CN106582663A - Method for in situ catalytic removal of tar in biomass pyrolysis process - Google Patents
Method for in situ catalytic removal of tar in biomass pyrolysis process Download PDFInfo
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- CN106582663A CN106582663A CN201610911792.7A CN201610911792A CN106582663A CN 106582663 A CN106582663 A CN 106582663A CN 201610911792 A CN201610911792 A CN 201610911792A CN 106582663 A CN106582663 A CN 106582663A
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 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 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 19
- 239000011280 coal tar Substances 0.000 claims description 7
- 239000010794 food waste Substances 0.000 claims description 4
- 241000264877 Hippospongia communis Species 0.000 claims description 3
- 229910052599 brucite Inorganic materials 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 239000011285 coke tar Substances 0.000 claims description 2
- 239000004058 oil shale Substances 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000004523 catalytic cracking Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000006057 reforming reaction Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract 1
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract 1
- 229960001545 hydrotalcite Drugs 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 239000011269 tar Substances 0.000 description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000011017 operating method Methods 0.000 description 7
- 238000005235 decoking Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- -1 Heterocyclic arene Chemical class 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 2
- 235000009496 Juglans regia Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002340 LaNiO3 Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a method for in situ catalytic removal of tar to effectively remove tar generated in a biomass pyrolysis process. Specifically, by means of a perovskite catalyst (by mass percentage, the catalyst includes 1-15% of an active component LaAxB1-xO3, wherein A can be the transition metal Fe, Cu, Zn, Zr, Mn, and Co; B can be Ni, Ce, Ru and Rh; the value of x is 0-1, and the balance a carrier component Al2O3, TiO2, ZrO2, SiO2, cordierite, honeycomb ceramics, hydrotalcite, or SBA-16 mesoporous molecular sieve), isothermal synchronous in situ catalytic cracking reforming reaction is carried out on a biomass volatile component at the position of the catalyst, after reaction the tar mass is obviously reduced, and the reaction device pipeline blockage situation is significantly improved. In addition, the catalyst adopted by the method also has the advantages of high activity, simple preparation, low cost, good carbon deposition resistance, and good stability, etc.
Description
Technical field
The present invention relates to green energy resource technical transform field, more particularly to a kind of to utilize perovskite catalyst situ catalytic
Biomass pyrolytic volatile matters, the method for realizing the coal-tar middle oil removing of pyrolytic process.
Background technology
Tradition non-renewable fossil energy such as oil, natural gas etc. are increasingly deficient, find substituting regenerative resource gesture and exist
Must go.As traditional agriculture big country, China's biomass (such as straw) energy abundance and reserves are huge, biomass pyrolytic is used as instantly
Research hot topic technology can prepare industrial widely used solid, liquid, gas tri-state product by base stock of biomass, realize life
The efficient utilization of the material energy.But the not yet complete industrialization of carbonization technology so far, wherein the problem being primarily present is
Entrainment ash is more in course of reaction high temperature volatiles causes separation difficulty, heavy tar liquefaction easily to block reaction tube
Road and tar grade it is not high, pyrolysis combustible gas calorific value it is not high.Heavy tar condensation point is higher therefore is easily liquefied as high viscosity
Liquid object, causes detached difficulty while blocking pipeline, affects the continuous operation of reaction unit, at the same reduce oil-producing,
The value of aerogenesis, therefore, it is difficult to making pyrolytic technique, extensively application promotes the well-being of mankind.
Situ catalytic ensure that the equality of temperature of biomass volatile matters and perovskite catalyst is synchronously fully contacted, can be fast in time
The most of tar steam of cracking reformation of speed, while tar is removed, facilitating the development of subsequent technique is carried out, and reduces production
Cost and energy consumption, improve the production efficiency of integrated artistic.
Catalytic cracking reaction can make the tar component that biomass pyrolytic is produced further crack generation micro-molecular gas, this
Sample not only can make the Mass lost of heavy tar, improve the operation conditions of device, while more combustible gases can be obtained, fill
Divide using the energy value of biomass.
