CN109420507B - Hydrodesulfurization catalyst containing macroporous alumina carrier and preparation method thereof - Google Patents
Hydrodesulfurization catalyst containing macroporous alumina carrier and preparation method thereof Download PDFInfo
- Publication number
- CN109420507B CN109420507B CN201710768137.5A CN201710768137A CN109420507B CN 109420507 B CN109420507 B CN 109420507B CN 201710768137 A CN201710768137 A CN 201710768137A CN 109420507 B CN109420507 B CN 109420507B
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- China
- Prior art keywords
- carrier
- styrene
- alumina
- catalyst
- potassium
- Prior art date
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- 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 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 53
- 239000011148 porous material Substances 0.000 claims description 53
- 239000000839 emulsion Substances 0.000 claims description 47
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 30
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 29
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- 239000011591 potassium Substances 0.000 claims description 27
- 229910052700 potassium Inorganic materials 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 229910052712 strontium Inorganic materials 0.000 claims description 24
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 22
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 20
- 241000219782 Sesbania Species 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 14
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 14
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 11
- 230000023556 desulfurization Effects 0.000 abstract description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 42
- 239000000203 mixture Substances 0.000 description 40
- 239000004005 microsphere Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 16
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- 238000001354 calcination Methods 0.000 description 9
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- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 8
- 229960001484 edetic acid Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 229910052799 carbon Inorganic materials 0.000 description 6
- 229940011182 cobalt acetate Drugs 0.000 description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
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- UWSAIOMORQUEHN-UHFFFAOYSA-L sodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(5+) Chemical compound [Na+].[Fe+5].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O UWSAIOMORQUEHN-UHFFFAOYSA-L 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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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
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/647—
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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 relates to a selective hydrodesulfurization catalyst containing a macroporous alumina carrier, which comprises the following components in mass percentage of oxides: the catalyst is used for hydrodesulfurization of catalytic gasoline and can solve the problems of low desulfurization rate, poor desulfurization selectivity and large octane value loss in the prior art.
Description
Technical Field
The invention relates to a selective hydrodesulfurization catalyst containing a macroporous alumina carrier and a preparation method thereof, belonging to the technical field of preparation of oil product hydrofining catalysts.
Background
In recent years, with the rapid development of the automobile industry, the global automobile conservation quantity is increased sharply, and the problem of environmental pollution caused by harmful substances discharged from automobile exhaust is gradually concerned by people. In order to reduce the emission of harmful substances in automobile exhaust, countries around the world have put increasing demands on the quality of automotive fuels. Meanwhile, China also accelerates the pace of upgrading the gasoline quality so as to meet the international advanced standard level of the motor gasoline in a short time.
Different from abroad, in gasoline pools in China, catalytic cracking gasoline (FCC gasoline) with high sulfur and high olefin content accounts for about 70%, so that the key for upgrading the quality of gasoline in China lies in the cleanness of FCC gasoline, namely, the reduction of the sulfur content in the FCC gasoline and the control of the olefin content. Although the traditional hydrodesulfurization technology can effectively realize the goal of desulfurization and olefin reduction of FCC gasoline, the traditional hydrodesulfurization technology is very easy to cause excessive hydrogenation saturation of olefin and has large octane value loss, so the traditional hydrodesulfurization technology is difficult to be accepted by refineries. For this reason, some new desulfurization techniques have been developed, and among them, the selective hydrodesulfurization technique is most representative.
For the selective hydrodesulfurization technology, it is one of the key technologies to develop a hydrodesulfurization catalyst with higher activity and good selectivity. At present, a catalyst for selective hydrodesulfurization reaction of oil products is mainly a supported catalyst, wherein the selection and preparation of a carrier material become the basis of the research and development work of the catalyst. The carrier is used as an important component of the supported catalyst, and besides the dispersibility of the active component can be improved, the pore structure of the carrier can provide a diffusion channel for reactant and product molecules, so that the utilization rate of the active component is improved. Based on the characteristics of the carrier, the selective hydrodesulfurization reaction process of the oil product is combined, and the carrier material with a reasonable macroporous structure is developed on the basis of the existing carrier material according to the difference of the molecular sizes of reactants and products, so that the mass transfer resistance can be effectively reduced and the mass transfer rate can be increased from the mass transfer angle, and the performance of the catalyst can be improved. Therefore, the development of support materials with a reasonably large pore structure is becoming a research hotspot and development trend for the upgrading of such catalysts.
The alumina is used as a traditional catalyst carrier material, has the characteristics of mature technology, adjustable pore structure, low use cost, easy processing and forming and the like, and is widely used for preparing oil refining chemical catalysts. According to the requirements of different reactions on pore structure and surface acidity, a variety of alumina production processes and products are formed, such as titanium-containing and zirconium-containing composite alumina products for improving the action between alumina and active metals; alumina products containing fluorine, chlorine and the like for improving the acidity of the surface of the alumina carrier; and alumina products with high bulk ratio, low bulk ratio, high specific surface area, high purity and the like. The pore structure of alumina comes from particles or stacking gaps among particles, the aperture of gamma-alumina synthesized by a conventional method is generally less than 15nm, and although researchers have carried out a great deal of research work in the synthesis of alumina with a macroporous structure in recent years, the number of alumina products containing the macroporous structure in the market is still small.
