CN106669682B - A kind of method of biomass pyrolytic catalyst and biomass pyrolytic preparing synthetic gas - Google Patents
A kind of method of biomass pyrolytic catalyst and biomass pyrolytic preparing synthetic gas Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 29
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 29
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 238000002309 gasification Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 11
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005087 graphitization Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000001934 delay Effects 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 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
- B01J23/002—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
- B01J23/70—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
- B01J23/78—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 alkali- or alkaline earth 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of biomass pyrolytic catalyst and biomass pyrolytic preparing synthetic gas.The catalyst, including biological semicoke, nickel oxide, I race and/or II race metal hydroxides, based on the total catalyst weight, biological semicoke are 80% ~ 95%, and nickel oxide is 0.5% ~ 10%, I race and/or II family metal oxide is 2.5% ~ 18%.Present invention simultaneously provides a kind of methods of biomass pyrolytic preparing synthetic gas, it include: that biomass and above-mentioned biomass pyrolytic catalyst are sent into microwave reactor to carry out pyrolytic gasification, thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar by purified treatment, the activated regeneration treatment of solid in reactor is recycled.The catalyst activity is high, preparation method is simple, can be recycled, and using the catalyst preparation synthesis gas, pyrolysis rate is fast, gas recovery ratio is high, obtains gas products quality height, can satisfy the requirement of synthetic liquid fuel, have applications well prospect.
Description
Technical field
The present invention relates to a kind of methods of biomass pyrolytic catalyst and biomass pyrolytic preparing synthetic gas.
Background technique
Biomass preparing synthetic gas technology is to realize low value biomass profound level and efficient one of the important channel utilized.It passes
System gasification mode is from outward appearance to inner essence heated by radiation, convection current and conduction, in order to avoid temperature gradient is excessive, heating speed
It tends not to too fastly, selective heating can not be carried out to each component of material, biomass is hindered to orient transformation of synthetic gas technology
Development.Compared with traditional heating mode, microwave heating can be strengthened due to its unique heat and mass rule and heating uniformity
Diabatic process inside material, thus material size is not specially required, and power consumption and material diameter in a certain range
It is inversely proportional.The characteristic of microwave fast heating can accelerate the generation of volatile relese and pyrolytic reaction, improve gasification of biomass speed
Rate, and controlled by reasonable temperature, it is possible to reduce secondary response simplifies final product, therefore the particularity of microwave heating
Its thermal decomposition product is set to have very big difference compared with traditional gasification technology.Microwave thermal is vented one's spleen middle CO and H2Total content is up to 62%, remote high
It is more obvious in the 25% of conventional pyrolytic, especially addition microwave absorption and catalyst effect, reach as high as 94%(volume basis
Content).In addition, the biological tar of by-product is almost without condensed-nuclei aromatics more than two rings；The non-microwave-heating semicoke of half coke ratio has
Higher reactivity, is highly suitable as raw material of synthetic gas.
CN201210401809.6 discloses under a kind of microwave field biomass and coke in zinc chloride as catalyst action
The lower method for carrying out pyrolytic gasification, pyrolysis gas rate are greater than 80%, and hydrogen content can reach 70% in gaseous product.
Metal oxide and its salt are mixed with charing biomass and carry out microwave-heating gasification by CN103387853A, then pass through vapor
It reforms to obtain and is rich in 99% or more (H2+ CO) synthesis gas product, H2/ CO is up to 1.12, biological efficiency of carbon con version reach 93% with
On.But the above method all has that catalyst is difficult to recycle, and in order to improve H2/ CO is consumed a large amount of
Vapor, increase energy consumption and gas consumption, process economy it is not high.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of biomass pyrolytic catalyst and biomass pyrolytic preparing synthetic gas
Method.The catalyst activity is high, preparation method is simple, can be recycled, utilizes the catalyst preparation synthesis gas, pyrolysis rate
Fastly, gas recovery ratio is high, obtains gas products quality height, can satisfy the requirement of synthetic liquid fuel, have applications well prospect.
