CN113617360B - Preparation method of catalytic heat carrier and application of catalytic heat carrier in self-heating pyrolysis liquefaction - Google Patents
Preparation method of catalytic heat carrier and application of catalytic heat carrier in self-heating pyrolysis liquefaction Download PDFInfo
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- CN113617360B CN113617360B CN202110881436.6A CN202110881436A CN113617360B CN 113617360 B CN113617360 B CN 113617360B CN 202110881436 A CN202110881436 A CN 202110881436A CN 113617360 B CN113617360 B CN 113617360B
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 98
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 91
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000919 ceramic Substances 0.000 claims abstract description 85
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000292 calcium oxide Substances 0.000 claims abstract description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000006004 Quartz sand Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 239000012798 spherical particle Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 32
- 229920000609 methyl cellulose Polymers 0.000 claims description 28
- 239000001923 methylcellulose Substances 0.000 claims description 28
- 235000010981 methylcellulose Nutrition 0.000 claims description 28
- 229910052684 Cerium Inorganic materials 0.000 claims description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052804 chromium Inorganic materials 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 24
- 238000005096 rolling process Methods 0.000 claims description 24
- 238000007580 dry-mixing Methods 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000002028 Biomass Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920001592 potato starch Polymers 0.000 claims description 10
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 5
- 210000001161 mammalian embryo Anatomy 0.000 claims description 5
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 claims description 4
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- MEXSQFDSPVYJOM-UHFFFAOYSA-J cerium(4+);disulfate;tetrahydrate Chemical compound O.O.O.O.[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MEXSQFDSPVYJOM-UHFFFAOYSA-J 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 4
- 238000007171 acid catalysis Methods 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012075 bio-oil Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 240000008042 Zea mays Species 0.000 description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 9
- 235000005822 corn Nutrition 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000012745 toughening agent Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- IYNQBRDDQSFSRT-UHFFFAOYSA-N chromium(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IYNQBRDDQSFSRT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- 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
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
-
- 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
-
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalytic heat carrier preparation, and particularly relates to a preparation method of a catalytic heat carrier and application of the catalytic heat carrier in self-heating pyrolysis liquefaction. The mixture of quartz sand and red mud is used as a ball seed, calcium carbonate is wrapped on the outer surface of spherical particles, calcium oxide is formed after calcination treatment, carbon dioxide in pyrolysis gas can be adsorbed, and the purpose of reducing acid and improving quality of biological oil is achieved; then the pseudo-boehmite is coated on the outer surface of the spherical particles, and a layer of gamma-Al is formed on the outer surface after calcination treatment 2 O 3 The catalyst can realize selective catalysis and acid catalysis on pyrolysis gas, increase the surface area of the porous ceramic carrier, act as a catalyst carrier, load metal salt solution by an excessive impregnation method, and dry and calcine to finally form the porous ceramic catalytic heat carrier with a catalyst coating. The prepared catalytic heat carrier has high mechanical strength, strong thermal shock resistance, good high-temperature adaptability, stable performance and low wear rate.
Description
Technical Field
The invention belongs to the technical field of catalytic heat carrier preparation, and particularly relates to a preparation method of a catalytic heat carrier and application of the catalytic heat carrier in self-heating pyrolysis liquefaction.
Background
The bio-oil produced by biomass pyrolysis and liquefaction can be used for obtaining high-quality fuel or chemical raw materials and other basic products in a certain conversion mode, but the bio-oil directly pyrolyzed has the problems of high oxygen content, strong acidity, complex components, difficult separation and purification and the like. Based on this, it is necessary to upgrade the bio-oil quality, generally by introducing a suitable catalyst, but the bio-oil quality upgrade brings about a decrease in bio-oil yield, so that a method for balancing the bio-oil quality and yield is needed.
The catalyst commonly used in biomass pyrolysis liquefaction mainly comprises metal salts, metal oxides, molecular sieves, carbon-based catalysts and the like. The metal oxide has wide application in biomass fast pyrolysis, and the catalytic action is mostly related to oxidation-reduction capability caused by polyvalent state or self acid/alkali characteristic, but exists in the form of particles or powder, so that the efficiency of heat and mass transfer is greatly reduced, the metal oxide has low mechanical strength and is easy to abrade, carbon deposition and inactivation are easy to occur in the pyrolysis process, carbon residue and catalyst are difficult to separate, continuous regeneration is required, recycling is difficult, the economic cost is increased, and the metal oxide is unfavorable for industrial popularization.
The ceramic ball has very wide application, becomes an indispensable product in the chemical industry, and has the remarkable characteristics of corrosion resistance, high temperature resistance, high mechanical strength, large heat storage and release capacity, good thermal shock stability, good heat conduction performance, small thermal expansion coefficient, high wear resistance, no pollution and the like. The ceramic balls in the V-shaped down tube have good heat storage capacity, heat is provided for the product, flow and heat and mass transfer behaviors among solid particles are enhanced, heat and mass transfer efficiency in the pyrolysis process is improved to a certain extent, and the bio-oil yield is increased. The ceramic balls have high mechanical strength, good fluidity, clean the reactor, prevent coke accumulation, and play a role in recycling the ceramic balls and high-value utilization of biochar after the subsequent separation of the carbon balls. However, the traditional ceramic balls only play a role of a carrier or heat accumulation, and have single property and effect.
