CN105582932A - Biomass synthetic gas catalyst, preparation method and application thereof - Google Patents
Biomass synthetic gas catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN105582932A CN105582932A CN201410563859.3A CN201410563859A CN105582932A CN 105582932 A CN105582932 A CN 105582932A CN 201410563859 A CN201410563859 A CN 201410563859A CN 105582932 A CN105582932 A CN 105582932A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- iron
- biomass
- based oxide
- oxide
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000002028 Biomass Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000002309 gasification Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000005453 pelletization Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 24
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 14
- 238000000197 pyrolysis Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- WGPCJVLKOFIRMS-UHFFFAOYSA-K n,n-diethylcarbamodithioate;iron(3+) Chemical class [Fe+3].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S.CCN(CC)C([S-])=S WGPCJVLKOFIRMS-UHFFFAOYSA-K 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 235000010333 potassium nitrate Nutrition 0.000 description 7
- 239000004323 potassium nitrate Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a biomass synthetic gas catalyst, a preparation method and an application thereof. The biomass synthetic gas catalyst includes, by weight, 8-45% of an iron-based oxide, 33-90% of biomass semicoke and 1-33% of tar. The preparation method comprises the steps of: mixing uniformly the tar, the iron-based oxide and the biomass, adding the mixture into a double-screw extruder to perform extruding pelletization to obtain the product. The catalyst is not liable to pulverize, is easy to recycle and is good in mixing effect with the biomass. When being used in a biomass producing synthetic gas process, the catalyst achieves high biomass gasification rate and high carbon conversion rate and can achieve high quality of a synthetic gas product, thereby satisfying requirement on synthetic liquid fuels. The catalyst is excellent in application prospect.
Description
Technical field
The present invention relates to a kind of biomass synthesis gas Catalysts and its preparation method and application.
Background technology
Utilize in technology biomass energy is numerous, biomass gasification technology is because ingredient requirement is low, gasification product utilization rate is high and it is few to pollute, gained gas products can, directly as fuel, also can be used as industrial chemicals, is one of main method of biomass energy utilization technologies. In traditional handicraft, because fixed bed is because ingredient requirement is consistent, heat transfer effect is poor, there is the problems such as the time of staying is short in fluid bed, all causes overall efficiency of carbon con version not high. In recent years, the efficiency of carbon con version of the high-temperature entrained flow of exploitation and segmented gasification technique (gasifying after first pyrolysis) has obvious lifting, but in course of reaction, needs to consume a large amount of oxygen, and energy consumption is also large, and operating cost is high, implements also and acquires a certain degree of difficulty. Distinct issues are to obtain high H/C(H2/ CO > 1.5) biomass synthesis gas product is target the needed material consumption of gasification, energy consumption are too high; Secondly, biomass synthesis gas quality is wayward, to the bad adaptability of raw material type, particle size. Trace it to its cause, the conduction of heat mechanism of this traditional ecto-entad has not only increased energy slippages, and has caused the uncontrollable of pyrolytic reaction. Biological particles (more than grade) for most through pulverizing, pyrolytic reaction is no longer leading by controlled chemical effect, because heat conduction makes living beings that repeatedly cracking occur, the otherness of biomass composition makes pyrolytic reaction be difficult to control, and product composition is complicated and changeable. Therefore, adopt suitable means to strengthen biomass gasification process, for setting up, efficient living beings Quick-gasifying technology is most important.
The heat and mass rule of heating using microwave uniqueness and better heating uniformity are not only conducive to improve the pyrolysis efficiency of living beings, and can promote the positive-effect of some reaction. Men é ndez etc. has compared different temperature and the different yield of pyrolysis way on product and the impacts of various product properties in " Energy&Fuels " (the 21st 1 phase of volume 373-378 page) " EvidenceofSelf-GasificationduringtheMicrowave-InducedPyr olysisofCoffeeHulls " literary composition. Found that, at 500 ~ 1000 DEG C of interval microwave-heatings, than the more gas of conventional pyrolysis energy output, and hydrogen yield is common electrically heated 1.3 ~ 1.4 times.
