WO2022165623A1 - 一种1,1,1,3‐四氯丙烷的制备方法 - Google Patents
一种1,1,1,3‐四氯丙烷的制备方法 Download PDFInfo
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- WO2022165623A1 WO2022165623A1 PCT/CN2021/074800 CN2021074800W WO2022165623A1 WO 2022165623 A1 WO2022165623 A1 WO 2022165623A1 CN 2021074800 W CN2021074800 W CN 2021074800W WO 2022165623 A1 WO2022165623 A1 WO 2022165623A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- preparation
- tetrachloropropane
- active component
- phosphate
- Prior art date
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- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 121
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000002360 preparation method Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005977 Ethylene Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 6
- -1 ester compound Chemical class 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 25
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000440 bentonite Substances 0.000 claims description 17
- 229910000278 bentonite Inorganic materials 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 229910021065 Pd—Fe Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229910017827 Cu—Fe Inorganic materials 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 16
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 101150003085 Pdcl gene Proteins 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 7
- 239000003426 co-catalyst Substances 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125368 controlled substance Drugs 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
Definitions
- the present application relates to a preparation method of 1,1,1,3-tetrachloropropane, which belongs to the technical field of chemical industry.
- Carbon tetrachloride is a by-product of a methane chloride plant. Carbon tetrachloride is a controlled substance that depletes the ozone layer under the Montreal Protocol, abbreviated as CTC. Completely stop the production and consumption of CTC except for raw material use, reagent use and special exempted use. In recent years, China's methane chloride has developed rapidly. Depending on the raw material market, it is difficult to digest and produce CTC. The cost of incinerating carbon tetrachloride is about 3,000 to 4,000 yuan per ton. Therefore, the comprehensive utilization of CTC has very important practical significance, which is related to the survival and safety of the entire industry chain.
- the metals and cocatalysts reported in literature reports mainly include: organic copper compounds and organic nitrile compounds; iron or its compounds, organic phosphorus compounds.
- the iron powder is commercially available iron powder; when the commercially available iron powder is used as the main catalyst, it is easy to agglomerate at the bottom of the reactor. membrane, which reduces the reactivity.
- a preparation method of 1,1,1,3-tetrachloropropane is provided.
- the preparation method adopts a supported iron main catalyst, which can significantly improve the problem of easy agglomeration of commercially available iron powders, while increasing the The specific surface area of iron is enlarged, and the second nano-metal component is added at the same time, which effectively solves the problem that the freshly prepared nano-iron catalyst is easily oxidized when exposed to the air, which is beneficial to the reaction.
- a preparation method of 1,1,1,3-tetrachloropropane comprises:
- the first catalyst includes a carrier and an active component supported on the carrier;
- the active component includes nano-zero valent iron
- the second catalyst includes an ester compound.
- the active component further includes at least one of platinum and copper.
- the active ingredient is selected from any one of zero-valent iron nanoparticles, Pd-Fe bimetallic nanoparticles, and Cu-Fe bimetallic nanoparticles.
- the carrier includes at least one of porous materials
- the porous material includes bentonite and/or activated carbon.
- the bentonite is obtained by modifying with a surfactant
- the activated carbon is obtained by acid modification treatment.
- the surfactant includes at least one of quaternary ammonium salts
- the acid includes any one of HCl, H 3 PO 4 , HNO 3 .
- the quaternary ammonium salt includes cetyltrimethylammonium bromide.
- the acid modification treatment is as follows: mixing activated carbon with an acid solution, and refluxing at 80-100° C. for 3-8 hours.
- the concentration of the acid solution is 10-30%.
- the mass-volume ratio of the activated carbon to the acid solution is 5-15:80-120 g/mL.
- the surfactant modification treatment is as follows: mixing the bentonite aqueous solution with the surfactant, adjusting the pH value to be acidic, stirring and washing at 50-80°C.
- the mass ratio of the bentonite to the surfactant is 30-60:15-25.
- the loading of the active component is 5.01-50.1 wt %.
- the upper limit of the loading amount of the active component is selected from 8wt%, 13wt%, 20wt%, 25wt%, 30wt%, 40wt%, or 50.1wt%; the lower limit is selected from 5.01wt% %, 8wt%, 13wt%, 20wt%, 25wt%, 30wt% or 40wt%.
- the mass ratio of the Fe to the Pd is 5-50:0.01-0.1;
- the mass ratio of the Cu to the Fe is 0.5-1.5:0.5-1.5.
- the mass ratio of the Fe to the Pd is 10-30:0.01-0.08.
- the mass ratio of the Fe to the Pd is 13-25:0.01-0.04.
- the mass ratio of the Cu to the Fe is 0.8-1.2:0.8-1.2.
- the mass ratio of the carbon tetrachloride to the first catalyst is 50:1 to 10;
- the first catalyst is based on the mass of the first catalyst itself.