Therefore, in order to balance the quality and yield of the bio-oil, the development of a novel multifunctional catalytic heat carrier by combining a catalyst design path and a heat exchange medium path becomes a key point of research.
Disclosure of Invention
The invention aims at: the preparation method of the catalytic heat carrier is easy to obtain raw materials, low in cost and suitable for industrial production; the catalytic heat carrier prepared by the method has high mechanical strength and stable performance, and can realize multistage catalysis; the invention also provides application of the catalyst in self-heating pyrolysis liquefaction.
The preparation method of the catalytic heat carrier provided by the invention comprises the following steps:
(1) Preparation of ceramic balls
Taking a mixture of quartz sand and red mud as aggregate, adding zinc borate, potato starch, activated carbon powder and zirconia powder, and dry-mixing to obtain a mixture; adding a methyl cellulose solution into the mixture for granulation to obtain spherical embryo particles; the ball embryo particles are dried, dried and calcined to prepare ceramic balls;
(2) Coated calcium oxide powder coating
Taking the ceramic balls prepared in the step (1) as ball seeds, adding a methylcellulose solution into the high-purity calcium carbonate as a raw material, granulating by adopting a rolling forming method, coating the calcium carbonate on the surfaces of the ceramic balls, and then airing, drying and calcining to obtain the ceramic balls coated with the calcium oxide powder coating;
(3) Coated alumina coating
Taking the ceramic ball coated with the calcium oxide powder coating prepared in the step (2) as a ball seed, taking pseudo-boehmite as a raw material, adding a methylcellulose solution, coating the pseudo-boehmite on the ball seed by adopting a rolling forming method, and then airing, drying and calcining to prepare the ceramic ball coated with the aluminum oxide coating;
(4) Supported metal salt solution
Adding a chromium source, a nickel source and a cerium source into deionized water simultaneously, adopting mechanical stirring and ultrasonic assisted dispersion to form a stable solution, immersing the ceramic balls coated with the aluminum oxide coating prepared in the step (3) into the mixed solution for 6-8h, and then drying and calcining to prepare the catalytic heat carrier.
Wherein:
in the step (1), 4 to 8 percent of zinc borate, 3 to 4 percent of potato starch, 3 to 4 percent of activated carbon powder and 10 to 15 percent of zirconia powder are added for dry mixing based on the mass sum of quartz sand and red mud as 100 percent; the rotation speed during dry mixing is 30-50 r/min, and the dry mixing time is 90-120 min.
Wherein: the mass ratio of the quartz sand to the red mud is 5-8:2-5.
And (3) adding the mixture into a spherical particle forming machine, and adding 0.5-1wt% of methyl cellulose solution for granulating.
And (3) airing the spherical blank particles in the step (1) at normal temperature for 12-18 h, then placing the spherical blank particles in a baking oven at 70-105 ℃ for drying for 8-12 h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating the spherical blank particles to 170-180 ℃ at a heating rate of 1.5-2.0 ℃/min for 1h, and then heating the spherical blank particles to 1000-1200 ℃ at a heating rate of 2-2.2 ℃/min for 2-3 h to prepare the ceramic balls.
The diameter of the ceramic ball prepared in the step (1) is 1-2 mm.
And (3) adding 0.5-1wt% of methyl cellulose solution in the step (2) and granulating by adopting a rolling forming method.
And (3) wrapping the calcium carbonate on the surface of the ceramic ball in the step (2), airing at normal temperature for 12-18 h, then placing the ceramic ball in a baking oven at 70-105 ℃ for drying for 8-12 h, finally placing the ceramic ball in a muffle furnace for calcining, heating to 170-180 ℃ at a heating rate of 2-4 ℃/min for 1h, and heating to 800-900 ℃ at a heating rate of 5-6 ℃/min for 1-2 h to prepare the ceramic ball coated with the calcium oxide powder coating.
The diameter of the ceramic ball coated with the calcium oxide powder coating prepared in the step (2) is 2-3 mm.
And (3) adding 0.5-1wt% of methyl cellulose solution into the mixture for granulation by adopting a rolling forming method.
And (3) wrapping the pseudo-boehmite on the ball seeds, airing the pseudo-boehmite at normal temperature for 12-18 h, then placing the pseudo-boehmite in a 100-105 ℃ oven for drying for 8-12 h, finally placing the pseudo-boehmite in a muffle furnace for calcination, heating the pseudo-boehmite to 170-180 ℃ at a heating rate of 3-4 ℃/min for 1h, and heating the pseudo-boehmite to 700-800 ℃ at a heating rate of 5 ℃/min for 1.5-2.5 h to prepare the ceramic ball coated with the alumina coating.
The diameter of the ceramic ball coated with the alumina coating prepared in the step (3) is 3-4 mm.
The molar concentration ratio of the chromium source, the nickel source and the cerium source in the step (4) is 4-5:1-2:2-3.
