CN115109608B - 一种制备低芳烃含量液体燃料的方法 - Google Patents
一种制备低芳烃含量液体燃料的方法 Download PDFInfo
- Publication number
- CN115109608B CN115109608B CN202210558078.XA CN202210558078A CN115109608B CN 115109608 B CN115109608 B CN 115109608B CN 202210558078 A CN202210558078 A CN 202210558078A CN 115109608 B CN115109608 B CN 115109608B
- Authority
- CN
- China
- Prior art keywords
- component
- catalyst
- liquid fuel
- selectivity
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 239000004480 active ingredient Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003245 coal Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910002515 CoAl Inorganic materials 0.000 claims description 4
- 229910015372 FeAl Inorganic materials 0.000 claims description 4
- 229910016583 MnAl Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000523 sample Substances 0.000 claims description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 2
- 229910018557 Si O Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- LRMLWYXJORUTBG-UHFFFAOYSA-N dimethylphosphorylmethane Chemical compound CP(C)(C)=O LRMLWYXJORUTBG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003502 gasoline Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000006690 co-activation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010496 migratory insertion reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
-
- 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
- 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
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明属于合成气直接制备液体燃料,具体涉及一种制备低芳烃含量液体燃料的方法。其以合成气为反应原料,在固定床或移动床上进行转化反应,所述催化剂为复合催化剂,由组分I和组II以机械混合方式复合在一起,组分I的活性成份为金属氧化物,组分II为磷改性的MWW分子筛;组分I中的活性成分与组分II中活性成分的重量比为0.1‑20。本发明反应过程具有很高的产品收率和选择性,由C5‑C11组成的液体燃料选择性可以达到50‑80%,C5‑C11中芳烃选择性低于35%,同时C5‑C11产物的异构正构比可达10‑70,C5‑C11异构烃中多支链产物比例可达30‑60%,具有很好的应用前景。
Description
技术领域
本发明属于合成气制备液体燃料,具体涉及一种制备低芳烃含量液体燃料的方法。
背景技术
随着经济的发展和生活水平的提高,液体燃料和化学品的需求量也逐年急剧上升。目前汽油生产主要由重石脑油的催化重整得到。随着全球石油资源日渐消耗和居高不下的原油价格,尤其对石油资源匮乏的我国而言,每年超过近60%的石油消耗量依赖进口,寻求一种可以替代的工艺路线,开发利用由煤、生物质等非油基碳资源制备液体燃料的方法,具有重要的社会意义和战略意义。
我国煤炭资源丰富,以煤炭为原料,经过气化得到合成气(即CO和H2的混合气),将合成气转化成甲醇,甲醇再经二甲醚制取汽油的简介技术路线已经成熟,并步入工业化,该路线为煤、天然气等碳资源制液体燃料提供了一条重要的新路线。然而,若能实现合成气直接转化,而不经过甲醇合成和甲醇脱水制二甲醚的直接路线,不仅可以简化工艺流程,而且可以减少单元操作,降低投资和能耗。传统的费托路径可以实现合成气直接转化制备液体燃料,然而受其反应机理的限制,CO和H2分子在催化剂表面发生解离吸附,生成表面C原子和O原子,C原子和O原子与吸附在催化剂表面的氢发生反应,形成亚甲基(CH2)中间体,同时放出水分子。亚甲基中间体通过迁移插入反应,在催化剂表面进行自由聚合,生成含不同碳原子数(从一到三十,有时甚至到上百个碳原子)的烃类产物。整个反应烃类产物碳原子数分布广,目标产物的选择性低,如汽油的选择性低于50%。使用氧化物+分子筛组成双功能催化剂可以将CO活化与C-C偶联分开在两个活性中心上进行从而打破传统费托中产物选择性的限制,可能获得高汽油选择性。但是一些适合合成汽油馏分的分子筛,例如最为常用的ZSM-5分子筛,容易生成芳烃,导致生产的汽油中芳烃含量过高,不利于环保;另一方面,产品中异构烃异构化程度不高,使得辛烷值不高。因此迫切需要开发适用于生成高异构汽油选择性,同时汽油中芳烃选择性较低的,高活性的合成气制汽油馏分(C5-C11)液体燃料的催化剂。
发明内容
针对上述问题,本发明提供了一种制备低芳烃含量液体燃料的方法,采用的催化剂组分I和组分II,其中组分II经过磷改性后提高了汽油的选择性,大大降低了汽油中芳烃的含量,同时生成的汽油段异构烃中的多支链烃占比大幅提高。
为了实现上述目的,本发明的技术方案如下:
本发明提供一种制备低芳烃含量液体燃料的方法,以合成气为反应原料,合成气为H2/CO混合气,在催化剂的作用下,在固定床或移动床上进行转化反应制得低芳烃含量液体燃料;所述催化剂包括组分I和组分II,所述组分I和组分II以机械混合方式复合在一起;所述组分Ⅰ的活性成份为金属氧化物,组分II为磷改性的MWW分子筛。
基于以上技术方案,优选的,所述金属氧化物为MnOx、MnCryO(x+1.5y)、MnAlyO(x+1.5y)、MnZryO(x+2y)、MnInyO(x+1.5y)、ZnO、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、In2O3、InyAlzMnO(x+1.5y+1.5z)、InyGazMnO(x+1.5y+1.5z)中的一种或二种以上,其中x为1~3.5,y为0.1~10,z为0.1~10;所述MnOx、ZnO、In2O3的比表面积是1-100m2/g;所述MnCryO(x+1.5y)、MnAlyO(x+1.5y)、MnZryO(x+2y)、MnInyO(x+1.5y)、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、InyAlzMnO(x+1.5y+1.5z)、InyGazMnO(x+1.5y+1.5z)的比表面积是5-150m2/g。
基于以上技术方案,优选的,所述组分Ⅱ中,磷改性的MWW分子筛为具有MWW拓扑结构的分子筛,骨架元素组成为Si-O、Si-O-Al、Si-O-Fe、Si-O-Ga、Si-O-B中的一种或二种以上;所使用的磷源包括磷酸铵、磷酸氢铵、磷酸二氢铵、磷酸、三甲基膦、三甲基氧膦中的一种或二种以上,磷含量为a,0<a≤20wt.%。
基于以上技术方案,优选的,所述磷改性MWW分子筛具有中强酸性,中强酸位点的量是0.05-0.5mol/kg,优选为0.05-0.4mol/kg,更优选为0.05-0.3mol/kg;其中,中强酸对应NH3-TPD脱附峰的峰顶对应的温度范围为200-500℃;用丙酮作为探针分子,13C-NMR化学位移位于210-220ppm范围。
基于以上技术方案,优选的,所述组分Ⅰ中的活性成份与组分II的重量比为0.1-20,优选为0.3-5。
基于以上技术方案,优选的,所述组分I中还包括分散剂,所述金属氧化物分散于分散剂中;所述分散剂为Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3、活性炭、石墨烯、碳纳米管中的一种或二种以上。
基于以上技术方案,优选的,所述组分Ⅰ中,分散剂的含量在0.05-90wt%,其余为金属氧化物。
基于以上技术方案,优选的,所述合成气H2/CO摩尔比为0.2-3.5,优选为0.3-2.5;反应压力为0.5-10MPa,优选为1-8MPa;反应温度为300-600℃,优选为320-450℃;反应空速为300-12000h-1,优选为1000-9000h-1。
基于以上技术方案,优选的,反应过程中,液体燃料的选择性可达50-80%,优选为65-80%,C5-C11中芳烃选择性低于35%,优选为低于30%,C5-C11异构烃中多支链产物比例可达30-60%,同时副产物甲烷选择性低于15%,优选为低于10%。
本发明具有如下有益效果:
1、本发明与传统的费托合成制液体燃料不同,实现了一步直接将合成气高效转化为液体燃料,同时大幅度降低了液体燃料中芳烃的选择性。
2、本发明产物中液体燃料选择性高,可达到50-80%,产物不需深冷便可分离,大大降低了分离的能耗与成本。
3、本发明中组分Ⅱ经过磷修饰之后,分子筛的上烯烃加氢、长链烃的裂解等副反应得到有效地抑制,大大提高了液体燃料的选择性。
4、本发明催化剂中组分Ⅱ的作用一方面是通过与组分Ⅰ进行耦合,将组分Ⅰ产生的活泼气相中间体进一步转化获得液体燃料,由于组分Ⅱ对串联反应平衡拉动的作用可以促进组分Ⅰ对合成气的活化转化进而提高转化率;另一方面本发明使用的组分Ⅱ中MWW分子筛的独特性质,可以高选择性的获得更多的液体燃料产物,同时大大降低液体燃料中芳烃含量,并大大提高了液体燃料中多支链异构烃的含量。
5、单独分别使用本发明中所述的组分Ⅰ或组分Ⅱ完全不能实现本发明的功能,例如单独使用组分Ⅰ产物中甲烷选择性非常高,且转化率很低,而单独使用组分Ⅱ几乎不能活化转化合成气,只有组分Ⅰ与组分Ⅱ协同催化才能实现高效的合成气转化,并获得优异的选择性。这是由于组分I可以活化合成气生成特定的活泼气相中间体,中间体经由气相扩散到组分Ⅱ的孔道内,由于本发明选择的MWW分子筛的独特性质,可以有效的将组分Ⅰ产生的活泼气相中间体进一步活化转化为液体燃料,同时保持较低的芳烃选择性(<35%)和较高的多支链异构烃比例。该分子筛有别于其他制液体燃料的分子筛,关键在于本分子筛能够高选择性的生成多支链异构烃(二甲基和三甲基异构烃),异构烃中多支链烃比例最高可达50%。因此组分Ⅱ的特殊结构使得产物具有特殊的选择性。
6、本发明中的复合催化剂的制备过程简单、条件温和;且反应过程具有很高的产品收率和选择性,C5-C11液体燃料的选择性可以达到50-80%,同时C5-C11中芳烃选择性低于35%,C5-C11产物的异构正构比最高可达70,C5-C11异构烃中多支链产物比例最高可达60%。
具体实施方式
下面通过实施例对本发明做进一步阐述,但是本发明的权利要求范围不受这些实施例的限制。同时,实施例只是给出了实现此目的的部分条件,但并不意味着必须满足这些条件才可以达到此目的。
样品的比表面积可以通过氮气或氩气物理吸附的方法进行测试。
一、催化剂组分Ⅰ的制备
本发明催化剂组分Ⅰ中金属氧化物可以通过购买市售的高比表面积的金属氧化物获得,也可以通过下述几种方法获得:
(1)共沉淀法制备催化剂组分ZnCrxAlzOy采用硝酸锌、硝酸铝、硝酸铬为前驱体(Zn/Cr/Al摩尔比为3.5:1:2,Zn为50mM),与碳酸铵,在室温下于水中混匀(其中碳酸铵作为沉淀剂,碳酸铵过量或者铵离子与金属离子的总摩尔比为1:1);将上述混合液90℃陈化20小时,然后取出洗涤、过滤和干燥,所得的固体在500℃空气气氛下焙烧,获得ZnCrAl金属氧化物,记为OX-1。
经检测,所得的ZnCrAl金属氧化物的比表面积为115m2/g。
(2)共沉淀法制备催化剂组分ZnAlxOy
采用硝酸锌、硝酸铝为前驱体(Zn/Al摩尔比为1/2,Zn为50mM),与碳酸氢铵,在室温下于水中混匀(其中碳酸氢铵作为沉淀剂,碳酸铵过量或者铵离子与金属离子的摩尔比为2:1);将上述混合液90℃陈化5小时,然后取出洗涤、过滤和干燥,所得的固体在500℃空气气氛下焙烧,获得ZnAl金属氧化物,记为OX-2。
经检测,所得的ZnAl金属氧化物的比表面积为150m2/g。
二、催化剂组分II(磷改性的MWW分子筛)的制备
本发明所描述的磷含量测试包括了ICP-OES、XRF等方法。但含量的测试方法不限于上述测试方法。
本发明所述的分子筛可以是商品的符合本发明的磷改性的MWW分子筛,也可以是自行合成的分子筛,这里以通过水热合成法制备的分子筛为例。
采用浸渍法制备组分Ⅱ,以商业MCM-22(购买自南开催化剂厂)为例:
取一定量的磷酸氢二铵溶于10ml H2O中,加入5g MCM-22分子筛,90℃搅干,550℃焙烧2h,分别获得磷含量为1wt.%和磷含量为4wt.%的磷改性的MCM-22,分别记为ZEO-1、ZEO-2。
对比例为商业MCM-22(购买自南开催化剂厂),记为ZEO-3。
三、催化剂的制备
将所需比例的组分Ⅰ和组分Ⅱ加入容器中,利用这些物料和/或容器的高速运动产生的挤压力、撞击力、裁剪力、摩擦力中的一种或两种以上作用实现分离、破碎、混匀目的,通过调变温度与载气气氛实现机械能、热能与化学能的转换,进一步调节不同组分间的相互作用。
机械混合过程中,可以设置混合温度为20-100℃,可以在气氛中或者直接在空气中进行,气氛选自以下任意的气体:
a)氮气和/或惰性气体;
b)氢气与氮气和/或惰性气体的混合气,其中氢气于混合气中的体积为5~50%;
c)CO与氮气和/或惰性气体的混合气,其中CO于混合气中的体积为5~20%;
d)O2与氮气和/或惰性气体的混合气,其中O2于混合气中的体积为5-20%,所述惰性气体为氦气、氩气、氖气中的一种或两种以上。机械混合可采用机械搅拌、球磨、摇床混合、机械研磨中的一种或二种以上进行复合,具体如下:
机械搅拌:在搅拌槽中,采用搅拌棒将组分Ⅰ和组分Ⅱ进行混合,通过控制搅拌时间(5min-120min)和速率(30-300转/min),可以调节组分Ⅰ和组分Ⅱ的混合程度和相对距离。
球磨:利用磨料与催化剂在研磨罐内高速翻滚,对催化剂产生强烈冲击、碾压,达到分散、混合组分Ⅰ和组分Ⅱ的作用。通过控制磨料(材质可以是不锈钢、玛瑙、石英。尺寸范围:5mm-15mm)与催化剂的比例(质量比范围:20-100:1),可以调节催化剂的粒度及相对距离。
摇床混合法:将组分Ⅰ和组分Ⅱ预混合,并装入容器中;通过控制摇床的往复振荡或圆周振荡,实现组分Ⅰ和组分Ⅱ的混合;通过调节振荡速度(范围:1-70转/分)和时间(范围:5min-120min),实现均匀混合并调节其相对距离。
机械研磨法:将组分Ⅰ和组分Ⅱ预混合,并装入容器中;在一定的压力(范围:5公斤-20公斤)下,通过研具与混合的催化剂进行相对运动(速率范围:30-300转/min),达到调节催化剂粒度、相对距离和实现均匀混合的作用。
具体的催化剂制备及其参数特征如表1所示。
表1催化剂的制备及其参数特征
催化剂编号 | 组分I | 组分II | I与II的比重 | 复合方式 |
Cat-1 | OX-1 | ZEO-1 | 1 | 机械搅拌 |
Cat-2 | OX-1 | ZEO-1 | 1 | 机械研磨 |
Cat-3 | OX-1 | ZEO-1 | 2 | 球磨 |
Cat-4 | OX-1 | ZEO-2 | 1 | 机械搅拌 |
Cat-5 | OX-2 | ZEO-1 | 1 | 摇床混合 |
Cat-6 | OX-1 | ZEO-1 | 0.5 | 摇床混合 |
Cat-7 | OX-1 | ZEO-3 | 1 | 机械搅拌 |
四、催化反应实例
将上述制备的复合催化剂装入固定床反应装置中,该装置配备气体质量流量计、在线产物分析色谱(反应器的尾气直接与色谱的定量阀连接,进行周期实时采样分析);合成气为H2/CO混合气,本发明的催化剂及对比例催化剂在固定床中的H2/CO比例、反应温度、反应压力、空速等参数如表2所示。
表2催化剂的具体应用及其效果数据
对比例1的催化中的组分II为未经过磷修饰的MCM-22分子筛,其液体燃料的选择性仅为30%。
对比例2的催化剂仅含有组分I,其产物中的液体燃料选择性为0。
对比例3的催化剂仅含有组分II,其CO转化率为0。
由以上结果可以看出,催化剂组分I和II之间的匹配至关重要,直接影响合成气转化过程中的CO的转化率以及液体燃料的选择性。
以上所述,仅是本发明的几个实施例,并非对本发明做任何形式的限制,虽然本发明以较佳实施例揭示如上,然而并非用以限制本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案的范围内,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 (6)
1.一种制备液体燃料的方法,其特征在于:以合成气为反应原料,合成气为H2/CO混合气,在催化剂的作用下,在固定床或移动床上进行转化反应,实现了一步直接将合成气转化为液体燃料,反应过程C5-C11液体燃料的选择性能够达到50-80%,C5-C11中芳烃选择性低于35%,C5-C11异构烃中多支链产物比例能够达到30-60%,同时副产物甲烷选择性低于15%;
所述催化剂包括组分I和组分II,所述组分I和组分II以机械混合方式复合在一起;所述组分Ⅰ的活性成份为金属氧化物,组分II为磷改性的MWW分子筛;