- the mass ratio of the carbon tetrachloride to the first catalyst is 50:1-6.
- the mass ratio of the carbon tetrachloride to the first catalyst is 50:1-4.
- the mass ratio of the carbon tetrachloride to the first catalyst is 50:3-6.
- the second catalyst includes at least one of phosphate and phosphite.
- the phosphate ester includes at least one of tributyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and dibutyl phosphate;
- the phosphite includes tributyl phosphite.
- the mass ratio of the second catalyst to the first catalyst is 1.25-5:1-6;
- the second catalyst is based on the mass of the second catalyst itself
- the first catalyst is based on the mass of the first catalyst itself.
- the mass ratio of the second catalyst to the first catalyst is 1.25-3:1-6.
- the mass ratio of the second catalyst to the first catalyst is 1.25-2:3-6.
- the preparation method includes: putting the carbon tetrachloride, the first catalyst and the second catalyst into a reactor, feeding the ethylene, and reacting to obtain the 1,1, 1,3-Tetrachloropropane.
- the feeding of the ethylene is specifically: feeding ethylene to replace the air in the reactor for more than 2 times before the reaction, and then continuously feeding ethylene to carry out the reaction.
- reaction conditions include: a pressure of 0.04-0.08 MPa.
- the upper limit of the pressure is selected from 0.05, 0.06, 0.07, 0.08MPa; the lower limit is selected from 0.04, 0.05, 0.06, 0.07MPa.
- the reaction conditions include: the temperature is 60-140°C.
- the upper temperature limit is selected from 80, 100, 120, 140°C; the lower limit is selected from 60, 80, 100, 120°C.
- reaction conditions include: the time is 2-10 hours.
- the upper limit of time is selected from 3, 5, 8, and 10 hours; the lower limit is selected from 2, 3, 5, and 8 hours.
- the reaction conditions include: the reaction is carried out under stirring, and the stirring speed is 800-2000 rpm.
- the upper limit of the rotation speed is selected from 1000, 1200, 1500, 1800, 2000 rpm; the lower limit is selected from 800, 1000, 1200, 1500, 1800 rpm.
- the catalyst iron used is nano-particles, and the particle size is smaller than that of commercially available iron powder or inorganic salts and other compound catalysts , the specific surface area is large, and the catalytic effect is better.
- the carrier is modified, which can better attach the active ingredients, increase the contact area with the nano-zero valent iron, and is conducive to the reaction conduct.
- the catalyst is selected from the group consisting of Fe/organic bentonite, Pd-Fe/organic bentonite, and Pd-Fe/modified activated carbon.
- the preparation method of the catalyst comprises the steps:
- the metal salt is FeCl 2 . 4H 2 O.
- the carrier is modified activated carbon.
- the reducing agent is KBH 4 .
- the second metal component is K 2 PdCl 6 .
- the solvent is an aqueous solution.
- the second aspect of the present invention provides a method for the reaction of carbon tetrachloride and ethylene to synthesize 1,1,1,3-tetrachloropropane, the method comprising the steps of: combining the catalyst described in the first aspect above with tetrafluoroethylene The carbon chloride is mixed, and the co-catalyst triethyl phosphite is added to form a catalyst-carbon tetrachloride mixed solution, and ethylene gas is continuously introduced to react at high temperature and high pressure.
- the co-catalyst is: tributyl phosphate, trimethyl phosphate, tributyl phosphite, triethyl phosphate, triphenyl phosphate, and dibutyl phosphate.
- reaction is carried out in a closed reactor.
- the mass ratio of the catalyst (calculated as nano zero-valent iron) to carbon tetrachloride is 0.0025-0.04:1.
- the feeding ratio of the triethyl phosphite to the catalyst (calculated as nano zero-valent iron): 1.25-5.
- reaction temperature is 80-140°C.
- reaction time is 2-7 hours.
- the pressure during the reaction is 0.04-0.08 MPa.
- the rotational speed of stirring is 1200 rpm.
- the reaction is repeated twice to observe the conversion rate and selectivity.
- 1,1,1,3-tetrachloropropane As a specific embodiment, the preparation method of 1,1,1,3-tetrachloropropane provided by this application is:
- the present application provides a catalyst for the reaction of carbon tetrachloride and ethylene to synthesize 1,1,1,3-tetrachloropropane
- the main catalyst is nano-Fe/organic bentonite or nano-Pd-Fe/organic Bentonite or nano-Pd-Fe/activated carbon, co-catalyst: triethyl phosphite.
- the present application provides a method for preparing a catalyst for the synthesis of 1,1,1,3-tetrachloropropane by carbon tetrachloride and ethylene, the method comprising the steps of:
- cetyl trimethyl ammonium bromide (i) cetyl trimethyl ammonium bromide (CTMAB) reacts with bentonite, thereby obtaining the organobentonite of CTMAB modification;
- ethanol-water is preferably used as the solvent to dissolve the ferrous salt.