The chromium source is chromium nitrate nonahydrate; the nickel source is one of nickel nitrate hexahydrate or nickel sulfate hexahydrate; the cerium source is one of cerous nitrate hexahydrate or cerous sulfate tetrahydrate.
Immersing the ceramic balls coated with the aluminum oxide coating prepared in the step (3) in the mixed solution for 6-8h, so that the chromium source, the nickel source and the cerium source are uniformly dispersed on the ceramic balls coated with the aluminum oxide coating.
The metal salt solution is loaded by the excessive dipping method in the step (4).
The drying temperature in the step (4) is 100-105 ℃, and the drying time is 8-12 h; the calcination is to heat up to 550-600 ℃ at a heating rate of 5-10 ℃/min for 1.0-2.0 h, so as to prepare the catalytic heat carrier.
According to the preparation method of the catalytic heat carrier, the mixture of quartz sand and red mud is used as a spherical seed, calcium carbonate is wrapped on the outer surface of spherical particles, calcium oxide is formed after calcination treatment, carbon dioxide in pyrolysis gas can be adsorbed, and decarboxylation and acid reduction treatment are carried out on compounds in biological oil; then the pseudo-boehmite is coated on the outer surface of the spherical particles, and a layer of gamma-Al is formed on the outer surface after calcination treatment 2 O 3 The active alumina layer has certain acid functional site and special pore structure, can realize selective catalysis and acid catalysis on pyrolysis gas, increase the surface area of the porous ceramic carrier, can serve as a catalyst carrier, load metal salt solution by an excessive impregnation method, and finally form the catalytic heat carrier with different types of metal oxides by drying and calcining. Meanwhile, zirconium oxide is introduced into the catalytic heat carrier, so that the toughness and impact strength of the material can be improved, and the service life of the material can be prolonged.
The application of the catalytic heat carrier prepared by the preparation method of the catalytic heat carrier in self-heating pyrolysis liquefaction comprises the steps of mixing biomass and the catalytic heat carrier in situ in a quartz boat, and then placing the mixture into a horizontal tubular furnace for pyrolysis for 5-15 min at 450-500 ℃ under the condition that the nitrogen flow rate is 600-1000 ml/min.
Wherein:
the mixing mass ratio of the biomass to the catalytic heat carrier is 1:3-20. Under laboratory conditions, the preferable mixing mass ratio of the biomass to the catalytic heat carrier is 1:3-5; under the condition of industrial application, the mixing mass ratio of the biomass to the catalytic heat carrier is 1:20.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the catalytic heat carrier has the advantages of simple preparation process, easily available raw materials and low cost, and is suitable for industrial production and application.
(2) The catalytic heat carrier prepared by the preparation method of the catalytic heat carrier has the advantages of high mechanical strength, strong thermal shock resistance, good high-temperature adaptability, stable performance and low abrasion rate, can realize multistage catalysis, and can carry out quality improvement treatment on biological oil and non-condensable gas.
(3) The catalytic heat carrier prepared by the preparation method of the catalytic heat carrier has excellent heat storage capacity, can transfer enough heat to biomass particles, has a certain heat and mass transfer effect, and has a certain catalytic effect when being used as a carrier.
(4) The catalytic heat carrier prepared by the preparation method of the catalytic heat carrier has rich pore structure and large specific surface area, and the substrate can utilize active metal to carry out surface modification treatment on the substrate so as to enhance the catalytic effect.
(5) The application of the catalytic heat carrier in self-heating pyrolysis liquefaction disclosed by the invention is that the catalytic heat carrier is mixed with biomass for pyrolysis liquefaction, so that the quality and yield of the biological oil can be well balanced.
Drawings
FIG. 1 is an SEM image of a catalytic heat carrier prepared in comparative example 2;
fig. 2 is an SEM image of the catalytic heat carrier prepared in example 1.
Detailed Description
The invention is further described below with reference to examples.
Comparative example 1
3g of crushed and dried corn stalks are laid in a quartz boat and then put in a horizontal tube furnace for pyrolysis for 10min at 500 ℃ under the condition of 800ml/min of nitrogen flow rate.
Comparative example 2
The preparation method of the catalytic heat carrier described in the comparative example 2 comprises the following steps:
(1) The mass ratio of quartz sand to red mud is 6:4, taking the two as ceramic aggregate, taking the sum of the two as 100%, adding 6% of zinc borate, 4% of potato starch, 4% of activated carbon powder and 10% of zirconia powder for dry mixing, wherein 10% of zirconia powder is taken as a toughening agent, adding the toughening agent into a mixer for mixing, and controlling the rotating speed to be 30r/min and the dry mixing time to be 100min.
(2) Adding the mixture into a spherical particle forming machine, slowly adding 0.5wt% methyl cellulose solution for granulating, and adopting a rolling forming method for granulating to obtain spherical embryo particles.
(3) The spherical blank particles are dried for 14 hours at normal temperature, then are placed in a baking oven at 105 ℃ for drying for 10 hours, finally are placed in a muffle furnace for calcination, are heated to 180 ℃ at a heating rate of 2 ℃/min, are insulated for 1 hour, are heated to 1000 ℃ at a heating rate of 2 ℃/min, and are insulated for 3 hours, so that ceramic balls with the diameter of 1.5mm are prepared.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 0.5wt% of methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted to wrap the calcium carbonate on the ball seeds.