CN102874750A discloses the method for the auxiliary pyrolysis living beings of coke and zinc chloride under a kind of microwave field, and pyrolysis gas rate is greater than 80%, and in gaseous product, hydrogen content can reach 70%. CN103387853A mixes metal oxide and salt thereof to carry out microwave-heating gasification with charing living beings, is then obtained and is rich in more than 99% (H by steam reforming2+ CO) synthesis gas product, H2/ CO is up to 1.12, and biological carbon conversion ratio reaches more than 93%. But the problem that said method all exists catalyst to be difficult to recycling use, and in order to improve H2/ CO, has consumed a large amount of steam, increases energy consumption and gas consumption, and process economy is not high.
Summary of the invention
For prior art deficiency, the invention provides a kind of biomass synthesis gas Catalysts and its preparation method and application. This catalyst is difficult for efflorescence, is easy to reclaim, and with living beings good mixing effect, is applied to living beings synthetic gas production process, biogas rate is high, and efficiency of carbon con version is high, obtains synthesis gas product quality high, can meet the requirement of synthetic liquid fuel, there is applications well prospect.
Biomass synthesis gas catalyst of the present invention, in catalyst weight percentage composition, comprises following component:
Iron-based oxide 8% ~ 45%, preferably 20% ~ 40%;
Living beings semicoke 33% ~ 90%, preferably 40% ~ 60%;
Tar 1% ~ 33%, preferably 10% ~ 20%.
Wherein, living beings semicoke and tar are material well known in the art, derive from solid (living beings semicoke) and liquid oil (tar) that biomass pyrolysis process produces.
Described iron-based oxide is by 50wt% ~ 90wt% iron oxide (Fe2O3) and 10wt% ~ 50wt% active component composition, active component is selected from the one or more combination in sodium oxide molybdena, nickel oxide, magnesia, potassium oxide, titanium oxide, zirconia, lanthana, selenium oxide or calcium oxide etc., the one or more combination in preferential oxidation nickel, magnesia and potassium oxide.
Described iron-based oxide adopts even coprecipitation method preparation, detailed process is as follows: by proportioning preparation molysite and active metal salt mixed aqueous solution, then under stirring condition, excessive urea liquid is joined and in mixed aqueous solution, carried out coprecipitation reaction by dropping mode, after reaction finishes, by precipitate and separate, washing, dry and roasting, obtain iron-based oxide;
Wherein, described molysite is one or more in molysite and the carboxylic acid molysite etc. of ferric nitrate, ferric sulfate, iron chloride, ferric phosphate, ammonium oxalate molysite, lignosulphonic acid molysite, ferric diethyl dithiocarbamate salt, ready denier oil acid class, and in mixed aqueous solution, the concentration of molysite is 0.5 ~ 0.8mol/L; Described active metal salt is selected from metal nitrate or chloride, and as soluble-salts such as magnesium nitrate, nickel nitrate, lanthanum nitrate, potassium nitrate, zirconium chloride, potassium chloride, calcium chloride, in mixed aqueous solution, the concentration of active metal salt is 0.2 ~ 0.6mol/L.
The concentration of described aqueous solution of urea is 2 ~ 10mol/L.
Described reaction temperature is 60-90 DEG C, and the reaction time is 2 ~ 8 hours;
Described separation, washing process are known for those skilled in the art, and separation can adopt the modes such as centrifugal or filtration, with deionized water washing precipitation to neutral.
Described drying condition is: be dried 4 ~ 12 hours at 60 ~ 150 DEG C; Roasting condition is 800 ~ 1000 DEG C of roastings 6 ~ 20 hours.
The preparation method of biomass synthesis gas catalyst of the present invention, comprises following content: tar, iron-based oxide and living beings semicoke are mixed, then join in double screw extruder, extruding pelletization, obtains product.
Described extrusion condition is as follows: 80 ~ 120 DEG C of extrusion temperatures, and extruded velocity is 0.05 ~ 0.15mm/s, and extruder head length is 6 ~ 20mm, and extruding diameter is 0.5 ~ 2mm.
