CN101723795A - Method for preparing methyl bromide, high-carbon hydrocarbon, methyl alcohol and dimethyl ether by methane - Google Patents
Method for preparing methyl bromide, high-carbon hydrocarbon, methyl alcohol and dimethyl ether by methane Download PDFInfo
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- CN101723795A CN101723795A CN200810121558A CN200810121558A CN101723795A CN 101723795 A CN101723795 A CN 101723795A CN 200810121558 A CN200810121558 A CN 200810121558A CN 200810121558 A CN200810121558 A CN 200810121558A CN 101723795 A CN101723795 A CN 101723795A
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- Prior art keywords
- catalyzer
- reaction
- hbr
- methane
- metallic compound
- Prior art date
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title abstract 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 title description 6
- 229940102396 methyl bromide Drugs 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012686 silicon precursor Substances 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 103
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 40
- -1 bromo alkane Chemical class 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052703 rhodium Inorganic materials 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Chemical group 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims description 18
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 3
- 229910003910 SiCl4 Inorganic materials 0.000 claims 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical group Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 68
- 238000002360 preparation method Methods 0.000 description 55
- 238000012360 testing method Methods 0.000 description 29
- 230000008569 process Effects 0.000 description 25
- 239000007789 gas Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000004480 active ingredient Substances 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 229910003902 SiCl 4 Inorganic materials 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 235000009508 confectionery Nutrition 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101150101537 Olah gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
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- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
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- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/6525—Molybdenum
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Abstract
The invention discloses a method which is characterized in that methane is converted into bromohydrocarbon by bromine oxidation reaction, and bromohydrocarbon is further prepared into high-carbon hydrocarbon, methyl alcohol and dimethyl ether. Firstly, methane, HBr/H2O and oxygen react to generate bromo-alkane; the catalyst is a composite catalyst prepared by mixed hydrolysis, drying and roasting of silicon precursor and metallic compound precursor capable of dissolving in water; then, the bromo-alkane is performed with de-HBr to prepare high-carbon hydrocarbon, or bromo-alkane reacts with water to prepare methyl alcohol and dimethyl.
Description
Technical field
The invention belongs to Sweet natural gas synthetic industrial chemicals field, the particularly method of bromine oxidation of methane.
Background technology
Along with the minimizing day by day of petroleum resources, conversion of natural gas is that the chemical of high added value has been subjected to increasing attention.Verify at present, abundant natural gas reserves is arranged on the earth, only Zhong Guo natural gas reserves just reaches 124 tcms, is the 22nd in the Natural Gas Reserve in World rank.Contain a large amount of methane in the Sweet natural gas, its content can from 60% to 99% variation, and all the other are mainly ethane and propane.A large amount of lower paraffin hydrocarbonss in the oilfield exploitation are still burnt with the torch form at present, have not only wasted resource, and have increased concentration of carbon dioxide in the atmosphere, have polluted environment.Effective research that utilizes also mainly concentrates on effective utilization of methane is studied to Sweet natural gas, and therefore the development and use to methane have great economic implications.
Methane (CH
4) be that a kind of molecular structure is similar to rare gas element, no any characteristic group own is by the sp of C atom
3Hydridization forms the good positive tetrahedron structure of symmetry, and the Average bond energy of c h bond is 414kJ/mol, is to be difficult in activatory molecule under the mild conditions, its gas phase CH
4, CH
3, CH
2Be respectively 420kJ/mol, 360kJ/mol, 520kJ/mol and 330kJ/mol with the c h bond dissociation energy of CH.Studying the activation conversion that activation of its c h bond and selective conversion can be other hydro carbons offers reference.
Conversion of natural gas is the fluid chemical raw material, provides a kind of effective way for solving from remote districts transportation low molecular weight alkanes.At present the method for utilizing Sweet natural gas that adopts mainly comprises and is translated into synthetic gas (mixture of hydrogen and carbon monoxide), subsequently synthetic gas is converted into liquid product.As adopt Fischer-Tropsch (F-T) method that synthetic gas is converted into synthetic oil, and then be transport fuel (Fischer, F., and Tropsch, H., Brennst.Chem.4,276 (1923) .) by conventional process for purification lifting.Although it can be the liquid fuel that is easier to transport with conversion of natural gas that the F-T synthetic method provides a kind of flow process, this method is a strong endothermic reaction in the process of preparing synthetic gas, needs a large amount of methane of burning to provide reaction needed heat.
It is research (Roy A.Periana, et al, the Science280 of methyl alcohol and acetic acid that people such as Periana have carried out methane conversion, 560 (1998), Roy A.Periana, et al, Science 301,814 (2003) .), but in reaction, generated can not circular treatment SO
2, and the vitriol oil as reactant and solvent after reaction since the generation of water and thinning can not continue to use, so make great efforts to study the industrialization of also failing to realize for many years through Periana group and the Catalytica Inc. of u s company.
In the research work of Olah (G.A.Olah, A.Molnar, Hydrocarbon Chemistry (Wiley, NewYork, 1995)), be with methane and simple substance bromine Br
2Reaction generates CH
3Br and HBr, and then hydrolysis CH
3Br preparing dimethy ether and methyl alcohol.And their the methane per pass conversion of report is lower than 20%.
The Xiao Ping Zhou of GRT Inc. of the U.S. etc. has designed with Br
2The alkane in the Sweet natural gas is converted into the flow process (CN02827498.9 of dme and methyl alcohol for media, US6472572, US6462243), the difference of this flow process and Olah report is to be to generate hydrobromic ether and HBr with alkane and bromine reaction, further generate purpose product and metal bromide then, last metal bromide and the oxygen reaction Br that regenerates with a kind of reactive metal oxide
2And metal oxide, finish the circulation of bromine.Above flow process all relates to using of simple substance bromine and step that needs are extra regeneration simple substance bromine, and to use in a large number and store simple substance bromine be breakneck.Because reaction is not a catalyzed reaction, but the stoichiometric chemistry reaction so need transmit stoichiometric metal oxide in reactive system, makes flow process complicated, and has increased energy consumption.
U.S. Dow Universal Tech. Corp. has reported and has used simple substance chlorine or hydrogenchloride to prepare methyl alcohol/dme as media that light olefin such as ethene, propylene and butylene, higher olefins comprise gasoline, halogen vinyl monomer and acetic acid (CN02813796.5).But this flow process uses hydrogenchloride to prepare methyl chloride as reaction intermediate.In this patent, use the metal oxyhalogenide as catalyzer, do not use carrier, the catalyzer instability, and employed metal is mainly rare earth metal, and price is higher relatively, and the highest of the per pass conversion of methane reaches 13.3%.