(5) Drying at normal temperature for 12h, drying in an oven at 105 ℃ for 8h, calcining in a muffle furnace, heating to 175 ℃ at a heating rate of 3 ℃/min for 1h, heating to 800 ℃ at a heating rate of 5 ℃/min for 2h, and heating the outer calcium carbonate to generate calcium oxide at high temperature to prepare the ceramic ball with the diameter of 2.2mm of the coated calcium oxide powder coating.
(6) Ceramic balls coated with calcium carbonate powder coating are used as ball seeds, pseudo-boehmite is used as a raw material, 0.5wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seeds by adopting a rolling forming method.
(7) Drying at normal temperature for 12h, drying in a drying oven at 105 ℃ for 10h, calcining in a muffle furnace, heating to 170 ℃ at a heating rate of 3 ℃/min for 1h, and heating to 750 ℃ at a heating rate of 5 ℃/min for 2.0h to prepare the catalytic heat carrier coated with the alumina coating and having a diameter of 3.1 mm.
The application of the catalytic heat carrier in self-heating pyrolysis liquefaction in comparative example 2 is that 3g of crushed and dried corn stalks are mixed with 15g of catalytic heat carrier in a quartz boat, and the mixture is put into a horizontal tube furnace for pyrolysis for 10min at 500 ℃ under the condition of 800ml/min of nitrogen flow rate.
Comparative example 3
The preparation method of the catalytic heat carrier described in the comparative example 3 comprises the following steps:
(1) The mass ratio of quartz sand to red mud is 5:5, taking the two as ceramic aggregate, taking the sum of the two as 100%, adding 8% of zinc borate, 3% of potato starch, 3% of activated carbon powder and 12% of zirconia powder for dry mixing, taking 12% of zirconia powder as a toughening agent, adding the powder into a mixer for mixing, and controlling the rotating speed at 50r/min and the dry mixing time at 90min.
(2) The mixture is added into a spherical particle forming machine, 1wt% methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted for granulation.
(3) The spherical blank particles are dried for 13 hours at normal temperature, then are placed in a baking oven at 105 ℃ for drying for 10 hours, finally are placed in a muffle furnace for calcination, are heated to 170 ℃ at a heating rate of 1.5 ℃/min, are insulated for 1 hour, are heated to 1100 ℃ at a heating rate of 2.0 ℃/min, and are insulated for 2.5 hours, so that ceramic balls with the diameter of 1.7mm are obtained.
(4) The firing formed ceramic ball is used as ball seed, pseudo-boehmite is used as raw material, 1wt% methyl cellulose solution is added, and the pseudo-boehmite is wrapped on the ball seed by adopting a rolling forming method.
(5) Drying at normal temperature for 12h, drying in an oven at 105 ℃ for 8h, and finally calcining in a muffle furnace, wherein the temperature is firstly increased to 180 ℃ at a heating rate of 3.5 ℃/min for 1h, then is increased to 800 ℃ at a heating rate of 5 ℃/min for 1.5h, and the ceramic ball with the diameter of 2.5mm coated with the alumina coating is prepared.
(6) Adding a chromium source, a nickel source and a cerium source into deionized water, adopting mechanical stirring and dispersion and ultrasonic assisted dispersion to form a stable solution, immersing ceramic balls coated with an alumina coating on the outer layer into the mixed solution for 6 hours, uniformly loading the chromium source, the nickel source and the cerium source on the ceramic balls, and drying and calcining to prepare the catalytic heat carrier.
The chromium source in the step (6) is chromium nitrate hexahydrate, the nickel source is nickel nitrate hexahydrate, and the cerium source is cerium nitrate hexahydrate.
The molar concentration ratio of the chromium source, the nickel source and the cerium source in the step (6) is 4.5:1:2.
The metal salt solution is loaded by the excessive dipping method in the step (6).
And (3) drying in the step (6) at 105 ℃ for 10 hours. The calcination is to heat up to 550 ℃ at a speed of 5 ℃/min for 1.0h, so as to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in self-heating pyrolysis liquefaction in comparative example 3 is that 3g of crushed and dried corn stalks are mixed with 15g of catalytic heat carrier impregnated with a supported catalyst in a quartz boat, and the mixture is placed in a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ under the condition of 800ml/min of nitrogen flow rate.
Comparative example 4
The preparation method of the catalytic heat carrier described in the comparative example 4 comprises the following steps:
(1) The mass ratio of quartz sand to red mud is 5:5, taking the two as ceramic aggregate, taking the sum of the two as 100%, adding 8% of zinc borate, 4% of potato starch, 3% of activated carbon powder and 10% of zirconia powder for dry mixing, taking 10% of zirconia powder as a toughening agent, adding the powder into a mixer for mixing, and controlling the rotating speed to be 60r/min and the dry mixing time to be 90min.
(2) The mixture is added into a spherical particle forming machine, 1wt% methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted for granulation.