Catalyst of the present invention is applied to producing synthetic gas by pyrolysis gasification of biomass, and detailed process is as follows:
(1) living beings and catalyst are sent into microwave moving-burden bed reactor and carry out pyrolytic gasification, obtain thermal decomposition product;
(2) thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar through purified treatment;
(3) in reactor, residual solids separates and reclaims iron-based oxide under outside magnetic fields, and the iron-based oxide of recovery is regenerated through high-temperature activation, recycles.
The described biomass material of step (1) is any living beings that contain lignocellulosic such as maize straw, rice husk, straw, wooden unit, leaf or branch; Raw material shape can be the living beings that comprise any shapes such as sheet material, circle, cylinder, taper, cuboid, and the maximum direction size of raw material is no more than 20mm, preferably 5 ~ 10mm.
The described pyrolytic gasification temperature of step (1) is 600 ~ 800 DEG C, 5 ~ 10 minutes reaction time, Microwave Power Density 4 × 105~8×105W/m3。
Thermal decomposition product described in step (1) is taking pyrolysis devolatilization product as main and a small amount of semicoke, and wherein in pyrolysis devolatilization product, uncondensable gas content reaches more than 90%.
The biomass material that step (1) is described and the mass ratio of catalyst are 1:0.1 ~ 1:0.5.
The described purified treatment of step (2) comprises the processes such as cyclonic separation, multi-stage condensing and filtration. Cyclonic separation of the present invention is mainly used in the separation of gas-solid, process without insulation, the heavy tar of partial condensation and the separated collection of living beings semicoke, and all the other tar and gas enter multi-stage condensing device, condensing mode is respectively water-cooled (25 ~ 50 DEG C), ice-cold (0 ~ 5 DEG C) and deep cooling (80 ~-40 DEG C), most of tar is condensed and separates, then obtains being rich in the biomass synthesis gas product of hydrogen and carbon monoxide through fabric filter.
Activating and regenerating condition described in step (3) is: 400 ~ 600 DEG C of regeneration temperatures, 4 ~ 6 hours time, in oxygen-containing atmosphere, regenerate, wherein said oxygen-containing atmosphere is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and the volume fraction of oxygen in gas phase is 5% ~ 50%.
In activating and regenerating process, in catalyst iron-based oxide can with biological burnt and gasification product generation reduction reaction, wherein iron oxide is partially reduced to tri-iron tetroxide (square formula (1) and (2)), through activating and regenerating, in iron-based oxide, tri-iron tetroxide is oxidized to iron oxide again, thereby has realized recycling of iron-based oxide.
C+6Fe2O3→4Fe3O4+CO2+78.6kJ/mol（1）；
CH4+12Fe2O3→8Fe3O4+CO2+2H2O+146.2kJ/mol（2）。
The present invention compared with prior art has the following advantages:
1, by iron-based oxide, the compound biomass synthesis gas catalyst of having prepared of biological Jiao and catalytic active component gasifies for the microwave-heating of living beings, utilize iron oxide in pyrolytic gasification process can with the essential characteristic of biological Jiao and reproducibility gasification product generation redox reaction, iron-based oxide in modification biological Pd/carbon catalyst is magnetized at pyrolytic process simultaneously, under outside magnetic fields, iron-based oxide (reduction-state) obtains separating and reclaims, and the simple activating and regenerating processing of process can regain the iron-based oxide of oxidation state, thereby realize recycling of catalyst, significantly reduce whole process costs.
2, use tar as binding agent Kaolinite Preparation of Catalyst, on the one hand the modification biological Pd/carbon catalyst after moulding can be mixed more uniformly with the biomass material of large-size in microwave moving bed, avoided living beings to have the problem in richness phase and stingy district in may causing mixed process with the difference of catalyst aspect density, volume; Tar can nature volatilization pyrolysis promote the continuous disintegration of catalyst and efflorescence in microwave pyrolytic process on the other hand, and this iron-based oxide (reduction-state) being conducive in catalyst is separated and reclaims from catalyst.