In order to obtain an alumina support material containing a macroporous structure, researchers obtain the macroporous alumina by methods such as a template agent and hydrothermal treatment. Among them, there are many documents related to the synthesis of a macroporous alumina material by a template method, and the method can be classified into a hard template and a soft template according to the type of the template. Good macroporous alumina can be obtained by a hard template agent method represented by activated carbon, and US4448896 discloses that carbon black is used as a pore-expanding agent to obtain macroporous alumina with pore size distribution of 15-300nm, but the macroporous alumina with concentrated pore size distribution is difficult to prepare due to nonuniform particle diameter distribution of the carbon black. CN201410347665.X discloses a preparation method of macroporous, high-strength alumina, which comprises adding pore-enlarging agent such as polyacrylamide, polyvinyl alcohol, alkyl cellulose, sesbania powder, starch, etc. to obtain macroporous aluminaThe pore-expanding agent is used in an amount of 10 to 30% based on the alumina, but no specific pore size range is disclosed. Although a good macroporous alumina carrier can be obtained by the hard template method, the dosage of the template is large, so that the processing cost is greatly increased, and the decomposition of a large amount of template does not meet the development requirement of low carbon and environmental protection. CN201010509425.7 discloses a method for co-pore-enlarging of hydrothermal and template agent, which is used for preparing an alumina carrier containing a macroporous structure, wherein the dosage of the template agent can be reduced to 3-10% through auxiliary pore-enlarging effect of hydrothermal, but the auxiliary hydrothermal causes the increase of energy consumption. CN200310103035.X discloses a preparation method of macroporous alumina, which comprises enlarging pores with polyvinyl alcohol, propanol, and polyethylene glycol soft template agent, and adding 1% polyethylene glycol to make the pore volume of 100nm or more account for 26.2% of the total pore volume. Compared with a hard template agent, the soft template agent has the advantages of low dosage and outstanding hole expansion effect, but the alcohol soft template agent with larger molecular weight has relatively poor solubility in water, so that the method is limited when the macroporous alumina is expanded. CN201410148773.4 discloses a preparation method of alumina porous microspheres, which comprises the following steps: 1) dissolving a surfactant in deionized water, and stirring to obtain a water phase; 2) mixing a chelating agent, an alumina precursor and n-octanol, and stirring to obtain an oil phase; 3) adding Span80 and a pore-forming agent into the oil phase, and stirring; 4) pouring the clear oil phase obtained in the step 3) into the water phase, and continuously stirring and emulsifying; 5) and 4) carrying out vacuum filtration on the product obtained in the step 4), washing the obtained filter cake, and drying to obtain the alumina porous microspheres. The metal porous microsphere with the internally closed macroporous structure is obtained by utilizing a pore-foaming agent and a sol-gel process in emulsion, wherein the microsphere has the internally closed macroporous structure, and the size of the microsphere is 1-100 mu m. The porous microspheres are prepared by utilizing the phase separation principle. The internal closed pore diameter is 50nm-5 μm. The pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or polyacrylic acid. The invention uses a large amount of surfactants, chelating agents and pore-forming agents, and has the advantages of more raw materials and complex synthesis process. CN201310748661.8 discloses a preparation method of an alumina/carbon aerogel composite material, which comprises the steps of mixing a water-soluble saccharide compound and a water-soluble polymer in a closed containerDissolving in water, adding aluminum salt or aluminum hydroxide, reacting at the temperature of 140-300 ℃, drying, and calcining at the temperature of 300-1500 ℃ in an inert atmosphere to obtain the alumina/carbon aerogel composite material. The alumina/carbon aerogel composite material with low density and high porosity is prepared by adopting a one-pot method, has the advantages of easily obtained raw materials, simple preparation process, low cost and the like, is light in weight and high in porosity, and can be used for catalyst carriers, gas sensitive elements, solid electrolytic diaphragms, molten steel oxygen probe materials and the like. CN201310499233.6 discloses a preparation method of an alumina carrier, which comprises the following steps: firstly, carrying out neutralization reaction on an alkaline precipitant aqueous solution and an acidic aluminum salt aqueous solution to obtain a precipitation slurry; then adding water-soluble resin into the precipitation slurry and carrying out aging treatment on the precipitation slurry by adopting microwave heating; and finally, filtering, washing, drying and molding the aged mixture to obtain the final alumina carrier. The alumina carrier prepared by the method has larger pore diameter and concentrated pore distribution, particularly the 10-20nm pores account for 60-80% of the total pore volume, and is suitable for being used as a carrier of a heavy oil hydrogenation catalyst. CN201310258011.5 relates to a tooth-shaped spherical alumina carrier, a corresponding hydrotreating catalyst and a preparation method thereof, and the tooth-shaped spherical alumina carrier comprises the following components: 0.5-4 parts by weight of a peptizing agent; 0.2 to 2 parts by weight of a lubricant; 0.2 to 3 parts by weight of a dispersant; 0.3-4 parts by weight of a pore-expanding agent; 100 parts by weight of aluminum hydroxide. The pore-expanding agent is one or a mixture of polyvinyl alcohol, sodium polyacrylate, starch derivatives or carbon black. The invention adds the anionic surfactant to reduce the adding amount of various auxiliary components and increase the specific surface area by 246m2And the pore-expanding agent is sodium polyacrylate. The dentiform spherical alumina carrier greatly reduces the content of various auxiliary agents such as peptizers, pore-expanding agents, dispersing agents, anionic surfactants and other components, thereby not only saving the cost, but also having the advantages of large specific surface area, high mechanical strength and the like. The invention uses peptizing agent, lubricant, dispersant, pore-expanding agent and other reagents, and the prepared alumina carrier has unimodal pore distribution. CN201110170283.0 discloses a three-dimensional ordered macroporous alumina and a preparation method thereof. The three-dimensional ordered macroporous alumina has macropore diameter of50-1000nm, particle diameter of 1-50mm, and mechanical strength of 80-280 g/mm. The method comprises the following steps: adding a carbohydrate compound and concentrated sulfuric acid into the monodisperse polymer microsphere emulsion to obtain a modified polymer microsphere colloidal crystal template, then filling alumina sol, and aging and roasting to obtain the three-dimensional ordered macroporous alumina. The method can greatly improve the adhesion of alumina precursors, enhance the mechanical strength of the material, and ensure that the macroporous material is not easy to be broken into fine powder and can still maintain higher integrity when the template agent is removed by high-temperature roasting. CN201110116418.5 provides mesoporous spherical alumina and a method for preparing the mesoporous spherical alumina by adopting a template agent for guidance. The method is characterized in that an oil column forming method is adopted, a template agent with a guiding function is added into the aluminum sol in the process of preparing the aluminum sol, and a large amount of mesoporous structures are generated in the alumina spheres due to the existence of the template agent with the guiding function in the forming and aging processes of the aluminum sol. The template agent is an organic monomer or a linear polymer, and the organic monomer is one of acrylic acid, ammonium acrylate, acrylamide or allyl alcohol. The specific surface area of the mesoporous spherical alumina is 150-300m2Per g, particle diameter of 0.1-5mm, pore volume of 0.7-1.5mL/g, pore diameter of 2-40nm of more than 97%, and bulk density of 0.3-0.8g/cm3The crushing strength is 70-250N/grain. The mesoporous spherical alumina prepared by the template agent has more centralized pore diameter, and can be used as a catalyst carrier or a catalyst in petrochemical industry and fine chemical industry.