(3) The spherical blank particles are dried for 12 hours at normal temperature, then are placed in a baking oven at 105 ℃ for drying for 10 hours, finally are placed in a muffle furnace for calcination, are heated to 170 ℃ at a heating rate of 1.5 ℃/min, are insulated for 1 hour, are heated to 1100 ℃ at a heating rate of 2.0 ℃/min, and are insulated for 2.5 hours, so that ceramic balls with the diameter of 1.6mm are obtained.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 1wt% of methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted to wrap the calcium carbonate on the ball seeds.
(5) Drying at normal temperature for 12h, drying in a baking oven at 105 ℃ for 8h, finally calcining in a muffle furnace, firstly raising the temperature from room temperature to 170 ℃ at a heating rate of 4 ℃/min for 1h, then raising the temperature to 850 ℃ at a heating rate of 5 ℃/min for 1.5h, and forming calcium oxide at high temperature by using calcium carbonate as an outer layer to prepare the ceramic ball with the diameter of 2.5mm and coated with the calcium oxide powder coating.
(6) Adding a chromium source, a nickel source and a cerium source into deionized water, adopting mechanical stirring and dispersion and ultrasonic assisted dispersion to form a stable solution, and immersing ceramic balls coated with an alumina coating on the outer layer into the mixed solution for 7h. The chromium source, the nickel source and the cerium source are dispersed and loaded on the ceramic balls uniformly, and the catalytic heat carrier is prepared through drying and calcining.
The chromium source in the step (6) is chromium nitrate hexahydrate, the nickel source is nickel nitrate hexahydrate, and the cerium source is nickel nitrate hexahydrate.
The molar concentration ratio of the chromium source, the nickel source and the cerium source in the step (6) is 5:2:3.
The metal salt solution is loaded by the excessive dipping method in the step (6).
The drying temperature in the step (6) is 105 ℃, and the drying time is 8 hours; the calcination is to heat up to 550 ℃ at a heating rate of 10 ℃/min for 2.0h, so as to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in self-heating pyrolysis liquefaction in comparative example 4 is that 3g of crushed and dried corn stalks are mixed with 15g of catalytic heat carrier impregnated with a supported catalyst in a quartz boat, and the mixture is placed in a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ under the condition of 800ml/min of nitrogen flow rate.
Example 1
The method for preparing the catalytic heat carrier of the present embodiment 1 comprises the following steps:
(1) The mass ratio of quartz sand to red mud is 7:3, taking the two as ceramic aggregate, taking the sum of the two as 100%, adding 8% of zinc borate, 3% of potato starch, 3% of activated carbon powder and 12% of zirconia powder for dry mixing, taking 12% of zirconia powder as a toughening agent, adding the powder into a mixer for mixing, and controlling the rotating speed at 50r/min and the dry mixing time at 120min.
(2) The mixture is added into a spherical particle forming machine, 1wt% methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted for granulation.
(3) The spherical blank particles are dried for 13 hours at normal temperature, then are placed in a baking oven at 105 ℃ for drying for 10 hours, finally are placed in a muffle furnace for calcination, are heated to 170 ℃ at a heating rate of 1.5 ℃/min, are insulated for 1 hour, are heated to 1100 ℃ at a heating rate of 2.0 ℃/min, and are insulated for 2.5 hours, so that ceramic balls with the diameter of 1.8mm are obtained.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 1wt% of methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted to wrap the calcium carbonate on the ball seeds.
(5) Drying at normal temperature for 13h, drying in an oven at 105 ℃ for 8h, finally calcining in a muffle furnace, heating to 170 ℃ at a heating rate of 4 ℃/min for 1h, heating to 850 ℃ at a heating rate of 6 ℃/min for 1.5h, and heating the outer calcium carbonate layer to generate calcium oxide at high temperature to prepare the ceramic ball with the diameter of 2.4mm and coated with the calcium oxide powder coating.
(6) The ceramic ball coated with the calcium oxide powder coating is used as a ball seed, pseudo-boehmite is used as a raw material, a 1wt% methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seed by adopting a rolling forming method.
(7) Drying at normal temperature for 12h, drying in a baking oven at 105 ℃ for 8h, calcining in a muffle furnace, heating to 180 ℃ at a heating rate of 3.5 ℃/min for 1h, and heating to 800 ℃ at a heating rate of 5 ℃/min for 1.5h to prepare the ceramic ball coated with the alumina coating and having a diameter of 3.3 mm.
(8) Adding a chromium source, a nickel source and a cerium source into deionized water, adopting mechanical stirring dispersion and ultrasonic assisted dispersion to form a stable solution, immersing ceramic balls coated with an alumina coating on the outer layer into the mixed solution for 8 hours, uniformly dispersing the chromium source, the nickel source and the cerium source on the ceramic balls in a dispersing load manner, and drying and calcining to prepare the catalytic heat carrier.
The chromium source in the step (8) is chromium nitrate hexahydrate, the nickel source is nickel nitrate hexahydrate, and the cerium source is cerium nitrate hexahydrate.