Biomass pyrolytic catalyst of the invention, including biological semicoke, nickel oxide, I race and/or II race metal hydroxide
Object, based on the total catalyst weight, biological semicoke are 80% ~ 95%, and nickel oxide is 0.5% ~ 10%, I race and/or II race metal oxygen
Compound is 2.5% ~ 18%；Wherein I race metal is selected from one or more of lithium, sodium, potassium, rubidium and caesium, II race metal be selected from magnesium,
One or more of calcium, strontium and barium, preferably potassium；The biological semicoke derives from solid caused by biomass pyrolysis process
Body, on the basis of biological semicoke weight, wherein carbon content 70% ~ 90%, hydrogen content 0.5% ~ 2.5%, oxygen content 8% ~ 25%, nitrogen content
It is no more than 0.5% no more than 2%, sulfur content, the degree of graphitization of biological semicoke is 40% ~ 80%.
The preparation method of biomass pyrolytic catalyst of the invention, including following content: by biological semicoke, nickel oxide and
I race and/or the mixing of II race metal hydroxides are placed in ball mill, and ball-milling treatment, then mixes above-mentioned crushing under room temperature
Even mixture is dried and roasts, and obtains biomass pyrolytic catalyst.
The I race and/or II race metal hydroxides be sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide,
One or more of cesium hydroxide, lithium hydroxide, barium hydroxide, rubidium hydroxide and strontium hydroxide etc., preferably potassium hydroxide.
100 ~ 150 revs/min of the rotational speed of ball-mill, processing time are 2 ~ 8 hours；
The drying condition are as follows: 1 ~ 4 hour dry at 80 ~ 150 DEG C；Roasting condition are as follows: 300 ~ 500 DEG C under nitrogen atmosphere
Roasting 2 ~ 6 hours.
Present invention simultaneously provides a kind of methods of biomass pyrolytic preparing synthetic gas, comprising:
(1) biomass and above-mentioned biomass pyrolytic catalyst are sent into microwave reactor and carry out pyrolytic gasification, be pyrolyzed
Product；
(2) thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar by purified treatment；
(3) the activated regeneration treatment of remaining solid (including catalyst and newly-generated biological semicoke) in reactor, is followed
Ring uses.
Biomass material described in step (1) be corn stover, rice husk, straw, wooden unit, leaf or branch etc. it is any containing
The biomass of lignocellulosic；Raw material shape can be the life including any shapes such as sheet material, circle, cylinder, taper, cuboids
Substance, raw material maximum direction size are no more than 20mm, preferably 5 ~ 10mm.
Pyrolytic gasification temperature described in step (1) be 500 ~ 800 DEG C, the reaction time 5 ~ 10 minutes, Microwave Power Density 1 ×
105~10×105W/m3。
The biological semicoke based on pyrolysis devolatilization product and on a small quantity of thermal decomposition product described in step (1), wherein pyrolysis is waved
Hair property product accounts for 92 ~ 98%, and biological semicoke is 2 ~ 8%；In pyrolysis devolatilization product uncondensable gas content reach 90% with
On.
The mass ratio of biomass material described in step (1) and biomass pyrolytic catalyst is 1:0.1 ~ 1:0.5.
Step (2) described purified treatment includes the processes such as cyclonic separation, multi-stage condensing and filtering.Cyclonic separation master of the present invention
It is used for the separation of gas-solid, biological semicoke to be separated and collected, and tar and gas enter multi-stage condensing device, and condensing mode is respectively
Water cooling (25 ~ 50 DEG C), ice-cold (0 ~ 5 DEG C) and deep cooling (- 80 ~ -40 DEG C), most of tar, which is condensed, to be separated, using fibre
Dimensional filter device is obtained to be rich in the biomass synthesis gas product of hydrogen and carbon monoxide.
Catalyst oxidation processes condition described in step (3): 200 ~ 500 DEG C of temperature, the time 4 ~ 6 hours, in oxygen-containing atmosphere
Middle regeneration, wherein the oxygen-containing atmosphere is in the mixture of air, the mixture of oxygen and nitrogen or oxygen and inert gas
One kind, the volume fraction of oxygen in the gas phase be 1% ~ 5%.
Activation of catalyst regeneration treating method described in step (3), comprising: by solid remaining in reactor, including urge
Agent and newly-generated biological semicoke carry out decentralized processing, drying and roasting, obtain regenerated catalyst；Wherein at the dispersion
Reason process: ammonia spirit is prepared according to the molar ratio of nickel oxide in catalyst and ammonia, it is molten that catalyst is first added slowly to ammonium hydroxide
In liquid and continue stirring until not until dissolution.The molar ratio of the nickel oxide and ammonia is 1:4 ~ 1:8, ammonia spirit concentration
It is 0.5 ~ 25%.The treatment temperature is 5 ~ 25 DEG C, and the processing time is 4 ~ 12 hours.The drying condition are as follows: 80 ~ 150
DEG C dry 4 ~ 12 hours；Roasting condition are as follows: roasted 4 ~ 12 hours for 300 ~ 500 DEG C under nitrogen atmosphere.