CN201010221302.3(CN102311134A) discloses a spherical integral macroporous alumina and a preparation method thereof. The method comprises the following steps: uniformly mixing the polymer microsphere emulsion, the alumina sol and the coagulant in a certain proportion, dispersing the mixture in an oil phase to form W/O type liquid drops, then heating the mixed phase system to enable the alumina sol in the water phase to be gelled into spheres, then separating the formed gel microspheres from the oil phase, and then aging, drying and roasting the gel microspheres in an ammonia water medium to obtain the spherical integral macroporous alumina. The alumina has the advantages of uniform and controllable macropore diameter within the range of less than 1 mu m, controllable size of spherical particles, higher mechanical strength, simple and easy forming process, and suitability for mass preparation. The polymer microsphere has a diameter of 50-1000nm, and is of polystyrene microsphere, n-butyl polybenegenate microsphere, polyacrylate microsphere, etc. The coagulant is hexamethylenetetramine and urea. The oil phase is organic hydrocarbon. The invention mainly prepares integral macroporous alumina, and the diameter of the macropores is uniform and controllable. The preparation process uses lipid microspheres, coagulant and the like, the preparation process is relatively complex, and the used reagent raw materials are various. Due to the use of the polymer microspheres, the structure of the inner pore channel of the alumina carrier is closed pores, namely the inner pore channel of the alumina carrier has no penetrability. CN200910204238.5(CN102040235) discloses a three-dimensional ordered macroporous alumina and a preparation method thereof. The method comprises the following steps: assembling monodisperse polymer microspheres into a colloidal crystal template, filling alumina sol prepared by a specific method into the template, and finally drying and roasting to obtain the macroporous alumina. The method can well control the compounding process of the aluminum sol and the polymer microspheres, and the network structure of the aluminum oxide gel is not damaged as far as possible, so that the prepared aluminum oxide not only has three-dimensional ordered macroporous channels, but also has higher specific surface area. The invention forms small window holes by moderate sintering of the template, and makes the big holes in the material communicate with the surrounding big holes through 12 small window holes. The alumina of the invention is suitable for being used as a heavy oil catalyst carrier and an adsorption separation material of organic macromolecules. When the catalyst is applied to a catalyst carrier material, the mass transfer capacity of materials in the catalyst can be improved, so that the activity and the selectivity of the catalyst are improved.
Adding aluminum hydroxide or alumina to rubber is more common, for example, CN103102686A provides a method for preparing an aluminum hydroxide-silicone rubber composite material, which is characterized in that: the composite heat-conducting silicon rubber is prepared by taking aluminum hydroxide as a filler and silicon rubber as a carrier in a direct-current electric field. The blending ratio of the aluminum hydroxide to the silicon rubber is 0:100-40: 60. The composite heat-conducting silicone rubber prepared under the condition of an external direct-current electric field can improve the effective heat conductivity by 30 percent. CN1130416C discloses a diene rubber composition containing alumina as reinforcing filler and a tire tread containing the same. With at least one diene elastomer asA rubber composition based on alumina as reinforcing filler and a coupling agent, the alumina having: BET specific surface area of 30-400m2g-1An average particle size of less than or equal to 500nm, a high proportion of Al-OH surface-reactive functional groups and a high dispersibility, the amount of coupling agent being 10 per square meter of alumina-7-10-5In particular, the composition is suitable for the manufacture of tires. CN1760274A relates to a silicone rubber composition for high voltage insulators. More precisely, it relates to addition-or peroxide-crosslinking silicone rubber compositions which have aluminium hydroxide as filler, the aluminium hydroxide used being untreated aluminium hydroxide.
In summary, macroporous alumina has been successfully applied to a plurality of catalyst systems, and has various improvements in the aspects of catalyst activity, selectivity and stability. Although the hard template agent can obtain a better macroporous structure, the hard template agent has certain defects in the aspect of adjusting the pore size; the solubility of the polyvinyl alcohol soft template agent in water is influenced by the polymerization degree of the polyvinyl alcohol soft template agent, so that the polyvinyl alcohol soft template agent is limited when being used for preparing the ultra-large pore alumina.
Disclosure of Invention
The invention aims to provide a selective hydrodesulfurization catalyst containing a macroporous alumina carrier, which adopts high-molecular styrene-butadiene rubber emulsion as a template agent to synthesize the macroporous alumina carrier with adjustable pore diameter and easily-controlled macroporous proportion, is prepared by loading a metal active component, and can be used for selective hydrodesulfurization of catalytic cracking gasoline.
The invention aims to solve the technical problems of improving the activity and selectivity of the existing hydrodesulfurization catalyst, being particularly suitable for hydrofining of high-sulfur high-olefin catalytic cracking gasoline and mainly solving the problems of low desulfurization rate, poor desulfurization selectivity and large octane number loss in the existing catalytic cracking gasoline selective hydrodesulfurization technology.
In order to solve the technical problem, the invention discloses a selective hydrodesulfurization catalyst containing a macroporous alumina carrier, which comprises 82-95wt%, preferably 75-90 wt%, molybdenum oxide with the content of 2-14wt%, preferably 5-12wt%, and cobalt oxide with the content of 1-5wt%, preferably 1-3wt%, in percentage by weight.
The catalyst disclosed by the invention is prepared by adopting a conventional impregnation method, namely a co-impregnation method or a step-by-step impregnation method, and the catalyst is prepared by adopting the following preparation method: preparing a dipping solution from soluble salt containing molybdenum and cobalt at normal temperature, dipping an alumina carrier containing macropores, aging at room temperature for 2-5h, drying at 80-150 ℃ for 2-8h, and roasting at 600 ℃ for 3-10h at 450-150 ℃ to obtain a catalyst finished product.
The hydrodesulfurization catalyst can also be added with an auxiliary agent of potassium, and the content of potassium oxide is 0.1-3.0wt% in percentage by weight of the catalyst.
The alumina carrier containing macropores has the pore size distribution of 60-400nm, preferably 60-200 nm, more preferably 80-180nm, the proportion of macropores is 2-70%, preferably 10-70%, the pore volume is 0.8-2.2mL/g, preferably 0.8-1.2mL/g or preferably 1.8-2.2mL/g, and the pore channels in the carrier have connectivity. The alumina carrier uses high molecular styrene-butadiene rubber emulsion as a pore-expanding agent, and the alumina carrier is easy to generate macropores, and the pore size distribution is more concentrated and ranges from 60 nm to 400 nm.
The pore diameter of the alumina carrier containing macropores can be realized by adjusting the molecular weight, the particle size and the addition amount of the pore-expanding agent. The pore size distribution can vary between 60-400nm, such as 60-90nm, 140-180nm, 240-300nm, etc. The proportion of macropores is 0.1-70%, and can be adjusted to 10-70%.
The invention also provides a preparation method of the macroporous alumina carrier, which comprises the steps of firstly adding pseudo-boehmite powder and sesbania powder into a kneader to be uniformly mixed; then preparing styrene-butadiene rubber emulsion with the particle size of 10-500nm, and adding organic acid or inorganic acid into the styrene-butadiene rubber emulsion, wherein the addition amount of the acid is 2-8 wt% of the pseudo-boehmite; then adding acid solution containing styrene-butadiene rubber emulsion into the pseudo-boehmite powder to be uniformly kneaded, wherein the adding amount of the acid solution containing the styrene-butadiene rubber emulsion is 0.1-45 wt%, preferably 0.5-30 wt%, more preferably 5-20 wt% of the pseudo-boehmite, and finally carrying out extrusion-molding-drying-roasting to obtain the macroporous alumina carrier.
