CN111774048A - Method for preparing alumina carrier, reforming protective agent and preparation method thereof - Google Patents
Method for preparing alumina carrier, reforming protective agent and preparation method thereof Download PDFInfo
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- CN111774048A CN111774048A CN202010671861.8A CN202010671861A CN111774048A CN 111774048 A CN111774048 A CN 111774048A CN 202010671861 A CN202010671861 A CN 202010671861A CN 111774048 A CN111774048 A CN 111774048A
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- reforming
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- 238000002407 reforming Methods 0.000 title claims abstract description 93
- 239000003223 protective agent Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 64
- 238000002156 mixing Methods 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 45
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 44
- 238000001914 filtration Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000012752 auxiliary agent Substances 0.000 claims description 26
- 230000004048 modification Effects 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 17
- 239000001099 ammonium carbonate Substances 0.000 claims description 17
- 239000004480 active ingredient Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 235000013877 carbamide Nutrition 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910000464 lead oxide Inorganic materials 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011814 protection agent Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 12
- 238000011068 loading method Methods 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 description 29
- 239000002245 particle Substances 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004645 aluminates Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 arsenide Chemical compound 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005303 weighing Methods 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
- 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
-
- 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
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/72—Copper
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/21—Attrition-index or crushing strength of granulates
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention provides a method for preparing an alumina carrier, a reforming protective agent and a preparation method thereof. The carrier obtained in the reaction process has larger pore diameter and specific surface area, is beneficial to internal diffusion of compounds such as sulfur, arsenic, chlorine and the like after loading active components, is convenient for loading active components, improves the removal effect of the reforming protective agent, also improves the capacity of the reforming protective agent for removing sulfide, chloride and arsenide, and avoids pore channel blockage after the compounds such as sulfur, arsenic, chlorine and the like are fixed in pore channels of the reforming protective agent, thereby prolonging the service life of the reforming protective agent.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a method for preparing an alumina carrier, a reforming protective agent and a preparation method thereof.
Background
The process of rearranging the molecular structure of hydrocarbons in gasoline fraction into new molecular structure under the condition of catalyst action is called catalytic reforming. Catalytic reforming technology is the main process for producing aromatics and high octane gasoline components from naphtha. Since the reforming catalyst is a noble metal catalyst, sulfides, arsenides and chlorides in the feedstock can poison the reforming catalyst, adversely affecting the reforming process. The reforming protection means that under the action of hydrogen and a reforming protective agent, naphtha removes impurities such as sulfide, arsenide, chloride and the like, so that the poisoning of a reforming catalyst is avoided, the reforming device can stably and durably operate, and meanwhile, the reforming device has greater flexibility in raw material selection.
The key to the reforming protection is the performance of the catalyst, i.e. the reforming protection agent. The preparation method of the conventional reforming protective agent comprises the steps of uniformly mixing the carrier, the active ingredients and the like, and sequentially carrying out extrusion molding, drying and roasting. Chinese patent document CN102807888A discloses a desulfurizing agent (i.e. reforming protecting agent) for reforming raw oil, the preparation method comprises the following steps: (1) weighing CuO, NiO, ZnO and a carrier, and uniformly mixing to obtain a mixture; (2) adding a certain amount of deionized water into the mixture, mixing and rolling, and extruding to form strips; (3) drying and roasting to obtain the desulfurizing agent for reforming raw oil. Wherein the carrier is aluminate cement or/and ordinary portland cement. However, the pore size and the surface area of the reforming protective agent obtained by the preparation method are small, so that the loading of active ingredients and the circulation of reactants are not facilitated, the distribution of active ingredients is not uniform, pore channels are easy to block, the activity of desulfurization reaction is low, and the desulfurization effect and the service life of the reforming protective agent are finally influenced.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the pore diameter and the surface area of the existing reforming protective agent are small to influence the desulfurization efficiency and the service life of the reforming protective agent, so that the method for preparing the alumina carrier, the reforming protective agent and the preparation method thereof are provided.
To this end, the present invention provides a process for preparing an alumina support comprising the steps of:
modifying a carrier precursor by using an alkaline solution, mixing the modified carrier precursor with a pore-forming agent, and sequentially carrying out first drying and roasting to obtain the alumina carrier, wherein the carrier precursor is aluminum hydroxide and/or aluminum oxide, and the pore-forming agent is at least one of ammonium carbonate, ammonium bicarbonate and urea.