Biological semicoke class catalyst had not only played the effect of catalytic pyrolysis in pyrolytic process, but participate in char Gasification,
Reform makes itself to be continuously available consumption in transformation and various redox reactions, and the metal oxide in catalyst can be with biology
Separation and aggregation occur for semicoke, and can generate new biological semicoke can be further exacerbated by metal in catalyst again in pyrolytic process
Oxide is unevenly distributed；In addition, metal oxide is easy to happen reduction meeting and is urged in synthesis gas atmosphere in catalyst
Phenomena such as agent coking carbon distribution, can also change and reduce the activity of catalyst.For this reason, it may be necessary to restore metal oxygen by oxidation processes
The composed structure (square formula (1)) of compound, then NiO and helper component MO are re-dissolved by the decentralized processing of ammonia spirit
And it is uniformly distributed (square formula (2), equation (3) and formula (4)), then by dry and calcination process (square formula
(5)) regenerated catalyst is obtained.
Ni + O2 + 469.9 kJ/mol(1 of → NiO)；
NiO + nNH3 + H2O → Ni(NH3)n(OH)2(2)；
MO + H2O → MOH(3)；
R-OM + H2O → MOH+R-OH(4)；
Ni(NH3)n(OH)2 → NiO + nNH3 + H2O(5).
Compared with the prior art, the present invention has the following advantages:
1, by biological semicoke, metal oxide (nickel oxide) and helper component is compound is prepared for biomass synthesis gas catalyst
Microwave-heating for biomass gasifies, and had not only played catalytic function based on biological char catalyst but also had been made the characteristics of participating in reaction
The phenomenon that at nickel oxide in biological semicoke and the separation aggregation of helper component pyrolytic process, at the same for catalyst coking and carbon distribution with
And reducing reaction occurs for nickel oxide pyrolytic gasification process, using the method for drying and roasting after initial oxidation again ammonification, solves gold
Belong to the Catalysts Deactivation Problems such as oxide and helper component separation aggregation, coking carbon distribution, realizes biological semicoke class catalyst
It recycles.
2, the regenerative process of biological semicoke class catalyst reaches the biological semicoke of elimination first with the method for gas mild oxidation
The coking carbon distribution of catalyst and the purpose for restoring metal oxide (nickel oxide) valence state；Recycle nickel oxide that can be formed with ammonium hydroxide
The feature of complex compound, disperses nickel oxide again, and helper component is also removed from biological semicoke；The biology that will finally obtain
Semicoke mixed system obtains the catalyst of activating and regenerating by dry and calcination process.
3, it can be obtained at a lower temperature using biomass pyrolytic catalyst assisted microwave synthesis pyrolysis of gasified bio-matter higher
Gasification efficiency and high-quality synthesis gas product, whole process do not introduce the exogenous gas consumption such as vapor, significantly reduces
Process energy consumption and production cost.
4, catalyst of the present invention is applied to biomass pyrogenation gasification process and can be realized gas recovery ratio to reach 90% or more, closes
Reach 90% or more, H at Gas content2/ CO is can be controlled between 1.0 ~ 2.0.
Specific embodiment
The present invention program is described in detail in following example, but the present invention is not limited by the following examples.
Embodiment 1
By biological semicoke (carbon content 69.97%, hydrogen content 2.47%, oxygen content 25.6%, nitrogen content 1.89%, sulfur content
0.07%, the degree of graphitization 41.61% of biological semicoke), nickel oxide and sodium hydroxide mixing be placed in ball mill, rotational speed of ball-mill
100 revs/min, ball-milling treatment 2 hours, then will crush the mixture mixed and dry 1 hour at 150 DEG C under room temperature, nitrogen
Lower 300 DEG C of atmosphere roast 2 hours, obtain biomass pyrolytic catalyst MWP-1, wherein biological semicoke mass percentage 95%, oxygen
Change nickel 0.5%, potassium hydroxide 4.5%, drying for standby.