The preparation method of the styrene-butadiene rubber emulsion as the pore-expanding agent comprises the following steps: adding a polymerization-grade styrene monomer, a polymerization-grade butadiene monomer, deionized water, an emulsifier, an electrolyte and an auxiliary agent into a polymerization system, wherein the total mass of the styrene monomer and the butadiene monomer is 100 parts, and the dosage of the styrene is 10-40 parts, preferably 20-35 parts; the dosage of the deionized water is 100-300 parts; the dosage of the emulsifier is 2-10 parts; the using amount of the electrolyte is 0.5-2 parts; the dosage of the auxiliary agent is 0.01-0.2 part. Under the condition of stirring, mixing the materials, pre-emulsifying for 20-40min to obtain an emulsion, cooling to 5-8 ℃, and adding an initiator and a regulator, wherein the amount of the initiator is 0.01-0.5 part and the amount of the regulator is 0.5-2 parts based on 100 parts of the total mass of the styrene monomer and the butadiene monomer; controlling the temperature to be 5-8 ℃, the pressure to be 0.1-0.3MPa and the reaction time to be 7-10h, and adding a terminator to terminate the polymerization reaction when the conversion rate of the two monomers reaches 60-70 percent to obtain the styrene butadiene rubber emulsion.
The particle size of the synthesized styrene-butadiene rubber emulsion is 10-500nm, the particle size is mainly controlled by the type and the amount of the emulsifier and the amount of the regulator, generally, the better the emulsifying effect of the emulsifier selected in the synthesis process, the more the emulsifier is used, and the more the regulator is used, the smaller the particle size of the synthesized rubber emulsion is.
The emulsifier is selected from one or more of nonionic emulsifiers (such as sorbitan ester, Tween series and span series, preferably sorbitan ester), amphoteric emulsifiers (such as carboxylic acids, sulfuric acid esters and phosphoric acid esters) and polymeric emulsifiers (such as carboxymethyl cellulose and p-styrene sulfonate) and the electrolyte is selected from one or more of potassium chloride, sodium bisulfate and sodium fluoride, preferably potassium chloride and the auxiliary agent comprises chelating agent (ethylene diamine tetraacetic acid and metal salts thereof, preferably iron sodium Ethylene Diamine Tetraacetic Acid (EDTA)), pH value regulator (KOH, Na and the like)2CO3Etc.) and surface tension modifiers (pentanol, hexanol, etc.), which may be selected from organic peroxides (diisophenylpropyl peroxide, dibenzoyl peroxide), oxidation-reduction systems (potassium persulfate-ferrous salt systems, preferably ferrous sulfate), azo-type initiators (azobisisobutyronitrile). Regulators are also called chain transferThe transfer agent is a compound containing sulfur, nitrogen, phosphorus and organic unsaturated bonds, and preferably mercaptan and thiuram disulfide. The terminator can be selected from p-phenylene, quinone, nitroso and sulfur-containing compounds.
The acid solution containing styrene-butadiene rubber emulsion is added in an amount of 0.1-45 wt% of the pseudoboehmite, and the acid is added in an amount of 2-8 wt%, preferably 3-5 wt% of the pseudoboehmite, and the acid used is various organic acids or inorganic acids commonly used in the art, such as acetic acid, citric acid, nitric acid, hydrochloric acid, and the like. The source and property of the pseudo-boehmite powder are not limited, and the pseudo-boehmite powder can be a product produced by a carbonization method, a nitric acid method, a sulfuric acid method, an ammonium method and other processes. Is suitable for pseudo-boehmite with different ranges of specific surface area, pore volume and pore diameter.
The kneading and extruding process of the macroporous alumina carrier comprises the following steps: slowly adding the prepared acid solution containing the pore-expanding agent into the mixed powder of the sesbania powder and the pseudo-boehmite which are mixed in advance, extruding and forming after kneading uniformly, and roasting for 4-6h at the temperature of 80-200 ℃ and 550-700 ℃ to finally obtain the alumina carrier containing macropores.
In order that the macroporous alumina carrier has better performance and is applied to a selective hydrodesulfurization catalyst of catalytic gasoline as a carrier, the alumina carrier is preferably introduced with auxiliary agents of boron, potassium and strontium, and the specific process comprises the following steps: firstly, adding pseudo-boehmite powder and sesbania powder into a kneader to be uniformly mixed; then adding an aqueous solution containing boric acid, potassium nitrate and strontium nitrate, preparing styrene-butadiene rubber emulsion with the particle size of 10-500nm, and adding organic acid or inorganic acid into the aqueous solution, wherein the addition amount of the acid is 2-8 wt% of the pseudo-boehmite; then adding an acid solution containing styrene-butadiene rubber emulsion into the pseudo-boehmite powder to be uniformly kneaded, wherein the adding amount of the acid solution containing the styrene-butadiene rubber emulsion is 0.1-45 wt%, preferably 0.5-30 wt%, more preferably 5-20 wt% of the pseudo-boehmite, and finally carrying out extrusion-molding-drying-roasting to obtain the macroporous alumina carrier modified by the aids of boron, potassium and strontium. The composition of the carrier is calculated by the mass of oxides: comprises 93-99.5 wt% of alumina, 0.1-2.5 wt% of boron oxide, 0.1-4.5 wt% of potassium oxide and 0.1-4.5 wt% of strontium oxide.
Through the modification of the additives of boron, potassium and strontium, the carrier is prepared into a selective hydrodesulfurization catalyst, such as a cobalt-molybdenum catalyst, which is beneficial to adjusting the acidity of the catalyst, reducing the polymerization of olefin in raw oil, inhibiting the carbon deposition in the catalyst from being inactivated and having low carbon deposition rate, thereby improving the hydrogenation stability of the catalyst.
The macroporous alumina carrier modified by the auxiliary agents of boron, potassium and strontium can be further improved, the potassium and the strontium are preferably used for carrying out surface modification on the carrier containing the auxiliary agents of boron, potassium and strontium, and the specific process comprises the following steps: preparing a potassium nitrate and strontium nitrate-containing aqueous solution as an impregnation carrier, and drying and roasting to obtain the composite carrier with the surface modified by the aid of potassium and strontium. The content of the potassium oxide and the strontium oxide on the surface of the composite carrier are controlled within the range of 0.1-4.5 wt% and 0.1-4.5 wt%, respectively.