Further, the carrier precursor is subjected to first impregnation in a strong alkali solution, and is sequentially subjected to filtration and second drying to realize modification of the carrier precursor.
Further, the method for preparing the alumina carrier comprises the following raw materials in parts by weight:
60-90 parts of aluminum hydroxide and/or aluminum oxide;
2-10 parts of pore-forming agent.
Further, the temperature of the first drying is 100-130 ℃, and the time is 2-4 h;
the roasting temperature is 400-500 ℃, and the roasting time is 2-8 h.
Further, the temperature of the first impregnation is 30-50 ℃, and the time is 60-90 min;
the strong alkali solution is potassium hydroxide solution or sodium hydroxide solution with the concentration of 2-5%.
Further, the temperature of the second drying is 100-120 ℃, and the time is 2-4 h.
Further, the alumina is at least one of SB powder and pseudo-boehmite.
The invention also provides a preparation method of the reforming protective agent, which comprises the following steps:
(1) modifying the carrier precursor by adopting an alkaline solution to obtain a modified aluminum source;
(2) and mixing the modified aluminum source, the pore-forming agent, the active ingredient, the binder and water, and sequentially carrying out forming, first drying and roasting to obtain the reforming protective agent.
Further, the preparation method of the reforming protective agent comprises the following raw materials in parts by weight:
60-90 parts of aluminum hydroxide and/or aluminum oxide;
2-10 parts of pore-forming agent;
20-50 parts of active ingredients;
5-10 parts of a binder;
the mass ratio of the total mass of the modified aluminum source, the pore-forming agent, the active ingredient and the binder to the water is (2.8-3.0): 1.
further, the active ingredient is at least one of IB and IIB group compounds or simple substances and platinum simple substances;
the binder is at least one of nitric acid, sesbania powder, polyacrylamide and methyl cellulose.
Further, the active component is at least one of zinc oxide, copper oxide, platinum and gold.
Further, the average particle size of the modified aluminum source is 3-10 nm.
Further, the mixing comprises the steps of:
carrying out first mixing on the modified aluminum source, the pore-forming agent, the active ingredient and the binder to obtain a dry mixture;
and carrying out second mixing on the dry mixture and water to obtain a wet mixture.
Further, the time of the first mixing is 15 min-30 min;
the second mixing time is 30 min-50 min.
Further, in the step (2), 10-40 parts of a modification auxiliary agent is added during mixing, and the modification auxiliary agent is obtained by performing second impregnation on the modification auxiliary agent in an alcohol solution and filtering.
Further, the auxiliary agent is at least one of a compound or a simple substance of groups IVA and VA.
Further, the auxiliary agent is one or more of silicon oxide, lead oxide and tin.
Further, the temperature of the second impregnation is 50-60 ℃, and the time is 90-120 min;
the alcohol solution is 10-20% ethanol, glycerol or isopropanol solution.
The invention also provides a reforming protective agent, which is prepared by adopting the preparation method of the reforming protective agent.
The technical scheme of the invention has the following advantages:
1. the invention provides a method for preparing an alumina carrier, a reforming protective agent and a preparation method thereof.A metaaluminate is formed by modifying aluminum hydroxide and/or aluminum oxide in a strong alkali solution, the metaaluminate and a pore-forming agent are subjected to a chemical reaction to obtain the aluminum hydroxide, and the aluminum hydroxide is roasted to obtain the alumina carrier. The carrier obtained in the reaction process has larger pore diameter and specific surface area, is beneficial to internal diffusion of compounds such as sulfur, arsenic, chlorine and the like after loading active components, is convenient for loading active components, improves the removal effect of the reforming protective agent, also improves the capacity of the reforming protective agent for removing sulfide, chloride and arsenide, and avoids pore channel blockage after the compounds such as sulfur, arsenic, chlorine and the like are fixed in pore channels of the reforming protective agent, thereby prolonging the service life of the reforming protective agent.
