CN113617360A - 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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- CN113617360A CN113617360A CN202110881436.6A CN202110881436A CN113617360A CN 113617360 A CN113617360 A CN 113617360A CN 202110881436 A CN202110881436 A CN 202110881436A CN 113617360 A CN113617360 A CN 113617360A
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 94
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 30
- 239000000919 ceramic Substances 0.000 claims abstract description 104
- 238000001035 drying Methods 0.000 claims abstract description 65
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000001354 calcination Methods 0.000 claims abstract description 47
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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
- 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 18
- 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 11
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- 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
- 238000005096 rolling process Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 238000007580 dry-mixing Methods 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 239000002028 Biomass Substances 0.000 claims description 13
- 229920001592 potato starch Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000010453 quartz Substances 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
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 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 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 claims description 4
- 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
- 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 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000012075 bio-oil Substances 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 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
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 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
- 239000010902 straw Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 239000012745 toughening agent Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005338 heat storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 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
- 230000001754 anti-pyretic effect Effects 0.000 description 2
- 239000002221 antipyretic Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- MEXSQFDSPVYJOM-UHFFFAOYSA-J cerium(4+);disulfate;tetrahydrate Chemical group O.O.O.O.[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MEXSQFDSPVYJOM-UHFFFAOYSA-J 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
- 230000000694 effects 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 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
- 238000001878 scanning electron micrograph Methods 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
- 239000000758 substrate Substances 0.000 description 1
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- 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
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- 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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- Materials Engineering (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention belongs to the technical field of preparation of catalytic heat carriers, 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 the ball particle, 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 bio-oil is achieved; then the pseudo-boehmite is wrapped on the outer surface of the spherical particles, and a layer of gamma-Al is formed on the outer surface after calcination treatment2O3Can realize the pyrolysis gasThe method comprises the steps of selective catalysis and acid catalysis, increasing the surface area of a porous ceramic carrier, serving as a catalyst carrier, loading a metal salt solution by an excess impregnation method, drying and calcining to finally form the porous ceramic catalysis type heat carrier with a catalyst coating. The prepared catalytic heat carrier has the advantages of 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 preparation of catalytic heat carriers, 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 generated by the pyrolysis and liquefaction of the biomass can obtain high-quality fuel or chemical raw materials and other basic products through 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, there is a need to improve bio-oil quality, generally by introducing a suitable catalyst, but the improvement of bio-oil quality will result in a decrease of bio-oil yield, and thus a method for balancing 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 application of metal oxide in biomass fast pyrolysis is wide, the catalytic action of the metal oxide is mostly related to the redox capability caused by the multivalence state of the metal oxide or the acid/alkali characteristics of the metal oxide, but the metal oxide exists in a particle or powder form, so that the heat transfer and mass transfer efficiency is greatly reduced, the mechanical strength of the metal oxide is low, the metal oxide is easy to wear, carbon deposition and inactivation are easy to occur in the pyrolysis process, carbon residue and a catalyst are difficult to separate, continuous regeneration is needed, the metal oxide is difficult to recycle, the economic cost is increased, and the metal oxide is not beneficial to industrial popularization.
The ceramic ball is widely applied, 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 quantity, good thermal shock stability, good heat conductivity, small thermal expansion coefficient, high wear resistance, no pollution and the like. The ceramic balls in the V-shaped downcomer have good heat storage capacity, provide heat for products, strengthen the flow and heat and mass transfer behaviors among solid particles, improve the heat and mass transfer efficiency in the pyrolysis process to a certain extent, and increase the yield of the bio-oil. The ceramic balls have high mechanical strength and good fluidity, the reactor is cleaned, coke accumulation is prevented, and after subsequent carbon ball separation, the ceramic balls are recycled and the biochar is utilized with high value to a certain extent. However, the traditional ceramic ball only plays a role of a carrier or heat storage, and has a single property and function.
Therefore, in order to balance the quality and yield of the bio-oil, a catalyst design path and a heat exchange medium path are combined into a whole, so that a novel multifunctional catalytic heat carrier is developed, and the development of the novel multifunctional catalytic heat carrier becomes a research focus.
Disclosure of Invention
The invention aims to: 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 multi-stage catalysis; the invention also provides the application of the self-heating pyrolysis liquefaction catalyst in the self-heating pyrolysis liquefaction.