After the surface of the macroporous alumina carrier is modified by potassium and strontium, the concentration difference is formed between the concentration of potassium and strontium on the surface of the macroporous alumina carrier and the concentration of potassium and strontium in the carrier, the content of potassium and strontium on the surface of the carrier is higher than that of potassium and strontium in the carrier, namely the molar content or the mass content of potassium oxide and strontium oxide on the surface of the carrier can be 2.1-3.0 times of that of potassium oxide and strontium oxide in the carrier. This makes the surface of the carrier tend to be uniformly distributed, and reduces the acidity of the surface of the carrier. The selective hydrodesulfurization catalyst prepared by adopting the carrier can improve the specific surface area of the catalyst, inhibit the surface carbon deposition inactivation of the catalyst, improve the dispersibility and the adhesiveness of active components such as cobalt and molybdenum on the carrier of the catalyst, and effectively solve the problem of activity reduction caused by the loss of the active components such as cobalt and molybdenum. The mol content or mass content of the potassium oxide and the strontium oxide on the surface of the carrier is preferably 2.1 to 3.0 times of the content of the potassium oxide and the strontium oxide inside the carrier, and the mol content or mass content of the potassium oxide and the strontium oxide is less than 2 times of the content of the potassium oxide and the strontium oxide, so that the aim of adjusting the surface acidity of the carrier, improving the dispersion degree and the adhesiveness of the active component on the carrier and inhibiting the loss of the active component can not be achieved.
The reactor used for evaluating the performance of the selective hydrodesulfurization catalyst provided by the invention can be a fixed bed adiabatic reactor, also can be a fixed bed isothermal reactor, and is preferably a fixed bed adiabatic reactor.
Compared with the prior art, the invention does not need to add reagents such as coagulant, dispersant, chelating agent and the like, and the preparation cost is greatly reduced. The synthesized styrene-butadiene rubber emulsion can be adjusted from thousand to hundred thousand by controlling the synthesis conditions and the dosage of the regulator, the particle size of the styrene-butadiene rubber emulsion is adjusted to be 20-400nm by coordinately controlling the type and the dosage of the emulsifier, and the aperture of the alumina can be further controlled according to the different particle sizes of the styrene-butadiene rubber emulsion.
The styrene-butadiene rubber emulsion as the pore-expanding agent is different from other polymer microspheres in the prior art, such as polystyrene microspheres, and has good solubility, so that the pore passage in the carrier has connectivity instead of a closed pore structure. The prepared alumina carrier contains a macroporous structure and a mesoporous structure, wherein the mesoporous range is 3-50nm, the mesoporous proportion is 20-75%, preferably 20-55%, the prepared alumina carrier is an alumina carrier containing meso-macropores, and the pore diameters are not uniform.
Drawings
FIG. 1 is a graph showing the pore size distribution of the alumina carrier containing macropores prepared in example 1.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
The main raw material sources for preparing the catalyst are as follows: the raw material reagents used in the invention are all commercial products.
The specific surface area and the mesoporous aperture of the alumina carrier containing macropores are tested by adopting a TStar II 3000 type full-automatic adsorption instrument produced by American Mac company. The pore volume and pore size distribution of the macroporous alumina support were measured using an AutoPore model IV9520 fully automatic mercury porosimeter manufactured by Michmark corporation, USA.
The sulfur content of the full-fraction FCC gasoline raw material and the reaction product is analyzed by a TSN-2000 type sulfur-nitrogen determinator. Research octane numbers of FCC gasoline raw materials and reaction products are tested by an octane number machine. The composition of FCC gasoline raw material and reaction product is analyzed by Agilent 7890B gas chromatograph, and data processing is completed by HW-2000PONA analysis special chromatographic workstation.
In each example, the content of cobalt oxide, molybdenum oxide, and the like in the catalyst was measured by an X-ray fluorescence method (see, "analytical methods in petrochemical industry (RIPP test method)", eds "Yancui et al, published by scientific publishers, 1990).
Example 1
Adding 25 parts (by mass ratio) of styrene, 75 parts of butadiene, 200 parts of deionized water, 3.0 parts of emulsifier sorbitan ester, 1.5 parts of electrolyte KCl and 0.09 part of chelating agent iron sodium Ethylene Diamine Tetraacetate (EDTA) into a 10L polymerization kettle, pre-emulsifying for 20min, cooling to 5 ℃, adding 0.04 part of initiator diisopropylbenzene hydroperoxide and 0.04 part of ferrous sulfate and 0.20 part of regulator tert-dodecyl mercaptan, reacting for 7h at 5 ℃, and adding a mercaptan terminating agent into the mixture with the conversion rate of the two monomers controlled to be about 60% to obtain the styrene-butadiene rubber emulsion with the particle size of about 200 nm.
250mL of deionized water was weighed in a beaker, 12.0g of 68% nitric acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. 9.0g of styrene-butadiene rubber emulsion is weighed and added into the prepared deionized water nitric acid solution, and the mixture is stirred uniformly to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, acid liquor of styrene butadiene rubber is added into the mixed powder, and the mixture is kneaded and extruded to form clover-shaped. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain macroporous alumina carrier A-1. The specific surface area and pore size distribution of the macroporous alumina support are shown in Table 1. FIG. 1 is a graph showing the pore size distribution of an alumina support A-1 containing macropores. As can be seen from fig. 1, the prepared alumina carrier has a structure with bimodal pore distribution.
Adding 13.00g of ammonium heptamolybdate and 13.21g of cobalt acetate into 70mL of distilled water to prepare a steeping liquor steeping carrier, aging the obtained catalyst precursor at room temperature for 4h, drying at 130 ℃ for 6h, and roasting at 590 ℃ for 5h to obtain the catalyst 1. Catalyst 1 consists essentially of: 3wt% of cobalt oxide, 8wt% of molybdenum oxide and 89 wt% of carrier.
Example 2
30 parts (mass ratio) of styrene, 70 parts of butadiene, 200 parts of deionized water, 4.0 parts of emulsifier sorbitan ester, 1.0 part of electrolyte KCl and 0.12 part of chelating agent iron sodium Ethylene Diamine Tetraacetate (EDTA) are added into a 10L polymerization kettle, pre-emulsification is carried out for 30min, after the temperature is cooled to 5 ℃, 0.04 part of hydrogen peroxide diisopropylbenzene, 0.04 part of ferrous sulfate and 0.40 part of regulator tert-dodecyl mercaptan are added into the mixture, the mixture is reacted for 7h at 5 ℃, and a p-phenylene glycol terminator is added into the mixture with the conversion rate of the two monomers controlled to be about 60 percent, so as to obtain the styrene-butadiene rubber emulsion with the particle size of about 100 nm.