2. According to the method for preparing the alumina carrier, the reforming protective agent and the preparation method thereof, provided by the invention, the crystal formed by the active ingredient and the aluminum element has the crystal form defect, and the full reaction of sulfide, arsenide and chloride with the active ingredient is facilitated, so that the utilization rate of the reforming protective agent and the accuracy of removing poison are improved, and the service life of the reforming protective agent is prolonged. The auxiliary agent is soaked in alcohol, which is not only beneficial to the dispersion of active components, but also has positive effect on the formation of a crystal grain structure with crystal form defects, and avoids the pore channel blockage caused by the formation and aggregation of large crystal grains. The modification treatment of the aluminum hydroxide and/or the aluminum oxide in the strong alkaline solution is also beneficial to increasing the mechanical strength of the reforming protective agent, thereby prolonging the service life of the reforming protective agent.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) preparation of the alumina carrier:
(1a) soaking 150g of pseudo-boehmite in 2% potassium hydroxide solution at 30 ℃ for 90min, filtering, drying at 100 ℃ for 4h, and then crushing to obtain a modified aluminum source with the average particle size of 10 nm;
(1b) the modified aluminum source was mixed with 10g of ammonium carbonate, dried at 100 ℃ for 4h, and calcined at 500 ℃ for 2h to obtain an alumina support.
(2) Loading active ingredients:
and (3) soaking the alumina carrier in 30 mass percent of zinc oxide soaking solution for 120min to obtain the reforming protective agent.
Example 2
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) preparation of the alumina carrier:
(1a) soaking 120gSB powder in 5% sodium hydroxide solution at 40 deg.C for 70min, filtering, drying at 130 deg.C for 2h, and pulverizing to obtain modified aluminum source with average particle diameter of 9 nm;
(1b) the modified aluminum source was mixed with 4g of ammonium bicarbonate and dried at 130 ℃ for 2h and calcined at 400 ℃ for 8h to give an alumina support.
(2) Loading active ingredients:
and (3) soaking the alumina carrier in a soaking solution with the mass fraction of platinum of 0.5%, and obtaining the reforming protective agent after 100 min.
Example 3
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) preparation of the alumina carrier:
(1a) soaking 180g of aluminum hydroxide in 3% potassium hydroxide solution at 50 ℃ for 60min, filtering, drying at 110 ℃ for 3h, and then crushing to obtain a modified aluminum source with the average particle size of 8 nm;
(1b) and mixing a modified aluminum source with 20g of urea, drying at 110 ℃ for 3h, and roasting at 450 ℃ for 5h to obtain the alumina carrier.
(2) Loading active ingredients:
and (3) soaking the alumina carrier in a soaking solution with copper oxide content of 30%, and obtaining the reforming protective agent after 100 min.
Example 4
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 150g of pseudo-boehmite in 2% potassium hydroxide solution at 30 ℃ for 90min, filtering, drying at 100 ℃ for 4h, and then crushing to obtain a modified aluminum source with the average particle size of 8 nm;
(2) mixing a modified aluminum source, 10g of ammonium carbonate, 70g of zinc oxide and 15g of sesbania powder for 15min to obtain a dry mixture;
(3) mixing the dry mixture with 85g of water for 50min to obtain a wet mixture;
(4) and extruding the wet mixture into strips, drying the strips at 100 ℃ for 4 hours, and roasting the strips at 500 ℃ for 2 hours to obtain the reforming protective agent.
Example 5
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 120g of SB powder in 5% sodium hydroxide solution at 40 ℃ for 70min, filtering, drying at 130 ℃ for 2h, and then crushing to obtain a modified aluminum source with the average particle size of 9 nm;
(2) mixing a modified aluminum source, 4g of ammonium bicarbonate, 40g of platinum and 10g of methyl cellulose for 30min to obtain a dry mixture;
(3) mixing the dry mixture with 58g of water for 30min to obtain a wet mixed material;
(4) and extruding the wet mixture into strips, drying the strips at 130 ℃ for 2 hours, and roasting the strips at 400 ℃ for 8 hours to obtain the reforming protective agent.
Example 6
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 180g of aluminum hydroxide in 3% potassium hydroxide solution at 50 ℃ for 60min, filtering, drying at 110 ℃ for 3h, and then crushing to obtain a modified aluminum source with the average particle size of 7 nm;
(2) mixing a modified aluminum source, 20g of urea, 100g of copper oxide and 20g of polyacrylamide for 20min to obtain a dry mixture;
(3) mixing the dry mixture with 114g of water for 40min to obtain a wet mixture;
(4) and extruding the wet mixture into strips, drying the strips at 110 ℃ for 3 hours, and roasting the strips at 450 ℃ for 5 hours to obtain the reforming protective agent.