A kind of methane activation route of contriver's design has at present obtained many scientific research institutions, company and scholar's attention gradually.Be included in the first step and use bromine to carry out the bromine oxidizing reaction to methane to obtain methyl bromide, and then in second step, methyl bromide is converted into the Chemicals of commercial value such as methyl alcohol, dme, acetic acid, acetic ester, high-carbon hydrocarbon etc.
In the research in this field, developed that the methane through non-synthetic gas route is acetic acid synthesized, the flow process (CN200410022850.8, CN200510031734.7, CN200610031377.9) of methyl alcohol, dme and high-carbon hydrocarbon.In these flow processs, at first the alkane component in the Sweet natural gas is converted into bromo alkane, and then bromo alkane is converted into corresponding product and reclaims HBr, HBr returns and produces bromo alkane in first reactor, to realize recycling of HBr.When first step reaction product is the bromo alkane of highly selective, can obtain methyl alcohol, dme or high-carbon hydrocarbon by second stage reaction; When first step product is mainly bromo alkane and carbon monoxide mixtures, can acetic acid synthesized and acetic ester.Thereby the main innovate point of this flow process is exactly bromo alkane and the carbon monoxide that obtains adapting to different downstream product demands by the performance that changes first step catalyzer.
In CN200610031377.9, the reaction of disclosed preparation bromo alkane is as follows:
In reaction with methane, HBr/H
2O and oxygen source (O
2, air or oxygen-rich air) be reactant, under the certain reaction temperature, in fixed-bed reactor, contact catalyzed reaction take place with first kind of catalyzer, generate purpose product C H
3Br and CH
2Br
2And by product CO and CO
2The loaded catalyst of used catalyzer for adopting pickling process to make, the presoma that is about to the water-soluble metal active ingredient is (as RuCl
3Deng) be dissolved in the solution, with carrier (as SiO
2) flood wherein, oven dry, roasting obtain then.Have characteristics such as active ingredient utilization ratio height, cost are low relatively with the catalyzer of this kind method preparation.But, since the active ingredient presoma in solution by in the process of drying, it is big that the concentration of solution constantly becomes, may there be the phenomenon of being separated out by crystallization because concentration is excessive, thereby in roasting process, form independently active ingredient bunch, rather than loaded on carrier surface uniformly, form active ingredient phenomenon pockety.In addition, even active ingredient is loaded on carrier surface, in reaction, along with the continuity of time may cause the loss of active ingredient, thereby reduce catalytic activity, and the catalytic stability of catalyzer is relatively poor to reaction.Therefore, seek the direction that the new method for preparing catalyzer becomes this process modification, development.
The reaction of the high-carbon hydrocarbon of the disclosed preparation of CN200610031377.9 C3～C13 is as follows:
n，m，x＝2，3，4，5，6，7，8，9，10，11，12，13
CH
3Br and CH
2Br
2Under second kind of catalyst action, take off the HBr condensation reaction and generate C
3～C
13High-carbon hydrocarbon.Used catalyzer is mainly the loaded catalyst of wet impregnation preparation, and carrier is the HZSM-5 molecular sieve with difunctional effect, and the presoma of active ingredient is a water-soluble metal salt, as magnesium nitrate etc.
In CN200410022850.8, the method that monobromethane prepares methyl alcohol and dme is disclosed, mainly adopt RuCl
3As catalyzer.Reaction formula is as follows:
2CH
3Br+2H
2O→2CH
3OH+2HBr
2CH
3Br+H
2O→2HBr+CH
3OCH
3
Summary of the invention
The present invention is the further improvements in methods that bromine oxidation of methane system bromo alkane and bromo alkane are converted into high-carbon hydrocarbon, methyl alcohol and dme.
An object of the present invention is to provide a kind of new method for preparing bromo alkane.
For this reason, technical scheme provided by the invention is, under first kind of catalyzer (being catalyst A) effect, by methane and HBr/H
2O, oxygen reaction generate bromo alkane, and described first kind of catalyzer is by mixed hydrolysis, oven dry, the composite catalyst that is prepared from of roasting then by metallic compound presoma and silicon precursor.Reaction formula is as follows:
Described metallic compound presoma is selected from least a in the muriate, bromide, iodide, nitrate, vitriol, carbonate, oxalate, acetate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr, La, and described silicon precursor is selected from SiCl
4, at least a in silicon unit acid esters solution or the silicon sol.
The concrete preparation process of first kind of catalyzer can for, with at least a in the muriate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr and La, bromide, iodide, nitrate, vitriol, carbonate, oxalate, the acetate is preparation of raw material corresponding metal salt brine solution, with SiCl
4, silicon unit acid esters solution is the silicon source, hydrolysis prepare silicon colloidal sol (also can directly adopt the commodity silicon sol); Aqueous metal salt is mixed with silicon sol, then oven dry, roasting.The catalyzer that adopts this method to be prepared from promptly is that metal simple-substance or the metallic compound by Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr or La is dispersed in SiO
2The middle mutually composite catalyst that forms of thing.
In the metallic compound presoma of first kind of catalyzer, the catalytic performance of the catalyzer of the muriate of Ru or Rh, bromide or nitrate and silicon precursor preparation is best, is the preferential metallic compound presoma of selecting of the present invention.
For the first kind of catalyzer that contains Ru, the quality percentage composition of Ru in catalyzer selects 0.05% to 2.00%, and the Ru content range is 0.10% to 1.40% preferably, and best Ru content range is 0.50% to 1.20%.For the first kind of catalyzer that contains Rh, the quality percentage composition of Rh in catalyzer selects 0.05% to 1.00%, and the Rh content range is 0.10% to 0.60% preferably, and best Rh content range is 0.30% to 0.50%.
Maturing temperature in first kind of catalyst preparation process is chosen in 500 to 1200 ℃, and maturing temperature is 600 to 1000 ℃ preferably, and best catalyzer maturing temperature is 700 to 900 ℃.
Methane, HBr/H
2O and O
2Temperature of reaction on catalyzer is 400 to 800 ℃, and range of reaction temperature is at 560 to 680 ℃ preferably, and best temperature of reaction is at 620 to 660 ℃.