The molar concentration ratio of the chromium source, the nickel source and the cerium source in the step (8) is 4.5:1:2.
The metal salt solution is loaded by the excessive dipping method in the step (8).
The drying temperature in the step (8) is 105 ℃ and the time is 12 hours; the calcination is to heat up to 600 ℃ at a heating rate of 10 ℃/min for 1.0h, so as to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in self-heating pyrolysis liquefaction in the embodiment 1 is that 3g of crushed and dried corn stalks are mixed with 9g of catalytic heat carrier impregnated with a supported catalyst in a quartz boat, and the mixture is placed in a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ under the condition of 800ml/min of nitrogen flow rate.
Example 2
The preparation method of the catalytic heat carrier of the embodiment 2 comprises the following steps:
(1) The mass ratio of quartz sand to red mud is 6:4, and the mass sum of the quartz sand and the red mud is 100 percent. Adding 6% of zinc borate, 4% of potato starch, 4% of activated carbon powder and 15% of zirconia powder for dry mixing, adding 15% of zirconia powder as a toughening agent into a mixer for mixing, and controlling the rotating speed at 30r/min and the dry mixing time at 120min.
(2) Adding the mixture into a spherical particle forming machine, slowly adding 0.65wt% methyl cellulose solution for granulating, and adopting a rolling forming method for granulating.
(3) The spherical blank particles are dried for 14 hours at normal temperature, then are placed in a 100 ℃ oven to be dried for 8 hours, finally are placed in a muffle furnace to be calcined, firstly are heated to 175 ℃ at a heating rate of 1.67 ℃/min, are kept warm for 1 hour, and then are heated to 1000 ℃ at a heating rate of 2.08 ℃/min, are kept warm for 3 hours, so that ceramic balls with the diameter of 1.3mm are obtained.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 0.5wt% of methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted to wrap the calcium carbonate on the ball seeds.
(5) Drying at normal temperature for 12h, drying in an oven at 105 ℃ for 10h, finally calcining in a muffle furnace, heating to 175 ℃ at a heating rate of 3 ℃/min for 1h, heating to 850 ℃ at a heating rate of 5 ℃/min for 2h, and heating the outer calcium carbonate to generate calcium oxide at high temperature to prepare the ceramic ball with the diameter of 2.4mm and coated with the calcium oxide coating.
(6) Ceramic balls coated with calcium oxide powder coating are used as ball seeds, pseudo-boehmite is used as a raw material, 0.5wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seeds by adopting a rolling forming method.
(7) Drying at normal temperature for 12h, drying in an oven at 105 ℃ for 10h, calcining in a muffle furnace, heating to 170 ℃ at a heating rate of 3 ℃/min for 1h, and heating to 750 ℃ at a heating rate of 5 ℃/min for 2.0h to obtain ceramic balls with the diameter of 3.5mm and coated with the alumina coating.
(8) Adding a chromium source, a nickel source and a cerium source into deionized water, adopting mechanical stirring dispersion and ultrasonic assisted dispersion to form a stable solution, immersing ceramic balls coated with an alumina coating on the outer layer into the mixed solution for 8 hours, uniformly dispersing the chromium source, the nickel source and the cerium source on the ceramic balls in a dispersing and loading manner, and drying and calcining to prepare the catalytic heat carrier.
The chromium source in the step (8) is chromium nitrate nonahydrate, the nickel source is nickel nitrate hexahydrate, and the cerium source is cerium sulfate tetrahydrate.
The molar concentration ratio of the chromium source, the nickel source and the cerium source in the step (8) is 4:1:2.
The metal salt solution is loaded by the excessive dipping method in the step (8).
The drying temperature in the step (8) is 105 ℃, and the drying time is 12 hours; the calcination is to heat up to 600 ℃ at a heating rate of 8 ℃/min for 1.5 hours, so as to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in self-heating pyrolysis liquefaction in the embodiment 2 is that 3g of crushed and dried corn stalks are mixed with 15g of catalytic heat carrier impregnated with a supported catalyst in a quartz boat, and the mixture is placed in a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ under the condition of 800ml/min of nitrogen flow rate.
Example 3
The preparation method of the catalytic heat carrier of the embodiment 3 comprises the following steps:
(1) The mass ratio of quartz sand to red mud is 8:2, and the mass sum of the quartz sand and the red mud is 100 percent. Adding 4% of zinc borate, 3% of potato starch, 3% of activated carbon powder and 15% of zirconia powder for dry mixing, adding 15% of zirconia powder as a toughening agent into a mixer for mixing, and controlling the rotating speed at 50r/min and the dry mixing time at 120min.
(2) Adding the mixture into a spherical particle forming machine, slowly adding 0.5wt% methyl cellulose solution for granulating, and adopting a rolling forming method for granulating.
(3) The spherical blank particles are dried for 12 hours at normal temperature, then are placed in a 105 ℃ oven for drying for 12 hours, finally are placed in a muffle furnace for calcination, are heated to 180 ℃ at a heating rate of 2.0 ℃/min, are insulated for 1 hour, are heated to 1200 ℃ at a heating rate of 2.2 ℃/min, and are insulated for 2.0 hours, so that ceramic balls with the diameter of 1.8mm are prepared.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 0.5wt% of methyl cellulose solution is slowly added for granulation, and a rolling forming method is adopted to wrap the calcium carbonate on the ball seeds.