The preparation method of the catalytic heat carrier comprises the following steps:
(1) preparation of ceramic balls
Taking a mixture of quartz sand and red mud as an 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 blank particles; drying, drying and calcining the spherical blank particles to obtain ceramic balls;
(2) coating with calcium oxide powder
Taking the ceramic ball prepared in the step (1) as a ball seed, taking high-purity calcium carbonate as a raw material, adding a methyl cellulose solution, granulating by adopting a rolling forming method, wrapping the calcium carbonate on the surface of the ceramic ball, and then airing, drying and calcining to obtain the ceramic ball 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, adding a methyl cellulose solution into the pseudo-boehmite serving as a raw material, wrapping the pseudo-boehmite on the ball seed by adopting a rolling forming method, and then airing, drying and calcining the wrapped ceramic ball to prepare the ceramic ball coated with the aluminum oxide coating;
(4) loaded metal salt solutions
And (3) simultaneously adding a chromium source, a nickel source and a cerium source into deionized water, dispersing into a stable solution by adopting mechanical stirring and ultrasonic assistance, immersing the ceramic ball coated with the alumina coating prepared in the step (3) into the mixed solution for 6-8 hours, and then drying and calcining to prepare the catalytic heat carrier.
Wherein:
adding 4-8% of zinc borate, 3-4% of potato starch, 3-4% of activated carbon powder and 10-15% of zirconium oxide powder into the mixture to be dry-mixed, wherein the sum of the mass of the quartz sand and the mass of the red mud is 100%; the rotating 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.
Adding the mixture into a spherical particle forming machine in the step (1), and adding 0.5-1 wt% of methyl cellulose solution for granulation.
Airing 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, and finally calcining the spherical blank particles in a muffle furnace, wherein the temperature is raised to 170-180 ℃ at the heating rate of 1.5-2.0 ℃/min for 1h, and then raised to 1000-1200 ℃ at the heating rate of 2-2.2 ℃/min for 2-3 h to prepare the ceramic ball.
The diameter of the ceramic ball prepared in the step (1) is 1-2 mm.
And (3) adding 0.5-1 wt% of methyl cellulose solution in the step (2) and granulating by a rolling forming method.
Wrapping calcium carbonate on the surface of the ceramic ball in the step (2), airing at normal temperature for 12-18 h, then drying in an oven at 70-105 ℃ for 8-12 h, and finally calcining in a muffle furnace, wherein the temperature is raised to 170-180 ℃ at the temperature raising rate of 2-4 ℃/min for 1h, and then raised to 800-900 ℃ at the temperature raising rate of 5-6 ℃/min for 1-2 h, so as 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 (4) adding 0.5-1 wt% of methyl cellulose solution in the step (3) and granulating by a rolling forming method.
Wrapping the pseudoboehmite on the ball seeds in the step (3), drying at normal temperature for 12-18 h, then drying in an oven at 100-105 ℃ for 8-12 h, and finally calcining in a muffle furnace, wherein the temperature is raised to 170-180 ℃ at the heating rate of 3-4 ℃/min for 1h, and then raised to 700-800 ℃ at the heating rate of 5 ℃/min for 1.5-2.5 h, so as to prepare the ceramic ball coated with the alumina coating.
And (4) 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 to the nickel source to 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.
And (4) immersing the ceramic ball coated with the alumina coating prepared in the step (3) into the mixed solution for 6-8 hours, so that the chromium source, the nickel source and the cerium source are uniformly dispersed on the ceramic ball coated with the alumina coating.
And (4) loading the metal salt solution by adopting an excess impregnation method.
The drying temperature in the step (4) is 100-105 ℃, and the drying time is 8-12 h; the calcination is carried out by raising the temperature to 550-600 ℃ at a temperature raising rate of 5-10 ℃/min and preserving the temperature for 1.0-2.0 h, so as to obtain 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 deacidification treatment are performed on compounds in bio-oil; then the pseudo-boehmite is wrapped on the outer surface of the spherical particles, and a layer of gamma-Al is formed on the outer surface after calcination treatment2O3The active alumina layer has certain acid functional sites and special pore structure, can realize selective catalysis and acid catalysis on pyrolysis gas, increases the surface area of the porous ceramic carrier, can serve as a catalyst carrier, then loads a metal salt solution by an excess impregnation method, and finally forms a catalytic heat carrier with different types of metal oxides. Meanwhile, the zirconium oxide is introduced into the catalytic heat carrier, so that the toughness of the material can be improved, the impact strength can be increased, and the service life of the material can be prolonged.