所述金属氧化物为MnOx、MnCryO(x+1.5y)、MnAlyO(x+1.5y)、MnZryO(x+2y)、MnInyO(x+1.5y)、ZnO、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、In2O3、InyAlzMnO(x+1.5y+1.5z)、InyGazMnO(x+1.5y+1.5z)中的一种或二种以上,其中x为1~3.5,y为0.1~10,z为0.1~10;所述MnOx、ZnO、In2O3的比表面积是1-100 m2/g;所述MnCryO(x+1.5y)、MnAlyO(x+1.5y)、MnZryO(x+2y)、MnInyO(x+1.5y)、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、InyAlzMnO(x+1.5y+1.5z)、InyGazMnO(x+1.5y+1.5z)的比表面积是5-150 m2/g;
所述组分Ⅱ中,磷改性的MWW分子筛的骨架元素组成为Si-O、Si-O-Al、Si-O-Fe、Si-O-Ga、Si-O-B中的一种或二种以上;所使用的磷源包括磷酸铵、磷酸氢铵、磷酸二氢铵、磷酸、三甲基膦、三甲基氧膦中的一种或二种以上,磷含量为a,0<a≤20 wt.%;所述磷改性MWW分子筛具有中强酸性,中强酸位点的量是0.05-0.5 mol/kg,其中,中强酸对应NH3-TPD脱附峰的峰顶对应的温度范围为200-500℃,用丙酮作为探针分子,13C-NMR化学位移位于210-220ppm范围。
2.根据权利要求1所述的方法,其特征在于:所述组分Ⅰ中的活性成份与组分II的重量比为0.1-20。
3.根据权利要求1所述的方法,其特征在于:所述组分Ⅰ中的活性成份与组分II的重量比为0.3-5。
4.根据权利要求1所述的方法,其特征在于:所述组分I中还包括分散剂,所述金属氧化物分散于分散剂中;所述分散剂为Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3、活性炭、石墨烯、碳纳米管中的一种或二种以上。
5. 根据权利要求1所述的方法,其特征在于:所述合成气H2/CO摩尔比为0.2-3.5;反应压力为0.5-10 MPa;反应温度为300-600 ℃;反应空速为300-12000 h-1。
6. 根据权利要求1所述的方法,其特征在于:所述合成气H2/CO摩尔比为0.3-2.5;反应压力为1-8MPa;反应温度为320-450℃;反应空速为1000-9000 h-1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210558078.XA CN115109608B (zh) | 2022-05-19 | 2022-05-19 | 一种制备低芳烃含量液体燃料的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210558078.XA CN115109608B (zh) | 2022-05-19 | 2022-05-19 | 一种制备低芳烃含量液体燃料的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115109608A CN115109608A (zh) | 2022-09-27 |
CN115109608B true CN115109608B (zh) | 2023-10-24 |
Family
ID=83326114
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210558078.XA Active CN115109608B (zh) | 2022-05-19 | 2022-05-19 | 一种制备低芳烃含量液体燃料的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115109608B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5349114A (en) * | 1993-04-05 | 1994-09-20 | Mobil Oil Corp. | Shape selective hydrocarbon conversions over modified catalyst |
CN103896740A (zh) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | 一种生产甲酚的方法 |
WO2015058636A1 (zh) * | 2013-10-21 | 2015-04-30 | 北京化工大学 | 一种甲烷直接转化制芳烃的方法 |
WO2019095985A1 (zh) * | 2017-11-15 | 2019-05-23 | 中国科学院大连化学物理研究所 | 一种芳烃合成用催化剂及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6906232B2 (en) * | 2002-08-09 | 2005-06-14 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