Example 7
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 150g of pseudo-boehmite in 2% potassium hydroxide solution at 30 ℃ for 90min, filtering, drying at 100 ℃ for 4h, and then crushing to obtain a modified aluminum source with the average particle size of 8 nm;
(2) mixing a modified aluminum source, 10g of ammonium carbonate, 70g of zinc oxide, 50g of tin and 15g of sesbania powder for 15min to obtain a dry mixture;
(3) mixing the dry mixture with 100g of water for 50min to obtain a wet mixture;
(4) and extruding the wet mixture into strips, drying the strips at 100 ℃ for 4 hours, and roasting the strips at 500 ℃ for 2 hours to obtain the reforming protective agent.
Example 8
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 120g of SB powder in 5% sodium hydroxide solution at 40 ℃ for 70min, filtering, drying at 130 ℃ for 2h, and then crushing to obtain a modified aluminum source with the average particle size of 10 nm;
(2) mixing a modified aluminum source, 4g of ammonium bicarbonate, 40g of platinum, 20g of lead oxide and 10g of methyl cellulose for 30min to obtain a dry mixture;
(3) mixing the dry mixture with 65g of water for 30min to obtain a wet mixed material;
(4) and extruding the wet mixture into strips, drying the strips at 130 ℃ for 2 hours, and roasting the strips at 400 ℃ for 8 hours to obtain the reforming protective agent.
Example 9
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 180g of aluminum hydroxide in 3% potassium hydroxide solution at 50 ℃ for 60min, filtering, drying at 110 ℃ for 3h, and then crushing to obtain a modified aluminum source with the average particle size of 8 nm;
(2) mixing a modified aluminum source, 20g of urea, 100g of copper oxide, 80g of silicon dioxide and 20g of polyacrylamide for 20min to obtain a dry mixture;
(3) mixing the dry mixture with 140g of water for 40min to obtain a wet mixed material;
(4) and extruding the wet mixture into strips, drying the strips at 110 ℃ for 3 hours, and roasting the strips at 450 ℃ for 5 hours to obtain the reforming protective agent.
Example 10
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 50g of tin in 15% glycerol solution at 50 ℃ for 120min, and filtering to obtain a modification auxiliary agent;
(2) soaking 150g of pseudo-boehmite in 2% potassium hydroxide solution at 30 ℃ for 90min, filtering, drying at 100 ℃ for 4h, and then crushing to obtain a modified aluminum source with the average particle size of 7 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 10g of ammonium carbonate, 70g of zinc oxide and 15g of sesbania powder for 15min to obtain a dry mixture;
(4) mixing the dry mixture with 100g of water for 50min to obtain a wet mixture;
(5) and extruding the wet mixture into strips, drying the strips at 100 ℃ for 4 hours, and roasting the strips at 500 ℃ for 2 hours to obtain the reforming protective agent.
Example 11
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) 20g of lead oxide is dipped in 10 percent isopropanol solution for 90min at 60 ℃, and the modified auxiliary agent is obtained after filtration;
(2) soaking 120gSB powder in 5% sodium hydroxide solution at 40 deg.C for 70min, filtering, drying at 130 deg.C for 2h, and pulverizing to obtain modified aluminum source with average particle diameter of 6 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 4g of ammonium bicarbonate, 40g of platinum and 10g of methyl cellulose for 30min to obtain a dry mixture;
(4) mixing the dry mixture with 65g of water for 30min to obtain a wet mixed material;
(5) and extruding the wet mixture into strips, drying the strips at 130 ℃ for 2 hours, and roasting the strips at 400 ℃ for 8 hours to obtain the reforming protective agent.
Example 12
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 80g of silicon dioxide in 20% ethanol solution at 55 ℃ for 100min, and filtering to obtain a modification auxiliary agent;
(2) soaking 180g of aluminum hydroxide in 3% potassium hydroxide solution at 50 ℃ for 60min, filtering, drying at 110 ℃ for 3h, and then crushing to obtain a modified aluminum source with the average particle size of 7 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 20g of urea, 100g of copper oxide and 20g of polyacrylamide for 20min to obtain a dry mixture;
(4) mixing the dry mixture with 140g of water for 40min to obtain a wet mixed material;
(5) and extruding the wet mixture into strips, drying the strips at 110 ℃ for 3 hours, and roasting the strips at 450 ℃ for 5 hours to obtain the reforming protective agent.