260mL of deionized water was weighed into a beaker, 15.0g of acetic acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. Weighing 15.0g of styrene-butadiene rubber emulsion, adding the styrene-butadiene rubber emulsion into the prepared deionized water acid solution, and uniformly stirring to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, acid liquor of styrene butadiene rubber is added into the mixed powder, and the mixture is kneaded and extruded to form clover-shaped. Drying at 150 deg.C for 6 hr, and calcining at 600 deg.C for 5 hr to obtain macroporous alumina carrier A-2. The specific surface area and pore size distribution of the macroporous alumina support are shown in Table 1.
Adding ammonium heptamolybdate and cobalt acetate into distilled water to prepare a steeping liquor to impregnate the carrier, aging the obtained catalyst precursor at room temperature for 3h, drying at 120 ℃ for 7h, and roasting at 550 ℃ for 7h to obtain the catalyst 2. Catalyst 2 mainly consists of: 4.5 wt% of cobalt oxide, 6 wt% of molybdenum oxide and 89.5 wt% of carrier.
Example 3
Adding 35 parts (by mass ratio) of styrene, 65 parts of butadiene, 200 parts of deionized water, 5.0 parts of lauroyl diethanolamide, 0.8 part of electrolyte KCl and 0.10 part of pH value regulator KOH into a 10L polymerization kettle, pre-emulsifying for 20min, cooling to 7 ℃, adding 0.05 part of initiator azobisisobutyronitrile and 0.60 part of regulator tert-dodecyl mercaptan, reacting for 7h at 7 ℃, controlling the conversion rate of the two monomers to be about 60%, and adding a mercaptan terminator to obtain the styrene-butadiene rubber emulsion with the particle size of about 50 nm.
260mL of deionized water was weighed into a beaker, 18.0g of acetic acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. And weighing 120.0g of styrene-butadiene rubber emulsion, adding the styrene-butadiene rubber emulsion into the prepared deionized water acid solution, and uniformly stirring to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, acid liquor of styrene butadiene rubber is added into the mixed powder, and the mixture is kneaded and extruded to form clover-shaped. Drying at 130 deg.C for 8 hr, and calcining at 700 deg.C for 4 hr to obtain macroporous alumina carrier A-3. The specific surface area and pore size distribution of the macroporous alumina support are shown in Table 1.
Adding ammonium heptamolybdate and cobalt nitrate into distilled water to prepare a steeping liquor to impregnate the carrier, aging the obtained catalyst precursor at room temperature for 5h, drying at 120 ℃ for 5h, and roasting at 600 ℃ for 5h to obtain the catalyst 3. Catalyst 3 mainly consists of: 2wt% of cobalt oxide, 12.5 wt% of molybdenum oxide and 85.5 wt% of carrier.
Example 4
Adding 28 parts (mass ratio) of styrene, 72 parts of butadiene, 200 parts of deionized water, 2.0 parts of sorbitan ester, 1.2 parts of electrolyte KCl and 0.13 part of chelating agent iron sodium Ethylene Diamine Tetraacetate (EDTA) into a 10L polymerization kettle, pre-emulsifying for 20min, cooling to 7 ℃, adding 0.04 part of diisobutyronitrile peroxide and 0.15 part of regulator tert-dodecyl mercaptan, reacting for 7h at 5 ℃, controlling the conversion rate of the two monomers to be about 60%, and adding a mercaptan terminator to obtain the styrene-butadiene rubber emulsion with the particle size of about 300 nm.
250mL of deionized water was weighed in a beaker, 10.0g of 68% nitric acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. 16.0g of styrene-butadiene rubber emulsion is weighed and added into the prepared deionized water acid solution, and the mixture is stirred uniformly to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, acid liquor of styrene butadiene rubber is added into the mixed powder, and the mixture is kneaded and extruded to form clover-shaped. Drying at 130 deg.C for 8 hr, and calcining at 600 deg.C for 6 hr to obtain macroporous alumina carrier A-4. The specific surface area and pore size distribution of the macroporous alumina support are shown in Table 1.
Adding ammonium heptamolybdate and cobalt acetate into distilled water to prepare a steeping liquor to impregnate the carrier, aging the obtained catalyst precursor at room temperature for 4h, drying at 130 ℃ for 4h, and roasting at 600 ℃ for 6h to obtain the catalyst 4. Catalyst 4 mainly consists of: 2.5 wt% of cobalt oxide, 9.5 wt% of molybdenum oxide and 88 wt% of carrier.
Comparative example 1
Weighing 300g of pseudo-boehmite powder and 15g of sesbania powder, uniformly mixing, measuring 250mL of deionized water by using a beaker, adding 12.0g of nitric acid with the concentration of 68% into the deionized water, uniformly mixing, adding into the mixed powder of the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain macroporous alumina carrier D-1. The specific surface area and pore size distribution of the macroporous alumina support are shown in Table 1. Comparative example 1 differs from example 1 in that no pore-expanding agent was added.
Adding 13.00g of ammonium heptamolybdate and 13.21g of cobalt acetate into 70mL of distilled water to prepare a steeping liquor steeping carrier, aging the obtained catalyst precursor at room temperature for 4h, drying at 130 ℃ for 6h, and roasting at 590 ℃ for 5h to obtain a comparative catalyst D-1. Comparative catalyst D-1 consists essentially of: 3wt% of cobalt oxide, 8wt% of molybdenum oxide and 89 wt% of carrier.
Example 5
Adding 25 parts (by mass ratio) of styrene, 75 parts of butadiene, 200 parts of deionized water, 3.0 parts of emulsifier sorbitan ester, 1.5 parts of electrolyte KCl and 0.09 part of chelating agent iron sodium Ethylene Diamine Tetraacetate (EDTA) into a 10L polymerization kettle, pre-emulsifying for 20min, cooling to 5 ℃, adding 0.04 part of initiator diisopropylbenzene hydroperoxide and 0.04 part of ferrous sulfate and 0.20 part of regulator tert-dodecyl mercaptan, reacting for 7h at 5 ℃, and adding a mercaptan terminating agent into the mixture with the conversion rate of the two monomers controlled to be about 60% to obtain the styrene-butadiene rubber emulsion with the particle size of about 200 nm.
250mL of deionized water was weighed in a beaker, 12.0g of 68% nitric acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. 9.0g of styrene-butadiene rubber emulsion is weighed and added into the prepared deionized water nitric acid solution, and the mixture is stirred uniformly to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, acid liquor of styrene butadiene rubber is added into the mixed powder, and the mixture is kneaded and extruded to form clover-shaped. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain macroporous alumina carrier A-1.