First kind of Preparation of catalysts of the present invention adopted the novel method that is different from traditional pickling process, and in the preparation process of this method, aqueous metal salt is (as RuCl
3Deng) mix with silicon sol and to form homogeneous system, metal-salt as active ingredient is evenly distributed in the silicon sol, be mixing between ion, molecular level between active ingredient and the silicon sol, through roasting process, active ingredient can be dispersed in SiO equally uniformly
2Carrier inside and surface, SiO wherein
2Except the carrier function that plays bearing catalyst, also has the effect of solvent in a kind of similar solution.And traditional pickling process is with SiO
2The carrier direct impregnation at aqueous metal salt (as RuCl
3Deng) in, may there be the phenomenon that causes metal-salt to be separated out because partial concn is excessive in the process of oven dry by crystallization, in roasting process, form independently active ingredient bunch, form active ingredient phenomenon pockety, and may cause the loss of active ingredient along with the continuity of time.Therefore, than the catalyzer that traditional employing pickling process is made, its active ingredient of first kind of catalyzer of the present invention distributes more even, and has better stability, catalytic effect significantly improves (as showing among the embodiment, the selectivity of monobromethane improves greatly).
Another object of the present invention provides a kind of new method for preparing high-carbon hydrocarbon.This method may further comprise the steps:
(a) on first kind of catalyzer (being catalyst A), methane and HBr/H
2O, oxygen reaction generate bromo alkane, and described first kind of catalyzer is the composite catalyst that is prepared from by mixed hydrolysis, oven dry, roasting by metallic compound presoma and silicon precursor; Reaction formula is as follows:
(b) hydrobromic ether is gone up reaction at second kind of catalyzer (being catalyst B) and is generated C
3To C
13High-carbon hydrocarbon and HBr, the HBr of generation utilizes as the circulating reaction medium, described second kind of catalyzer is to be carried on the carrier by the active metallic compound presoma, the loaded catalyst that is prepared from through oven dry, roasting.Reaction formula is as follows:
n，m，x＝2，3，4，5，6，7，8，9，10，11，12，13
For step (a), described metallic compound presoma is selected from least a in the muriate, bromide, iodide, nitrate, vitriol, carbonate, oxalate, acetate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr, La, and described silicon precursor is selected from SiCl
4, at least a in silicon unit acid esters solution or the silicon sol.
The concrete preparation process of first kind of catalyzer can for, with at least a in the muriate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr and La, bromide, iodide, nitrate, vitriol, carbonate, oxalate, the acetate is preparation of raw material corresponding metal salt brine solution, with SiCl
4, silicon unit acid esters solution is the silicon source, hydrolysis prepare silicon colloidal sol (also can directly adopt the commodity silicon sol); Aqueous metal salt is mixed with silicon sol, then oven dry, roasting.The catalyzer that adopts this method to be prepared from promptly is that metal simple-substance or the metallic compound by Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr or La is dispersed in SiO
2The middle mutually composite catalyst that forms of thing.
In the metallic compound presoma of first kind of catalyzer, the catalytic performance of the catalyzer of the muriate of Ru or Rh, bromide or nitrate and silicon precursor preparation is best, is the preferential metallic compound presoma of selecting of the present invention.
For the first kind of catalyzer that contains Ru, the quality percentage composition of Ru in catalyzer selects 0.05% to 2.00%, and the Ru content range is 0.10% to 1.40% preferably, and best Ru content range is 0.50% to 1.20%.For the first kind of catalyzer that contains Rh, the quality percentage composition of Rh in catalyzer selects 0.05% to 1.00%, and the Rh content range is 0.10% to 0.60% preferably, and best Rh content range is 0.30% to 0.50%.Maturing temperature in first kind of catalyst preparation process is chosen in 500 to 1200 ℃, and maturing temperature is 600 to 1000 ℃ preferably, and best catalyzer maturing temperature is 700 to 900 ℃.
Methane, HBr/H
2O and O
2Temperature of reaction on catalyzer is 400 to 800 ℃, and range of reaction temperature is at 560 to 680 ℃ preferably, and best temperature of reaction is at 620 to 660 ℃.
For step (b), at least a in muriate, bromide, iodide, nitrate, vitriol, carbonate, oxalate and the acetate that described active metallic compound presoma is Zn or Mg.
Described carrier is a kind of among molecular sieve HZSM-5, HY, H β, 3A, 4A, 5A or the 13X, preferred HZSM-5.HZSM-5 is as a kind of typical Lewis acid, and except bearing active ingredient, making the equally distributed function of active ingredient, it also bears acid catalysed effect to reaction.HY, H β, 3A, 4A, 5A or 13X etc. also are industrial molecular sieves with lewis acidity commonly used, and they have different pore size distributions and/or different lewis acidity intensity each other.
Described second kind of Preparation of catalysts method is pickling process, is specially, and the soluble salt of active metallic compound presoma Zn or Mg is made into the aqueous solution, the molecular sieve that adds requirement then, at room temperature soak for some time, oven dry then, corresponding catalyst is made in last roasting.
For the second kind of catalyzer that contains Zn, Zn mass percent calculating content range with ZnO in catalyzer is 0.10% to 20.0%, and the ZnO content scope is 0.50% to 15.0% preferably, and best content range is 1.0% to 10.0%.For the second kind of catalyzer that contains Mg, Mg mass percent calculating content range with MgO in catalyzer is 0.10% to 20.0%, and the MgO content range is 0.50% to 18.0% preferably, and best content range is 1.0% to 15.0%.
Bromo alkane CH
3Br and CH
2Br
2The temperature of reaction of taking off HBr system high-carbon hydrocarbon on catalyzer is 150 to 500 ℃, and temperature of reaction is at 200 to 400 ℃ preferably, and best temperature of reaction is at 240 to 300 ℃.
The 3rd purpose of the present invention provides a kind of new method for preparing methyl alcohol and dme.This method may further comprise the steps:
(a) on first kind of catalyzer (being catalyst A), methane and HBr/H
2O, oxygen reaction generate bromo alkane, and described first kind of catalyzer is the composite catalyst that is prepared from by mixed hydrolysis, oven dry, roasting by metallic compound presoma and silicon precursor; Reaction formula is as follows:
(b) CH of step (a) reaction generation
3Br and water react in the presence of two (being catalyzer C) of second kind of catalyzer and generate methyl alcohol and/or dme; Reaction formula is as follows:
For step (a), described metallic compound presoma is selected from least a in the muriate, bromide, iodide, nitrate, vitriol, carbonate, oxalate, acetate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr, La, and described silicon precursor is selected from SiCl
4, at least a in silicon unit acid esters solution or the silicon sol.