According to the application of the catalytic heat carrier prepared by the preparation method of the catalytic heat carrier in the self-heating pyrolysis liquefaction, biomass and the catalytic heat carrier are mixed in situ in a quartz boat, and then the quartz boat is placed in a horizontal tubular furnace, and pyrolysis is carried out 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 the laboratory condition, the preferable mixing mass ratio of the biomass to the catalytic heat carrier is 1: 3-5; under industrial application conditions, the mixing mass ratio of the biomass to the catalytic heat carrier is preferably 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 obtained 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 wear rate, can realize multi-stage catalysis, and can improve the quality of bio-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 certain heat and mass transfer effects, and has certain catalytic effects when being used as a carrier.
(4) The catalytic heat carrier prepared by the preparation method of the catalytic heat carrier has rich pore structures and large specific surface area, and a substrate can be subjected to surface modification treatment by using active metals, so that the catalytic effect is enhanced.
(5) The catalytic heat carrier is mixed with biomass for pyrolysis and liquefaction, so that the quality and yield of the bio-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 picture of the catalytic heat carrier prepared in example 1.
Detailed Description
The present invention is further described below with reference to examples.
Comparative example 1
3g of crushed and dried corn straws are flatly laid in a quartz boat and then put into a horizontal tubular furnace to be pyrolyzed for 10min at 500 ℃ under the condition of the nitrogen flow rate of 800 ml/min.
Comparative example 2
The preparation method of the catalytic heat carrier described in this comparative example 2 consists of the following steps:
(1) selecting quartz sand and red mud according to a mass ratio of 6: and 4, taking the two as ceramic aggregate, adding 6% of zinc borate, 4% of potato starch, 4% of activated carbon powder and 10% of zirconia powder for dry mixing, wherein the 10% of zirconia powder is taken as a toughening agent, adding into a mixer for mixing, and controlling the rotating speed at 30r/min and the dry mixing time at 100 min.
(2) And adding the mixture into a spherical particle forming machine, slowly adding 0.5 wt% of methyl cellulose solution for granulation, and granulating by adopting a rolling forming method to obtain spherical blank particles.
(3) Airing the spherical blank particles at normal temperature for 14h, then placing the spherical blank particles in a 105 ℃ oven for drying for 10h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating to 180 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, then heating to 1000 ℃ at the heating rate of 2 ℃/min, preserving heat for 3h, and preparing the ceramic spheres with the diameter of 1.5 mm.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 0.5 wt% of methyl cellulose solution is slowly added for granulation, and the calcium carbonate is wrapped on the ball seeds by adopting a rolling forming method.
(5) Drying the ceramic ball at normal temperature for 12h, then placing the ceramic ball in a 105 ℃ oven for drying for 8h, finally placing the ceramic ball in a muffle furnace for calcining, firstly heating to 175 ℃ at the heating rate of 3 ℃/min, preserving heat for 1h, then heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, generating calcium oxide at the outer layer of calcium carbonate at high temperature, and preparing the ceramic ball coated with the calcium oxide powder coating and having the diameter of 2.2 mm.
(6) The ceramic ball coated with the calcium carbonate powder coating is used as a ball seed, the pseudo-boehmite is used as a raw material, 0.5 wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seed by a rolling forming method.
(7) Drying the alumina coated catalyst for 12 hours at normal temperature, then placing the alumina coated catalyst in a 105 ℃ oven for drying for 10 hours, finally calcining the alumina coated catalyst in a muffle furnace, firstly heating the alumina coated catalyst to 170 ℃ at a heating rate of 3 ℃/min, preserving the heat for 1 hour, then heating the alumina coated catalyst to 750 ℃ at a heating rate of 5 ℃/min, preserving the heat for 2.0 hours, and preparing the catalytic heat carrier coated with the alumina coating and having the diameter of 3.1 mm.
The application of the catalytic heat carrier in the self-heating pyrolysis liquefaction in the comparative example 2 is that 3g of crushed and dried corn straws are mixed with 15g of catalytic heat carrier in a quartz boat, and the mixture is put into a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ and under the nitrogen flow rate of 800 ml/min.