Adding 13.00g of ammonium heptamolybdate, 13.21g of cobalt acetate and 4.27g of potassium nitrate into 70mL of distilled water to prepare a steeping liquor impregnation carrier, aging the obtained catalyst precursor for 4h at room temperature, drying for 6h at 130 ℃, and roasting for 5h at 590 ℃ to obtain the catalyst 5. Catalyst 5 mainly consists of: 3wt% of cobalt oxide, 8wt% of molybdenum oxide, 1.5 wt% of potassium oxide and 87.5 wt% of carrier.
Example 6
Adding 25 parts (by mass ratio) of styrene, 75 parts of butadiene, 200 parts of deionized water, 3.0 parts of emulsifier sorbitan ester, 1.5 parts of electrolyte KCl and 0.09 part of chelating agent iron sodium Ethylene Diamine Tetraacetate (EDTA) into a 10L polymerization kettle, pre-emulsifying for 20min, cooling to 5 ℃, adding 0.04 part of hydrogen peroxide diisopropylbenzene and 0.04 part of ferrous sulfate as an initiator, and 0.20 part of regulator tert-dodecyl mercaptan, reacting for 7h at 5 ℃, and adding a mercaptan terminating agent into the mixture with the conversion rate of the two monomers controlled to be about 60% to obtain the styrene-butadiene rubber emulsion with the particle size of about 200 nm.
250mL of deionized water was weighed in a beaker, 12.0g of 68% nitric acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. 9.0g of styrene-butadiene rubber emulsion is weighed and added into the prepared deionized water nitric acid solution, and the mixture is stirred uniformly to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, and then 2.23g of boric acid, 2.08g of potassium nitrate and 1.67g of strontium nitrate are respectively weighed and completely dissolved in 60mL of distilled water to prepare the aqueous solution containing boron, potassium and strontium. Adding the aqueous solution into a mixture of pseudo-boehmite powder and sesbania powder, adding acid liquor of styrene-butadiene rubber into the mixture, and kneading and extruding the mixture into a clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain macroporous alumina carrier A-6 modified with boron, potassium and strontium as assistants.
Adding ammonium heptamolybdate and cobalt nitrate into distilled water to prepare a steeping liquor to impregnate the carrier A-6, aging the obtained catalyst precursor at room temperature for 4h, drying at 110 ℃ for 3h, and roasting at 550 ℃ for 4h to obtain the catalyst C-1. Catalyst C-1 mainly consists of: 3wt% of cobalt oxide, 7 wt% of molybdenum oxide and 90 wt% of carrier.
Example 7
Adding 25 parts (by mass ratio) of styrene, 75 parts of butadiene, 200 parts of deionized water, 3.0 parts of emulsifier sorbitan ester, 1.5 parts of electrolyte KCl and 0.09 part of chelating agent iron sodium Ethylene Diamine Tetraacetate (EDTA) into a 10L polymerization kettle, pre-emulsifying for 20min, cooling to 5 ℃, adding 0.04 part of hydrogen peroxide diisopropylbenzene and 0.04 part of ferrous sulfate as an initiator, and 0.20 part of regulator tert-dodecyl mercaptan, reacting for 7h at 5 ℃, and adding a mercaptan terminating agent into the mixture with the conversion rate of the two monomers controlled to be about 60% to obtain the styrene-butadiene rubber emulsion with the particle size of about 200 nm.
250mL of deionized water was weighed in a beaker, 12.0g of 68% nitric acid was added to the deionized water and mixed well, and the mixture was placed in a 80 ℃ water bath. 9.0g of styrene-butadiene rubber emulsion is weighed and added into the prepared deionized water nitric acid solution, and the mixture is stirred uniformly to obtain the acid solution containing the pore-expanding agent. 300g of pseudo-boehmite powder and 15g of sesbania powder are weighed and mixed uniformly, and then 2.23g of boric acid, 2.08g of potassium nitrate and 1.67g of strontium nitrate are respectively weighed and completely dissolved in 60mL of distilled water to prepare the aqueous solution containing boron, potassium and strontium. Adding the aqueous solution into a mixture of pseudo-boehmite powder and sesbania powder, adding acid liquor of styrene-butadiene rubber into the mixture, and kneading and extruding the mixture into a clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain macroporous alumina carrier A-6 modified with boron, potassium and strontium as assistants.
The method comprises the following steps of modifying the surface of a macroporous alumina carrier A-6 modified by additives of boron, potassium and strontium by using potassium and strontium, wherein the specific process comprises the following steps: preparing potassium nitrate and strontium nitrate into impregnation liquid, respectively weighing 4.83g of potassium nitrate and 3.84g of strontium nitrate, completely dissolving in 30mL of distilled water, diluting with deionized water to prepare the impregnation liquid to impregnate the alumina carrier A-6, and drying and roasting to obtain the alumina composite carrier A-7 with the potassium and strontium surface modified.
Adding ammonium heptamolybdate and cobalt acetate into distilled water to prepare a steeping liquor to impregnate the carrier, aging the obtained catalyst precursor at room temperature for 2h, drying at 150 ℃ for 5h, and roasting at 500 ℃ for 9h to obtain the catalyst C-2. Catalyst C-2 mainly consists of: 1.5 wt% of cobalt oxide, 13 wt% of molybdenum oxide and 85.5 wt% of alumina composite carrier.
The performance evaluation is carried out on the selective hydrodesulfurization catalysts C-1 and C-2, and the evaluation result is as follows: the desulfurization rates of the products of the catalysts C-1 and C-2 are 83.1 percent and 84.5 percent respectively, the olefin reduction amounts are 1.9 percent and 1.7 percent respectively, and the octane number loss is 0.6 unit and 0.5 unit respectively. Therefore, the selective hydrodesulfurization catalyst prepared by adopting the macroporous alumina carrier modified by the additives of boron, potassium and strontium can solve the problems of low desulfurization rate, poor desulfurization selectivity and large octane value loss of the catalyst in the prior art.
And then, carrying out stability inspection on the selective hydrodesulfurization catalysts C-1 and C-2, wherein the reaction is carried out for 500 hours, the desulfurization rates of the products of the catalysts C-1 and C-2 are 81.6 percent and 83.8 percent respectively, the octane number loss is 0.6 unit and 0.4 unit respectively, the carbon deposition rates are 2.5 and 2.1, the reaction performance of the catalysts is stable, the active components are not easy to lose, and the carbon deposition rate is low, thereby showing that the hydrodesulfurization stability is good.