(5) Drying at normal temperature for 12h, drying in an oven at 105 ℃ for 8h, calcining in a muffle furnace, heating to 180 ℃ at a heating rate of 3.5 ℃/min for 1h, heating to 900 ℃ at a heating rate of 5 ℃/min for 1.0h, and heating the outer calcium carbonate to generate calcium oxide at high temperature to prepare the ceramic balls with the diameter of 2.5mm and coated with the calcium oxide powder coating.
(6) Ceramic balls coated with calcium oxide powder coating are used as ball seeds, pseudo-boehmite is used as a raw material, 0.5wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seeds by adopting a rolling forming method.
(7) Drying at normal temperature for 12h, drying in a baking oven at 105 ℃ for 8h, calcining in a muffle furnace, heating to 175 ℃ at a heating rate of 4 ℃/min, preserving heat for 1h, heating to 700 ℃ at a heating rate of 5 ℃/min, preserving heat for 2.5h, and obtaining the ceramic balls with the diameter of 3.8mm and coated with the alumina coating.
(8) Adding a chromium source, a nickel source and a cerium source into deionized water, adopting mechanical stirring dispersion and ultrasonic assisted dispersion to form a stable solution, immersing ceramic balls coated with an alumina coating on the outer layer into the mixed solution for 7 hours, uniformly dispersing the chromium source, the nickel source and the cerium source on the ceramic balls in a dispersing load manner, and drying and calcining to prepare the catalytic heat carrier.
The chromium source in the step (8) is chromium nitrate hexahydrate, the nickel source is nickel sulfate hexahydrate, and the cerium source is cerium nitrate hexahydrate.
The molar concentration ratio of the chromium source, the nickel source and the cerium source in the step (8) is 4.5:1.5:2.5.
The metal salt solution is loaded by the excessive dipping method in the step (8).
The drying temperature in the step (8) is 105 ℃, and the drying time is 10 hours; the calcination is to heat up to 550 ℃ at a heating rate of 5 ℃/min for 2.0h, so as to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in self-heating pyrolysis liquefaction in embodiment 3 is applied to biomass pyrolysis liquefaction under industrial conditions.
The catalytic heat carrier heated by high-temperature flue gas and the corn stalk powder subjected to drying treatment are jointly conveyed into a VDT reactor (the VDT reactor is a pyrolysis liquefaction system disclosed in a biomass pyrolysis liquefaction system heated by a solid heat storage ball of patent No. CN 102206496A), wherein the mass ratio of the catalytic heat carrier to the corn stalk subjected to drying treatment is 20:1, the corn stalk and the catalytic heat carrier are contacted and heated to about 500 ℃ in the mixing flow process of the V-shaped downcomer, non-condensable gas, biological oil and carbon residue are generated after catalytic pyrolysis reaction, and the catalytic heat carrier is sieved out and conveyed to a heating device again for carrying out a fever reaction by a lifting device for recycling.
The physical properties of the catalytic heat carrier are shown in table 1 below:
TABLE 1 physical Properties of catalytic Heat Carrier
As can be seen from table 1: the apparent porosity of the catalytic heat carrier prepared by modifying the ceramic balls with the metal salt solution is improved, which indicates that the metal salt solution changes the surface morphology of the porous ceramic and increases the apparent porosity. Meanwhile, the thermal shock resistance and the heat conductivity coefficient of the catalytic heat carrier are improved.
TABLE 2 yield of biological oils in pyrolysis liquefaction
In comparative examples 2 to 4 and examples 1 to 3, the bio-oil yield was improved to a different extent than in comparative example 1 after the addition of the catalytic heat carrier, but the yield data of comparative examples 2 to 4 were inferior to those of examples 1 to 3. This also verifies that this novel catalytic heat carrier improves bio-oil quality and also improves bio-oil yield at the same time as catalytic pyrolysis.
TABLE 3 essential component content of biological oils
As is clear from the biological oil components of comparative examples 1 to 4 and examples 1 to 3 shown in Table 3, the acid content was reduced from 33.21% before catalysis to 7.84% after catalysis, and the relative content of the bound ketones was increased, indicating that the catalytic heat carrier promoted the carboxylic acid ketonization reaction of the biological oil. And the relative content of the furan and phenol high-value chemicals is increased, which provides guarantee for extracting the high-value chemicals and manufacturing fuels from the subsequent biological oil.