Describe about the method for the tar of generation and catalysis in removing biomass pyrolysis process in Patents and document
Agent.Such as：Chinese patent, publication number：CN101396660A, describes a kind of composite catalyst of biomass char oil-breaking, should
Catalyst is mainly by NiO, Fe2O3With dolomite composition, above-mentioned catalyst has preferable tar removal effect, but the catalyst is steady
It is qualitative poor, and in the reaction easily sintering causes coking deactivation, ultimately results in activity decrease substantially, tar removal effect is not
It is good；Chinese patent, publication number：CN103468294A, the method for describing a kind of wood vinegar tar removing in manufacturing process, uses
It is poor and can not make full use of the value of tar that physical method collects tar effect；Chinese patent, publication number：
CN103045307A, describe it is a kind of prepare the pyrolysis gasification method without tar hydrogen-rich gas and pyrolysis gasifying device, adopted
Decoking remove tar removing, wherein high temperature pyrolysis for high temperature pyrolysis, partial oxidation and pyrolysis char catalytic cracking reaction
Power consumption is serious, and semicoke catalysis catalysis activity is not good enough, and decoking effect has to be hoisted.
Guo Dongyan etc. (electrical tar precipitator is used for biomass gas purifying and combustion gas allows the research [J] of highest oxygen content. and can
The renewable sources of energy, 2012,30 (10):52-54.) tar removing is removed using electrostatic decoking method, clearance is higher, but electrostatic decoking method
Equipment energy consumption height, complex operation, costly, short life, limit its development and application.Compared to the venturi in decoking technology
Method, cyclonic separation method, electric method of trapping and high-temperature cracking method, catalystic pyrolysis devoke efficiency high, convenient operation, with low cost because of it
It is considered as the mode that preferably devokes.(the Catalytic Decomposition of Biomass Tars with such as Gusta
Dolomites[J].Energy Fuels,2009,23(4):2264-2272.) using cheap rich in mineral resources, containing various gold
The dolomite of category element (Ca, Mg, Fe, Mn etc.) has carried out the research of performing catalytic pyrolysis on tar, as a result shows the metal in dolomite
Composition can promote the catalyzed conversion of tar, but natural minerals catalyst activity is poor, easily sinters during the course of the reaction
Carbon deposit and inactivate；(the Catalytic destruction of tar in biomass derived producer such as Zhang
gas[J].Energy Conversion and Management,2004,45(7-8):995-1014.) use nickel-base catalyst
The transition problem of research tar, has obtained higher tar destruction rate, although nickel-base catalyst catalysis activity is higher, in reaction
During easy coking deactivation.
In biomass pyrolysis process produce high temperature pyrolysis volatile matters in containing the atoms such as sulfur, phosphorus, nitrogen and be difficult crack
Heterocyclic arene etc., the easy condensation of above-mentioned substance is condensed into macromole coke and is attached to catalyst surface, so as to cause catalyst to be lived
Property component inactivation, service life reduce and be not easily recycled.
Perovskite catalyst can adulterate various different metallic elements, can improve while high catalytic activity is ensured
The area carbon of catalyst, sintering situation, improve its reaction stability and service life, while also having low price, preparing
Simple the advantages of.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention provides a kind of situ catalytic removing biomass pyrolysis process
Coal-tar middle oil method, i.e., using perovskite catalyst equality of temperature synchronization In-stiu catalysis reforming biomass volatiles, reach
The purpose of removing tar.
The technical scheme that the present invention takes is as follows：A kind of coal-tar middle oil method of situ catalytic removing biomass pyrolysis process,
This method makes biomass material produce volatiles under conditions of high temperature anaerobic, using perovskite catalyst (catalyst
Component is calculated in mass percent, wherein active component LaAxB1-xO3- A be transition-metal Fe, Cu, Zn, Zr, Mn, Co；B is Ni,
Ce, Ru, Rh；Between x values 0-1:1-15%, remaining is carrier components-Al2O3, TiO2, ZrO2, SiO2, cordierite, honeycomb pottery
Porcelain, brucite, SBA-16 mesopore molecular sieves) equality of temperature synchronization In-stiu catalysis reforming biomass volatiles.With operation
Simply, improve plant running situation, catalyst easily to prepare and the advantages of catalysis activity height, good stability, high tar removal efficiency.