- ethanol-water is preferably used as the solvent to dissolve the ferrous salt.
- ethanol is used as the solvent, which has the effect of eliminating air bubbles.
- the newly prepared catalyst avoids prolonged exposure to air and is easily oxidized.
- the present application provides a method for the reaction of carbon tetrachloride and ethylene to synthesize 1,1,1,3-tetrachloropropane, the method comprising the steps of: combining the catalyst of the present invention with a cocatalyst , carbon tetrachloride is mixed, put into a stainless steel autoclave with mechanical stirring, pass ethylene gas, and heat to react.
- Said reaction generates hydrogen chloride, which is very easy to corrode equipment.
- a reaction kettle that is resistant to corrosion and high temperature and pressure is used.
- the co-catalyst/main catalyst feeding ratio is 3-4 (molar ratio).
- the main catalyst/carbon tetrachloride feeding ratio is 0.006-0.01 (molar ratio).
- the reactor needs to be replaced with ethylene gas three times to remove the residual air in the reactor. During the reaction, ethylene was continued until the end of the reaction.
- the reaction temperature of the reaction is 80-120°C. More preferably, the temperature of the reaction is 100-110°C.
- the preferred reaction time is 3-6 hours.
- the present application provides a method for recovering a catalyst for the synthesis of 1,1,1,3-tetrachloropropane from carbon tetrachloride and ethylene.
- the method comprises the steps of: using the catalyst of the present invention to catalyze the reaction After completion, filter, separate the reaction solution from the catalyst, add a co-catalyst, and conduct the reaction again.
- conversion rate (addition amount of carbon tetrachloride-residual amount of carbon tetrachloride)/addition amount of carbon tetrachloride*100%;
- organobentonite was added to 250mL, 0.162mol/L FeCl 2 .
- 4H 2 O ethanol-water mixed solution, (ethanol:water 5:1) stirred for 6h; PH ⁇ 3 was adjusted with 1mol/L HCl; 250mL, 0.316mol/L NaBH4 aqueous solution of 250mL, 0.316mol /L NaBH4 aqueous solution was dripped into the above solution, stirred for 2h, the whole process was nitrogen, isolated from the air, to prevent the nano-zero valent iron from being oxidized by oxygen in the air. Filter, wash with deionized water and alcohol. Dry in a vacuum oven.
- organobentonite was added to 250mL, 0.162mol/L FeCl 2 .
- 4H 2 O ethanol-water mixed solution, (ethanol:water 5:1) stirred for 6h; PH ⁇ 3 was adjusted with 1mol/L HCl; 250 mL of 0.316 mol/L NaBH 4 aqueous solution of 0.316 mol/L was added dropwise to the above solution, stirred for 2 h, then 0.071 g of K 2 PdCl 4 was added, and the stirring was continued for 1 h.
- the whole process is filled with nitrogen to isolate the air and prevent the nano-zero valent iron from being oxidized by oxygen in the air. Filter, wash with deionized water and alcohol. Dry in a vacuum oven.
- activated carbon (20% H 3 PO 4 treatment) was added to 250mL, 0.06mol/L FeCl 2 .
- the preparation method of 4# catalyst is only different in that the activated carbon treated with 20% H 3 PO 4 is replaced by the activated carbon treated with 20% HCl, and other preparation conditions are the same.
- the preparation method of 5# catalyst is only different in that the activated carbon treated with 20% H 3 PO 4 is replaced by the activated carbon treated with 20% HNO 3 , and other preparation conditions.
- the Fe-Pd/activated carbon (20% H3PO4 treatment) catalyst was obtained by drying in a vacuum drying oven, which was denoted as 7# catalyst.