TABLE 1 specific surface area and pore size distribution of macroporous alumina supports
And (3) evaluating the performances of the selective hydrodesulfurization catalysts 1-5 and the comparative catalyst D-1. The catalyst is filled into a 10mL reactor and is pre-vulcanized, the vulcanized oil is straight-run gasoline, and the vulcanizing agent is CS2At a concentration of 1 wt%; the vulcanization pressure is 2.8MPa, the volume ratio of hydrogen to oil is 300:1, and the volume space velocity is 2h-1The vulcanization procedure is vulcanization treatment at 230 ℃ and 270 ℃ for 6 h. After the vulcanization treatment is finished, the catalytic cracking gasoline is switched to be replaced for 10 hours, and the reaction process conditions are adjusted as follows: the temperature of the reactor is 260 ℃, the reaction pressure is 1.6MPa, and the volume space velocity is 3h-1The volume ratio of hydrogen to oil is 250: 1. Inverse directionSampling analysis should begin after about 50 h.
The evaluation results are shown in table 2.
TABLE 2 evaluation results of catalyst reactivity
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Desulfurization rate% | 82.7 | 81.9 | 83.3 | 82.1 | 82.9 | 79.0 |
| Reduction of olefins by% | 1.8 | 2.5 | 2.2 | 1.7 | 1.6 | 5.2 |
| Loss of octane number | 0.5 | 0.8 | 0.6 | 0.5 | 0.4 | 2.3 |
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (7)
1. A hydrodesulfurization catalyst containing a macroporous alumina carrier is characterized in that the catalyst contains 82-95wt% of macroporous alumina carrier by total weight percent of the catalyst, styrene-butadiene rubber emulsion is used as a pore-expanding agent as the carrier, and the pore size distribution of the alumina carrier is 60-200 nm, the proportion of macropores is 2-70%, and the pore volume is 0.8-2.2 ml/g; the content of molybdenum oxide is 2-14wt%, and the content of cobalt oxide is 1-5 wt%; the alumina carrier is introduced with the auxiliary agents of boron, potassium and strontium, and the alumina carrier comprises the following components in mass percentage: comprises 93-99 wt% of alumina, 0.1-2.5 wt% of boron oxide, 0.1-4.5 wt% of potassium oxide and 0.1-4.5 wt% of strontium oxide, wherein the mass content of the potassium oxide and the strontium oxide on the surface of the carrier is 2.1-3.0 times of the content of the potassium oxide and the strontium oxide in the carrier; the pore passage in the carrier has connectivity; the preparation method of the alumina carrier containing macropores comprises the following steps: firstly, adding pseudo-boehmite powder and sesbania powder into a kneader to be uniformly mixed, and then adding an aqueous solution containing boric acid, potassium nitrate and strontium nitrate; preparing styrene-butadiene rubber emulsion with the particle size of 10-500nm, and adding organic acid or inorganic acid into the styrene-butadiene rubber emulsion, wherein the addition amount of the acid is 2-8 wt% of the pseudo-boehmite; then adding acid liquor containing styrene-butadiene rubber emulsion into the pseudo-boehmite powder and the sesbania powder to be uniformly kneaded, wherein the adding amount of the acid liquor containing the styrene-butadiene rubber emulsion is 0.1-45 wt% of the pseudo-boehmite, and carrying out extrusion, forming, drying and roasting to obtain an alumina carrier modified by the aid of potassium and strontium; preparing an alumina carrier which is used as a steeping liquor and is modified by the aid of potassium and strontium for steeping, and drying and roasting the alumina carrier to obtain a composite carrier which is surface-modified by the aid of potassium and strontium; the preparation method of the styrene-butadiene rubber emulsion as the pore-expanding agent comprises the following steps: adding a polymerization-grade styrene monomer, a polymerization-grade butadiene monomer, deionized water, an emulsifier, an electrolyte and an auxiliary agent into a polymerization system, wherein the total mass of the styrene monomer and the butadiene monomer is 100 parts, and the dosage of the styrene is 10-40 parts; the dosage of the deionized water is 100-300 parts; the dosage of the emulsifier is 2-10 parts; the using amount of the electrolyte is 0.5-2 parts; the dosage of the auxiliary agent is 0.01 to 0.2 portion, the materials are mixed and pre-emulsified for 20 to 40min under the stirring condition to form emulsion, the emulsion is cooled to 5 to 8 ℃, and then the initiator and the regulator are added, wherein the dosage of the initiator is 0.01 to 0.5 portion and the dosage of the regulator is 0.5 to 2 portions based on 100 portions of the total mass of the styrene monomer and the butadiene monomer; controlling the temperature to be 5-8 ℃, the pressure to be 0.1-0.3MPa and the reaction time to be 7-10h, and adding a terminator to terminate the polymerization reaction when the conversion rate of the two monomers reaches 60-70% to obtain styrene-butadiene rubber emulsion; the preparation process of the hydrodesulfurization catalyst is as follows: preparing soluble salt containing molybdenum and cobalt into impregnation liquid, impregnating alumina carrier containing macropores, aging at room temperature for 2-5h, drying at 80-150 ℃ for 2-8h, and roasting at 600 ℃ for 3-10h to obtain the catalyst finished product.
2. The hydrodesulfurization catalyst of claim 1 wherein the molybdenum oxide is present in an amount of 5 to 12wt% and the cobalt oxide is present in an amount of 1 to 3 wt%.
3. The hydrodesulfurization catalyst of claim 1 further comprising potassium promoter, wherein the potassium oxide is present in an amount of from about 0.1 wt% to about 3.0wt% based on the weight of the catalyst.
4. The hydrodesulfurization catalyst of claim 1, wherein the alumina support further comprises a mesoporous structure, wherein the mesopores are in a range of 3-50nm, and the proportion of the mesopores is 20-75%.
5. The hydrodesulfurization catalyst of claim 1 wherein the alumina support has a pore size distribution of 80 to 90nm, or 140 to 180nm, or 240 to 300 nm.
6. The hydrodesulfurization catalyst according to claim 4, wherein the alumina carrier has a macropore proportion of 10 to 70%, a pore volume of 0.8 to 1.2ml/g or 1.8 to 2.2ml/g, and a mesopore proportion of 20 to 55%.
7. The hydrodesulfurization catalyst of claim 1 wherein the styrene is used in an amount of 20 to 35 parts.
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| CN101337186A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone |
| CN103086381A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Porous silica microsphere preparation method |
| CN107081155A (en) * | 2017-06-02 | 2017-08-22 | 钦州学院 | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization |
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| CN101337186A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone |
| CN103086381A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Porous silica microsphere preparation method |
| CN107081155A (en) * | 2017-06-02 | 2017-08-22 | 钦州学院 | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization |
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