Example 13
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 50g of silicon dioxide in 20% ethanol solution at 50 ℃ for 110min, and filtering to obtain a modification auxiliary agent;
(2) soaking 167g of pseudo-boehmite in 2% potassium hydroxide solution at 40 ℃ for 90min, filtering, drying at 100 ℃ for 4h, and then crushing to obtain a modified aluminum source with the average particle size of 6 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 10g of ammonium carbonate, 16g of nitric acid and 50g of zinc oxide for 15min to obtain a dry mixture;
(4) mixing the dry mixture with 98g of water for 30min to obtain a wet mixture;
(5) and extruding the wet mixture into strips, drying the strips at 100 ℃ for 4 hours, and roasting the strips at 500 ℃ for 2 hours to obtain the reforming protective agent.
Example 14
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) 20g of lead oxide is soaked in 10 percent ethanol solution at 50 ℃ for 120min, and the modified auxiliary agent is obtained after filtration;
(2) soaking 171gSB powder in 5% sodium hydroxide solution at 50 deg.C for 80min, filtering, drying at 120 deg.C for 2 hr, and pulverizing to obtain modified aluminum source with average particle diameter of 3 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 10g of ammonium bicarbonate, 16g of sesbania powder and 50g of copper oxide for 30min to obtain a dry mixture;
(4) mixing the dry mixture with 89g of water for 50min to obtain a wet mixture;
(5) and extruding the wet mixture into strips, drying the strips at 130 ℃ for 2 hours, and roasting the strips at 400 ℃ for 8 hours to obtain the reforming protective agent.
Example 15
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) 20g of tin is dipped in 10 percent isopropanol for 90min at 60 ℃, and the modification auxiliary agent is obtained after filtration;
(2) soaking 169g of aluminum hydroxide in 3% potassium hydroxide solution at 40 ℃ for 80min, filtering, drying at 110 ℃ for 3h, and then crushing to obtain a modified aluminum source with the average particle size of 4 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 18g of urea, 18g of polyacrylamide and 70g of platinum for 20min to obtain a dry mixture;
(4) mixing the dry mixture with 100g of water for 40min to obtain a wet mixture;
(5) and extruding the wet mixture into strips, drying the strips at 110 ℃ for 3 hours, and roasting the strips at 450 ℃ for 5 hours to obtain the reforming protective agent.
Example 16
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) soaking 70g of lead oxide in 10% ethanol solution at 60 ℃ for 90min, and filtering to obtain a modification auxiliary agent;
(2) dipping 123gSB powder in 5% sodium hydroxide solution at 50 ℃ for 90min, filtering, drying at 105 ℃ for 3.5h, and then crushing to obtain a modified aluminum source with the average particle size of 5 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 4g of ammonium carbonate, 10g of methyl cellulose and 50g of platinum for 15min to obtain a dry mixture;
(4) mixing the dry mixture with 88g of water for 30-50 min to obtain a wet mixed material;
(5) and extruding the wet mixture into strips, drying the strips at 120 ℃ for 2.5 hours, and roasting the strips at 400 ℃ for 7.5 hours to obtain the reforming protective agent.
Example 17
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) immersing 70g of tin in a glycerol solution with the concentration of 20% for 100min at 55 ℃, and filtering to obtain a modification auxiliary agent;
(2) soaking 138gSB powder in 2.5% potassium hydroxide solution at 50 deg.C for 80min, filtering, drying at 100 deg.C for 4h, and pulverizing to obtain modified aluminum source with average particle diameter of 4 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 8g of ammonium bicarbonate, 12g of nitric acid and 70g of copper oxide for 30min to obtain a dry mixture;
(4) mixing the dry mixture with 100g of water for 50min to obtain a wet mixture;
(5) and extruding the wet mixture into strips, drying the strips at 130 ℃ for 2 hours, and roasting the strips at 400 ℃ for 8 hours to obtain the reforming protective agent.
Example 18
The embodiment provides a reforming protective agent, and the preparation method comprises the following steps:
(1) 60g of lead oxide is dipped in isopropanol with the concentration of 20 percent for 100min at the temperature of 55 ℃, and the modified auxiliary agent is obtained after filtration;
(2) soaking 138gSB powder in 2% sodium hydroxide solution at 40 deg.C for 80min, filtering, drying at 120 deg.C for 2h, and pulverizing to obtain modified aluminum source with average particle diameter of 6 nm;
(3) mixing a modified aluminum source, a modification auxiliary agent, 6g of urea, 14g of methylcellulose and 50g of gold for 20min to obtain a dry mixture;
(4) mixing the dry mixture with 90g of water for 30min to obtain a wet mixture;
(5) and extruding the wet mixture into strips, drying the strips at 100 ℃ for 4 hours, and roasting the strips at 500 ℃ for 2 hours to obtain the reforming protective agent.