- the modified method of the carrier activated carbon is carried out according to the following steps:
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- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本申请公开了一种1,1,1,3‐四氯丙烷的制备方法,包括:在第一催化剂和第二催化剂存在下,将含有四氯化碳和乙烯的原料反应,获得所述1,1,1,3‐四氯丙烷;所述第一催化剂包括载体和负载在所述载体上的活性组分;所述活性组分包括纳米零价铁;所述第二催化剂包括酯类化合物。所述制备方法采用负载型铁催化剂,可以显著改善单纯市售铁粉做催化剂时容易团聚的问题,同时增大了铁的比表面积,有利于反应的进行。
Description
本申请涉及一种1,1,1,3‐四氯丙烷的制备方法,属于化工技术领域。
四氯化碳是甲烷氯化物装置的副产物,四氯化碳是《蒙特利尔议定书》规定的消耗臭氧层受控物质,简称:CTC。除原料用途、试剂用途和特殊豁免用途外,完全停止CTC的生产和消费。近年来,中国甲烷氯化物发展迅猛,依靠原料用途市场难以消化生产的CTC,焚烧处理四氯化碳约需3000~4000元/吨的成本。因此,CTC综合利用具有十分重要的现实意义,关系到整个产业链的生存和安全。
文献报道中报道的金属和助催化剂主要有:有机铜化合物和有机腈类化合物;铁或其化合物、有机磷化合物类。
目前所用的铁或其化合物、有机磷化合物类催化剂中铁粉为市售铁粉;市售铁粉作为主催化剂时,容易在反应釜釜底团聚,市由于长时间接触空气,表面形成一层氧化膜,使得反应活性降低。
综上所述,本领域尚缺乏一种比市售铁粉分散性更好、与反应物接触面积更大、选择性更高的四氯化碳合成1,1,1,3‐四氯丙烷反应催化剂。
发明内容
根据本申请的一个方面,提供一种1,1,1,3‐四氯丙烷的制备方法,所述制备方法采用负载型铁主催化剂,可以显著改善市售铁粉容易团聚的问题,同时增大了铁的比表面积,同时添加第二种纳米金属组分,有效解决新鲜制备的纳米铁催化剂暴露于空气中容易被氧化的问题,有利于反应的进行。
一种1,1,1,3‐四氯丙烷的制备方法,所述制备方法包括:
在第一催化剂和第二催化剂存在下,将含有四氯化碳和乙烯的原料反应,获得所述1,1,1,3‐四氯丙烷;
所述第一催化剂包括载体和负载在所述载体上的活性组分;
所述活性组分包括纳米零价铁;
所述第二催化剂包括酯类化合物。
可选地,所述活性组分还包括铂、铜中的至少一种。
可选地,所述活性成分选自零价铁纳米粒子、Pd‐Fe双金属纳米粒子、Cu‐Fe双金属纳米粒子中的任一种。
可选地,所述载体包括多孔材料中的至少一种
可选地,所述多孔材料包括膨润土和/或活性炭。
可选地,所述膨润土经过表面活性剂改性处理得到;
所述活性炭经过酸改性处理得到。
可选地,所述表面活性剂包括季铵盐中的至少一种;
所述酸包括HCl、H
3PO
4、HNO
3中的任一种。
可选地,所述季铵盐包括十六烷基三甲基溴化铵。
可选地,所述酸改性处理为:将活性炭与酸溶液混合,80~100℃下回流3~8h。
可选地,所述酸溶液的浓度为10~30%。
可选地,所述活性炭与所述酸溶液的质量体积比为5~15:80~120g/mL。
可选地,所述表面活性剂改性处理为:将膨润土水溶液与表面活性剂混合,调节pH值至酸性,50~80℃下,搅拌,洗涤。
可选地,所述膨润土与所述表面活性剂的质量比为30~60:15~25。
可选地,所述表面活性剂改性处理更具体地为:膨润土50g配制10%泥浆;加入19.2g十六烷基三甲基溴化铵。PH=5;70℃,搅拌2h,抽滤,去离子水洗涤3次;分析:2%AgNO
3检测不出溴。100℃烘箱过夜。
可选地,所述第一催化剂中,所述活性组分的负载量为5.01~50.1wt%。
可选地,所述第一催化剂中,所述活性组分的负载量上限选自8wt%、13wt%、20wt%、25wt%、30wt%、40wt%、或50.1wt%;下限选自5.01wt%、8wt%、13wt%、20wt%、25wt%、30wt%或40wt%。
可选地,所述Pd‐Fe双金属纳米粒子中,所述Fe和所述Pd的质量比为5~50:0.01~0.1;
所述Cu‐Fe双金属纳米粒子中,所述Cu和所述Fe的质量比为0.5~1.5:0.5~1.5。
可选地,所述Pd‐Fe双金属纳米粒子中,所述Fe和所述Pd的质量比为10~30:0.01~0.08。
可选地,所述Pd‐Fe双金属纳米粒子中,所述Fe和所述Pd的质量比为13~25:0.01~0.04。
可选地,所述Cu‐Fe双金属纳米粒子中,所述Cu和所述Fe的质量比为0.8~1.2:0.8~1.2。
可选地,所述四氯化碳与所述第一催化剂的质量比为50:1~10;
其中,第一催化剂以第一催化剂自身的质量计。
可选地,所述四氯化碳与所述第一催化剂的质量比为50:1~6。