Comparative example 3
The preparation method of the catalytic heat carrier described in this comparative example 3 consists of the following steps:
(1) selecting quartz sand and red mud in a mass ratio of 5: and 5, taking the two as ceramic aggregate, adding 8% of zinc borate, 3% of potato starch, 3% of activated carbon powder and 12% of zirconium oxide powder into the ceramic aggregate to be dry-mixed, taking the 12% of zirconium oxide powder as a toughening agent, adding the ceramic aggregate and the activated carbon powder into a mixer to be mixed, and controlling the rotating speed at 50r/min and the dry-mixing time at 90 min.
(2) And adding the mixture into a spherical particle forming machine, slowly adding 1 wt% of methyl cellulose solution for granulation, and granulating by adopting a rolling forming method.
(3) And drying the spherical blank particles at normal temperature for 13h, then placing the spherical blank particles in a 105 ℃ oven for drying for 10h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating to 170 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 1h, then heating to 1100 ℃ at the heating rate of 2.0 ℃/min, preserving heat for 2.5h, and obtaining the ceramic spheres with the diameter of 1.7 mm.
(4) The ceramic ball formed by firing is taken as a ball seed, the pseudo-boehmite is taken as a raw material, 1 wt% of 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, then placing in a 105 ℃ oven for drying for 8h, finally placing in a muffle furnace for calcining, firstly heating to 180 ℃ at the heating rate of 3.5 ℃/min and preserving heat for 1h, then heating to 800 ℃ at the heating rate of 5 ℃/min and preserving heat for 1.5h, and finally obtaining the ceramic ball coated with the alumina coating and with the diameter of 2.5 mm.
(6) Adding a chromium source, a nickel source and a cerium source into deionized water, dispersing by adopting mechanical stirring and ultrasonic-assisted dispersion to form a stable solution, immersing a ceramic ball coated with an aluminum oxide coating on the outer layer into the mixed solution for 6 hours to uniformly load the chromium source, the nickel source and the cerium source on the ceramic ball, and drying and calcining to prepare the catalytic heat carrier.
The chromium source in the step (6) is chromium nitrate nonahydrate, the nickel source is nickel nitrate hexahydrate, and the cerium source is cerium nitrate hexahydrate.
The molar concentration ratio of the chromium source to the nickel source to the cerium source in the step (6) is 4.5:1: 2.
And (4) loading the metal salt solution by adopting an excess impregnation method in the step (6).
In the step (6), the drying is carried out for 10 hours at 105 ℃. The calcination is carried out by raising the temperature to 550 ℃ at the speed of 5 ℃/min and preserving the temperature for 1.0h to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in the self-heating pyrolysis liquefaction in the comparative example 3 is that 3g of crushed and dried corn straws are mixed with 15g of catalytic heat carrier impregnated with a supported catalyst in a quartz boat, and the mixture is put into a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ and under the condition of nitrogen flow rate of 800 ml/min.
Comparative example 4
The preparation method of the catalytic heat carrier described in this comparative example 4 consists of the following steps:
(1) selecting quartz sand and red mud in a mass ratio of 5: and 5, taking the two as ceramic aggregate, adding 8% of zinc borate, 4% of potato starch, 3% of activated carbon powder and 10% of zirconia powder into the ceramic aggregate to be dry-mixed, taking 10% of zirconia powder as a toughening agent, adding the ceramic aggregate and the activated carbon powder into a mixer to be mixed, and controlling the rotating speed at 60r/min and the dry-mixing time at 90 min.
(2) And adding the mixture into a spherical particle forming machine, slowly adding 1 wt% of methyl cellulose solution for granulation, and granulating by adopting a rolling forming method.
(3) Airing the spherical blank particles at normal temperature for 12h, then placing the spherical blank particles in a 105 ℃ oven for drying for 10h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating to 170 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 1h, then heating to 1100 ℃ at the heating rate of 2.0 ℃/min, preserving heat for 2.5h, and obtaining the ceramic spheres with the diameter of 1.6 mm.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 1 wt% of methyl cellulose solution is slowly added for granulation, and the ball seeds are wrapped with the calcium carbonate by adopting a rolling forming method.
(5) Drying at normal temperature for 12h, then placing in a 105 ℃ oven for drying for 8h, finally placing in a muffle furnace for calcining, firstly heating from room temperature to 170 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 1h, then heating to 850 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1.5h, generating calcium oxide at the outer layer of calcium carbonate at high temperature, and preparing the ceramic ball coated with the calcium oxide powder coating and having the diameter of 2.5 mm.
(6) Adding a chromium source, a nickel source and a cerium source into deionized water, dispersing by adopting mechanical stirring and ultrasonic-assisted dispersion to form a stable solution, and immersing the ceramic ball coated with the alumina coating on the outer layer into the mixed solution for 7 hours. And uniformly dispersing the dispersed load of 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 nonahydrate, 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.
And (4) loading the metal salt solution by adopting an excess impregnation method in the step (6).
In the step (6), the drying temperature is 105 ℃, and the drying time is 8 hours; the calcination is carried out by heating to 550 ℃ at the heating rate of 10 ℃/min and preserving the heat for 2.0h to prepare the catalytic heat carrier.
The application of the catalytic heat carrier in the self-heating pyrolysis liquefaction of the comparative example 4 is that 3g of crushed and dried corn straws are mixed with 15g of catalytic heat carrier impregnated with the supported catalyst in a quartz boat, and the mixture is put into a horizontal tube furnace to be pyrolyzed for 10min at 500 ℃ and under the condition of nitrogen flow rate of 800 ml/min.
Example 1
The preparation method of catalytic heat carrier described in this example 1 consists of the following steps:
(1) selecting quartz sand and red mud in a mass ratio of 7: and 3, taking the two as ceramic aggregate, adding 8% of zinc borate, 3% of potato starch, 3% of activated carbon powder and 12% of zirconium oxide powder into the ceramic aggregate to be dry-mixed, taking the 12% of zirconium oxide powder as a toughening agent, adding the ceramic aggregate and the activated carbon powder into a mixer to be mixed, and controlling the rotating speed at 50r/min and the dry-mixing time at 120 min.
(2) And adding the mixture into a spherical particle forming machine, slowly adding 1 wt% of methyl cellulose solution for granulation, and granulating by adopting a rolling forming method.
(3) And drying the spherical blank particles at normal temperature for 13h, then placing the spherical blank particles in a 105 ℃ oven for drying for 10h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating to 170 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 1h, then heating to 1100 ℃ at the heating rate of 2.0 ℃/min, preserving heat for 2.5h, and obtaining the ceramic spheres with the diameter of 1.8 mm.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 1 wt% of methyl cellulose solution is slowly added for granulation, and the ball seeds are wrapped with the calcium carbonate by adopting a rolling forming method.
(5) Drying at normal temperature for 13h, then placing in a 105 ℃ oven for drying for 8h, finally placing in a muffle furnace for calcining, firstly heating to 170 ℃ at the heating rate of 4 ℃/min, preserving heat for 1h, then heating to 850 ℃ at the heating rate of 6 ℃/min, preserving heat for 1.5h, generating calcium oxide at the outer layer of calcium carbonate at high temperature, and preparing the ceramic ball coated with the calcium oxide powder coating and having the diameter of 2.4 mm.
(6) The ceramic ball coated with the calcium oxide powder coating is used as a ball seed, the pseudo-boehmite is used as a raw material, 1 wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seed by adopting a rolling forming method.
(7) Drying the ceramic ball at normal temperature for 12h, then placing the ceramic ball in a 105 ℃ oven for drying for 8h, finally placing the ceramic ball in a muffle furnace for calcining, firstly heating to 180 ℃ at the heating rate of 3.5 ℃/min and preserving heat for 1h, then heating to 800 ℃ at the heating rate of 5 ℃/min and preserving heat for 1.5h, and preparing the ceramic ball coated with the alumina coating and having the diameter of 3.3 mm.
(8) Adding a chromium source, a nickel source and a cerium source into deionized water, dispersing by adopting mechanical stirring and ultrasonic-assisted dispersion to form a stable solution, immersing a ceramic ball coated with an aluminum oxide coating on the outer layer into the mixed solution for 8 hours to uniformly disperse the dispersed loads of the chromium source, the nickel source and the cerium source on the ceramic ball, 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 nitrate hexahydrate.
The molar concentration ratio of the chromium source to the nickel source to the cerium source in the step (8) is 4.5:1: 2.
And (4) loading the metal salt solution by adopting an excess impregnation method in the step (8).
In the step (8), the drying temperature is 105 ℃, and the time is 12 hours; the calcination is carried out by heating to 600 ℃ at the heating rate of 10 ℃/min and preserving the heat for 1.0h to prepare the catalytic heat carrier.
In the application of the catalytic heat carrier in the self-heating pyrolysis liquefaction described in this embodiment 1, 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 ℃ and under the nitrogen flow rate of 800 ml/min.
Example 2
The preparation method of the catalytic heat carrier described in this example 2 consists of the following steps:
(1) the mass ratio of the quartz sand to the red mud is 6:4, and the sum of the mass 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, taking 15% of zirconia powder as a toughening agent, adding into a mixer for mixing, and controlling the rotating speed at 30r/min and the dry mixing time at 120 min.
(2) And adding the mixture into a spherical particle forming machine, slowly adding 0.65 wt% of methyl cellulose solution for granulation, and granulating by adopting a rolling forming method.
(3) And drying the spherical blank particles at normal temperature for 14h, then placing the spherical blank particles in a 100 ℃ oven for drying for 8h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating to 175 ℃ at the heating rate of 1.67 ℃/min, preserving heat for 1h, then heating to 1000 ℃ at the heating rate of 2.08 ℃/min, preserving heat for 3h, and obtaining the ceramic spheres with the diameter of 1.3 mm.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 0.5 wt% of methyl cellulose solution is slowly added for granulation, and the calcium carbonate is wrapped on the ball seeds by adopting a rolling forming method.
(5) Drying the ceramic ball at normal temperature for 12h, then placing the ceramic ball in a 105 ℃ oven for drying for 10h, finally placing the ceramic ball in a muffle furnace for calcining, firstly heating to 175 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 1h, then heating to 850 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h, generating calcium oxide at the outer layer of calcium carbonate at high temperature, and preparing the ceramic ball coated with the calcium oxide coating and having the diameter of 2.4 mm.
(6) The ceramic ball coated with the calcium oxide powder coating is used as a ball seed, the pseudo-boehmite is used as a raw material, 0.5 wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seed by a rolling forming method.
(7) Drying at normal temperature for 12h, then placing in a 105 ℃ oven for drying for 10h, finally placing in a muffle furnace for calcining, firstly heating to 170 ℃ at the heating rate of 3 ℃/min, preserving heat for 1h, then heating to 750 ℃ at the heating rate of 5 ℃/min, preserving heat for 2.0h, and preparing the ceramic ball coated with the alumina coating and with the diameter of 3.5 mm.
(8) Adding a chromium source, a nickel source and a cerium source into deionized water, dispersing by adopting mechanical stirring and ultrasonic-assisted dispersion to obtain a stable solution, immersing the ceramic ball coated with the alumina coating on the outer layer into the mixed solution for 8 hours to uniformly disperse the dispersed load of the chromium source, the nickel source and the cerium source on the ceramic ball, and drying and calcining to obtain 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 to the nickel source to the cerium source in the step (8) is 4:1: 2.
And (4) loading the metal salt solution by adopting an excess impregnation method in the step (8).
In the step (8), the drying temperature is 105 ℃, and the drying time is 12 h; the calcination is carried out by raising the temperature to 600 ℃ at the temperature raising rate of 8 ℃/min and preserving the temperature for 1.5h to prepare the catalytic heat carrier.
In the application of the catalytic heat carrier in the self-heating pyrolysis liquefaction described in this embodiment 2, 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 ℃ and under the nitrogen flow rate of 800 ml/min.
Example 3
The preparation method of the catalytic heat carrier described in this example 3 consists of the following steps:
(1) the mass ratio of the quartz sand to the red mud is 8:2, and the quartz sand and the red mud are used as ceramic aggregates and the mass sum is 100%. Adding 4% of zinc borate, 3% of potato starch, 3% of activated carbon powder and 15% of zirconia powder for dry mixing, taking 15% of zirconia powder as a toughening agent, adding into a mixer for mixing, and controlling the rotating speed at 50r/min and the dry mixing time at 120 min.
(2) And adding the mixture into a spherical particle forming machine, slowly adding 0.5 wt% of methyl cellulose solution for granulation, and granulating by adopting a rolling forming method.
(3) Airing the spherical blank particles at normal temperature for 12h, then placing the spherical blank particles in a 105 ℃ oven for drying for 12h, finally placing the spherical blank particles in a muffle furnace for calcining, firstly heating to 180 ℃ at the heating rate of 2.0 ℃/min, preserving heat for 1h, then heating to 1200 ℃ at the heating rate of 2.2 ℃/min, preserving heat for 2.0h, and preparing the ceramic spheres with the diameter of 1.8 mm.
(4) The ceramic balls formed by firing are used as ball seeds, high-purity calcium carbonate is used as a raw material, 0.5 wt% of methyl cellulose solution is slowly added for granulation, and the calcium carbonate is wrapped on the ball seeds by adopting a rolling forming method.
