LU502470B1 - Method for green recycling and comprehensive utilization of red mud waste and lignin waste - Google Patents
Method for green recycling and comprehensive utilization of red mud waste and lignin waste Download PDFInfo
- Publication number
- LU502470B1 LU502470B1 LU502470A LU502470A LU502470B1 LU 502470 B1 LU502470 B1 LU 502470B1 LU 502470 A LU502470 A LU 502470A LU 502470 A LU502470 A LU 502470A LU 502470 B1 LU502470 B1 LU 502470B1
- Authority
- LU
- Luxembourg
- Prior art keywords
- lignin
- red mud
- waste
- comprehensive utilization
- molecular sieve
- Prior art date
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- 229920005610 lignin Polymers 0.000 title claims abstract description 75
- 239000002699 waste material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 22
- 239000012075 bio-oil Substances 0.000 claims abstract description 15
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000008878 coupling Effects 0.000 claims abstract description 11
- 238000010168 coupling process Methods 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- 239000004566 building material Substances 0.000 claims abstract description 10
- 238000001226 reprecipitation Methods 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 3
- 238000000197 pyrolysis Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003337 fertilizer Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011449 brick Substances 0.000 claims description 3
- 239000011469 building brick Substances 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1321—Waste slurries, e.g. harbour sludge, industrial muds
- C04B33/1322—Red mud
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
- C04B35/62209—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse using woody material, remaining in the ceramic products
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4837—Lignin
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- Dispersion Chemistry (AREA)
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Abstract
The invention relates to the technical field of a waste resource utilization, and in particular to a method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste. The method includes the following steps: 1) extracting and separating the lignin from agricultural and forestry wastes, waste residues rich in lignin matrix generated by a paper industry or a biological refining industry to obtain high-purity lignin; 2) performing a harmless modification treatment on the red mud by an acid dissolution-alkali reprecipitation coupling roasting method; 3) preparing hydrocarbon-rich bio-oil, biochar and syngas with a catalytic pyrolysis on the lignin by using the modified red mud and a molecular sieve catalyst; and 4) further applying the modified red mud after a reaction to fields of adsorption materials and building materials.
Description
DESCRIPTION LU502470
TECHNICAL FIELD The invention relates to the technical field of waste resource utilization, and in particular to a method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste.
BACKGROUND Red mud is a solid waste residue produced by alumina industry. On average, one to two tons of the red mud are produced for every ton of alumina produced. China is a big alumina producer, producing millions of tons of the red mud every year. With a rapid development of society, a demand for the alumina is increasing, so an output of the red mud is gradually increasing. A chemical composition of the red mud is mainly composed of Na,O, Al,Os, SiO», Fe;0s, TiO; and CaO, etc. The red mud has a strong alkalinity (pH>12) and a trace radioactivity (containing natural radioactive elements, such as uranium and thorium, etc.), and also contains a small amount of fluoride. The red mud belongs to a strong alkaline waste residue and has a serious alkali pollution. At present, a treatment method of the red mud in enterprises is mainly to build dams and pile the red mud up in an open air. On the one hand, this method occupies a large amount of land, increases maintenance and management costs, and on the other hand, this method pollutes a land and a groundwater. Moreover, after the red mud is dried, the dried red mud forms dust flying with wind, resulting in an increase of PM concentration in an atmosphere, polluting the air, affecting a health of human beings, animals and plants, and seriously damaging an ecological environment. Therefore, a harmless treatment of the red mud is of great significance to a green recycling development of alumina enterprises. It is necessary to reduce a negative environmental impact brought by the red mud. However, how to realize a high-value utilization of the red mud still faces severe challenges.
As a second major component of biomass, natural reserves of lignin are second only to cellulose resources, and the lignin is regenerated at a rate of about 50 billion tons per year. The lignin is mainly derived from agricultural and forestry wastes, a paper industry, biogh&/502470 engineering and a biorefinery industry. From a current situation, abundant lignin resources have not been effectively developed and utilized. For example, the paper industry needs to extract and separate 1.4 billion tons of cellulose resources from plants every year, resulting in up to 50 million tons of lignin waste residue. At present, main treatment methods are to discharge the lignin waste residue directly into the outside rivers in a form of "black liquor" or to carry out simple concentration and combustion treatments, resulting in serious water resources and atmospheric environmental pollution. Unreasonable treatments not only waste resources, but also cause further pollution damage to the environment. Therefore, the development of a related lignin high value-added conversion process is urgently needed.