-
2022
- 2022-05-19 CN CN202210558078.XA patent/CN115109608B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5349114A (en) * | 1993-04-05 | 1994-09-20 | Mobil Oil Corp. | Shape selective hydrocarbon conversions over modified catalyst |
CN103896740A (zh) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | 一种生产甲酚的方法 |
WO2015058636A1 (zh) * | 2013-10-21 | 2015-04-30 | 北京化工大学 | 一种甲烷直接转化制芳烃的方法 |
WO2019095985A1 (zh) * | 2017-11-15 | 2019-05-23 | 中国科学院大连化学物理研究所 | 一种芳烃合成用催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN115109608A (zh) | 2022-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10464859B2 (en) | Method for preparing aromatic hydrocarbon with carbon dioxide hydrogenation | |
CN107774302B (zh) | 一种催化剂及合成气直接转化制液体燃料联产低碳烯烃的方法 | |
CN100471561C (zh) | 合成气制备低碳烯烃的催化剂及制法和应用 | |
CN108970638B (zh) | 一种催化剂与合成气直接转化制液体燃料联产低碳烯烃的方法 | |
KR20100040750A (ko) | 알코올을 원료로 하는 조성물의 제조방법 | |
CN101024192A (zh) | 一种用于合成气制备低碳烯烃的催化剂及制法和应用 | |
CN108970635B (zh) | 一种催化剂和合成气直接转化制液体燃料联产低碳烯烃的方法 | |
CN110743611B (zh) | 一种纳米复合催化剂及其制备方法和应用 | |
CN109939723A (zh) | 一种催化剂及合成气直接转化制乙烯的方法 | |
CN108970637B (zh) | 一种催化剂及合成气直接转化制液体燃料联产低碳烯烃的方法 | |
CN107661773B (zh) | 一种催化剂及合成气直接转化制液体燃料联产低碳烯烃的方法 | |
CN115109608B (zh) | 一种制备低芳烃含量液体燃料的方法 | |
CN111205159B (zh) | 合成气制低碳烯烃的方法 | |
CN100395314C (zh) | 一种芳构化催化剂及其制法与应用 | |
CN111346666A (zh) | 一种催化剂及合成气直接转化制高芳烃含量的液体燃料的方法 | |
CN111346671B (zh) | 一种催化剂及合成气直接转化制低芳烃液体燃料的方法 | |
CN111073684B (zh) | 一种生产清洁汽油的工艺方法 | |
CN103657707A (zh) | 低碳烃芳构化催化剂制备方法 | |
CN112973779A (zh) | 一种zsm-22分子筛的后处理方法及其在合成气一步法制液体燃料中的应用 | |
CN111686789A (zh) | 一种Na原子修饰的MOR基催化剂及合成气直接转化制液体燃料的方法 | |
CN112295597B (zh) | 一种催化合成气直接转化制富含btx的芳烃的催化剂及其应用 | |
CN112973775B (zh) | 一种含mcm-22分子筛的催化剂及其在合成气一步法制液体燃料中的应用 | |
CN111718751A (zh) | 一种直馏柴油催化转化制芳烃和轻质油的方法 | |
CN112844448B (zh) | 一种催化合成气与甲苯直接转化制乙苯的催化剂及其应用 | |
CN116173935A (zh) | 一种催化合成气直接转化制低芳烃含量汽油的催化剂及其应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |