min, and the gas-phase fluorine source is calcined at 600 ℃ for 6h. The temperature was lowered to room temperature and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 380 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 6h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of the tetrafluoro-dichloroethane and the methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro-dichloroethane is 50mL/min. The reaction pressure is normal pressure and the airspeed is 7500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 55%, the selectivity of the target product 2, 3-tetrafluoropropene is 86%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 10
11.36g of La are weighed out 2 (SO 4 ) 3 Placing in a quartz porcelain boat, transferring into a tube furnace, and taking CHClF as gas phase fluorine source 2 The flow rate of the gas-phase fluorine source is controlled to be 40mL/min, and the gas-phase fluorine source is calcined at 600 ℃ for 6h. The temperature was lowered to room temperature and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 380 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 7h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of tetrafluoro dichloroethane and methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro dichloroethane is 70mL/min. The reaction pressure is normal pressure, and the airspeed is 10500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours, sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 60%, and the target product 2, 3-tetrafluoropropene is selectedSelectivity is 87%, the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 11
11.36g of La are weighed out 2 (SO 4 ) 3 Placing in a quartz porcelain boat, transferring into a tube furnace, and taking CHClF as gas phase fluorine source 2 The flow rate of the gas-phase fluorine source is controlled to be 40mL/min, and the gas-phase fluorine source is calcined at 600 ℃ for 6h. The temperature was lowered to room temperature and the catalyst was collected. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 380 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 7h, and the temperature is raised to the catalyst reaction temperature of 400 ℃. And introducing a mixed gas of tetrafluoro dichloroethane and methane, wherein the gas volume flow ratio is 1:4, and the tetrafluoro dichloroethane is 70mL/min. The reaction pressure is normal pressure and the airspeed is 10500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 63%, the selectivity of the target product 2, 3-tetrafluoropropene is 87%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 12
Weigh 9.81g LaCl 3 Dissolved in 500mL of N, N-dimethylformamide, heated in a water bath, and 56g of PVDF was gradually added to the heated solution in the water bath with stirring. And (3) placing the transparent colloid which is uniformly stirred into a blast drying oven at 120 ℃ for drying, and collecting the catalyst. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, 2mL of LaOF catalyst was first charged in N 2 Pretreating in atmosphere at 350deg.C, N 2 The flow is 10mL/min, the pretreatment time is 4h, the mixed gas of the tetrafluoro dichloroethane and the methane is introduced after the temperature is raised to the catalyst reaction temperature of 400 ℃, and the gas volume flow ratio is 1:8, wherein the tetrafluoro dichloroethane is 60mL/min. The reaction pressure is normal pressure and the airspeed is 16200h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours and sampling analysis is carried out, the conversion rate of the tetrafluorodichloroethane is 58%, the selectivity of the target product 2, 3-tetrafluoropropene is 85%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
Example 13
Weigh 9.81g LaCl 3 Dissolved in 500mL of N, N-dimethylformamide, heated in a water bath, and 56g of PVDF was gradually added to the heated solution in the water bath with stirring. And (3) placing the transparent colloid which is uniformly stirred into a blast drying oven at 120 ℃ for drying, and collecting the catalyst. Placing it in a tube furnace O 2 Roasting for 4 hours at 400 ℃ in the atmosphere to obtain the catalyst LaOF, tabletting, crushing and sieving by a 20-40-mesh sample separating sieve.
In a fixed bed reactor with a gas chromatography system, a 2mLLaOF catalyst is first loaded in N 2 Pretreating in atmosphere at 400 deg.C, N 2 The flow is 10mL/min, the pretreatment time is 6h, and after the pretreatment, the mixed gas of the tetrafluoro-dichloroethane and the methane is introduced, wherein the gas volume flow ratio is 1:8, and the tetrafluoro-dichloroethane is 50mL/min. The reaction pressure is normal pressure and the space velocity is 13500h -1 . After chromatographic on-line detection, the reaction is carried out for 30 hours for sampling analysis, the conversion rate of the tetrafluorodichloroethane is 60%, the selectivity of the target product 2, 3-tetrafluoropropene is 86%, and the rest is CF 3 CClCH 2 (HFO-1233 xf). And the selectivity is basically kept unchanged within 30-50 h of catalytic reaction, and the conversion rate is basically not reduced.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and the scope of the present invention should not be considered limited to the specific forms set forth in the examples.