At present, the high-value utilization of the red mud focuses on a flue gas desulfurization, a removal of organic pollutants, a hydrogen production by an ammonia decomposition, a methane production by anaerobic digestion, building materials, bio-oil upgrading and thermochemical conversion of biomass. A modification of the red mud may further optimize the structural characteristics and a catalytic performance of the red mud. High-quality bio-oil may be prepared by catalytic pyrolysis of lignin, but there are still some problems such as a low yield and a low selectivity of target products, and a rapid deactivation of the catalyst. In view of an excellent catalytic performance of the red mud, the red mud provides a possibility for its high-value utilization in the field of lignin catalytic pyrolysis. Therefore, it is of great significance to firstly modify the red mud, reduce its strong alkalinity and create conditions for its high value-added utilization, and introduce the red mud into the process of lignin catalytic pyrolysis, so as to increase a production of the target products and slow down the rapid deactivation of the catalyst. In addition, the high-value utilization of two typical waste resources, the red mud and the lignin, may promote the development of cross-industry waste coupling utilization technology, which is the key to the development of green circular economy.
SUMMARY An objective of the invention is to provide a method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste, so as to solve a problem of a waste resource utilization, promote a resource utilization and harmless treatment of the red mud waste, enhance an application potential of the red mud in the field of lignin catalytic conversion,
and achieve the objective of green recycling and comprehensive utilization of the red mud ahd/502470 lignin waste.
In order to achieve the above objective, the invention is realized by a following technical scheme: the method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste, including following steps: 1) extracting and separating the lignin from agricultural and forestry wastes, waste residues rich in lignin matrix generated by a paper industry or a biological refining industry to obtain high-purity lignin; 2) performing a harmless modification treatment on the red mud by an acid dissolution-alkali reprecipitation coupling roasting method; 3) preparing hydrocarbon-rich bio-oil, biochar and syngas with a catalytic pyrolysis on the lignin by using the modified red mud and a molecular sieve catalyst; and 4) further applying the modified red mud after a reaction to fields of adsorption materials and building materials.
Optionally, in the step 1), lignin extraction and separation methods include a Klason method, an organic solvent method, an ionic liquid method or an enzymatic hydrolysis method.
Optionally, in the step 2), in the acid dissolution-alkali reprecipitation coupling roasting method for the red mud, an inorganic acid with a concentration of 5-7mol/L is used for an acid dissolution treatment, and the inorganic acid is hydrochloric acid, sulfuric acid or phosphoric acid; an alkali precipitation treatment adopts 30-40% ammonia water by mass, and a roasting treatment temperature is 635-660°C.
Optionally, in the step 2), a waste liquid obtained from the modification treatment may be used to remove inorganic impurities contained in the lignin itself, including alkali metals and alkaline earth metals.
Optionally, in the step 3), the molecular sieve catalyst is one or more of HZSM-5, HP and H-USY. The above molecular sieve catalysts are all commercial molecular sieves.
Optionally, in the step 3), an equipment used in the lignin catalytic pyrolysis is a fixed-bed pyrolysis reactor, an reaction temperature is 450-650°C, the modified red mud and molecular sieve catalyst are arranged in layers, a mass ratio of the modified red mud to the molecular sieve catalyst 1s 1:0.7-1.5, and the ratio of the lignin mass to a sum of the modified red mud and thé/502470 molecular sieve catalyst is 1:1.5-2.2, and nitrogen is used to ensure an inert atmosphere of pyrolysis.
Optionally, the hydrocarbon-rich bio-oil is refined, separated and extracted into aromatic compounds for improving an octane number of gasoline or diesel; the biochar is used for preparing activated carbon materials or carbon-based compound fertilizers; after the separation and a purification, the syngas is used as a reaction raw material of Fischer-Tropsch synthesis.
Optionally, the adsorption material fields include a sewage purification field, a waste dyeing liquid field and a heavy metal adsorption field; the fields of building materials include a field of concrete preparation, a field of building bricks and a field of permeable bricks.
The invention has following advantages.
1. The invention adopts the acid dissolution-alkali reprecipitation coupling roasting method to perform the harmless modification treatment on the red mud, so that physical and chemical properties of the red mud are significantly improved and conditions for a high added value utilization are created. The modification process of the red mud significantly reduces inherent strong alkaline elements such as Na and Ca, and reduces a strong alkalinity of the red mud. moreover, the modified waste liquid may be used to remove inorganic impurities such as alkali metals and alkaline earth metals inherent in a lignin structure.
2. The modified red mud according to the invention may be used as a low-cost catalyst coupled with a molecular sieve catalyst to realize the catalytic pyrolysis of lignin to prepare hydrocarbon-rich bio-oil, and simultaneously co-produce biochar and syngas. Among them, the content of aromatic components in hydrocarbon-rich bio-oil may be as high as 70%, and the selectivity of monocyclic aromatic hydrocarbons may be as high as 60%. The hydrocarbon-rich bio-oil is refined and separated to extract aromatic compounds, so that an octane number of gasoline or diesel is better improved. In addition, biochar may be further used to prepare activated carbon materials or carbon-based compound fertilizers, and syngas may be further separated and purified as the reaction raw material of Fischer-Tropsch synthesis.
3. The present invention promotes a resource utilization of the red mud and the lignin waste through a co-treatment mode of "treating waste with waste". On the one hand, the resource and harmless treatment of the red mud reduces a waste management cost of alumina enterprises,
enhances a competitiveness of the enterprises and promotes a green circular development of thé/502470 enterprises. On the other hand, an introduction of the low-cost catalyst of the modified red mud during the catalytic pyrolysis of lignin increases a content of aromatic compounds in the bio-oil, co-produces high-value biochar and syngas, slows down a rapid deactivation of commercial catalyst, improves an economic efficiency of catalytic pyrolysis technology, and realized the energy utilization of lignin waste residue. This method provides a basic reference for the development of cross-industry waste coupling utilization technology, and is of great significance to the development of green circular economy.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is a process flow chart of green recycling and comprehensive utilization of red mud and lignin waste according to the present invention.
DESCRIPTION OF THE INVENTION In order to make an objective, technical schemes and advantages of embodiments of the present invention clearer, the technical schemes in the embodiments of the present invention are clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative labor are within the scope of the present invention.
Embodiment 1: As shown in Fig. 1, a method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste includes following steps: 1) separating and preparing high-purity lignin resources from waste residues rich in lignin matrix produced by agricultural and forestry wastes by a Klason method, 2) carrying out a harmless modification of the red mud by an acid dissolution-alkali reprecipitation coupling roasting method; where specifically, 25 Kg of the red mud is mixed with 150 L of sulfuric acid (concentration 6 mol/L) and digested at 85°C for 2 h, and a brown suspension is obtained; under a vigorous stirring, 36% ammonia water is added into the suspension dropwise until a pH is about 8; a mixture is subjected to an ultrasonic treatment for 15 min, followed by filtering, washing with distilled water and ethanol to neutrality, and drying in an air drying oven at 105°C for 12 h; ahd/502470 then, a dried product is ground and sieved to 60-80 mesh, and transferred to a muffle furnace for roasting at 650°C for 5 h to obtain a low-cost catalyst for a modified red mud; among them, a waste liquid obtained from the modification treatment may be further used to remove inorganic impurities such as alkali metals and alkaline earth metals contained in the lignin itself; 3) co-producing hydrocarbon-rich bio-oil, biochar and syngas with a catalytic pyrolysis on the lignin by using the modified red mud and a molecular sieve catalyst (commercial molecular sieve HZSM-5) on a fixed-bed pyrolysis reactor, and controlling a reaction temperature at 450-520°C; among them, the modified red mud and the molecular sieve catalyst are arranged in layers in a catalytic layer inside a reaction tube, a mass ratio of the modified red mud to the molecular sieve catalyst is 1:1, the ratio of a lignin mass to a sum of the modified red mud and the molecular sieve catalyst is 1:2, nitrogen is used to ensure an inert atmosphere required for the whole pyrolysis, and a Lignin pyrolysis gas passes through the modified red mud and the molecular sieve catalyst in turn, thus finally realizing a graded conversion of the pyrolysis gas; and 4) further applying the modified red mud after the reaction to fields of adsorption materials and building materials.