可选地,所述四氯化碳与所述第一催化剂的质量比为50:1~4。
可选地,所述四氯化碳与所述第一催化剂的质量比为50:3~6。
可选地,所述第二催化剂包括磷酸酯、亚磷酸酯中的至少一种。
可选地,所述磷酸酯包括磷酸三丁酯、磷酸三甲酯、磷酸三乙酯、磷酸三苯酯、磷酸二丁酯中的至少一种;
所述亚磷酸酯包括亚磷酸三丁酯。
可选地,所述第二催化剂和所述第一催化剂的质量比为1.25~5:1~6;
其中,第二催化剂以第二催化剂自身的质量计,第一催化剂以第一催化剂自身的质量计。
可选地,所述第二催化剂和所述第一催化剂的质量比为1.25~3:1~6。
可选地,所述第二催化剂和所述第一催化剂的质量比为1.25~2:3~6。
可选地,所述制备方法包括:将所述四氯化碳、所述第一催化剂和所述第二催化剂放入反应器中,通入所述乙烯,反应,获得所述1,1,1,3‐四氯丙烷。
可选地,所述通入所述乙烯具体为:反应前先通入乙烯置换反应器中的空气2次以上,再持续通入乙烯进行反应。
可选地,所述反应的条件包括:压力0.04~0.08MPa。
可选地,所述压力的上限选自0.05、0.06、0.07、0.08MPa;下限选自0.04、0.05、0.06、0.07MPa。
可选地,所述反应的条件包括:温度为60~140℃。
可选地,温度上限选自80、100、120、140℃;下限选自60、80、100、120℃。
可选地,所述反应的条件包括:时间为2~10小时。
可选地,所述时间上限选自3、5、8、10小时;下限选自2、3、5、8小时。
可选地,所述反应的条件包括:在搅拌下反应,搅拌转速为800~2000转/分钟。
可选地,所述转速上限选自1000、1200、1500、1800、2000转/分钟;下限选自800、1000、1200、1500、1800转/分钟。
本申请能产生的有益效果包括:
1)本申请所提供的1,1,1,3‐四氯丙烷的制备方法,将催化剂活性成分铁负载于载体上,可以显著改善单纯市售铁粉做催化剂时容易团聚的问题,催化性能好,且反应结束后催化剂容易从反应釜中脱除。
2)本申请所提供的1,1,1,3‐四氯丙烷的制备方法,所采用的催化剂铁为纳米颗粒,与市售铁粉或者无机盐及其他化合物催化剂相比,颗粒度更小,比表面积大,催化效果更佳。
3)本申请所提供的1,1,1,3‐四氯丙烷的制备方法,载体经过改性,可以更好地附着活性成分,增大了与纳米零价铁的接触面积,有利于反应的进行。
下面结合实施例详述本申请,但本申请并不局限于这些实施例。
如无特别说明,本申请的实施例中的原料均通过商业途径购买。
其中,市售铁粉购于国药集团化学试剂有限公司,CAS:7439‐89‐6。
本申请中,第一催化剂等同于主催化剂;第二催化剂等同于助催化剂。
作为一种具体实施方式,本申请提供了一种四氯化碳与乙烯合成1,1,1,3‐四氯丙烷的方法,所述方法中所采用的催化剂具有利用率高、选择性好的优点。
在本发明的第一方面,提供了一种氯化副产物四氯化碳合成1,1,1,3‐四氯丙烷反应催化剂,所述催化剂包括催化有效量的金属组分:纳米零价铁或纳米Pd‐Fe双金属;和有机膨润土或活性炭载体。
在另一优选例中,所述催化剂选自下组:Fe/有机膨润土、Pd‐Fe/有机膨润土、Pd‐Fe/改性活性炭。
在另一优选例中,所述催化剂的制备方法包括步骤:
(i)用加入有载体(机膨润土)的金属盐(FeSO
4
.7H
2O)乙醇‐水溶液与还原剂(NaBH
4)溶液进行还原反应,从而得到有机膨润土负载的纳米零价铁;继续加入第二金属组分(PdCl
2);继续还原反应;获得的催化剂中Pd含量为:0.04%。抽滤,真空干燥箱干燥。整个反应过程持续通入氮气,隔绝空气。
在另一优选例中,所述的金属盐为FeCl
2
.4H
2O。
在另一优选例中,所述载体为改性的活性炭。
在另一优选例中,所述还原剂为KBH
4。
在另一优选例中,所述第二金属组分为K
2PdCl
6。
在另一优选例中,所述溶剂为水溶液。
本发明的第二方面,提供了一种四氯化碳与乙烯合成1,1,1,3‐四氯丙烷反应的方法,所述方法包括步骤:将上述第一方面所述的催化剂与四氯化碳混合,添加助催化剂亚磷酸三乙酯,形成催化剂‐四氯化碳混合溶液,持续通入乙烯气,高温高压反应。
在另一优选例中,所述助催化剂为:磷酸三丁酯、磷酸三甲酯、亚磷酸三丁酯、磷酸三乙酯、磷酸三苯酯、磷酸二丁酯。
在另一优选例中,所述反应在密闭反应釜中进行。
在另一优选例中,所述催化剂(以纳米零价铁计)与四氯化碳的投料质量比为0.0025~0.04:1。
在另一优选例中,所述亚磷酸三乙酯与所述催化剂(以纳米零价铁计)的投料比:1.25~5。
在另一优选例中,所述反应温度为80~140℃。
在另一优选例中,所述反应的时间为2~7小时。
在另一优选例中,反应过程中压力为0.04~0.08MPa。
在另一优选例中,进行搅拌的转速1200转/分钟。
在另一优选例中,所述的催化剂回收后,继续重复两次反应,观察转化率和选择性。
作为一种具体实施方案,本申请所提供的1,1,1,3‐四氯丙烷的制备方法为:
