CN111957324A - Method for recycling waste catalyst - Google Patents
Method for recycling waste catalyst Download PDFInfo
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- CN111957324A CN111957324A CN202010812284.XA CN202010812284A CN111957324A CN 111957324 A CN111957324 A CN 111957324A CN 202010812284 A CN202010812284 A CN 202010812284A CN 111957324 A CN111957324 A CN 111957324A
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- catalyst
- waste
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- fresh catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000007500 overflow downdraw method Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 2
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 5
- 229910001950 potassium oxide Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for recycling waste catalysts, which is to prepare the same kind of fresh catalysts by taking the whole waste catalysts as raw materials, wherein the waste catalysts comprise waste iron-based catalysts used in the industries of ammonia synthesis reaction, water gas shift reaction, Fischer-Tropsch synthesis reaction and the like, and the same kind of fresh catalysts are prepared by respectively adopting a melting method and a precipitation method. The novel method for recycling the waste catalyst has the advantages of simple process, high economic benefit and social benefit and the like, and all substances in the waste catalyst can be recycled. This is an ideal way for recycling the waste catalyst.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a method for recycling a waste catalyst.
Background
Iron-based catalysts have found wide industrial application. The main chemical reactions using iron as the main catalyst, such as more than 10 catalytic reactions of ammonia synthesis, water gas shift, Fischer-Tropsch synthesis, desulfurization, ethylbenzene dehydrogenation, butane dehydrogenation and oxidative dehydrogenation, and olefin preparation by alkane dehydrogenation. Table 1 shows the industrial applications of ammonia synthesis, water gas shift, fischer-tropsch synthesis, etc. with iron as the main catalyst, which are large in scale and consume tens of thousands of tons of catalyst per year.
TABLE 1 chemical reactions and chemical forms with iron as the main catalyst
The conventional recovery methods for various industrial waste catalysts are generally divided into two types: indirect recovery treatment and direct recovery treatment. The indirect recovery treatment method is a method for separating and extracting metals and high-value substances in the waste catalyst. The direct recovery treatment method is to treat the waste catalyst as a whole, usually by acid, alkali or other processes, to make the carrier and important components into chemicals, which are provided to other chemical production as raw materials. The common features of these two methods of recovering spent catalyst are: firstly, the waste catalyst is processed in an isolated way; secondly, only part of important or effective components in the waste catalyst are recycled; and the secondary pollution can be caused. In summary, the waste catalyst contains a large amount of useful substances, and if the waste catalyst is not discarded, not only a large amount of resources are wasted, but also surface water and underground water sources are polluted.
Chinese patent document CN102000613A describes a method for deactivating and regenerating an iron-based catalyst, wherein the regenerated iron-based catalyst is a catalyst used for producing polyphenylene ether by using 2, 6-dimethylphenol, and contains Fe2O3、In2O3The recovery method comprises the following steps: taking the inactivated catalyst, introducing air, and roasting at 450-500 ℃ to remove coke in the catalyst; then crushing, and dissolving by using a mixed solution of 10-63% nitric acid and hydrochloric acid at 60-150 ℃. Reaction to acidificationDetecting the reaction solution, and calculating chromium nitrate, sodium silicate and indium which need to be supplemented according to the detection result; then adding ammonia water to adjust the solution to be neutral, filtering, drying a filter cake, soaking by using a calcium oxalate solution, and roasting at 480 ℃ for 4 hours to obtain the regenerated catalyst. The patented technology produces large quantities of polluting gases and waste liquids.
Chinese patent document CN100383221A introduces an application method of an iron-containing waste catalyst in Fischer-Tropsch synthesis heavy hydrocarbon hydrocracking, namely, the waste iron-based catalyst such as Fischer-Tropsch synthesis, carbon monoxide conversion and ammonia synthesis is used for mixed hydrocracking reaction of Fischer-Tropsch synthesis heavy hydrocarbon, wherein the addition amount of the waste iron catalyst is 0.1-10 wt%, the hydrocracking reaction uses a suspension bed reactor, and the process conditions are as follows: the pressure is 2.0-20.0 MPa, the temperature is 370-500 ℃, and the volume ratio of hydrogen to oil is 300-1500. The method makes full use of the waste iron-based catalyst, has a good environment-friendly effect, and has the defect of low recovery rate of the waste catalyst.
In view of the above, it is urgently needed to develop a method for recycling waste catalysts, which is simple, low in cost, high in utilization rate and free from secondary pollution.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a novel method for recycling a waste catalyst, which comprises the following steps: the recovery of the waste catalyst is connected with the preparation of the same kind of fresh catalyst for integral treatment, namely the waste catalyst is integrally used as a raw material to prepare the same kind of fresh catalyst, so that all components in the waste catalyst are effectively recovered and utilized.
A method for recycling a waste catalyst is characterized in that a waste catalyst is integrally used as a raw material to prepare a similar fresh catalyst;
the waste catalyst comprises waste iron-based catalyst used in the industries of ammonia synthesis reaction, water gas shift reaction, Fischer-Tropsch synthesis reaction and the like;
based on the total mass of the waste catalyst, the main chemical components of the waste catalyst comprise 65-92 wt% of Fe and oxides thereof as main active components and 8-35 wt% of cocatalyst, wherein the cocatalyst is one or more of oxides of Co, Al, K, Ca, Mg, Ba, V, Zr, Ti, Zn, Cr, Mo, W, Si and the like.
The main chemical components of the fresh catalyst prepared by the method are generally not less than those of the waste catalyst.
In the method, the addition amount of the waste catalyst is 10-60 wt% of the prepared fresh catalyst.
In the process according to the invention, the supplementary addition of cocatalyst is the difference between the amount of substance of the components required for the fresh catalyst prepared and the amount of substance of the corresponding components carried over by the spent catalyst.
In the fresh catalyst prepared by the invention, the chemical form of the active component Fe comprises Fe3O4、Fe1-xO、Fe2O3One or more of them, and Fe2+With Fe3+The molar ratio of (A) to (B) is 0-10: 1, wherein x is more than or equal to 0 and less than 1, and the Fe2O3Comprising alpha-Fe2O3、γ-Fe2O3One or two of them.
In a preferred embodiment, the fresh catalyst is a molten iron catalyst, is an ammonia synthesis or Fischer-Tropsch synthesis catalyst, is prepared by a fusion method, and comprises the steps of mixing, fusing, cooling, crushing and screening raw materials of magnetite powder, a waste catalyst and a supplementary catalyst promoter to obtain the fresh catalyst with the required particle size. Specifically, according to the mixing ratio of the waste catalyst and the magnetite powder, the waste catalyst and the supplementary cocatalyst are weighed according to the specified amounts respectively, are ground and mixed uniformly, are placed in a resistance furnace for high-temperature melting, flow the melted material into a water jacket type cooling tank for rapid cooling to room temperature after melting, and are crushed and screened to the required particle size.
In another preferred embodiment, the fresh catalyst is a water gas shift catalyst, the waste catalyst is dissolved by a nitric acid solution at 40-80 ℃, metal nitrates of a specified amount of promoters (such as Cr and K) are added into a filtrate obtained after filtration, then an ammonia water solution is added to adjust to be neutral for coprecipitation, a filter cake is dried after filtration and roasted to obtain catalyst powder, and the catalyst powder is extruded and formed in a disc type rotary forming machine to obtain the fresh catalyst with the required granularity. The roasting temperature is preferably 500 ℃ and the time is preferably 4 hours.
The invention also provides a fresh catalyst prepared by the method for recycling the waste catalyst.
The invention also provides the application of the fresh catalyst in the industrial fields of ammonia synthesis, water gas shift, Fischer-Tropsch synthesis and the like.
Compared with the prior art, the invention has the main advantages that:
(1) the invention takes the whole waste catalyst as the raw material to prepare the similar fresh catalyst, and all the components in the waste catalyst are recycled.
(2) The invention prepares the same kind of fresh catalyst by using the whole waste catalyst as the raw material, greatly reduces the production cost, has simple method and less secondary pollution.
(3) The invention makes full use of various waste iron-based catalysts and has environmental protection significance.
(4) The invention prepares the same kind of fresh catalyst by using the whole waste catalyst as the raw material, thereby greatly improving the comprehensive economic benefit and social benefit of the iron-based catalyst.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
55.1 parts by weight of magnetite powder, 41.4 parts by weight of waste ammonia synthesis catalyst recovered from a certain plant, 1.0 part by weight of alumina, 0.7 part by weight of potassium oxide, 1.8 parts by weight of calcium oxide, 0.2 part by weight of magnesium oxide, 0.1 part by weight of vanadium oxide and 0.3 part by weight of titanium oxide are proportioned, placed in a mixer, uniformly mixed, put into an electric melting furnace for melting, cooled, crushed, ground and screened to obtain the ferrous oxide based ammonia synthesis catalyst with the required granularity. The catalyst is identified by XRD, and has main phaseIs FeO, Fe2+With Fe3+Is 6.86: 1. At 15MPa, H2:N2The molar ratio is 3:1, and the space velocity is 30000h-1The outlet ammonia concentration was determined under the conditions. After heat-resistance at 500 ℃ for 20 hours, the outlet ammonia concentration of the catalyst after heat-resistance was measured, and the results are shown in Table 2.
Example 2
Mixing 75.0 parts by weight of magnetite powder, 5.3 parts by weight of waste ammonia synthesis catalyst recovered from a certain plant B, 1.9 parts by weight of alumina, 1.0 part by weight of potassium oxide and 2.1 parts by weight of calcium oxide in a mixer, melting in an electric melting furnace, cooling, crushing, grinding corners and sieving to obtain Fe with required granularity3O4Catalyst for ammonia synthesis. The catalyst is identified by XRD, and the main phase is Fe3O4Of Fe2+With Fe3+Is 0.53: 1. The catalyst is at 15MPa and H2:N2The molar ratio is 3:1, and the space velocity is 30000h-1The outlet ammonia concentration was determined under the conditions. After the catalyst was heat-resistant at 500 ℃ for 20 hours, the outlet ammonia concentration of the catalyst after heat-resistance was measured, and the results are shown in Table 2.
Example 3
According to 79.9 parts by weight of wastewater coal gas shift catalyst recovered from a certain third factory, adding 2.13 parts by weight of chromium trioxide and 0.11 part by weight of potassium oxide, dissolving the waste catalyst with a nitric acid solution at 40-80 ℃, adding a specified amount of metal nitrates of promoters Cr and K in the filtrate obtained after filtering for coprecipitation, then adding an ammonia water solution to adjust to neutrality, drying the filter cake after filtering, and roasting at 500 ℃ for 4 hours to obtain catalyst powder. And extruding and molding the powder in a disc type rotary molding machine to obtain the water gas shift catalyst with the required particle size. The catalyst is identified by XRD, and the main phase is Fe2O3，Fe2+With Fe3+Is 0: 1. The water-steam molar ratio is 0.58, the pressure is 3MPa, and the space velocity is 2500h-1The CO conversion rate before and after the heat resistance was measured under the conditions of 350 ℃ and 400 ℃ and the results are shown in Table 3.
Example 4
55 parts by weight of magnetite powder40.5 parts of waste Fischer-Tropsch synthesis reaction catalyst recovered from a butane plant, 1.2 parts of alumina, 0.9 part of potassium oxide, 2.2 parts of calcium oxide, 0.4 part of samarium oxide and 0.4 part of zirconia are proportioned, placed in a mixer, mixed and stirred for a period of time, mixed uniformly and then put into an electric melting furnace for melting. And after the melting is finished, putting the liquid molten material into a cooling tank with a water jacket, cooling to below 200 ℃, crushing, grinding corners and screening the cooled molten material to obtain the FeO-based molten iron catalyst with the required granularity for the Fischer-Tropsch synthesis reaction. The catalyst is identified by XRD, and the main phases are FeO and Fe2+With Fe3+Is 7.45: 1. At n (H)2)/n(CO)＝2.0，P＝1.4MPa，t＝305℃；Sv＝12600h-1And under the condition of 1.5g of catalyst, various performance indexes such as CO conversion rate, hydrocarbon selectivity and the like are measured, and the results are shown in Table 4.
Comparative example
The raw materials are mixed according to the proportion of 70.2 parts by weight of magnetite powder, 23.2 parts by weight of iron powder, 1.8 parts by weight of alumina, 0.6 part by weight of potassium oxide, 1.8 parts by weight of calcium oxide, 0.8 part by weight of magnesium oxide, 0.6 part by weight of vanadium oxide, 0.6 part by weight of zirconium oxide and 0.3 part by weight of titanium oxide, and the mixture is put into a stirrer to be uniformly mixed and then is put into an electric furnace to be melted. And after the melting is finished, putting the liquid melt into a cooling tank, cooling to below 200 ℃, crushing and screening the cooled frit to obtain the ferrous oxide based ammonia synthesis catalyst with the required granularity. The catalyst is identified by XRD, and the main phases are FeO and Fe2+With Fe3+Is 5.86: 1. At 15MPa, H2:N2The molar ratio is 3:1, and the space velocity is 30000h-1The outlet ammonia concentration was measured under the conditions, and after heat-resistance at 500 ℃ for 20 hours, the outlet ammonia concentration after heat-resistance was measured, and the results are shown in Table 2.
TABLE 2 detection results of ammonia synthesis catalyst performance
TABLE 3 detection results of water gas shift catalyst performance
TABLE 4 Fischer-Tropsch Synthesis catalyst Performance test results
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A method for recycling a waste catalyst is characterized in that the whole waste catalyst is used as a raw material to prepare a similar fresh catalyst;
the waste catalyst comprises waste iron-based catalyst used in ammonia synthesis reaction, water gas shift reaction and Fischer-Tropsch synthesis reaction;
based on the total mass of the waste catalyst, the main chemical components of the waste catalyst comprise 65-92 wt% of Fe and oxides thereof and 8-35 wt% of cocatalyst, wherein the cocatalyst is one or more of oxides of Co, Al, K, Ca, Mg, Ba, V, Zr, Ti, Zn, Cr, Mo, W and Si.