Embodiment 2: A method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste includes following steps: 1) separating and preparing high-purity lignin resources from waste residues rich in lignin matrix produced in a paper industry by an organic solvent method; 2) carrying out a harmless modification of the red mud by an acid dissolution-alkali reprecipitation coupling roasting method; where specifically, 25 Kg of the red mud is mixed with 150 L of hydrochloric acid (concentration 7 mol/L) and digested at 85°C for 2.5 h, and a brown suspension is obtained; under a vigorous stirring, 30% ammonia water is added into the suspension dropwise until a pH is about 8; a mixture is subjected to an ultrasonic treatment for 15 min, followed by filtering,
washing with distilled water and ethanol to neutrality, and drying in an air drying oven at 105%U502470 for 12 h; and then, a dried product is ground and sieved to 60-80 mesh, and transferred to a muffle furnace for roasting at 635°C for 6 h to obtain a low-cost catalyst for a modified red mud; among them, a waste liquid obtained from the modification treatment may be further used to remove inorganic impurities such as alkali metals and alkaline earth metals contained in the lignin itself; 3) co-producing hydrocarbon-rich bio-oil, biochar and syngas with a catalytic pyrolysis on the lignin by using the modified red mud and a molecular sieve catalyst (commercial molecular sieve H-USY) on a fixed-bed pyrolysis reactor, and controlling a reaction temperature at 580-650°C: among them, the modified red mud and the molecular sieve catalyst are arranged in layers in a catalytic layer inside a reaction tube, a mass ratio of the modified red mud to the molecular sieve catalyst is 1:0.7, the ratio of a lignin mass to a sum of the modified red mud and the molecular sieve catalyst is 1:2.2, nitrogen is used to ensure an inert atmosphere required for the whole pyrolysis, and a Lignin pyrolysis gas passes through the modified red mud and the molecular sieve catalyst in turn, thus finally realizing a graded conversion of the pyrolysis gas; and 4) further applying the modified red mud after the reaction to fields of adsorption materials and building materials.
Embodiment 3: A method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste includes following steps: 1) separating and preparing high-purity lignin resources from waste residues rich in lignin matrix produced by a biorefinery industry by enzyme hydrolysis; 2) carrying out a harmless modification of the red mud by an acid dissolution-alkali reprecipitation coupling roasting method; where specifically, 25 Kg of the red mud is mixed with 150 L of phosphoric acid (concentration 5 mol/L) and digested at 85°C for 2 h, and a brown suspension is obtained; under a vigorous stirring, 40% ammonia water is added into the suspension dropwise until a pH is about 8; a mixture is subjected to an ultrasonic treatment for 18 min, followed by filtering,
washing with distilled water and ethanol to neutrality, and drying in an air drying oven at 105%U502470 for 12 h; and then, a dried product is ground and sieved to 60-80 mesh, and transferred to a muffle furnace for roasting at 660°C for 4.5 h to obtain a low-cost catalyst for a modified red mud; among them, a waste liquid obtained from the modification treatment may be further used to remove inorganic impurities such as alkali metals and alkaline earth metals contained in the lignin itself; 3) co-producing hydrocarbon-rich bio-oil, biochar and syngas with a catalytic pyrolysis on the lignin by using the modified red mud and a molecular sieve catalyst (commercial molecular sieve HP) on a fixed-bed pyrolysis reactor; and controlling a reaction temperature at 500-580°C; among them, the modified red mud and the molecular sieve catalyst are arranged in layers in a catalytic layer inside a reaction tube, a mass ratio of the modified red mud to the molecular sieve catalyst is 1:1.5, the ratio of a lignin mass to a sum of the modified red mud and the molecular sieve catalyst is 1:1.5, nitrogen is used to ensure an inert atmosphere required for the whole pyrolysis, and a Lignin pyrolysis gas passes through the modified red mud and the molecular sieve catalyst in turn, thus finally realizing a graded conversion of the pyrolysis gas; and 4) further applying the modified red mud after the reaction to fields of adsorption materials and building materials.