3, use modification biological Pd/carbon catalyst assisted microwave synthesis pyrolysis of gasified bio-matter can obtain at a lower temperature the synthesis gas product of higher gasification efficiency and high-quality, whole process is not introduced the exogenous gas consumptions such as steam, has significantly reduced process energy consumption and production cost.
4, catalyst of the present invention is applied to biomass pyrogenation gasification process and can realizes gas recovery ratio and reach more than 90%, and synthesis gas content reaches more than 90%, H2/ CO can be controlled between 1.0 ~ 2.0.
Detailed description of the invention
Embodiment is elaborated to the present invention program below, but the present invention is not subject to the restriction of following embodiment.
Embodiment 1
According to the ratio of ferric nitrate, nickel nitrate and potassium nitrate mol ratio 1:0.5:0.5, take the ferric nitrate of 1mol, nickel nitrate and the 0.5mol potassium nitrate of 0.5mol is mixed with 2L solution, mixed solution mixed by dropping mode with 4.5L urea liquid (2mol/L) and stir 8h, keeping reaction system constant temperature at 60 DEG C simultaneously. In this process, sediment forms gradually, after reacting completely, and centrifugation, and by sedimentation and filtration, extremely neutral with deionized water washing, be deposited in 60 DEG C of dry 12h, then at 800 DEG C of calcination 20h, after cooling, gained iron-based oxide is defined as Fe naturally1.0Ni0.5K0.5O2.25, drying for standby.
Embodiment 2
According to the ratio of ferric nitrate, nickel nitrate, magnesium nitrate and potassium nitrate mol ratio 1:0.2:0.6:0.2, take the ferric nitrate of 1mol, nickel nitrate, 0.6mol magnesium nitrate and the 0.2mol potassium nitrate of 0.2mol is mixed with 2L solution, mixed solution mixed by dropping mode with isopyknic urea liquid (4.44mol/L) and stir 2h, keeping reaction system constant temperature at 90 DEG C simultaneously. In this process, sediment forms gradually, after reacting completely, and centrifugation, and by sedimentation and filtration, extremely neutral with deionized water washing, be deposited in 90 DEG C of dry 6h, then at 950 DEG C of calcination 20h, after cooling, gained iron-based oxide is defined as Fe naturally1.0Ni0.2Mg0.6K0.2O2.4, drying for standby.
Embodiment 3
According to the ratio of ferric nitrate, nickel nitrate, lanthanum nitrate and potassium nitrate mol ratio 1.5:0.3:0.05:0.15, take the ferric nitrate of 1.5mol, nickel nitrate, 0.05mol lanthanum nitrate and the 0.15mol potassium nitrate of 0.3mol is mixed with 2L solution, by mixed solution with mix by dropping mode and stir 2h with the urea liquid (9mol/L) of 1L, keep reaction system constant temperature at 90 DEG C simultaneously. In this process, sediment forms gradually, after reacting completely, and centrifugation, and by sedimentation and filtration, extremely neutral with deionized water washing, be deposited in 150 DEG C of dry 4h, then at 1000 DEG C of calcination 6h, after cooling, gained iron-based oxide is defined as Fe naturally1.5Ni0.3La0.05K0.15O2.7, drying for standby.