Claims (10)
1. From tetrafluoro-diA process for preparing 2, 3-tetrafluoropropene by co-cracking chloroethane and methane includes such steps as loading lanthanum fluoride as catalyst in nickel tube reactor, heating to pretreatment temp. and introducing N 2 The catalyst is pretreated by gas, then heated to catalytic cracking temperature and introduced into tetrafluorodichloroethane to carry out co-cracking reaction with methane, so as to prepare 2, 3-tetrafluoropropene.
2. The method for preparing 2, 3-tetrafluoropropene by co-cracking tetrafluorodichloroethane and methane in one step according to claim 1, wherein the catalyst is lanthanum fluoride doped with O element, and the preparation method is that lanthanum fluoride LaF is generated by reacting a lanthanum source and a fluorine source as raw materials 3 Then at O 2 Roasting for 2-6 h at 350-450 ℃ in the atmosphere to obtain the lanthanum fluoride catalyst doped with O element, which is named as catalyst LaOF.
3. A process for the preparation of 2, 3-tetrafluoropropene in one step from the co-pyrolysis of tetrafluorodichloroethane and methane according to claim 2, characterized in that the lanthanum source is La (NO 3 ) 3 、La 2 O 3 、La 2 (CO 3 ) 3 、La 2 (SO 4 ) 3 、LaCl 3 At least one of the fluorine sources is NH 4 HF 2 HF solution, CHClF 2 And one of PVDF.
4. A process for preparing 2, 3-tetrafluoropropene in one step from the co-pyrolysis of tetrafluorodichloroethane and methane according to claim 3, characterized in that the lanthanum fluoride LaF is prepared by precipitation 3 When the fluorine source is NH 4 HF 2 Or HF solution, the preparation process is as follows: stirring lanthanum source and fluorine source in deionized water, stirring at 60-120deg.C for 4-12 hr, and reacting to obtain LaF 3 Precipitating, centrifuging, washing, and drying to obtain lanthanum fluoride LaF 3 。
5. A process as claimed in claim 3, wherein the process is carried out by co-cracking with tetrafluorodichloroethane and methaneThe method for preparing 2, 3-tetrafluoropropene in a step is characterized in that a precipitation method is adopted to prepare lanthanum fluoride LaF 3 When the fluorine source is PVDF, the preparation process is as follows: adding lanthanum source and fluorine source into N, N-dimethylformamide solvent, stirring under water bath heating to form transparent colloid, and oven drying in 115-130deg.C air drying oven to obtain lanthanum fluoride LaF 3 。
6. A process for preparing 2, 3-tetrafluoropropene in one step by co-cracking tetrafluorodichloroethane and methane according to claim 3, characterized in that lanthanum fluoride LaF is prepared by ball milling 3 When the fluorine source is NH 4 HF 2 Or PVDF, the preparation process is as follows: placing a lanthanum source and a fluorine source into a ball milling tank according to a mass ratio of 1:2.5-5, and performing ball milling under the conditions of a ball milling rotating speed of 120-180r/min and a ball milling time of 2-4h to obtain lanthanum fluoride LaF 3 。
7. A process for preparing 2, 3-tetrafluoropropene in one step from the co-pyrolysis of tetrafluorodichloroethane and methane according to claim 3, characterized in that lanthanum fluoride LaF is prepared by the gas phase calcination method 3 When the fluorine source is CHClF 2 The preparation process comprises the following steps: placing a lanthanum source into a tube furnace, introducing a gas-phase fluorine source, and roasting at 500-700 ℃ for 2-8h to obtain lanthanum fluoride LaF 3 。
8. A process for the preparation of 2, 3-tetrafluoropropene in one step from the co-cracking of tetrafluorodichloroethane and methane according to claim 1, characterized in that the temperature of the co-cracking reaction is between 350 and 550 ℃, preferably between 380 and 470 ℃.
9. A process for the preparation of 2, 3-tetrafluoropropene in one step from the co-cracking of tetrafluorodichloroethane and methane according to claim 1, characterized in that the volumetric flow ratio of tetrafluorodichloroethane to methane is 1: 1-10, preferably the ratio of the volume flow of the materials is 1:3 to 5; the feeding volume flow of the tetrafluoro dichloroethane is 10-90 mL/min, preferably 30-70 mL, based on the catalyst loading of 2 mL;
the space velocity of the whole reaction is 600h -1 ～29700h -1 Preferably 3600h -1 ～12600h -1 。
10. A process for the preparation of 2, 3-tetrafluoropropene in one step from the co-pyrolysis of tetrafluorodichloroethane and methane according to claim 1, characterized in that N is used 2 The catalyst is pretreated at the temperature of 200-500 ℃ for 2-10 h, preferably 300-400 ℃ and 4-8 h.
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