The preparation method of catalyst of the present invention, the catalyst prepares active component forerunner initially with citric acid complex method
Body, recycles equi-volume impregnating to prepare the operations such as catalyst, drying, load, roasting and is obtained, and comprises the following steps that：
(1) required carrier is weighed by above-mentioned mass percent, roasting 1-5 hours under the conditions of being placed in 450-850 DEG C；
(2) catalyst activity component presoma is prepared using citric acid complex method：Weigh the solvable of a certain amount of La, A and B
Salt (such as nitrate, chlorate, sulfate etc., wherein preferably nitrate) and citric acid, wherein n (La3+)：n(Ap+)：n(Bq +)：N (citric acid)=1-2：x：1-x：1-3 (wherein between x values 0-1), above-mentioned soluble salt is made and mix after solution, then will
Citric acid makes solution, then citric acid is at the uniform velocity instilled into hybrid metal with the speed of 1-5 drops per second using citric acid complex method
In saline solution, stirring and drying moisture obtains gel-like product at 60-100 DEG C；
(3) the product that (2) step obtains is completely dried under the conditions of 100-110 DEG C；
Using equi-volume impregnating by step (3) in the product that obtains be carried on the step carrier that (1) middle roasting is completed,
Dipping temperature is 10-60 DEG C, and dip time is 1-6 hours；
(5) the product by step (4) is completely dried under the conditions of 50-110 DEG C；
(6) the product by step (5) is heated to 400-800 DEG C and constant temperature 1-6 hours in Muffle furnace, after cooling, as institute
State catalyst.
The physical characteristics of the catalyst：Carrier granular size be 0.8-1.5mm, specific surface area 280-360m2/ g, pore volume
0.6-0.9cm3/ g, aperture is 6-10nm.
The specific implementation step of this method is as follows：
(1) weigh appropriate biomass material and be placed in pyrolysis oven epimere, weigh appropriate above-mentioned catalyst and be placed in pyrolysis oven hypomere；
(2) pyroreaction at 500 DEG C -850 DEG C, occurs in catalyst position same while producing biomass pyrolytic volatile matters
Warm synchronization In-stiu catalysis reforming reaction；
(3) the removal efficiency of tar is calculated.
The invention has the characteristics that and advantage：
(1) the method in the present invention is mainly used in biomass, changing food waste, sludge, oil shale, coal and industrial residue etc.
Carbonaceous material carbonization process.In 500-850 DEG C of pyrolytic process, raw material gasifies at high temperature generation volatile matters, this
When this method can effectively increase the contact area of substrate and catalyst, give full play to the catalytic performance of catalyst, can be effective
The tar produced in course of reaction is removed, improves the operation conditions of reaction unit.
(2) the positive effect of the present invention is：The gaseous state volatile matters that carbonization process high temperature is produced, can be by calcium titanium
Ore deposit catalyst equality of temperature synchronization In-stiu catalysis reformation tar component therein, realizes the purpose of decoking.
Specific embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
Weigh 50g γ-Al2O3Carrier, in 550 DEG C of Muffle kiln roasting 4 hours.Take La (NO3)3·6H2O5.63g、Ni
(NO3)2·6H2O3.78g is dissolved in 30mL deionized waters, stirring and dissolving, separately take monohydrate potassium 5.46g be dissolved in 20mL go from
In sub- water, stirring and dissolving (wherein n (La3+)：n(Ni2+)：N (citric acid)=1: 1: 2), by monohydrate potassium solution with per second
The speed of 2 drops are at the uniform velocity instilled in mixed salt solution, and 80 DEG C of stirring in water bath 8h obtain spawn, then by this gelling material
24h is dried in 105 DEG C of baking ovens for matter until thoroughly drying.Take the presoma 3.19g after drying to be dissolved in 40mL deionized waters and making
Impregnation liquid, pours impregnation liquid into γ-Al that roasting is completed2O3In carrier, dip loading 5h at 25 DEG C, then in 65 DEG C of baking ovens
24h is dried until thoroughly drying moisture, finally in Muffle kiln roasting, heating rate is 5 DEG C/min, and temperature is 750 DEG C, is kept
4h, final finished product catalyst A.Each component mass percent is consisted of in the catalyst：LaNiO3：6%；γ-Al2O3：
94%.Weigh the 100g catalyst to be placed in fixed bed reactors hypomere, reactor epimere is equipped with 200g reaction raw materials corn stalks
Stalk, wherein corn straw are made up of the natural organic high-molecular compound such as cellulose, hemicellulose and lignin, containing abundant
Carbon-chain structure.It is similarly under the conditions of 550 DEG C for 550 DEG C, nitrogen protection, normal pressure, catalyst temperature furnace temperature is pyrolyzed, carries out same
Warm synchronization In-stiu catalysis reformation volatile matters reaction, and carried out the examination that dry distilling is catalyzed pyrolytic reaction：Use acetone collection liquid
State tar is weighed after revolving and draws heavy tar quality.As a result show that heavy tar removal efficiency is after addition catalyst
78%.
Embodiment 2
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst B of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaFe0.5Ni0.5O3：3%；TiO2：97%, calcination condition is 800 DEG C of constant temperature 6h.Weighing 100g should urge
Agent is placed in fixed bed reactors hypomere, and reactor epimere is equipped with 180g reaction raw materials walnut shells, wherein contains in walnut shell
Abundant lignin component, lignin is the fragrance containing oxo phenylpropanol and its derivant structure unit in a kind of molecular structure
Property high polymer.It is similarly under the conditions of 600 DEG C for 600 DEG C, nitrogen protection, normal pressure, catalyst temperature furnace temperature is pyrolyzed, carries out same
Warm synchronization In-stiu catalysis reformation volatile matters reaction, and carried out the examination that dry distilling is catalyzed pyrolytic reaction：Use acetone collection liquid
State tar is weighed after revolving and draws heavy tar quality.As a result show that heavy tar removal efficiency is after addition catalyst
76%.
Embodiment 3
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst C of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaCu0.3Ni0.7O3：9%；ZrO2：91%, calcination condition is 700 DEG C of constant temperature 6h.Weighing 10g should urge
Agent is placed in fixed bed reactors hypomere, and reactor epimere is equipped with 20g reaction raw materials birch wood flours, wherein contains in birch wood flour
There is the carbon containing high molecular polymer such as abundant lignin, cellulose.It is 650 DEG C, nitrogen protection, normal pressure, urges in pyrolysis furnace temperature
Agent temperature is similarly under the conditions of 650 DEG C, carries out equality of temperature synchronization In-stiu catalysis reformation volatile matters reaction, and has carried out dry distilling
The examination of catalysis pyrolytic reaction：Weighed after revolving with acetone collection tar liquid and draw heavy tar quality.As a result show
Heavy tar removal efficiency after catalyst is added to be 77%.
Embodiment 4
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst D of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaZn0.2Ce0.8O3：15%；SiO2：85%, calcination condition is 550 DEG C of constant temperature 5h.Weighing 200g should
Catalyst is placed in fixed bed reactors hypomere, and reactor epimere is equipped with 400g reaction raw materials changing food wastes, wherein changing food waste
In contain large amount of organic.700 DEG C of conditions are similarly furnace temperature is pyrolyzed for 700 DEG C, nitrogen protection, normal pressure, catalyst temperature
Under, equality of temperature synchronization In-stiu catalysis reformation volatile matters reaction is carried out, and carried out the examination that dry distilling is catalyzed pyrolytic reaction：With third
Ketone collection tar liquid is weighed after revolving and draws heavy tar quality.As a result heavy tar removing after addition catalyst is shown
Rate is 80%.
Embodiment 5
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst E of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaCu0.6Ru0.4O3：12%；Brucite：88%, calcination condition is 600 DEG C of constant temperature 4h.Weigh 50g
The catalyst is placed in fixed bed reactors hypomere, and reactor epimere is equipped with 110g reaction raw materials sludge.It is in pyrolysis furnace temperature
750 DEG C, nitrogen protection, normal pressure, catalyst temperature be similarly under the conditions of 750 DEG C, carry out equality of temperature synchronization In-stiu catalysis and reform
Volatile matters react, and have carried out the examination that dry distilling is catalyzed pyrolytic reaction：Tar liquid is collected with acetone to weigh after revolving
Go out heavy tar quality.As a result show that heavy tar removal efficiency is 78% after addition catalyst.
Embodiment 6
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst F of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaZr0.1Rh0.9O3：7%；Cordierite：93%, calcination condition is 800 DEG C of constant temperature 5h.Weighing 5g should
Catalyst is placed in fixed bed reactors hypomere, and reactor epimere is equipped with 10g reaction raw materials oil shales.It is in pyrolysis furnace temperature
800 DEG C, nitrogen protection, normal pressure, catalyst temperature be similarly under the conditions of 800 DEG C, carry out equality of temperature synchronization In-stiu catalysis and reform
Volatile matters react, and have carried out the examination that dry distilling is catalyzed pyrolytic reaction：Tar liquid is collected with acetone to weigh after revolving
Go out heavy tar quality.As a result show that heavy tar removal efficiency is 82% after addition catalyst.
Embodiment 7
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst G of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaMn0.3Ce0.7O3：5%；Ceramic honey comb：95%, calcination condition is 750 DEG C of constant temperature 4h.Weigh 50g
The catalyst is placed in fixed bed reactors hypomere, and reactor epimere is equipped with 100g reaction raw materials coals.It is 850 in pyrolysis furnace temperature
DEG C, nitrogen protection, normal pressure, catalyst temperature be similarly under the conditions of 850 DEG C, carry out equality of temperature synchronization In-stiu catalysis and reform volatilization
Divide reaction, and carry out the examination that dry distilling is catalyzed pyrolytic reaction：Weighed after revolving with acetone collection tar liquid and draw weight
Matter quality of coke tar.As a result show that heavy tar removal efficiency is 80% after addition catalyst.
Embodiment 8
The reagent of corresponding mass is weighed, operating procedure is with the finished product catalyst H of embodiment 1.Each component in the catalyst
Mass percent is consisted of：LaCo0.7Ni0.3O3：14%；SBA-16 mesopore molecular sieves：86%, calcination condition is 700 DEG C of constant temperature
5h.Weigh the 120g catalyst to be placed in fixed bed reactors hypomere, reactor epimere is equipped with 250g reaction raw materials industrial residues
Colophonium.It is similarly under the conditions of 500 DEG C for 500 DEG C, nitrogen protection, normal pressure, catalyst temperature furnace temperature is pyrolyzed, carries out equality of temperature same
Step In-stiu catalysis reformation volatile matters reaction, and carried out the examination that dry distilling is catalyzed pyrolytic reaction：It is burnt liquid to be collected with acetone
Oil is weighed after revolving and draws heavy tar quality.As a result show that heavy tar removal efficiency is 82% after addition catalyst.
Claims (4)
1. a kind of situ catalytic removes the coal-tar middle oil method of biomass pyrolysis process, it is characterised in that：Pyrolysis furnace high-temperature is produced
Biomass volatile matters there is equality of temperature synchronization In-stiu catalysis weight in catalyst position while through perovskite catalyst
Whole reaction, quality of coke tar is decreased obviously after reaction.
It is 2. according to claim 1 to remove the coal-tar middle oil perovskite catalyst of biomass pyrolysis process for situ catalytic,
It is characterized in that：The catalytic component is calculated in mass percent, wherein active component LaAxB1-xO3(A is transition-metal Fe, Cu,
Zn, Zr, Mn, Co；B is Ni, Ce, Ru, Rh；Between x values 0-1)：1-15%, remaining is carrier components-Al2O3, TiO2,
ZrO2, SiO2, cordierite, ceramic honey comb, brucite, SBA-16 mesopore molecular sieves.
3. catalyst according to claim 2, it is characterised in that：The shape of the carrier is not unique, and its shape includes ball
Shape, strip, ingot shape, cellular, ring-type, screen waviness shape.
4. a kind of situ catalytic according to claim 1 removes the coal-tar middle oil method of biomass pyrolysis process, and its feature exists
In：Methods described is applicable not only to the pyrolysis of biomass, applies also for changing food waste, sludge, oil shale, coal, industrial residue
Pyrolysis.
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