The concrete preparation process of first kind of catalyzer can for, with at least a in the muriate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr and La, bromide, iodide, nitrate, vitriol, carbonate, oxalate, the acetate is preparation of raw material corresponding metal salt brine solution, with SiCl
4, silicon unit acid esters solution is the silicon source, hydrolysis prepare silicon colloidal sol (also can directly adopt the commodity silicon sol); Aqueous metal salt is mixed with silicon sol, then oven dry, roasting.The catalyzer that adopts this method to be prepared from promptly is that metal simple-substance or the metallic compound by Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr or La is dispersed in SiO
2The middle mutually composite catalyst that forms of thing.
In the metallic compound presoma of first kind of catalyzer, the catalytic performance of the catalyzer of the muriate of Ru or Rh, bromide or nitrate and silicon precursor preparation is best, is the preferential metallic compound presoma of selecting of the present invention.
For the first kind of catalyzer that contains Ru, the quality percentage composition of Ru in catalyzer selects 0.05% to 2.00%, and the Ru content range is 0.10% to 1.40% preferably, and best Ru content range is 0.50% to 1.20%.For the first kind of catalyzer that contains Rh, the quality percentage composition of Rh in catalyzer selects 0.05% to 1.00%, and the Rh content range is 0.10% to 0.60% preferably, and best Rh content range is 0.30% to 0.50%.
Maturing temperature in first kind of catalyst preparation process is chosen in 500 to 1200 ℃, and maturing temperature is 600 to 1000 ℃ preferably, and best catalyzer maturing temperature is 700 to 900 ℃.
Methane, HBr/H
2O and O
2Temperature of reaction on catalyzer is 400 to 800 ℃, and range of reaction temperature is at 560 to 680 ℃ preferably, and best temperature of reaction is at 620 to 660 ℃.
For step (b), described second kind of catalyzer (two) is selected from RhCl
3, RuCl
3, FeCl
3Or CoCl
3In at least a.
CH wherein
3Br and H
2The mol ratio of O is 1: 50 to 10: 1, preferred 1: 10 to 1: 1, and most preferably 1: 8 to 1: 5.
The temperature of reaction of step (b) is 0～400 ℃, preferred 100～300 ℃, and further preferred 150～200 ℃, most preferably 180 ℃; Pressure is 0.50～100atm, preferred 10～50atm, optimum 20atm.
In the present invention, monobromethane and the reaction of water are than the CH described in the CN02813796.5 patent
3The Cl hydrolysis is easily with much efficient.In an embodiment of the present invention, the once through yield of methyl alcohol and dme can reach more than 90%, and the water that step (a) generates just in time runs out non-wastewater discharge.
Embodiment
(1) methane system monobromethane
Embodiment 1
Preparation of catalysts:
Weighing 6.300g oxalic acid solid is dissolved in the 100mL deionized water and obtains solution A, the RhCl of weighing metering quality 0.10224g
33H
2O is dissolved in the 50mL deionized water and obtains solution B, and weighing 34.5831g tetraethoxysilane liquid joins and forms the immiscible liquid of two-phase in the solution A.Solution became even water white homogeneous phase solution after 1h was stirred in sealing, add solution B, continue to stir 0.5h, then this mixing solutions is put into 120 ℃ of oven for drying to colloidal solid, subsequently this colloidal solid is inserted that the heat-up rate with 200 ℃/h is heated to 900 ℃ in the retort furnace, lower the temperature after keeping this temperature 10h, equitemperature takes out catalyzer after reducing to room temperature, be sized to the 20-60 order, finally obtain 0.40%Rh/SiO
2-900-10 catalyzer (the quality percentage composition of " 0.40% " expression respective metal, " 900-10 " represents 900 ℃ of catalyzer that roasting 10h makes, and be same under the marking method).
The test of catalyzer:
Adopt flow reactor of fixed bed, be reflected under the normal pressure and carry out.Reactor is that internal diameter is the quartz glass tube of 14mm, and catalyst levels 5.00g reacts in homemade tube furnace.Reaction gas is CH
4, O
2, N
2(interior mark is used), flow is respectively 20.0mL/min, 5.0mL/min, 5.0mL/min.Reaction solution is hydrobromic acid aqueous solution (HBr/H
2O), concentration is 〉=40wt%.Catalyzer begins to be warming up to 660 ℃ after reactant gases feeds 0.5h, during when temperature rises to more than 400 ℃, begin to feed HBr/H with 6.5mL/h speed
2O solution.Behind the stable reaction 2h, the component content of beginning sampling analysis tail gas is collected data.
Experimental result shows, methane conversion is 35.8%, product is mainly monobromethane, and the methenyl bromide of a spot of methylene bromide, carbon monoxide, carbonic acid gas and trace, tetrabromomethane (mass spectrum＜Agilent 6890N/5973N 〉) can detect its existence, but at chromatogram＜Agilent 6820N〉in can not accurately detect).Wherein the selectivity of monobromethane is 90.8%, and the selectivity of methylene bromide is 2.1%, and carbon monoxide selective is 5.8%, and carbon dioxide selectivity is 1.3%.
In above-mentioned catalyst preparation process, can be under different maturing temperatures different time of roasting to obtain catalyzer with different specific surface areas, can be preparation of raw material corresponding metal salt brine solution with the water-soluble salts such as muriate, bromide or nitrate of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr or La, also can use SiCl
4Wait other silicon unit acid esters to be raw material hydrolysis prepare silicon sol solution or directly to use the commodity silicon sol solution, this type of catalyzer that makes, all having shown after tested has catalytic activity to bromine oxidation of methane reaction, just transformation efficiency and selectivity are variant, do not change reaction product, embodiment 2-60 has only listed small portion catalyst experiment result.
Embodiment 2～6
Preparation of catalysts:
According to Preparation of catalysts method among the embodiment 1, use the RhCl of different concns
33H
2Obtain solution B in the O solution 50.0mL deionized water, wherein RhCl
33H
2The concentration of O solution is the conversion amount of required different mass mark Rh.Obtain each catalyzer shown in the table 1.
The test of catalyzer:
According to the test condition of catalyzer among the embodiment 1, under identical reaction conditions, react.Experimental result is listed in table 1.