The hydrocarbon-rich bio-oil prepared in embodiments 1-3 has an aromatic component content as high as 70% and a monocyclic aromatic selectivity as high as 60%, and may be refined, separated and extracted to extract aromatic compounds for improving an octane number of gasoline or diesel oil.
The biochar may be further used as a raw material for preparing activated carbon or carbon-based compound fertilizer, and the syngas may be further separated and purified as a reaction raw material for Fischer-Tropsch synthesis. In addition, the introduction of the modified red mud further reduces an amount of carbon deposited on a surface of the molecular sieve catalyst during the lignin catalytic pyrolysis, and slows down a rapid deactivation of the catalyst.
The reacted modified red mud may be applied to the fields of sewage purification, waste dyeing liquid and heavy metal adsorption when used as an adsorption material, and may be used as the raw material for preparing concrete, building bricks and permeable bricks when used asld}502470 building material.
The above embodiments are only used to illustrate technical schemes of the invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that it is still possible to modify the technical solutions described in the foregoing embodiments, or to equivalently replace some technical features thereof; these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of various embodiments of the present invention.
Claims (8)
1. À method for a green recycling and comprehensive utilization of a red mud waste and a lignin waste, characterized by comprising the following steps: 1) extracting and separating the lignin from agricultural and forestry wastes, waste residues rich in lignin matrix generated by a paper industry or a biological refining industry to obtain high-purity lignin; 2) performing a harmless modification treatment on the red mud by an acid dissolution-alkali reprecipitation coupling roasting method; 3) preparing hydrocarbon-rich bio-oil, biochar and syngas with a catalytic pyrolysis on the lignin by using the modified red mud and a molecular sieve catalyst; and 4) further applying the modified red mud after a reaction to fields of adsorption materials and building materials.
2. The method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste according to claim 1, characterized in that in the step 1), lignin extraction and separation methods include a Klason method, an organic solvent method, an ionic liquid method or an enzymatic hydrolysis method.
3. The method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste as claimed in claim 1, characterized in that in the step 2), in the acid dissolution-alkali reprecipitation coupling roasting method for the red mud, an inorganic acid with a concentration of 5-7mol/L is used for an acid dissolution treatment, and the inorganic acid is hydrochloric acid, sulfuric acid or phosphoric acid; an alkali precipitation treatment adopts 30-40% ammonia water by mass, and a roasting treatment temperature is 635-660°C.
4. The method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste as claimed in claim 1, characterized in that in the step 2), a waste liquid obtained from the modification treatment may be used to remove inorganic impurities contained in the lignin itself, including alkali metals and alkaline earth metals.
5. The method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste according to claim 1, characterized in that in the step 3), the molecular sieve catalyst is one or more of HZSM-5, HB and H-USY.
6. The method for the green recycling and comprehensive utilization of the red mud wasté/502470 and the lignin waste as claimed in claim 1, characterized in that in the step 3), an equipment used in the lignin catalytic pyrolysis is a fixed-bed pyrolysis reactor, an reaction temperature is 450-650°C, the modified red mud and molecular sieve catalyst are arranged in layers, a mass ratio of the modified red mud to the molecular sieve catalyst is 1:0.7-1.5, and the ratio of the lignin mass to a sum of the modified red mud and the molecular sieve catalyst is 1:1.5-2.2, and nitrogen is used to ensure an inert atmosphere of pyrolysis.
7. The method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste according to claim 1, characterized in that the hydrocarbon-rich bio-oil is refined, separated and extracted into aromatic compounds for improving an octane number of gasoline or diesel; the biochar is used for preparing activated carbon materials or carbon-based compound fertilizers; after the separation and a purification, the syngas is used as a reaction raw material of Fischer-Tropsch synthesis.
8. The method for the green recycling and comprehensive utilization of the red mud waste and the lignin waste according to claim 1, characterized in that the adsorption material fields include a sewage purification field, a waste dyeing liquid field and a heavy metal adsorption field; the fields of building materials include a field of concrete preparation, a field of building bricks and a field of permeable bricks.
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