(5) Drying at normal temperature for 12h, then placing in a 105 ℃ oven for drying for 8h, finally placing in a muffle furnace for calcining, firstly heating to 180 ℃ at the heating rate of 3.5 ℃/min and preserving heat for 1h, then heating to 900 ℃ at the heating rate of 5 ℃/min and preserving heat for 1.0h, generating calcium oxide at the high temperature of the outer calcium carbonate, and preparing the ceramic ball coated with the calcium oxide powder coating and having the diameter of 2.5 mm.
(6) The ceramic ball coated with the calcium oxide powder coating is used as a ball seed, the pseudo-boehmite is used as a raw material, 0.5 wt% of methyl cellulose solution is added, and the pseudo-boehmite is coated on the ball seed by a rolling forming method.
(7) Drying the ceramic ball at normal temperature for 12h, then placing the ceramic ball in a 105 ℃ oven for drying for 8h, finally calcining the ceramic ball in a muffle furnace, firstly heating the ceramic ball to 175 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 1h, then heating the ceramic ball to 700 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2.5h, and obtaining the ceramic ball coated with the alumina coating and with the diameter of 3.8 mm.
(8) Adding a chromium source, a nickel source and a cerium source into deionized water, dispersing by adopting mechanical stirring and ultrasonic-assisted dispersion to form a stable solution, immersing a ceramic ball coated with an aluminum oxide coating on the outer layer into the mixed solution for 7 hours to uniformly disperse the dispersed loads of the chromium source, the nickel source and the cerium source on the ceramic ball, 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 sulfate hexahydrate, and the cerium source is cerous nitrate hexahydrate.
The molar concentration ratio of the chromium source to the nickel source to the cerium source in the step (8) is 4.5:1.5: 2.5.
And (4) loading the metal salt solution by adopting an excess impregnation method in the step (8).
In the step (8), the drying temperature is 105 ℃, and the drying time is 10 hours; the calcination is carried out by raising the temperature to 550 ℃ at the temperature raising rate of 5 ℃/min and preserving the temperature for 2.0h to prepare the catalytic heat carrier.
The application of the catalytic heat carrier described in this embodiment 3 in self-heating pyrolysis liquefaction is applied to biomass pyrolysis liquefaction under industrial conditions.
The catalytic heat carrier heated by high-temperature flue gas and the dried corn straw powder are jointly conveyed into a VDT reactor (the VDT reactor is a pyrolysis liquefaction system disclosed in a solid heat storage ball heating biomass pyrolysis liquefaction system with the patent number of CN 102206496A), wherein the mass ratio of the catalytic heat carrier to the dried corn straw is 20:1, the corn straw and the catalytic heat carrier are contacted and heated to about 500 ℃ in the mixed flowing process in a V-shaped descending pipe, non-condensable gas, biological oil and residual carbon are generated after catalytic pyrolysis reaction, the catalytic heat carrier is screened out and then conveyed to a heating device again through a lifting device for carrying out antipyretic reaction, and the antipyretic reaction is recycled.
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 the ceramic balls through the modification treatment of the metal salt solution is improved, which indicates that the metal salt solution changes the surface form of the porous ceramic and increases the apparent porosity. Meanwhile, the thermal shock resistance strength and the heat conductivity coefficient of the catalytic heat carrier are improved.
TABLE 2 yield of bio-oil in pyrolytic liquefaction
In comparative examples 2-4 and examples 1-3, the yield of bio-oil was improved to a different extent than comparative example 1 after the addition of the catalytic heat carrier, but the yield data of comparative examples 2-4 was inferior to that of examples 1-3. The method also proves that the novel catalytic heat carrier improves the bio-oil quality by catalytic pyrolysis and improves the bio-oil yield.
TABLE 3 essential component content of bio-oil
As can be seen from the bio-oil compositions of comparative examples 1 to 4 and examples 1 to 3 described 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 ketone substances was increased, which indicates that the catalytic heat carrier promotes the carboxylic acid ketonization reaction of the bio-oil. And the relative content of furan and phenol high-value chemicals is increased, which provides guarantee for extracting the high-value chemicals from the subsequent bio-oil and manufacturing fuels.