The experimental result of table 1 embodiment 1～6 (influence of Rh content)
Embodiment 7～12
Preparation of catalysts:
According to Preparation of catalysts method among the embodiment 1, in retort furnace, use different maturing temperature and time.Finally obtain having the catalyzer of different specific surface areas, i.e. the catalyzer of each shown in the table 2.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, under identical reaction conditions, react.Experimental result is listed in table 2.
(influence of maturing temperature in the catalyst preparation process, catalyzer is formed 0.40%Rh/SiO to the experimental result of table 2 embodiment 1, embodiment 7～12
2)
Embodiment 13～16
Preparation of catalysts:
Obtain 0.40%Rh/SiO according to Preparation of catalysts method among the embodiment 1
2-900-10 catalyzer.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, under different temperature of reaction, react.Experimental result is listed in table 3.
The experimental result of table 3 embodiment 1, embodiment 13～16 (influence of temperature of reaction)
Embodiment 17～22
Preparation of catalysts:
Obtain 0.40%Rh/SiO according to Preparation of catalysts method among the embodiment 1
2-900-10 catalyzer.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, at different HBr/H
2React under the charging situation of O solution.Experimental result is listed in table 4.
The experimental result of table 4 embodiment 1, embodiment 17～22 (influence of temperature of reaction)
Embodiment 23～25
Preparation of catalysts:
Obtain 0.40%Rh/SiO according to Preparation of catalysts method among the embodiment 1
2-900-10 catalyzer.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, catalyst levels is 10.00g, reaction feed gas CH
4, O
2, N
2The flow of (interior mark is used) is respectively 40.0mL/min, 10.0mL/min, 10.0mL/min, at different HBr/H
2React under the charging situation of O solution.Experimental result is listed in table 5.
The experimental result of table 5 embodiment 23～25 (different HBr/H during catalyst levels 10.00g
2The influence of O charging)
Embodiment 26～28
Preparation of catalysts:
Obtain 0.40%Rh/SiO according to Preparation of catalysts method among the embodiment 1
2-900-10 catalyzer.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, catalyst levels is 10.00g, CH
4And N
2Flow is 40.0mL/min and 10.0mL/min, HBr/H
2O solution feed speed is 10.0mL/h.O
2Flow is respectively 9.0mL/min (embodiment 26), 8.0mL/min (embodiment 27), 7.0mL/min (embodiment 28) reacts.Experimental result is listed in table 6.
The experimental result of table 6 embodiment 25～28 (different CH
4/ O
2The influence of charging)
Embodiment 29～39
Preparation of catalysts:
According to Preparation of catalysts method among the embodiment 1, at the RhCl of dissolving same amount
33H
2On the basis of O, dissolve the CuNO of 2.0%Cu mass percent corresponding measurement quality 0.76034g simultaneously
33H
2O makes solution B, obtains catalyzer 2.0%Cu0.40%Rh/SiO
2-900-10 (embodiment 29).Preparation contains other metals of 2.0% massfraction and all kinds of catalyzer of 0.4%Rh massfraction (embodiment 30～40) after the same method, and these catalyzer can be referred to as Rh based bi-component catalyzer.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, under identical reaction conditions, to react, experimental result is listed in table 7.
The experimental result of table 7 embodiment 1, embodiment 29～39
Embodiment 41～46
Preparation of catalysts:
Obtain 0.40%Rh/SiO according to Preparation of catalysts method among the embodiment 11
2-700-10 catalyzer.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 1, reaction feed gas CH
4, O
2, N
2The flow of (interior mark is used) is respectively 20.0mL/min, 10.0mL/min, 5.0mL/min, HBr/H
2The feeding rate of O solution is 8.0mL/h, reacts under different temperature of reaction.Experimental result is listed in table 8.
The experimental result of table 8 embodiment 41～46 (influence of temperature of reaction)
Embodiment 47～48
Preparation of catalysts:
Weighing 6.300g oxalic acid solid is dissolved in the 100mL deionized water and obtains solution A, weighing 0.10%Pt massfraction measures quality 0.01727g chloride monohydrate accordingly and is dissolved in the 50mL deionized water and obtains solution B, and weighing 34.6872g tetraethoxysilane liquid joins and forms the immiscible liquid of two-phase in the solution A.Solution became even water white homogeneous phase solution after 1h was stirred in sealing, add solution B, continue to stir 0.5h, then this mixing solutions is put into 120 ℃ of oven for drying to colloidal solid, subsequently this colloidal solid is inserted that the heat-up rate with 200 ℃/h is heated to 900 ℃ in the retort furnace, keep this temperature 10h, equitemperature takes out catalyzer after reducing to room temperature, be sized to the 20-60 order, finally obtain catalyzer 0.10%Pt/SiO
2-900-10 (embodiment 47).Same method makes catalyzer 0.10%Pd/SiO
2-1000-5 (embodiment 48).
The test of catalyzer:
Adopt flow reactor of fixed bed, be reflected under the normal pressure and carry out.Reactor is that internal diameter is the silica tube of 14mm, and catalyst levels 5.00g reacts in homemade tube furnace.Reaction gas is CH
4, O
2, N
2(interior mark is used), flow is respectively 20.0mL/min, 5.0mL/min, 5.0mL/min.Reaction liquid is hydrobromic acid aqueous solution (HBr/H
2O), concentration is 〉=40wt%.Catalyzer begins to be warming up to 660 ℃ after reactant gases feeds 0.5h, during when temperature rises to more than 400 ℃, begin to feed HBr/H with 6.5mL/h speed
2O solution.Behind the stable reaction 2h, the component content of beginning sampling analysis tail gas is collected data.Experimental result is listed in table 9.
The experimental result of table 9 embodiment 47～47 (containing the influence of Pt, Pd in the catalyzer)
Embodiment 49～58
Preparation of catalysts:
Weighing 6.300g oxalic acid solid is dissolved in the 100mL deionized water and obtains solution A, and weighing 0.10%Ru mass percent measures quality 0.02587gRuCl accordingly
33H
2O is dissolved in the 50mL deionized water and obtains solution B, and weighing 34.583g tetraethoxysilane liquid joins and forms the immiscible liquid of two-phase in the solution A.Solution became even water white homogeneous phase solution after 1h was stirred in sealing, add solution B, continue to stir 0.5h, then this mixing solutions is put into 120 ℃ of oven for drying to colloidal solid, subsequently this colloidal solid is inserted that the heat-up rate with 200 ℃/h is heated to 900 ℃ in the retort furnace, keep this temperature 10h, equitemperature takes out catalyzer after reducing to room temperature, be sized to the 20-60 order, finally obtain 0.10%Ru/SiO
2-900-10 catalyzer (embodiment 49).Prepare the catalyzer of different Ru quality percentage compositions, i.e. each catalyzer shown in the embodiment shown in the table 9 49～58 with same method.