在带有机械搅拌的100ml不锈钢高压反应釜中加入50g四氯化碳,再加入1~10g的催化剂,铁负载量:5~25%;(铁负载量以投料计)然后通乙烯置换反应釜内残留的空气两次,待此步完成后充入乙烯气体到0.04~0.08MPa,加热升温至60~140℃),反应2~10小时;一直通乙烯至反应结束,反应完成后,自然冷却,取反应液进行气相色谱分析。
作为一种具体实施方式,本申请提供一种四氯化碳与乙烯合成1,1,1,3‐四氯丙烷反应催化剂,所述主催化剂为纳米Fe/有机膨润土或纳米Pd‐Fe/有机膨润土或纳米Pd‐Fe/活性炭,助催化剂为:亚磷酸三乙酯。
作为一种具体实施方式,本申请提供一种四氯化碳与乙烯合成1,1,1,3‐四氯丙烷反应催化剂的制备方法,所述方法包括步骤:
(i)十六烷基三甲基溴化铵(CTMAB)与膨润土进行反应,从而得到CTMAB改性的有机膨润土;
(ii)改性的膨润土浸渍亚铁盐;例如:FeSO
4
.7H
2O或FeCl
2
.4H
2O, 溶剂为乙醇‐水体系或纯水。
(iii)上述亚铁溶液被NaBH
4或KBH
4还原剂还原。整各还原过程持续通入氮气,保持无氧环境。
(iv)继续加入K
2PdCl
4或者PdCl
2,搅拌至完全反应。
(v)真空干燥箱干燥,整个过程避免长时间接触空气,防止制备出的纳米铁被氧化。
其中优选地为乙醇‐水作为溶剂溶解亚铁盐,一方面还原过程中会生成大量的气泡,选用乙醇作为溶剂,有消解气泡的作用。新制备的催化剂避免长时间接触空气,很容易就被氧化。
作为一种具体实施方式,本申请提供一种四氯化碳与乙烯合成1,1,1,3‐四氯丙烷反应的方法,所述方法包括步骤:将本发明所述的催化剂与助催化剂、四氯化碳混合,加入带有机械搅拌的不锈钢高压反应釜中,通入乙烯气,加热进行反应。
所述的反应有氯化氢生成,极易腐蚀设备,优选地,用耐腐蚀耐高温高压的反应釜。
优选地,所述催化剂中,助催化剂/主催化剂投料比为3~4(摩尔比)。
优选地,主催化剂/四氯化碳投料比为0.006~0.01(摩尔比)。投料完毕,需用乙烯气置换反应釜三次,以除去反应釜内残存的空气。反应过程中持续通乙烯直至反应结束。
在优选的实施例中,所述反应的反应温度为80‐120℃。更优选地,所述反应的温度为100‐110℃。优选的反应时间为3‐6小时。
作为一种具体实施方式,本申请一种四氯化碳与乙烯合成1,1,1,3‐四氯丙烷反应催化剂回收方法,所述方法包括步骤:在用本发明所述的催化剂催化反应完毕后,过滤,反应液和催化剂进行分离,加入助催化剂,重新进行反应。
应理解,在本申请范围内,本申请的上述各技术特征和在下文(如具体实施例)中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方案。限于篇幅,在此不再一一累述。
在本申请中,转化率=(四氯化碳加入量‐四氯化碳剩余量)/四氯化碳加入量*100%;
选择性=(四氯丙烷产率/转化率)*100%;
产率=实际四氯丙烷产量/理论产量。
实施例1催化剂的制备
将5g有机膨润土加入到250mL、0.054mol/L FeSO
4
.7H
2O溶液中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.108mol/L KBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥。
实施例2催化剂的制备
将5g有机膨润土加入到250mL、0.054mol/L FeCl
2
.4H
2O溶液中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.108mol/L KBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥。
实施例3催化剂的制备
将5g有机膨润土加入到250mL、0.162mol/L FeSO
4
.7H
2O乙醇—水混合溶液中,(乙醇:水=5:1)搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.316mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥。
实施例4催化剂的制备
将5g有机膨润土加入到250mL、0.162mol/L FeCl
2
.4H
2O乙醇—水混合溶液中,(乙醇:水=5:1)搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.316mol/L NaBH
4水溶液滴入上述溶液中,搅拌 2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥。
实施例5催化剂的制备
将5g有机膨润土加入到250mL、0.162mol/L FeCl
2
.4H
2O乙醇—水混合溶液中,(乙醇:水=5:1)搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.316mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,后加入0.071gK