2. The method of claim 1, wherein the fresh catalyst is prepared with no less than the spent catalyst major chemical component.
3. The method according to claim 1, wherein the amount of the spent catalyst added is 10 to 60 wt% of the fresh catalyst prepared.
4. The process of claim 1, wherein the make-up amount of cocatalyst is the difference between the amount of material of each component required for the fresh catalyst prepared and the amount of material of the corresponding component carried over by the spent catalyst.
5. The process of claim 1, wherein the fresh catalyst is prepared such that the active component, Fe, is in a chemical form comprising Fe3O4、Fe1-xO、Fe2O3One or more of them, and Fe2+With Fe3+The molar ratio of (A) to (B) is 0-10: 1, wherein x is more than or equal to 0 and less than 1, and the Fe2O3Comprising alpha-Fe2O3、γ-Fe2O3One or two of them.
6. The method according to any one of claims 1 to 5, wherein the fresh catalyst is an ammonia synthesis or Fischer-Tropsch synthesis catalyst, and is prepared by a fusion method, and comprises the steps of mixing, melting, cooling, crushing and screening raw materials of magnetite powder, waste catalyst and supplementary promoter to obtain the fresh catalyst with the required particle size.
7. The method according to any one of claims 1 to 5, wherein the fresh catalyst is a water gas shift catalyst, the waste catalyst is dissolved by a nitric acid solution at 40 to 80 ℃, a specified amount of metal nitrate of a promoter is added into the filtrate obtained after filtration, then an ammonia water solution is added to adjust the filtrate to be neutral for coprecipitation, the filter cake is dried after filtration and roasted to obtain catalyst powder, and the catalyst powder is extruded and formed in a disc type rotary forming machine to obtain the fresh catalyst with the required particle size.
8. Fresh catalyst prepared by the process according to any one of claims 1 to 7.
9. Use of the fresh catalyst of claim 8 in industrial fields including ammonia synthesis, water gas shift, fischer-tropsch synthesis.
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| CN114570412A (en) * | 2022-02-18 | 2022-06-03 | 贵州理工学院 | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091997A (en) * | 1986-12-13 | 1994-09-14 | 浙江工学院 | Ferrous oxide catalyst for amino synthesis and preparation method |
| US6838487B1 (en) * | 2003-12-04 | 2005-01-04 | Rentech, Inc. | Method and apparatus for regenerating an iron-based Fischer-Tropsch catalyst |
| CN101745393A (en) * | 2010-01-15 | 2010-06-23 | 浙江工业大学 | Fischer-Tropsch synthesis fused iron catalyst with high activity and stability and preparation and application thereof |
| CN101767009A (en) * | 2009-12-31 | 2010-07-07 | 浙江工业大学 | Low-temperature Fischer-Tropsch synthesis fused iron catalyst, preparation and application thereof |
| CN102000613A (en) * | 2010-11-02 | 2011-04-06 | 蓝星化工新材料股份有限公司 | Method for regenerating activity of deactivated ferritic catalyst |
| CN108854476A (en) * | 2017-05-10 | 2018-11-23 | 神华集团有限责任公司 | Protective agent of methanol synthesis catalyst and its preparation method and application |
-
2020
- 2020-08-13 CN CN202010812284.XA patent/CN111957324A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091997A (en) * | 1986-12-13 | 1994-09-14 | 浙江工学院 | Ferrous oxide catalyst for amino synthesis and preparation method |
| US6838487B1 (en) * | 2003-12-04 | 2005-01-04 | Rentech, Inc. | Method and apparatus for regenerating an iron-based Fischer-Tropsch catalyst |
| CN101767009A (en) * | 2009-12-31 | 2010-07-07 | 浙江工业大学 | Low-temperature Fischer-Tropsch synthesis fused iron catalyst, preparation and application thereof |
| CN101745393A (en) * | 2010-01-15 | 2010-06-23 | 浙江工业大学 | Fischer-Tropsch synthesis fused iron catalyst with high activity and stability and preparation and application thereof |
| CN102000613A (en) * | 2010-11-02 | 2011-04-06 | 蓝星化工新材料股份有限公司 | Method for regenerating activity of deactivated ferritic catalyst |
| CN108854476A (en) * | 2017-05-10 | 2018-11-23 | 神华集团有限责任公司 | Protective agent of methanol synthesis catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 李忠铭: "《现代工业化学 第二版》", 31 August 2018, 华中科技大学出版社 * |
| 邵景景, 中国矿业大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570412A (en) * | 2022-02-18 | 2022-06-03 | 贵州理工学院 | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application |
| CN114570412B (en) * | 2022-02-18 | 2024-03-08 | 贵州理工学院 | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application |
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