Embodiment 2
By biological semicoke (carbon content 80.5%, hydrogen content 1.99%, oxygen content 15.96%, nitrogen content 1.5%, sulfur content
0.05%, the degree of graphitization 50.71% of biological semicoke), nickel oxide and sodium hydroxide mixing be placed in ball mill, rotational speed of ball-mill
150 revs/min, ball-milling treatment 8 hours, then will crush the mixture mixed and dry 4 hours at 80 DEG C under room temperature, nitrogen atmosphere
It encloses lower 500 DEG C to roast 6 hours, obtains biomass pyrolytic catalyst MWP-2, wherein biological semicoke mass percentage 80%, oxidation
Nickel 2%, sodium hydroxide 18%, drying for standby.
Embodiment 3
By biological semicoke (carbon content 84.79%, hydrogen content 0.95%, oxygen content 12.17%, nitrogen content 2.02%, sulfur content
0.07%, the degree of graphitization 52.34% of biological semicoke), nickel oxide and potassium hydroxide mixing be placed in ball mill, rotational speed of ball-mill
150 revs/min, ball-milling treatment 8 hours, then will crush the mixture mixed and dry 4 hours at 80 DEG C under room temperature, nitrogen atmosphere
It encloses lower 500 DEG C to roast 6 hours, obtains biomass pyrolytic catalyst MWP-3, wherein biological semicoke mass percentage 87.5%, oxygen
Change nickel 10%, potassium hydroxide 2.5%, drying for standby.
Embodiment 4
By biological semicoke (carbon content 87.15%, hydrogen content 1.21%, oxygen content 10.12%, nitrogen content 1.45%, sulfur content
0.07%, the degree of graphitization 79.87% of biological semicoke), nickel oxide and potassium hydroxide mixing be placed in ball mill, rotational speed of ball-mill
150 revs/min, ball-milling treatment 8 hours, then will crush the mixture mixed and dry 4 hours at 80 DEG C under room temperature, nitrogen atmosphere
It encloses lower 500 DEG C to roast 6 hours, obtains biomass pyrolytic catalyst MWP-4, wherein biological semicoke mass percentage 80%, oxidation
Nickel 10%, potassium hydroxide 10%, drying for standby.
Embodiment 5
By biological semicoke (carbon content 87.15%, hydrogen content 1.21%, oxygen content 10.12%, nitrogen content 1.45%, sulfur content
0.07%, the degree of graphitization 79.87% of biological semicoke), nickel oxide and calcium hydroxide mixing be placed in ball mill, rotational speed of ball-mill
150 revs/min, ball-milling treatment 8 hours, then will crush the mixture mixed and dry 4 hours at 80 DEG C under room temperature, nitrogen atmosphere
It encloses lower 500 DEG C to roast 6 hours, obtains biomass pyrolytic catalyst MWP-5, wherein biological semicoke mass percentage 80%, oxidation
Nickel 10%, calcium hydroxide 10%, drying for standby.
Embodiment 6
Biomass (φ 4mm × 6mm) and biomass pyrolytic catalyst MWP-1 is micro- according to the mass ratio feeding of 1:0.1
Wave reactor progress pyrolytic gasification, 800 DEG C of temperature, the reaction time 5 minutes, power density 10 × 105W/m3.The gas of generation passes through
It crosses the purified treatments such as cyclonic separation, multi-stage condensing and filtering and obtains the biomass synthesis gas product of high-quality, yield 95.5%,
Synthesis Gas content reaches 90.1%, H2/ CO is 1.45.Remaining solid is in 1% oxygen and 99% nitrogen mixture atmosphere in reactor
Under, in 200 DEG C oxidation processes 6 hours, wait be cooled to room temperature, according to the ratio of nickel oxide in catalyst and the molar ratio 1:8 of ammonia
Ammonia spirit is prepared, and the solid after oxidation processes is added slowly in 0.5% ammonia spirit and is continued stirring until at 25 DEG C not exist
Until dissolution, in 150 DEG C of dry 4h after being stirred for 4 hours, lower 300 DEG C of nitrogen atmosphere are roasted 12 hours, after calcination process
Biomass pyrolytic catalyst circulation be able to maintain using biomass synthesis gas product yield after 20 times 90% or more, synthesis gas contains
Amount is not less than 85%, H2/ CO is not less than 1.2.