Claims (7)
1. A preparation method of a catalytic heat carrier is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of ceramic balls
Taking a mixture of quartz sand and red mud as aggregate, adding zinc borate, potato starch, activated carbon powder and zirconia powder, and dry-mixing to obtain a mixture; adding a methyl cellulose solution into the mixture for granulation to obtain spherical embryo particles; the ball embryo particles are dried, dried and calcined to prepare ceramic balls;
(2) Coated calcium oxide powder coating
Taking the ceramic balls prepared in the step (1) as ball seeds, adding a methylcellulose solution into the high-purity calcium carbonate as a raw material, granulating by adopting a rolling forming method, coating the calcium carbonate on the surfaces of the ceramic balls, and then airing, drying and calcining to obtain the ceramic balls coated with the calcium oxide powder coating;
(3) Coated alumina coating
Taking the ceramic ball coated with the calcium oxide powder coating prepared in the step (2) as a ball seed, taking pseudo-boehmite as a raw material, adding a methylcellulose solution, coating the pseudo-boehmite on the ball seed by adopting a rolling forming method, and then airing, drying and calcining to prepare the ceramic ball coated with the aluminum oxide coating;
(4) Supported metal salt solution
Adding a chromium source, a nickel source and a cerium source into deionized water simultaneously, dispersing by mechanical stirring and ultrasonic assisted dispersing to obtain a stable solution, immersing the ceramic balls coated with the aluminum oxide coating prepared in the step (3) into the mixed solution for 6-8h, and then drying and calcining to obtain a catalytic heat carrier;
wherein:
in the step (1), 4 to 8 percent of zinc borate, 3 to 4 percent of potato starch, 3 to 4 percent of activated carbon powder and 10 to 15 percent of zirconia powder are added for dry mixing according to the mass sum of quartz sand and red mud being 100 percent; the rotation speed during dry mixing is 30-50 r/min, and the dry mixing time is 90-120 min;
in the step (1), the mass ratio of the quartz sand to the red mud is 5-8:2-5;
the chromium source in the step (4) is chromium nitrate nonahydrate; the nickel source is one of nickel nitrate hexahydrate or nickel sulfate hexahydrate; the cerium source is one of cerium nitrate hexahydrate or cerium sulfate tetrahydrate;
in the step (4), the molar concentration ratio of the chromium source, the nickel source and the cerium source is 4-5:1-2:2-3;
in the step (4), the excessive dipping method is adopted to load the metal salt solution;
in the step (4), the drying temperature is 100-105 ℃ and the drying time is 8-12 h; the calcination is to heat from room temperature to 550-600 ℃ for 1.0-2.0 h at a heating rate of 5-10 ℃/min, so as to prepare the catalytic heat carrier.
2. The method for preparing a catalytic heat carrier according to claim 1, wherein: adding the mixture into a spherical particle forming machine, and adding 0.5-1wt% of methyl cellulose solution for granulating;
drying the spherical blank particles in the step (1) at normal temperature for 12-18 h, then drying the spherical blank particles in an oven at 70-105 ℃ for 8-12 h, finally calcining the spherical blank particles in a muffle furnace, heating the spherical blank particles to 170-180 ℃ at a heating rate of 1.5-2.0 ℃/min for 1h, and heating the spherical blank particles to 1000-1200 ℃ at a heating rate of 2-2.2 ℃/min for 2-3 h to prepare ceramic balls;
the diameter of the ceramic ball prepared in the step (1) is 1-2 mm.
3. The method for preparing a catalytic heat carrier according to claim 1, wherein: adding 0.5-1wt% methyl cellulose solution into the step (2) and granulating by adopting a rolling forming method;
and (2) wrapping the calcium carbonate on the surface of the ceramic ball, airing at normal temperature for 12-18 h, then placing the ceramic ball in a 70-105 ℃ oven for drying for 8-12 h, finally placing the ceramic ball in a muffle furnace for calcination, firstly heating to 170-180 ℃ at a heating rate of 2-4 ℃/min for 1h, and then heating to 800-900 ℃ at a heating rate of 5-6 ℃/min for 1-2 h to prepare the ceramic ball coated with the calcium oxide powder coating.
4. The method for preparing a catalytic heat carrier according to claim 1, wherein: the diameter of the ceramic ball coated with the calcium oxide powder coating prepared in the step (2) is 2-3 mm.
5. The method for preparing a catalytic heat carrier according to claim 1, wherein: adding 0.5-1wt% methyl cellulose solution into the step (3) and granulating by adopting a rolling forming method;
wrapping pseudo-boehmite on a ball seed, airing at normal temperature for 12-18 h, then drying in a baking oven at 100-105 ℃ for 8-12 h, finally calcining in a muffle furnace, heating to 170-180 ℃ at a heating rate of 3-4 ℃/min for 1h, and heating to 700-800 ℃ at a heating rate of 5 ℃/min for 1.5-2.5 h to prepare the ceramic ball coated with the alumina coating;
the diameter of the ceramic ball coated with the alumina coating prepared in the step (3) is 3-4 mm.
6. The application of the catalytic heat carrier prepared by the preparation method of claim 1 in self-heating pyrolysis liquefaction, which is characterized in that: mixing biomass and catalytic heat carrier in situ in a quartz boat, and then placing the mixture into a horizontal tubular furnace for pyrolysis at 450-500 ℃ for 5-15 min under the condition that the nitrogen flow rate is 600-1000 ml/min.
7. The use of a catalytic heat carrier according to claim 6 in self-heating pyrolysis liquefaction, characterized in that: the mixing mass ratio of the biomass to the catalytic heat carrier is 1:3-20.
Priority Applications (1)
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