2PdCl
4,继续搅拌1h。整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥。
实施例6催化剂的制备
将5g有机膨润土加入到250mL、0.03mol/L FeCl
2
.4H
2O乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.06mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥,得到Fe/膨润土催化剂,记为8#催化剂。XRF测定催化剂中Fe负载量:5wt%。
实施例7催化剂的制备
将5g有机膨润土加入到250mL、0.06mol/L FeCl
2
.4H
2O乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调pH<3;将配制好的250mL、0.12mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥,得到Fe/膨润土催化剂,记为9#催化剂。XRF测定催化剂中Fe负载量:13wt%。
实施例8催化剂的制备
将5g有机膨润土加入到250mL、0.162mol/L FeCl
2
.4H
2O乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调pH<3; 将配制好的250mL、0.316mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h。整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥,得到Fe/膨润土催化剂,记为1#催化剂。XRF测定:Fe负载量:25wt%。
实施例9催化剂的制备
将5g有机膨润土加入到250mL、0.06mol/L FeCl
2
.4H
2O乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.12mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,后加入0.071gK
2PdCl
4,继续搅拌1h。整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥得到Pd‐Fe/膨润土催化剂,记为2#催化剂。XRF测定:Pd负载量:0.04%;Fe负载量:13wt%。
实施例10催化剂的制备
将5g活性炭(20%H
3PO
4处理)加入到250mL、0.06mol/L FeCl
2
.4H
2O乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.12mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥得到Fe/活性炭(20%H
3PO
4处理),记为3#催化剂。XRF测定催化剂中Fe负载量:13wt%。
实施例11催化剂的制备
4#催化剂的制备方法与3#相比,区别仅在于把20%H
3PO
4处理的活性炭换成20%HCl处理的活性炭,其他制备条件相同。
实施例12催化剂的制备
5#催化剂的制备方法与3#相比,区别仅在于把20%H
3PO
4处理的活性炭换成20%HNO
3处理的活性炭,其他制备条件。
实施例13催化剂的制备
将5g活性炭(20%H
3PO
4处理)加入到250mL、0.06mol/L FeCl
2
.4H
2O和相同摩尔量的氯化铜的乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.25mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥,得到Cu‐Fe(Cu:Fe=1:1)/活性炭(20%H
3PO
4处理)催化剂,记为6#催化剂。XRF测定催化剂中Fe负载量:13wt%;Cu负载量:12.8wt%;约为1:1。
实施例14催化剂的制备
将5g活性炭(20%H
3PO
4处理)加入到250mL、0.06mol/L FeCl
2
.4H
2O乙醇—水混合溶液(乙醇:水=5:1)中,搅拌6h;用1mol/L HCl调PH<3;将配制好的250mL、0.12mol/L NaBH
4水溶液滴入上述溶液中,搅拌2h,后加入0.019gK
2PdCl
4,继续搅拌1h。整个过程通氮气,隔绝空气,防止纳米零价铁被空气中氧气氧化。过滤,去离子水洗、醇洗。真空干燥箱干燥得到Fe‐Pd/活性炭(20%H3PO4处理)催化剂,记为7#催化剂。XRF测定:Fe负载量:13wt%;Pd负载量:0.1wt%。
上述3#~7#催化剂的制备中,载体活性炭改性方法按以下步骤进行:
分别配置20%的HCl溶液,20%的H
3PO
4溶液或20%的HNO
3溶液。取10g活性炭样品放入250mL的圆底烧瓶中,并分别加入100mL上述溶液,在100℃下搅拌回流5h。待其冷却后,过滤活性炭样品,并用去离子水洗涤至中性,过滤得到滤饼。将处理后的活性炭滤饼放入烘箱内,在110℃干燥10h。
实施例15 1,1,1,3‐四氯丙烷的制备
在带有机械搅拌的100ml间歇式不锈钢高压反应釜中加入50g 四氯化碳,再加入4g的8#催化剂,亚磷酸三乙酯:1.3g;然后通乙烯置换反应釜内残留的空气两次,待此步完成后充入乙烯气体到0.04MPa,加热升温至60℃,反应3小时;一直通乙烯至反应结束,反应完成后,自然冷却,取反应液进行气相色谱分析。结果表明:四氯化碳单程转化率:63.5%;选择性:87.2%。
实施例16 1,1,1,3‐四氯丙烷的制备
在带有机械搅拌的100ml间歇式不锈钢高压反应釜中加入50g四氯化碳,再加入3g的9#催化剂,亚磷酸三乙酯:1.3g;然后通乙烯置换反应釜内残留的空气两次,待此步完成后充入乙烯气体到0.08MPa,加热升温至100℃,反应6小时;一直通乙烯至反应结束,反应完成后,自然冷却,取反应液进行气相色谱分析。结果表明:四氯化碳单程转化率:96.8%;选择性:98.7%
实施例17 1,1,1,3‐四氯丙烷的制备
在带有机械搅拌的100ml间歇式不锈钢高压反应釜中加入50g四氯化碳,再加入6g的1#催化剂,亚磷酸三乙酯:1.3g;然后通乙烯置换反应釜内残留的空气两次,待此步完成后充入乙烯气体到0.08MPa,加热升温至140℃,反应10小时;一直通乙烯至反应结束,反应完成后,自然冷却,产物均结焦,为黑色固体。
实施例18~24、对比例1 1,1,1,3‐四氯丙烷的制备
实验条件:亚磷酸三乙酯:1.3g、CCl4:50g、温度:100℃、压力:0.08MPa、时间:3h;催化剂添加量:3g;所用催化剂种类及反应结果如表1所示。
表1 13~19所用催化剂种类及反应结果
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (18)
- 一种1,1,1,3‐四氯丙烷的制备方法,其特征在于,所述制备方法包括:在第一催化剂和第二催化剂存在下,将含有四氯化碳和乙烯的原料反应,获得所述1,1,1,3‐四氯丙烷;所述第一催化剂包括载体和负载在所述载体上的活性组分;所述活性组分包括纳米零价铁;所述第二催化剂包括酯类化合物。
- 根据权利要求1所述的制备方法,其特征在于,所述活性组分还包括铂、铜中的至少一种。
- 根据权利要求1所述的制备方法,其特征在于,所述活性组分选自零价铁纳米粒子、Pd‐Fe双金属纳米粒子、Cu‐Fe双金属纳米粒子中的任一种。
- 根据权利要求1所述的制备方法,其特征在于,所述载体包括多孔材料中的至少一种。
- 根据权利要求4所述的制备方法,其特征在于,所述多孔材料包括膨润土和/或活性炭。
- 根据权利要求5所述的制备方法,其特征在于,所述膨润土经过表面活性剂改性处理得到;所述活性炭经过酸改性处理得到。
- 根据权利要求6所述的制备方法,其特征在于,所述表面活性剂包括季铵盐中的至少一种;所述酸包括HCl、H 3PO 4、HNO 3中的任一种。
- 根据权利要求7所述的制备方法,其特征在于,所述季铵盐包括十六烷基三甲基溴化铵。
- 根据权利要求1所述的制备方法,其特征在于,所述第一催化剂中,所述活性组分的负载量为5.01~50.1wt%。
- 根据权利要求3所述的制备方法,其特征在于,所述Pd‐Fe双金属纳米粒子中,所述Fe和所述Pd的质量比为5~50:0.01~0.1;所述Cu‐Fe双金属纳米粒子中,所述Cu和所述Fe的质量比为0.5~1.5:0.5~1.5。
- 根据权利要求1所述的制备方法,其特征在于,所述四氯化碳与所述第一催化剂的质量比为50:1~10;其中,第一催化剂以第一催化剂自身的质量计。
- 根据权利要求1所述的制备方法,其特征在于,所述第二催化剂包括磷酸酯、亚磷酸酯中的至少一种。
- 根据权利要求1所述的制备方法,其特征在于,所述磷酸酯包括磷酸三丁酯、磷酸三甲酯、磷酸三乙酯、磷酸三苯酯、磷酸二丁酯中的至少一种;所述亚磷酸酯包括亚磷酸三丁酯。
- 根据权利要求1所述的制备方法,其特征在于,所述第二催化剂和所述第一催化剂的质量比为1.25~5:1~6;其中,第二催化剂以第二催化剂自身的质量计,第一催化剂以第一催化剂自身的质量计。
- 根据权利要求1所述的制备方法,其特征在于,所述制备方法包括:将所述四氯化碳、所述第一催化剂和所述第二催化剂放入反应器中,通入所述乙烯,反应,获得所述1,1,1,3‐四氯丙烷。
- 根据权利要求1或15所述的制备方法,其特征在于,所述反应的条件包括:压力0.04~0.08MPa。
- 根据权利要求1或15所述的制备方法,其特征在于,所述反应的条件包括:温度为60~140℃;时间为2~10小时。
- 根据权利要求1或15所述的制备方法,其特征在于,所述反应的条件包括:在搅拌下反应,搅拌转速为800~2000转/分钟。
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