Embodiment 7
Biomass (φ 4mm × 6mm) and biomass pyrolytic catalyst MWP-2 is micro- according to the mass ratio feeding of 1:0.1
Wave reactor progress pyrolytic gasification, 800 DEG C of temperature, the reaction time 5 minutes, power density 6 × 105W/m3.The gas of generation passes through
The purified treatments such as cyclonic separation, multi-stage condensing and filtering obtain the biomass synthesis gas product of high-quality, and yield 94.6% closes
Reach 92.3%, H at Gas content2/ CO is 1.55.Remaining solid is under 1% oxygen and 99% nitrogen mixture atmosphere in reactor,
In 200 DEG C oxidation processes 6 hours, wait be cooled to room temperature, according to the ratio of nickel oxide in catalyst and the molar ratio 1:8 of ammonia prepare
Ammonia spirit, and the solid after oxidation processes is added slowly in 0.5% ammonia spirit and is continued stirring until at 25 DEG C not dissolve
Until, in 150 DEG C of dry 4h after being stirred for 4 hours, lower 300 DEG C of nitrogen atmosphere are roasted 12 hours, the life after calcination process
Material pyrolysis catalyst circulation is able to maintain using biomass synthesis gas product yield after 20 times 90% or more, and synthesis Gas content is not
Lower than 85%, H2/ CO is not less than 1.3.
Embodiment 8
Biomass (φ 4mm × 6mm) and biomass pyrolytic catalyst MWP-3 is micro- according to the mass ratio feeding of 1:0.5
Wave reactor progress pyrolytic gasification, 550 DEG C of temperature, the reaction time 10 minutes, power density 6 × 105W/m3.The gas of generation passes through
It crosses the purified treatments such as cyclonic separation, multi-stage condensing and filtering and obtains the biomass synthesis gas product of high-quality, yield 92.9%,
Synthesis Gas content reaches 91.1%, H2/ CO is 1.72.Remaining solid is in 5% oxygen and 95% nitrogen mixture atmosphere in reactor
Under, in 300 DEG C oxidation processes 6 hours, wait be cooled to room temperature, according to the ratio of nickel oxide in catalyst and the molar ratio 1:4 of ammonia
Ammonia spirit is prepared, and the solid after oxidation processes is added slowly to continue stirring until not in 25% ammonia spirit and at 5 DEG C molten
Until solution, in 80 DEG C of dry 12h after being stirred for 12 hours, lower 500 DEG C of nitrogen atmosphere are roasted 4 hours, after calcination process
Biomass pyrolytic catalyst circulation is able to maintain using biomass synthesis gas product yield after 20 times 90% or more, and Gas content is synthesized
Not less than 85%, H2/ CO is not less than 1.5.
Embodiment 9
Biomass (φ 4mm × 6mm) and biomass pyrolytic catalyst MWP-4 is micro- according to the mass ratio feeding of 1:0.5
Wave reactor progress pyrolytic gasification, 550 DEG C of temperature, the reaction time 10 minutes, power density 6 × 105W/m3.The gas of generation passes through
It crosses the purified treatments such as cyclonic separation, multi-stage condensing and filtering and obtains the biomass synthesis gas product of high-quality, yield 92.5%,
Synthesis Gas content reaches 94.2%, H2/ CO is 1.98.Remaining solid is in 5% oxygen and 95% nitrogen mixture atmosphere in reactor
Under, in 300 DEG C oxidation processes 6 hours, wait be cooled to room temperature, according to the ratio of nickel oxide in catalyst and the molar ratio 1:4 of ammonia
Ammonia spirit is prepared, and the solid after oxidation processes is added slowly to continue stirring until not in 25% ammonia spirit and at 5 DEG C molten
Until solution, in 80 DEG C of dry 12h after being stirred for 12 hours, lower 500 DEG C of nitrogen atmosphere are roasted 4 hours, after calcination process
Biomass pyrolytic catalyst circulation is able to maintain using biomass synthesis gas product yield after 20 times 92% or more, and Gas content is synthesized
Not less than 90%, H2/ CO is not less than 1.8.