Claims (10)
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 an 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 blank particles; drying, drying and calcining the spherical blank particles to obtain ceramic balls;
(2) coating with calcium oxide powder
Taking the ceramic ball prepared in the step (1) as a ball seed, taking high-purity calcium carbonate as a raw material, adding a methyl cellulose solution, granulating by adopting a rolling forming method, wrapping the calcium carbonate on the surface of the ceramic ball, and then airing, drying and calcining to obtain the ceramic ball 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, adding a methyl cellulose solution into the pseudo-boehmite serving as a raw material, wrapping the pseudo-boehmite on the ball seed by adopting a rolling forming method, and then airing, drying and calcining the wrapped ceramic ball to prepare the ceramic ball coated with the aluminum oxide coating;
(4) loaded metal salt solutions
And (3) simultaneously adding a chromium source, a nickel source and a cerium source into deionized water, dispersing by adopting mechanical stirring and ultrasonic-assisted dispersion to obtain a stable solution, immersing the ceramic balls coated with the alumina coating prepared in the step (3) into the mixed solution for 6-8 hours, and then drying and calcining to obtain the catalytic heat carrier.
2. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: adding 4-8% of zinc borate, 3-4% of potato starch, 3-4% of activated carbon powder and 10-15% of zirconium oxide powder into the mixture to be dry-mixed, wherein the sum of the mass of the quartz sand and the mass of the red mud is 100%; the rotating speed during dry mixing is 30-50 r/min, and the dry mixing time is 90-120 min.
3. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: the mass ratio of the quartz sand to the red mud in the step (1) is 5-8: 2-5.
4. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: adding the mixture into a spherical particle forming machine in the step (1), and adding 0.5-1 wt% of methyl cellulose solution for granulation;
airing 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, and finally calcining the spherical blank particles in a muffle furnace, wherein the temperature is raised to 170-180 ℃ at the heating rate of 1.5-2.0 ℃/min for 1h, and then raised to 1000-1200 ℃ at the 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.
5. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: adding 0.5-1 wt% of methyl cellulose solution in the step (2) and granulating by a rolling forming method;
wrapping calcium carbonate on the surface of the ceramic ball in the step (2), airing at normal temperature for 12-18 h, then drying in an oven at 70-105 ℃ for 8-12 h, and finally calcining in a muffle furnace, wherein the temperature is raised to 170-180 ℃ at the temperature raising rate of 2-4 ℃/min for 1h, and then raised to 800-900 ℃ at the temperature raising rate of 5-6 ℃/min for 1-2 h, so as to prepare the ceramic ball coated with the calcium oxide powder coating.
6. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: the diameter of the ceramic ball coated with the calcium oxide powder coating prepared in the step (2) is 2-3 mm.
7. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: adding 0.5-1 wt% of methyl cellulose solution in the step (3) and granulating by a rolling forming method;
wrapping the pseudoboehmite on the ball seeds in the step (3), drying at normal temperature for 12-18 h, then drying in an oven at 100-105 ℃ for 8-12 h, and finally calcining in a muffle furnace, wherein the temperature is raised to 170-180 ℃ at the heating rate of 3-4 ℃/min for 1h, and then raised to 700-800 ℃ at the heating rate of 5 ℃/min for 1.5-2.5 h to prepare the ceramic ball coated with the alumina coating;
and (4) the diameter of the ceramic ball coated with the alumina coating prepared in the step (3) is 3-4 mm.
8. Process for the preparation of a catalytic heat carrier according to claim 1, characterized in that: 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 cerous nitrate hexahydrate or cerous sulfate tetrahydrate;
the molar concentration ratio of the chromium source to the nickel source to the cerium source in the step (4) is 4-5: 1-2: 2-3;
loading the metal salt solution by adopting an excess impregnation 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 carried out by heating from room temperature to 550-600 ℃ at a heating rate of 5-10 ℃/min and preserving the temperature for 1.0-2.0 h, so as to obtain the catalytic heat carrier.
9. The use of the catalytic heat carrier prepared by the preparation method of claim 1 in the self-heating pyrolysis liquefaction, which is characterized in that: mixing the biomass and a catalytic heat carrier in situ in a quartz boat, and then putting the quartz boat into a horizontal tube furnace for pyrolysis at 450-500 ℃ for 5-15 min under the condition that the nitrogen flow rate is 600-1000 ml/min.
10. Use of a catalytic heat carrier according to claim 9 in autothermal pyrolysis liquefaction, characterized in that: the mixing mass ratio of the biomass to the catalytic heat carrier is 1: 3-20.
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