Comparative example 1
The comparative example provides a reforming protectant, the method of preparation comprising the steps of:
soaking 150g of pseudo-boehmite in 30 mass percent of soaking solution of zinc oxide, and obtaining the reforming protective agent after 120 min.
Comparative example 2
The comparative example provides a reforming protectant, the method of preparation comprising the steps of:
(1) mixing 150g of pseudo-boehmite, 10g of ammonium carbonate, 70g of zinc oxide and 15g of sesbania powder for 15min to obtain a dry mixture;
(2) mixing the dry mixture with 140g of water for 50min to obtain a wet mixed material;
(3) and extruding the wet mixture into strips, drying the strips at 100 ℃ for 4 hours, and roasting the strips at 500 ℃ for 2 hours to obtain the reforming protective agent.
Test example 1
The reforming protectors of examples 1-8 and comparative examples 1-2 were tested for specific surface area, pore volume, strength, and breakthrough sulfur capacity, and the results are shown in table 1.
TABLE 1
From the test results, the reforming protective agents provided in examples 1 to 18 have higher specific surface area and strength, and simultaneously have higher pore volume and breakthrough sulfur capacity, thereby having higher removal efficiency.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (13)
1. A method for preparing an alumina support, comprising the steps of:
modifying a carrier precursor by using an alkaline solution, mixing the modified carrier precursor with a pore-forming agent, and sequentially carrying out first drying and roasting to obtain the alumina carrier, wherein the carrier precursor is aluminum hydroxide and/or aluminum oxide, and the pore-forming agent is at least one of ammonium carbonate, ammonium bicarbonate and urea.
2. The method for preparing the alumina carrier as claimed in claim 1, wherein the carrier precursor is first impregnated in a strong alkaline solution, and is then sequentially filtered and dried for the second time to modify the carrier precursor.
3. The method for preparing an alumina carrier according to claim 1 or 2, which is characterized by comprising the following raw materials in parts by weight:
60-90 parts of aluminum hydroxide and/or aluminum oxide;
2-10 parts of pore-forming agent.
4. The method for preparing an alumina carrier according to claim 2 or 3,
the first dipping temperature is 30-50 ℃ and the time is 60-90 min;
the strong alkali solution is potassium hydroxide solution or sodium hydroxide solution with the concentration of 2-5%.
5. The process for preparing an alumina support according to any one of claims 1 to 4,
the temperature of the first drying is 100-130 ℃, and the time is 2-4 h;
the roasting temperature is 400-500 ℃, and the roasting time is 2-8 h.
6. A preparation method of a reforming protective agent is characterized by comprising the following steps:
(1) modifying the carrier precursor by adopting an alkaline solution to obtain a modified aluminum source;
(2) and mixing the modified aluminum source, the pore-forming agent, the active ingredient, the binder and water, and sequentially carrying out forming, first drying and roasting to obtain the reforming protective agent.
7. The preparation method of the reforming protection agent according to claim 6, characterized by comprising the following raw materials in parts by weight:
60-90 parts of aluminum hydroxide and/or aluminum oxide;
2-10 parts of pore-forming agent;
20-50 parts of active ingredients;
5-10 parts of a binder;
the mass ratio of the total mass of the modified aluminum source, the pore-forming agent, the active ingredient and the binder to the water is (2.8-3.0): 1.
8. the method of claim 6 or 7, wherein the reforming protective agent is a mixture of a hydrocarbon compound and a hydrocarbon compound,
the active component is at least one of IB and IIB group compounds or simple substances and platinum simple substances;
the binder is at least one of nitric acid, sesbania powder, polyacrylamide and methyl cellulose.
9. The method of claim 6 or 7, wherein the reforming protective agent is a mixture of a hydrocarbon compound and a hydrocarbon compound,
the active component is at least one of zinc oxide, copper oxide, platinum and gold.
10. The method for preparing a reforming protection agent according to any one of claims 6 to 9, wherein 10 to 40 parts of a modification aid is further added during the mixing in step (2), and the modification aid is obtained by performing second impregnation of the modification aid in an alcohol solution and filtering.
11. The method of claim 10, wherein the auxiliary agent is at least one of a group IVA and VA compound or a simple substance.
12. The method for preparing a reforming protection agent according to claim 11, wherein the auxiliary agent is one or more of silicon oxide, lead oxide and tin.
13. A reforming protectant, the preparation method of the reforming protectant being as described in any one of claims 6-12.
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