Embodiment 4
By iron-based oxide Fe1.0Ni0.5K0.5O2.25, after living beings semicoke and tar mixes according to the ratio of mass ratio 1:10:1,80 DEG C of extrusion temperatures, extruded velocity is 0.05mm/s, extruder head length is 6mm, extruding diameter is to extrude slivering under 0.5mm condition, is of a size of φ 0.5mm × 4mm, and continues at 105 DEG C of dry 4h. Gained catalyst is defined as Fe1.0Ni0.5K0.5O2.25/C。
Embodiment 5
By iron-based oxide Fe1.0Ni0.2Mg0.6K0.2O2.4, after living beings semicoke and tar mixes according to the ratio of mass ratio 1:1:0.5,110 DEG C of extrusion temperatures, extruded velocity is 0.15mm/s, extruder head length is 20mm, extruding diameter is to extrude slivering under 2mm condition, is of a size of φ 2mm × 4mm, and continues at 105 DEG C of dry 4h. Gained catalyst is defined as Fe1.0Ni0.2Mg0.6K0.2O2.4/C。
Embodiment 6
By iron-based oxide Fe1.5Ni0.3La0.05K0.15O2.7, after living beings semicoke and tar mixes according to the ratio of mass ratio 1:1:0.1,120 DEG C of extrusion temperatures, extruded velocity is 0.15mm/s, extruder head length is 20mm, extruding diameter is to extrude slivering under 2mm condition, is of a size of φ 2mm × 4mm, and continues at 105 DEG C of dry 4h. Gained catalyst is defined as Fe1.5Ni0.3La0.05K0.15O2.7/C。
Embodiment 7
By biomass material (φ 4mm × 6mm) and catalyst Fe1.0Ni0.5K0.5O2.25/ C sends into microwave moving-burden bed reactor according to 1:0.1 ratio and carries out pyrolytic gasification, and temperature is 600 DEG C, 10 minutes reaction time, power density 4 × 105W/m3. The gas generating obtains the biomass synthesis gas product of high-quality through purified treatment such as cyclonic separation, multi-stage condensing and filtrations, yield is 90.1%, and synthesis gas content reaches 91.2%, H2/ CO is 1.5. Residual solid (comprising catalyst) separates and reclaims iron-based oxide (reduction-state) under outside magnetic fields, and activating and regenerating condition is 400 DEG C, and 6 hours time, the iron-based oxide after calcination process can recycle.
Embodiment 8
By biomass material (φ 4mm × 6mm) and catalyst Fe1.0Ni0.2Mg0.6K0.2O2.4/ C sends into microwave moving-burden bed reactor according to 1:0.5 ratio and carries out pyrolytic gasification, and temperature is 800 DEG C, 5 minutes reaction time, power density 8 × 105W/m3. The gas generating obtains the biomass synthesis gas product of high-quality through purified treatment such as cyclonic separation, multi-stage condensing and filtrations, yield is 95.8%, and synthesis gas content reaches 92.8%, H2/ CO is 1.88. Residual solid (comprising catalyst) separates and reclaims iron-based oxide (reduction-state) under outside magnetic fields, and activating and regenerating condition is 600 DEG C, and 4 hours time, the iron-based oxide after calcination process can recycle.
Embodiment 9
By biomass material (φ 4mm × 6mm) and catalyst Fe1.5Ni0.3La0.05K0.15O2.7/ C sends into microwave moving-burden bed reactor according to 1:0.5 ratio and carries out pyrolytic gasification, and temperature is 800 DEG C, 10 minutes reaction time, power density 8 × 105W/m3. The gas generating obtains the biomass synthesis gas product of high-quality through purified treatment such as cyclonic separation, multi-stage condensing and filtrations, yield is 92.2%, and synthesis gas content reaches 90.2%, H2/ CO is 1.92. Residual solid (comprising catalyst) separates and reclaims iron-based oxide (reduction-state) under outside magnetic fields, and activating and regenerating condition is 600 DEG C, and 4 hours time, the iron-based oxide after calcination process can recycle.
Claims (15)
1. a biomass synthesis gas catalyst, is characterized in that: in catalyst weight percentage composition, comprise following component: iron-based oxide 8% ~ 45%, living beings semicoke 33% ~ 90%, tar 1% ~ 33%.
2. according to catalyst claimed in claim 1, it is characterized in that: in catalyst weight percentage composition, comprise following component: iron-based oxide 20% ~ 40%, living beings semicoke 40% ~ 60%, tar 10% ~ 20%.
3. according to the catalyst described in claim 1 or 2, it is characterized in that: iron-based oxide is by 50wt% ~ 90wt% iron oxide (Fe2O3) and 10wt% ~ 50wt% active component composition, active component is selected from the one or more combination in sodium oxide molybdena, nickel oxide, magnesia, potassium oxide, titanium oxide, zirconia, lanthana, selenium oxide or calcium oxide.