The test of catalyzer:
Adopt flow reactor of fixed bed, be reflected under the normal pressure and carry out.Reactor is that internal diameter is the silica tube of 14mm, and catalyst levels 5.00g reacts in homemade tube furnace.Reaction gas is CH
4, O
2, N
2(interior mark is used), flow is respectively 20.0mL/min, 5.0mL/min, 5.0mL/min.Reaction liquid is hydrobromic acid aqueous solution (HBr/H
2O), concentration is 〉=40wt%.Catalyzer begins to be warming up to 660 ℃ after reactant gases feeds 0.5h, during when temperature rises to more than 400 ℃, begin to feed HBr/H with 6.5mL/h speed
2O solution.Behind the stable reaction 2h, the component content of beginning sampling analysis tail gas is collected data.
Embodiment 59～60
The comparative example of this group embodiment for adopting sol-gel method and pickling process to prepare catalyzer respectively.
Preparation of catalysts:
Weighing 6.300g oxalic acid solid is dissolved in the 100mL deionized water and obtains solution A, and weighing 34.5831g tetraethoxysilane liquid joins and forms the immiscible liquid of two-phase in the solution A.Solution became even water white homogeneous phase solution after 1h was stirred in sealing, then this mixing solutions is put into 120 ℃ of oven for drying to colloidal solid, subsequently this colloidal solid is inserted that the heat-up rate with 200 ℃/h is heated to 900 ℃ in the retort furnace, keep this temperature 10h, equitemperature is reduced to back below 300 ℃ and is taken out catalyzer, be sized to the 20-60 order, finally obtain support of the catalyst SiO
2
The corresponding RuCl of the different 0.1%Ru massfractions of weighing load quality mark
33H
2O metering quality 0.02587g is dissolved in the 50mL deionized water and obtains solution B.Take by weighing the SiO that 10.0g has prepared
2Carrier joins and stirs 0.5h in the solution B, leaves standstill after 3h waits this solution to be put into 120 ℃ of oven for drying, subsequently sample is inserted in the retort furnace constant temperature 8h under 450 ℃ of temperature, and equitemperature takes out catalyzer after reducing to room temperature, finally obtains catalyzer 0.1%Ru/SiO
2-900-10-IM (embodiment 59).Produce 0.1%Rh/SiO with same preparation method
2-900-10-IM (embodiment 60).
The test of catalyzer:
Adopt flow reactor of fixed bed, be reflected under the normal pressure and carry out.Reactor is that internal diameter is the silica tube of 14mm, and catalyst levels 5.00g reacts in homemade tube furnace.Reaction gas is CH
4, O
2, flow is respectively 20.0mL/min, 5.0mL/min.Reaction liquid is hydrobromic acid aqueous solution (HBr/H
2O), concentration is 〉=40wt%.Catalyzer begins to be warming up to 660 ℃ after reactant gases feeds 0.5h, during when temperature rises to more than 400 ℃, begin to feed HBr/H with 6.0mL/h speed
2O solution.Behind the stable reaction 2h, the component content of beginning sampling analysis tail gas is collected data.Experimental result is listed in table 10.
The experimental result of table 10 embodiment 49～60 (influence that contains the Ru catalyzer of sol-gel method and immersion process for preparing)
(2) monobromethane system high-carbon hydrocarbon
Embodiment 61
Preparation of catalysts:
Weighing loading ZnO massfraction is 5.0% corresponding Zn (NO
3)
26H
2O 2.8856g is dissolved in the 100mL deionized water and obtains settled solution with the glass stick stirring, the HZSM-5 carrier of weighing 15.00g joins in the solution, 40-60min is stirred in sealing, leave standstill and soak 90 ℃ of water-bath 4h behind the 12h, put into 120 ℃ of oven for drying again, subsequently sample is inserted in the retort furnace at 450 ℃ of following constant temperature 8h, equitemperature takes out catalyzer after reducing to room temperature, compressing tablet is sized to the 20-60 order and promptly obtains catalyzer 5.0%Zn/HZSM-5-450-8 (" 5.0% " expression load respective metal oxide content, " 450-8 " represents 450 ℃ of catalyzer that roasting 8h makes, and be same under the marking method).
The test of catalyzer:
Adopt fixed-bed reactor, be reflected under the normal pressure and carry out.Reactor is the Glass tubing of internal diameter 14mm, and catalyst levels is 8.00g, reacts in the aluminum heating jacket.Utilize the N of flow for 5.0mL/min
2As interior mark and carrier gas, reaction gas is CH
3Br, flow are 7.76mL/min.Catalyzer is at N
2Begin to be warming up to 300 ℃ after feeding 0.5h.The component content of beginning sampling analysis tail gas is collected data behind the stable reaction 2h.
Experiment draws: the transformation efficiency of monobromethane is 99.63%, and gas-phase product is C
2-C
5Alkane, alkene and remaining monobromethane; Liquid product is mainly C
5-C
13Alkane, alkene and aromatic hydrocarbons.
The active metallic compound presoma also can be with water-soluble salts such as the muriate of Zn or Mg and bromide, the deallocation system aqueous solution.
Embodiment 62～66
Preparation of catalysts:
Obtain the 5.0%Zn/HZSM-5-450-8 catalyzer according to Preparation of catalysts method among the embodiment 61.
The test of catalyzer:
According to the testing method of catalyzer among the embodiment 61, under different temperature of reaction, react.Experimental result is listed in table 11.
The experimental result of table 11 embodiment 61～66 (influence of temperature of reaction)
Embodiment 67～72
Preparation of catalysts:
According to Preparation of catalysts method among the embodiment 61, use the Zn (NO of different amounts
3)
26H
2The solution of O and the preparation of 100mL deionized water, wherein Zn (NO
3)
26H
2The concentration of O solution is the conversion amount of required load different mass mark ZnO.Finally obtain each catalyzer shown in the table 12.
The test of catalyzer:
According to the test condition of catalyzer among the embodiment 61, catalyzer at 300 ℃ of activation 4h, reacts in the time of 260 ℃ earlier then.Experimental result is listed in table 12.
The experimental result of table 12 embodiment 63,66～72 (influence of ZnO charge capacity)
Embodiment 73～78
Preparation of catalysts:
According to Preparation of catalysts method among the embodiment 61, use different molecular sieve carrier (HY, H β, 3A, 4A, 5A, 13X) to prepare each catalyzer shown in the table 13.
The test of catalyzer:
According to the test condition of catalyzer among the embodiment 61, catalyzer at 300 ℃ of activation 4h, reacts in the time of 260 ℃ earlier then.Experimental result is listed in table 13.
The experimental result of table 13 embodiment 73～78 (influence of different carriers)
Embodiment 79～85
Preparation of catalysts:
Corresponding Mg (the NO of weighing load different Mg O massfraction
3)
26H
2O metering quality is dissolved in the 100.00mL deionized water and obtains settled solution with the glass stick stirring, the HZSM-5 of weighing 15.00g (Si/Al=360) carrier joins in the solution, 40-60min is stirred in sealing, leave standstill and soak 90 ℃ of water-bath 4h behind the 12h, put into 120 ℃ of oven for drying again, subsequently sample is inserted in the retort furnace at 450 ℃ of following constant temperature 8h, equitemperature takes out catalyzer after reducing to room temperature, and compressing tablet is sized to the 20-60 order and promptly obtains the catalyzer shown in the table 14.
The test of catalyzer:
According to the test condition of catalyzer among the embodiment 61, catalyzer at 300 ℃ of activation 4h, reacts in the time of 260 ℃ earlier then.Experimental result is listed in table 14.
The experimental result of table 14 embodiment 79～85 (influence of MgO charge capacity)
(3) monobromethane prepares methyl alcohol, dme
Embodiment 86
In reaction, use step autoclave reactor.Inner liner of reaction kettle has polytetrafluoroethylmaterial material, and the useful volume of reactor is 1.60mL, is placed with a little stirring magneton in the still.The distilled water that in reactor, adds 0.40mL, the RuCl of 18.00mg
3CH with 0.50g
3Br.With after the autoclave sealing, reaction (under the magnetic stirrer condition) is 6 hours under 180 ℃, 20atm.Reaction makes temperature of reaction kettle drop to room temperature after finishing, and opens reactor, analyzes the composition of liquid.CH
3The transformation efficiency of Br is 60.5%, and the selectivity of product dme and methyl alcohol is respectively 43.7% and 56.2%.
Embodiment 87～89
CH
3Br is 0.50g, changes CH
3The amount of Br.Test-results is listed in table 15.
The different CH of table 15
3Br/H
2The O mol ratio is to the influence of test-results
Reaction conditions: RuCl
318.00mg, t=6h, T=180 ℃, other is identical with embodiment 86.
Embodiment 90～94
CH
3Br is 0.50g, CH
3Br is 0.70g, changes the reaction times.Test-results is listed in table 16.
Table 16 reaction times is to the influence of test-results
Reaction conditions: RuCl
318.00mg T=180 ℃, other is identical with embodiment 86.
Embodiment 95～98
CH
3Br is 0.50g, CH
3Br is 0.70g, changes temperature of reaction.Test-results is listed in table 17.
Table 17 temperature of reaction is to the influence of test-results
Reaction conditions: RuCl
318.00mg other is identical with embodiment 86.
(4) methane prepares the cascade reaction of high-carbon hydrocarbon or methyl alcohol and dme
Embodiment 99: the two-stage series connection reaction of preparation high-carbon hydrocarbon
Prepare in the monobromethane reaction at bromine oxidation of methane, adopt flow reactor of fixed bed, be reflected under the normal pressure and carry out.Reactor is that internal diameter is the quartz glass tube of 14mm, and catalyzer is that mass percent is 0.4% Rh/SiO
2, catalyst levels 5.00g, specific surface area of catalyst are 1.89m
2/ g.In tube furnace, react.Reaction gas is CH
4, O
2, N
2(interior mark usefulness, promptly by stratographic analysis in order to accurate calculating methane conversion), flow is respectively 20.0mL/min, 5.0mL/min, 5.0mL/min.Reaction solution hydrobromic acid aqueous solution (HBr/H
2O, concentration for 〉=40wt%) flow is 6.5mL/h.Catalyzer begins to be warming up to 660 ℃ after reactant gases feeds 0.5h, during when temperature rises to more than 400 ℃, begin to feed HBr/H with 6.5mL/h speed
2O solution.
The mix products (comprising methane, monobromethane, methylene bromide, carbon monoxide and carbonic acid gas) that said process is produced carries out second stage reaction under catalyst action, catalyzer is 3.0%Mg/HZSM-5-450-8.Catalyzer at 300 ℃ of activation 4h, reacts in the time of 260 ℃ earlier then.By gas-chromatography the content of the second stage each composition of reaction product is analyzed behind the stable reaction 2h, calculating two-stage reaction series connection back methane conversion is 35.2%, and the selectivity of product medium high carbon hydrocarbon, carbon monoxide and carbonic acid gas is respectively 93.2%, 5.6% and 1.2%.
Embodiment 100: the two-stage series connection reaction of preparation methyl alcohol and dme
Prepare in the monobromethane reaction at bromine oxidation of methane, adopt flow reactor of fixed bed, be reflected under the normal pressure and carry out.Reactor is that internal diameter is the quartz glass tube of 14mm, and catalyzer is that mass percent is 0.4% Rh/SiO
2, catalyst levels 5.00g, specific surface area of catalyst are 1.89m
2/ g.In tube furnace, react.Reaction gas is CH
4, O
2, N
2(interior mark usefulness, promptly by stratographic analysis in order to accurate calculating methane conversion), flow is respectively 20.0mL/min, 5.0mL/min, 5.0mL/min.Reaction solution hydrobromic acid aqueous solution (HBr/H
2O, concentration for 〉=40wt%) flow is 6.5mL/h.Catalyzer begins to be warming up to 660 ℃ after reactant gases feeds 0.5h, during when temperature rises to more than 400 ℃, begin to feed HBr/H with 6.5mL/h speed
2O solution.
Monobromethane in the mix products of said process generation, methylene bromide through after the condensation separation, are got 0.50g and 0.70g water and carry out second stage reaction under catalyst action, and catalyzer is the RhCl of 0.012g
3, temperature of reaction is 180 ℃, and pressure is 20atm, and the reaction times is 8h.By gas-chromatography the content of the second stage each composition of reaction product is analyzed, calculating two-stage reaction series connection back methane conversion is 35.6%, and the transformation efficiency of dme, methyl alcohol, monobromethane, methylene bromide, carbon monoxide and carbonic acid gas is respectively 64.5%, 25.6%, 1.5%, 1.0%, 5.9% and 1.5% in the product.
Claims (7)
1. method for preparing bromo alkane, on first kind of catalyzer, methane and HBr/H
2O, oxygen reaction generate bromo alkane, and described first kind of catalyzer is the composite catalyst that is prepared from by mixed hydrolysis, oven dry, roasting by metallic compound presoma and silicon precursor.
2. according to the described method of claim 1, it is characterized in that described metallic compound presoma is selected from muriate, bromide, iodide, nitrate, vitriol, carbonate, oxalate, acetate at least a of Ru, Rh, Pd, Pt, Ni, Cu, Zn, Ag, Ce, V, W, Cd, Mo, Mn, Cr, La.
3. according to the described method of claim 1, it is characterized in that described silicon precursor is selected from least a in SiCl4, silicon unit's acid esters or the silicon sol solution.
4. one kind prepares C
3～C
13The method of high-carbon hydrocarbon, may further comprise the steps,
(a) on first kind of catalyzer, methane and HBr/H
2O, oxygen reaction generate bromo alkane, and described first kind of catalyzer is the composite catalyst that is prepared from by mixed hydrolysis, oven dry, roasting by metallic compound presoma and silicon precursor; With
(b) bromo alkane reacts on second kind of catalyzer and generates C
3To C
13High-carbon hydrocarbon and HBr, the HBr of generation utilizes as the circulating reaction medium, described second kind of catalyzer is to be carried on the carrier by the active metallic compound presoma, the loaded catalyst that is prepared from through oven dry, roasting.
5. method according to claim 4, it is characterized in that the active metallic compound presoma in described (b) step is selected from least a in muriate, bromide, iodide, nitrate, vitriol, carbonate, oxalate and the acetate of Zn or Mg.
6. method according to claim 4 is characterized in that, the carrier in described (b) step is at least a in HZSM-5, HY, H β, 3A, 4A, 5A or the 13X molecular sieve.
7. a method that is used to prepare methyl alcohol and dme may further comprise the steps,
(a) on first kind of catalyzer, methane and HBr/H
2O, oxygen reaction generate bromo alkane, and described first kind of catalyzer is the composite catalyst that is prepared from by mixed hydrolysis, oven dry, roasting by metallic compound presoma and silicon precursor; With
(b) hydrobromic ether is gone up with the water reaction at second kind of catalyzer (two) and is generated methyl alcohol, dme and HBr, and the HBr of generation is as the utilization of circulating reaction medium, and described second kind of catalyzer (two) is selected from RhCl
3, RuCl
3, FeCl
3Or CoCl
3In at least a.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810121558A CN101723795A (en) | 2008-10-13 | 2008-10-13 | Method for preparing methyl bromide, high-carbon hydrocarbon, methyl alcohol and dimethyl ether by methane |
| PCT/CN2009/074382 WO2010043161A1 (en) | 2008-10-13 | 2009-10-10 | Methods for preparing methyl bromide, higher hydrocarbon, methanol and dimethyl ether from methane |
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| CN200810121558A CN101723795A (en) | 2008-10-13 | 2008-10-13 | Method for preparing methyl bromide, high-carbon hydrocarbon, methyl alcohol and dimethyl ether by methane |
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| CN101723795A true CN101723795A (en) | 2010-06-09 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105709751A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from bromomethane, and preparation method and application thereof |
| CN105709750A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Copper pillared montmorillonite catalyst, and preparation method and application thereof |
| CN106146239A (en) * | 2016-07-07 | 2016-11-23 | 浙江大学 | A kind of method being prepared aromatic hydrocarbons by methane conversion continuously |
| WO2020000170A1 (en) * | 2018-06-26 | 2020-01-02 | Rhodia Operations | Metal-iodide catalytic system for direct etherification from aldehydes and/or ketones |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980096B (en) * | 2014-05-06 | 2016-02-10 | 南通大学 | Extractive distillation with salt is separated the method for methyl tertiary butyl ether and methylene dichloride |
| CN104492411B (en) * | 2014-12-16 | 2016-06-29 | 华东师范大学 | A kind of ZnO/SiO2-γ-Al2O3Catalyzing hydrolysis Celfume prepares the method for methanol and dimethyl ether |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6452058B1 (en) * | 2001-05-21 | 2002-09-17 | Dow Global Technologies Inc. | Oxidative halogenation of C1 hydrocarbons to halogenated C1 hydrocarbons and integrated processes related thereto |
| CN100425588C (en) * | 2004-01-17 | 2008-10-15 | 湖南大学 | Novel flow chart for preparing acetic acid, methanol and dimethyl ether from methane by non synthetic gas process |
| JP2007244975A (en) * | 2006-03-15 | 2007-09-27 | Ryukoku Univ | Automotive exhaust gas treatment catalyst and manufacturing method thereof |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
| CN101284232B (en) * | 2007-04-13 | 2013-01-16 | 微宏动力系统（湖州）有限公司 | Bromomethane prepared by bromine oxidation of methane and catalyst for conversing the bromomethane into hydrocarbon |
-
2008
- 2008-10-13 CN CN200810121558A patent/CN101723795A/en active Pending
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- 2009-10-10 WO PCT/CN2009/074382 patent/WO2010043161A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105709751A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from bromomethane, and preparation method and application thereof |
| CN105709750A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Copper pillared montmorillonite catalyst, and preparation method and application thereof |
| CN105709750B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of copper pillared montmorillonite catalyst and its preparation method and application |
| CN106146239A (en) * | 2016-07-07 | 2016-11-23 | 浙江大学 | A kind of method being prepared aromatic hydrocarbons by methane conversion continuously |
| CN106146239B (en) * | 2016-07-07 | 2018-12-11 | 浙江大学 | A method of by methane, continuously conversion prepares aromatic hydrocarbons |
| WO2020000170A1 (en) * | 2018-06-26 | 2020-01-02 | Rhodia Operations | Metal-iodide catalytic system for direct etherification from aldehydes and/or ketones |
| CN112930334A (en) * | 2018-06-26 | 2021-06-08 | 罗地亚经营管理公司 | Metal-iodide catalytic system for direct etherification from aldehydes and/or ketones |
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| Publication number | Publication date |
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| WO2010043161A1 (en) | 2010-04-22 |
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