Embodiment 10
Biomass (φ 4mm × 6mm) and biomass pyrolytic catalyst MWP-5 is micro- according to the mass ratio feeding of 1:0.5
Wave reactor progress pyrolytic gasification, 800 DEG C of temperature, the reaction time 10 minutes, power density 10 × 105W/m3.The gas of generation passes through
It crosses the purified treatments such as cyclonic separation, multi-stage condensing and filtering and obtains the biomass synthesis gas product of high-quality, yield 93.7%,
Synthesis Gas content reaches 90.8%, H2/ CO is 1.84.Remaining solid is in 5% oxygen and 95% nitrogen mixture atmosphere in reactor
Under, in 500 DEG C oxidation processes 4 hours, wait be cooled to room temperature, according to the ratio of nickel oxide in catalyst and the molar ratio 1:4 of ammonia
Ammonia spirit is prepared, and the solid after oxidation processes is added slowly to continue stirring until not in 25% ammonia spirit and at 5 DEG C molten
Until solution, in 80 DEG C of dry 12h after being stirred for 12 hours, lower 500 DEG C of nitrogen atmosphere are roasted 4 hours, after calcination process
Biomass pyrolytic catalyst circulation is able to maintain using biomass synthesis gas product yield after 20 times 90% or more, and Gas content is synthesized
Not less than 85%, H2/ CO is not less than 1.6.
Comparative example 1
By biological semicoke (carbon content 87.15%, hydrogen content 1.21%, oxygen content 10.12%, nitrogen content 1.45%, sulfur content
0.07%, the degree of graphitization 79.87% of biological semicoke) and zinc chloride mixing be placed in ball mill, 150 revs/min of rotational speed of ball-mill, room
Ball-milling treatment 8 hours under the conditions of temperature, the mixture that then will crush mixing is 4 hours dry at 80 DEG C, the lower 500 DEG C of roastings of nitrogen atmosphere
It burns 6 hours, obtains biomass pyrolytic catalyst MWP-6, wherein biological semicoke mass percentage 80%, zinc chloride 20%, dry
It is spare.
Biomass (φ 4mm × 6mm) and biomass pyrolytic catalyst MWP-6 is micro- according to the mass ratio feeding of 1:0.5
Wave reactor progress pyrolytic gasification, 550 DEG C of temperature, the reaction time 10 minutes, power density 6 × 105W/m3.The gas of generation passes through
It crosses the purified treatments such as cyclonic separation, multi-stage condensing and filtering and obtains the biomass synthesis gas product of high-quality, yield 87.5%,
Synthesize Gas content 80.5%, H2/ CO is 1.12.
Claims (12)
1. a kind of biomass pyrolytic catalyst, it is characterised in that: including biological semicoke, nickel oxide, I race and/or II race metallic hydrogen
Oxide, based on the total catalyst weight, biological semicoke are 80% ~ 95%, and nickel oxide is 0.5% ~ 10%, I race and/or II race gold
Belonging to hydroxide is 2.5% ~ 18%；The biological semicoke derives from solid caused by biomass pyrolysis process, with biology half
On the basis of burnt weight, wherein carbon content 70% ~ 90%, hydrogen content 0.5% ~ 2.5%, oxygen content 8% ~ 25%, nitrogen content are no more than 2%, sulphur
Content is no more than 0.5%, and the degree of graphitization of biological semicoke is 40% ~ 80%.
2. catalyst described in accordance with the claim 1, it is characterised in that: I race metal is selected from one of lithium, sodium, potassium, rubidium and caesium
Or it is several；II race metal is selected from one or more of magnesium, calcium, strontium and barium.
3. a kind of preparation method of biomass pyrolytic catalyst of any of claims 1 or 2, it is characterised in that in following
Hold: biological semicoke, nickel oxide and I race and/or II race metal hydroxides being mixed and are placed in ball mill, under room temperature ball
Mill processing, then the mixture that above-mentioned crushing mixes is dried and is roasted, obtain biomass pyrolytic catalyst.
4. according to the method for claim 3, it is characterised in that: the I race and/or II race metal hydroxides is hydrogen-oxygen
Change sodium, potassium hydroxide, magnesium hydroxide, calcium hydroxide, cesium hydroxide, lithium hydroxide, barium hydroxide, rubidium hydroxide and strontium hydroxide
One or more of.
5. according to the method for claim 3, it is characterised in that: 100 ~ 150 revs/min of the rotational speed of ball-mill handles the time
It is 2 ~ 8 hours.
6. according to the method for claim 3, it is characterised in that: the drying condition are as follows: small in 80 ~ 150 DEG C of dryings 1 ~ 4
When；Roasting condition are as follows: roasted 2 ~ 6 hours for 300 ~ 500 DEG C under nitrogen atmosphere.
7. a kind of method of biomass pyrolytic preparing synthetic gas, characterized by comprising: (1) by biomass and the claims 1
Or catalyst described in 2 is sent into microwave reactor and carries out pyrolytic gasification, obtains thermal decomposition product；(2) thermal decomposition product is by purification
Reason obtains biomass synthesis gas and a small amount of liquid tar；(3) remaining solid includes catalyst and newly-generated life in reactor
Object semicoke is recycled through oxidation, activating and regenerating processing；
Oxidation processes condition described in step (3):, the time 4 ~ 6 hours, regenerating in oxygen-containing atmosphere by 200 ~ 500 DEG C of temperature, wherein
The oxygen-containing atmosphere is air, the mixture of oxygen and nitrogen or one of oxygen and the mixture of inert gas, oxygen
Volume fraction in the gas phase is 1% ~ 5%；Activating and regenerating processing method described in step (3), comprising: will be remaining in reactor
Solid carries out decentralized processing, drying and roasting including catalyst and newly-generated biological semicoke, obtains regenerated catalyst；Wherein
The decentralized processing process: ammonia spirit is prepared according to the molar ratio of nickel oxide in catalyst and ammonia, first delays catalyst
Slowly until being added in ammonia spirit and continuing stirring until no longer dissolution；The molar ratio of the nickel oxide and ammonia is 1:4 ~ 1:8,
Ammonia spirit concentration is 0.5 ~ 25%；The treatment temperature is 5 ~ 25 DEG C, and the processing time is 4 ~ 12 hours；The dried strip
Part are as follows: 4 ~ 12 hours dry at 80 ~ 150 DEG C；Roasting condition are as follows: roasted 4 ~ 12 hours for 300 ~ 500 DEG C under nitrogen atmosphere.
8. according to the method for claim 7, it is characterised in that: biomass material described in step (1) is to contain wooden fibre
Tie up the biomass of element；Raw material maximum direction size is no more than 20mm.
9. according to the method for claim 7, it is characterised in that: pyrolytic gasification temperature described in step (1) is 500 ~ 800
DEG C, the reaction time 5 ~ 10 minutes, Microwave Power Density 1 × 105~10×105W/m3。
10. according to the method for claim 7, it is characterised in that: pyrolysis devolatilization produces in thermal decomposition product described in step (1)
Object accounts for 92 ~ 98%, and biological semicoke is 2 ~ 8%.
11. according to the method for claim 7, it is characterised in that: biomass material and biomass pyrolytic described in step (1)
The mass ratio of catalyst is 1:0.1 ~ 1:0.5.
12. according to the method for claim 7, it is characterised in that: step (2) described purified treatment includes cyclonic separation, more
Grade condensation and filter process；Wherein cyclonic separation is mainly used for the separation of gas-solid, and biological semicoke is separated and collected, and tar and gas
Body enters multi-stage condensing device, and condensing mode is respectively 25 ~ 50 DEG C of water cooling, ice-cold 0 ~ 5 DEG C and deep cooling -80 ~ -40 DEG C, most of coke
Oil, which is condensed, to be separated, and is obtained using fabric filter to be rich in the biomass synthesis gas product of hydrogen and carbon monoxide.
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| CN114433141A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst and gasification raw material for biological coke gasification reaction |
| CN112973747B (en) * | 2021-02-23 | 2022-05-17 | 中山大学 | Preparation method of transition metal carbide catalyst and application of transition metal carbide catalyst in preparation of high value-added synthesis gas from biomass solid waste |
| CN113148983B (en) * | 2021-04-14 | 2022-10-21 | 淮阴工学院 | Method for preparing carbon nano tube/porous carbon material and hydrogen-rich synthetic gas by biomass pyrolysis |
| CN114733527B (en) * | 2022-04-08 | 2023-05-12 | 同济大学 | Preparation method of Ca-Ni ash-based catalyst and hydrogen-rich synthetic gas |
| CN115212911B (en) * | 2022-09-21 | 2022-12-20 | 中国农业科学院农业环境与可持续发展研究所 | Nickel-loaded nitrogen-doped hierarchical pore biochar material and preparation method and application thereof |
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