4. according to the catalyst described in claim 1 or 2, it is characterized in that: described iron-based oxide adopts even coprecipitation method preparation, detailed process is as follows: preparation molysite and active metal salt mixed aqueous solution, then under stirring condition, excessive urea liquid is joined and in mixed aqueous solution, carried out coprecipitation reaction by dropping mode, after reaction finishes, by precipitate and separate, washing, dry and roasting, obtain iron-based oxide.
5. according to catalyst claimed in claim 4, it is characterized in that: described molysite is one or more in molysite and the carboxylic acid molysite of ferric nitrate, ferric sulfate, iron chloride, ferric phosphate, ammonium oxalate molysite, lignosulphonic acid molysite, ferric diethyl dithiocarbamate salt, ready denier oil acid class, and in mixed aqueous solution, the concentration of molysite is 0.5 ~ 0.8mol/L; Described active metal salt is selected from active metal nitrate or chloride, and in mixed aqueous solution, the concentration of active metal salt is 0.2 ~ 0.6mol/L; The concentration of described aqueous solution of urea is 2 ~ 10mol/L.
6. according to catalyst claimed in claim 4, it is characterized in that: described reaction temperature is 60-90 DEG C, the reaction time is 2 ~ 8 hours.
7. according to catalyst claimed in claim 4, it is characterized in that: described drying condition is: be dried 4 ~ 12 hours at 60 ~ 150 DEG C; Roasting condition is 800 ~ 1000 DEG C of roastings 6 ~ 20 hours.
8. the preparation method of the biomass synthesis gas catalyst described in a claim 1 or 2, it is characterized in that comprising following content: tar, iron-based oxide and living beings semicoke are mixed, then join in double screw extruder, extruding pelletization, obtains product.
9. in accordance with the method for claim 8, it is characterized in that: described extrusion condition is as follows: 80 ~ 120 DEG C of extrusion temperatures, extruded velocity is 0.05 ~ 0.15mm/s, and extruder head length is 6 ~ 20mm, and extruding diameter is 0.5 ~ 2mm.
10. the catalyst described in claim 1 or 2 is applied to a producing synthetic gas by pyrolysis gasification of biomass, it is characterized in that detailed process is as follows: (1) is sent living beings and catalyst into microwave moving-burden bed reactor and carried out pyrolytic gasification, obtains thermal decomposition product; (2) thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar through purified treatment; (3) in reactor, residual solids separates and reclaims iron-based oxide under outside magnetic fields, and the iron-based oxide of recovery is regenerated through high-temperature activation, recycles.
11. according to application claimed in claim 10, it is characterized in that: the described living beings of step (1) are any living beings that contain lignocellulosic, and the maximum direction size of raw material is no more than 20mm.
12. according to application claimed in claim 10, it is characterized in that: the described pyrolytic gasification temperature of step (1) is 600 ~ 800 DEG C, 5 ~ 10 minutes reaction time, Microwave Power Density 4 × 105~8×105W/m3。
13. according to application claimed in claim 10, it is characterized in that: the biomass material that step (1) is described and the mass ratio of catalyst are 1:0.1 ~ 1:0.5.
14. according to application claimed in claim 10, it is characterized in that: the described purified treatment of step (2) comprises cyclonic separation, multi-stage condensing and filter process.
15. according to application claimed in claim 10, it is characterized in that: the activating and regenerating condition described in step (3) is: 400 ~ 600 DEG C of regeneration temperatures, 4 ~ 6 hours time, in oxygen-containing atmosphere, regenerate, wherein said oxygen-containing atmosphere is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and inert gas, and the volume fraction of oxygen in gas phase is 5% ~ 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410563859.3A CN105582932B (en) | 2014-10-22 | 2014-10-22 | A kind of biomass synthesis gas catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410563859.3A CN105582932B (en) | 2014-10-22 | 2014-10-22 | A kind of biomass synthesis gas catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105582932A true CN105582932A (en) | 2016-05-18 |
| CN105582932B CN105582932B (en) | 2017-10-27 |
Family
ID=55923053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410563859.3A Active CN105582932B (en) | 2014-10-22 | 2014-10-22 | A kind of biomass synthesis gas catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105582932B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159317A (en) * | 2017-06-16 | 2017-09-15 | 江苏大学 | A kind of method of decaying catalyst combining and regenerating in catalytic pyrolysis of biomass |
| CN107794064A (en) * | 2017-10-20 | 2018-03-13 | 农业部规划设计研究院 | A kind of disturbance formula inner member rotary kiln pyrogenation reactor and biomass pyrolytic carbonize method |
| CN107983362A (en) * | 2017-11-30 | 2018-05-04 | 同济大学 | A kind of method for preparing catalyst and Application way from waste |
| CN108117891A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | The method and system of biomass microwave pyrolysis orientation gasification |
| CN108114721A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of continuous production method of catalyst and biomass preparing synthetic gas |
| CN108114753A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of bio-oil reforming catalyst |
| CN111378511A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| CN112745960A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Auxiliary agent for biomass pyrolysis treatment and preparation method and application thereof |
| CN114100618A (en) * | 2021-12-13 | 2022-03-01 | 东北电力大学 | Iron-based porous carbon catalyst and preparation method and application thereof |
| CN114433168A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for biological coke gasification reaction and biological coke gasification raw material |
| CN117000294A (en) * | 2022-04-29 | 2023-11-07 | 中国石油化工股份有限公司 | Catalytic cracking catalyst regeneration system and regeneration method |
| RU2825350C1 (en) * | 2023-12-05 | 2024-08-26 | федеральное государственное автономное образовательное учреждение высшего образования "Тюменский государственный университет" | Method for microwave processing of solid organic material into fuel gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242922A (en) * | 2013-05-31 | 2013-08-14 | 青岛新奥胶城燃气有限公司 | Method for preparing fuel gas by burning biomass |
| CN103387853A (en) * | 2013-08-06 | 2013-11-13 | 上海中科高等研究院 | Method for producing synthesis gas by microwave gasification of biochar |
| CN103394356A (en) * | 2013-08-20 | 2013-11-20 | 山东省科学院能源研究所 | Biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof |
| CN103551182A (en) * | 2013-11-01 | 2014-02-05 | 河南省科学院能源研究所有限公司 | Catalyst for splitting decomposition of biomass tar and preparation method thereof |
-
2014
- 2014-10-22 CN CN201410563859.3A patent/CN105582932B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242922A (en) * | 2013-05-31 | 2013-08-14 | 青岛新奥胶城燃气有限公司 | Method for preparing fuel gas by burning biomass |
| CN103387853A (en) * | 2013-08-06 | 2013-11-13 | 上海中科高等研究院 | Method for producing synthesis gas by microwave gasification of biochar |
| CN103394356A (en) * | 2013-08-20 | 2013-11-20 | 山东省科学院能源研究所 | Biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof |
| CN103551182A (en) * | 2013-11-01 | 2014-02-05 | 河南省科学院能源研究所有限公司 | Catalyst for splitting decomposition of biomass tar and preparation method thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114753B (en) * | 2016-11-28 | 2020-08-11 | 中国石油化工股份有限公司 | Biomass oil reforming catalyst |
| CN108117891A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | The method and system of biomass microwave pyrolysis orientation gasification |
| CN108114721A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of continuous production method of catalyst and biomass preparing synthetic gas |
| CN108114753A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of bio-oil reforming catalyst |
| CN108114721B (en) * | 2016-11-28 | 2020-08-11 | 中国石油化工股份有限公司 | Catalyst and continuous production method for preparing synthesis gas from biomass |
| CN107159317A (en) * | 2017-06-16 | 2017-09-15 | 江苏大学 | A kind of method of decaying catalyst combining and regenerating in catalytic pyrolysis of biomass |
| CN107794064A (en) * | 2017-10-20 | 2018-03-13 | 农业部规划设计研究院 | A kind of disturbance formula inner member rotary kiln pyrogenation reactor and biomass pyrolytic carbonize method |
| CN107983362B (en) * | 2017-11-30 | 2021-06-22 | 同济大学 | A kind of catalyst preparation method and utilization method derived from waste |
| CN107983362A (en) * | 2017-11-30 | 2018-05-04 | 同济大学 | A kind of method for preparing catalyst and Application way from waste |
| CN111378511A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| CN111378511B (en) * | 2018-12-28 | 2021-05-04 | 中国石油化工股份有限公司 | Biomass microwave gasification utilization method and system |
| CN112745960A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Auxiliary agent for biomass pyrolysis treatment and preparation method and application thereof |
| CN114433168A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for biological coke gasification reaction and biological coke gasification raw material |
| CN114433168B (en) * | 2020-10-30 | 2024-02-09 | 中国石油化工股份有限公司 | Catalyst for bio-coke gasification reaction and bio-coke gasification raw material |
| CN114100618A (en) * | 2021-12-13 | 2022-03-01 | 东北电力大学 | Iron-based porous carbon catalyst and preparation method and application thereof |
| CN114100618B (en) * | 2021-12-13 | 2023-08-11 | 东北电力大学 | A kind of iron-based porous carbon catalyst and its preparation method and application |
| CN117000294A (en) * | 2022-04-29 | 2023-11-07 | 中国石油化工股份有限公司 | Catalytic cracking catalyst regeneration system and regeneration method |
| RU2825350C1 (en) * | 2023-12-05 | 2024-08-26 | федеральное государственное автономное образовательное учреждение высшего образования "Тюменский государственный университет" | Method for microwave processing of solid organic material into fuel gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105582932B (en) | 2017-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105582932A (en) | Biomass synthetic gas catalyst, preparation method and application thereof | |
| CN105524662A (en) | Method for preparing synthetic gas through microwave pyrolysis and gasification of biomass | |
| CN104591087B (en) | A kind of biomass chemical chain reformation hydrogen production and the collaborative technique of suppression tar generation | |
| CN108114721B (en) | Catalyst and continuous production method for preparing synthesis gas from biomass | |
| CN108117891B (en) | Method and system for biomass microwave pyrolysis directional gasification | |
| CN106669682A (en) | Biomass pyrolysis catalyst and method for preparing synthesis gas through biomass pyrolysis | |
| CN106824001A (en) | A kind of device of two-stage biological matter hydro-thermal catalytic activation reaction | |
| CN103933991A (en) | Perovskite type composite oxide catalyst for producing controllable synthesis gas | |
| CN106076386A (en) | A kind of preparation method of cobalt sesquioxide/class graphene carbon nitrogen compound composite catalyst | |
| CN106006554B (en) | A kind of carbide slag prepares the system and method for hydrogen-rich gas and calcium carbide | |
| CN110437884B (en) | Method for hydrogen production and power generation through biomass charcoal catalysis | |
| CN104192799B (en) | High-temperature metallurgical slag particulate catalytic gasified bio-matter produces hydrogen-rich gas device and method | |
| CN102703134B (en) | Method for preparing medium-high temperature gas desulfurizing agent by microwave radiation | |
| CN106241735B (en) | A kind of carbide slag prepares the system and method for hydrogen-rich gas and calcium carbide | |
| CN108726833A (en) | A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process | |
| CN107267218A (en) | The method and system of solid fuel pyrolysis gasification | |
| CN103408014B (en) | System for producing calcium carbide by using biomass fuel | |
| CN102553882A (en) | Energy-saving calcining method for increasing activity of coal gangue | |
| CN105217569A (en) | A kind of method of recycled wood materials reformation high purity hydrogen and realize the device of the method | |
| CN216472276U (en) | Solid-phase normal-pressure oxidation system for preparing potassium manganate | |
| CN116064985A (en) | Method and system for reducing organic solid waste heat pyrolysis and reforming coupled iron ore powder | |
| CN111377398B (en) | Method for preparing hydrogen and carbon monoxide by biomass pyrolysis and gasification | |
| CN103949263B (en) | For the perovskite mixed oxides catalyst and preparation method thereof of methane methyl alcohol | |
| CN113562722A (en) | Method for producing carbon nano tube by using semicoke-based catalyst prepared by microfluidization bed | |
| CN106311253A (en) | Composite catalyst for preparing hydrogen-rich gas through biomass gasification and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |