WO2024050836A1 - Nickel-based catalyst, and preparation method therefor and use thereof - Google Patents
Nickel-based catalyst, and preparation method therefor and use thereof Download PDFInfo
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- WO2024050836A1 WO2024050836A1 PCT/CN2022/118223 CN2022118223W WO2024050836A1 WO 2024050836 A1 WO2024050836 A1 WO 2024050836A1 CN 2022118223 W CN2022118223 W CN 2022118223W WO 2024050836 A1 WO2024050836 A1 WO 2024050836A1
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- nickel
- based catalyst
- suspension
- catalyst precursor
- active component
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 title claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 244000215068 Acacia senegal Species 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002161 passivation Methods 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 2
- 238000009718 spray deposition Methods 0.000 abstract 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- 229930192474 thiophene Natural products 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/04—Benzene
Definitions
- the invention relates to the field of chemical engineering, and in particular to a nickel catalyst and its preparation method and use.
- Benzene is an important chemical raw material. Benzene feedstock usually contains a certain amount of sulfur impurities.
- One of the purposes of the present invention is to provide a nickel-based catalyst precursor that can efficiently and stably remove sulfur from benzene in view of the shortcomings of the existing technology.
- the second object of the present invention is to provide a method for preparing the above-mentioned nickel-based catalyst precursor.
- the catalyst is prepared through a spray molding scheme. Compared with the catalyst prepared by the impregnation method, the active components are dispersed more evenly, and the resulting product has larger pores, which is beneficial to the reaction raw materials. Diffusion, the preparation process is simple, the processing cost is low, and the three wastes are produced less.
- the present invention also provides a use of the above-mentioned nickel-based catalyst precursor or the prepared nickel-based catalyst for removing sulfur from benzene, which can efficiently remove sulfur from benzene under mild conditions, so that the sulfur in the treated benzene can be removed
- the content is less than 10ppb, meeting the actual needs of enterprises.
- a nickel-based catalyst precursor including an active component, a binder, and a composite carrier.
- the active component is a mixture of nickel and magnesium oxide
- the composite carrier is an oxidized catalyst.
- silicon, alumina, cerium oxide, zirconium oxide, and molecular sieves are obtained by spray molding.
- a composite additive is included, and the composite additive is one or more of lanthanum, cerium, praseodymium, neodymium, samarium, and neodymium rare earth oxides.
- the mass ratio of nickel and magnesium oxide in the active component is 30-80:1-30, and the mass ratio of nickel and composite carrier in the active component is 30-80:30-60.
- the mass ratio of nickel and composite additives is 30-80:1-30.
- the adhesive is one or more of gum arabic, sesbania powder, starch and citric acid.
- the molecular sieve is one or more of ZSM-5, MCM-22, USY, ⁇ molecular sieve, MCM-41 and SBA-15.
- the precursor of nickel is one or more of nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, and nickel nitrate
- the precursor of magnesium oxide is one of light magnesium oxide and heavy magnesium oxide.
- the precursor of the composite additive is one or more of nitrate, hydroxide, and oxide.
- the invention also provides a nickel-based catalyst, which is prepared by using any of the above-mentioned nickel-based catalyst precursors through extrusion, drying, shaping, reduction and passivation.
- the technical solution to achieve the second object of the present invention is: the preparation method of any of the above-mentioned nickel-based catalyst precursors, including the following steps:
- suspension A Take the materials according to the proportion, stir and mix the other components except the adhesive in deionized water to obtain suspension A.
- the solid content of suspension A is 30-50wt%;
- Suspension A is homogeneously dispersed in a cold water bath for 1-3 hours;
- the present invention also provides the use of any of the above-mentioned nickel-based catalyst precursors or nickel-based catalysts for removing sulfur from benzene.
- the removal method is to contact the nickel-based catalyst precursor or nickel-based catalyst at 40-200°C for 0.1h-10h under a pressure of 0.2MPa-1.5MPa.
- the nickel-based catalyst precursor of the present invention provides micropores and mesopores through the composite carrier, and macropores and stacked pores through the binder, forming a nickel-based catalyst precursor with multi-pore distribution, which can effectively meet the needs of different sulfur content, especially for the purpose of sulfur removal in benzene solutions of thiophene.
- the nickel-based catalyst precursor of the present invention is also added with a composite additive to make the active sites of the catalyst more stable, and the active nickel microcrystalline particles are not easy to aggregate and grow, so that the desulfurization activity of the catalyst remains stable.
- the nickel-based catalyst precursor of the present invention is prepared by spray molding, which makes the active metal nickel crystallites smaller and more uniformly dispersed, resulting in more active sites with desulfurization performance and efficient and stable removal of raw materials. It also has the advantages of lower adsorption temperature and lower sulfur removal price per unit weight of catalyst.
- the nickel-based catalyst precursor of the present invention limits the content and ratio of each component. If the content of the active components of nickel and magnesium oxide is too low, there will be fewer active sites and the worse the sulfur adsorption performance will be;
- the composite additive needs to reach a limited ratio to completely block the aggregation of nickel crystals to ensure the initial activity and long-term activity of the catalyst; the specific ratio of the composite carrier and binder provides the ratio of micropores, mesopores and macropores Balanced, it can better disperse the active sites. If other ratios are used, the active sites will be unevenly dispersed and the desulfurization activity will be reduced.
- the preparation method of the nickel-based catalyst precursor of the present invention is prepared by spray molding. Compared with the preparation of catalysts by the impregnation method, the catalyst precursor prepared by this method has more uniform dispersion of active metals, and the resulting product has larger pores, which is conducive to the reaction. Diffusion of raw materials; compared with the precipitation method for preparing catalyst precursors, this method has a simpler preparation process, lower processing costs, and produces less three wastes.
- the nickel-based catalyst precursor or nickel-based catalyst prepared by the present invention can effectively remove sulfur in benzene to a content below 10 ppb at 40-200°C and under a pressure of 0.2MPa-1.5MPa. Meet the actual needs of enterprises.
- the equipment or parts whose specific structure is not indicated are usually conventional equipment or parts in the chemical industry. If the specific connection method is not indicated, they are usually the conventional connection methods in the chemical industry or the connection methods recommended by the manufacturer.
- the raw materials used meet relevant national or industry standard requirements.
- nickel carbonate 5g magnesium oxide, 2.99g lanthanum nitrate, 3.83g praseodymium nitrate and 24g ⁇ -Al 2 O 3 , add to 150g deionized water, stir in a homogenizer for 3 hours under a cold water bath; then add 20g molecular sieve MCM-22, 2.5g sesbania powder and 2.5g citric acid were stirred in a homogenizer for 3 hours, and then spray-molded in a spray molding machine to obtain a nickel catalyst precursor.
- the obtained nickel-based precursor is kneaded, extruded, dried, shaped, roasted, reduced and passivated to obtain a granular nickel-based catalyst.
- a conventional desulfurization tower is used to remove the raw material benzene with a thiophene concentration of 10ppm, and the residence time is 0.1h-10h. , the separated benzene is obtained at the bottom of the tower, and the concentration of thiophene is ⁇ 10ppb.
- the sulfur capacity of the nickel-based precursor or particulate nickel-based catalyst is 12.5 g/kg.
- nickel carbonate 10g magnesium oxide, 2.99g lanthanum nitrate, 3.83g praseodymium nitrate and 33g ⁇ -Al 2 O 3 , add them to 150g deionized water, stir in a homogenizer for 3 hours under a cold water bath; then add 26g of molecular sieve MCM-22, 3.5g of sesbania powder and 3.5g of citric acid were stirred in a homogenizer for 3 hours, and then spray-molded in a spray molding machine to obtain a nickel-based catalyst precursor.
- the obtained nickel-based precursor is kneaded, extruded, dried, shaped, roasted, reduced and passivated to obtain a granular nickel-based catalyst.
- the nickel-based catalyst precursor or granular nickel-based catalyst prepared in Example 1 is used to remove raw material benzene with a thiophene concentration of 10 ppm using a conventional desulfurization tower at 120°C and a pressure of 0.5 MPa.
- the residence time is 0.1h- 10h, separated benzene is obtained at the bottom of the tower, and the concentration of thiophene is ⁇ 10ppb.
- the sulfur capacity of the nickel-based catalyst precursor or particulate nickel-based catalyst is 5.5 g/kg.
- Example 2 Using a nickel-based catalyst that is directly flaked in industrial applications, using the desulfurization conditions of Example 2, the raw material benzene with a thiophene concentration of 10 ppm is removed, the residence time is 0.1h-10h, and benzene is separated at the bottom of the tower, with a final sulfur capacity of 0.3 g/kg.
- Example 2 Using a nickel-based catalyst that is directly extruded in industrial applications, using the desulfurization conditions in Example 2, the raw material benzene with a thiophene concentration of 10 ppm is removed, the residence time is 0.1h-10h, and benzene is separated at the bottom of the tower, with a final sulfur capacity of 0.4 g/kg.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A nickel-based catalyst precursor, comprising an active component, an adhesive, and a composite support. The active component is a mixture of nickel and magnesium oxide, and the composite support is one or more of silicon oxide, aluminum oxide, cerium oxide, zirconium oxide, and a molecular sieve. The nickel-based catalyst precursor is obtained by means of spray forming, and can efficiently and stably remove sulfur in benzene. The present invention further provides a preparation method for the catalyst precursor, comprising the steps of: 1) weighing materials according to proportions, stirring components except an adhesive in deionized water and mixing same well to obtain a suspension A, the solid content of the suspension A being 30-50 wt%; 2) homogenizing and dispersing the suspension A under a cold water bath condition for 1-3 h; 3) adding the adhesive in an addition amount of 1-5% to form a suspension B; 4) homogenizing and dispersing the suspension B under the cold water bath condition for 1-3 h; and 5) performing spray forming on the suspension B. The active component is more uniformly dispersed, and the obtained product has larger pore channels which are conducive to the diffusion of reaction raw materials. The preparation process is simple, the processing cost is low, and less three wastes are generated.
Description
本发明涉及化工领域，特别涉及一种镍系催化剂及其制备方法和用途。The invention relates to the field of chemical engineering, and in particular to a nickel catalyst and its preparation method and use.
苯是一种重要的化工原料。苯原料中通常含有一定量的硫杂质。Benzene is an important chemical raw material. Benzene feedstock usually contains a certain amount of sulfur impurities.
苯作为原料用于合成目标产品时，通过需要使用贵金属作为催化剂。苯中含有的硫与贵金属催化剂生成稳定的硫化物，使得催化剂的活性中心减少，且生成的硫化物容易堵塞催化剂孔隙，造成催化剂中毒甚至失活，导致需要频发再生或更换贵金属催化剂，严重影响化工企业的正常生产，且导致生产成本较高。When benzene is used as a raw material to synthesize target products, it is necessary to use precious metals as catalysts. The sulfur contained in benzene and the precious metal catalyst generate stable sulfides, which reduces the active center of the catalyst, and the generated sulfide easily blocks the pores of the catalyst, causing catalyst poisoning or even deactivation, resulting in the need for frequent regeneration or replacement of the precious metal catalyst, which has serious consequences. The normal production of chemical companies results in higher production costs.
因此，如何高效、稳定的除去原料苯中的硫，尤其是有机硫，如噻吩，是本领域技术人员亟待解决的问题。Therefore, how to efficiently and stably remove sulfur from raw material benzene, especially organic sulfur, such as thiophene, is an urgent problem for those skilled in the art.
发明内容Contents of the invention
本发明的目的之一是针对现有技术的不足，提供一种镍系催化剂前驱体，可高效、稳定的除去苯中的硫。One of the purposes of the present invention is to provide a nickel-based catalyst precursor that can efficiently and stably remove sulfur from benzene in view of the shortcomings of the existing technology.
本发明的目的之二是提供上述镍系催化剂前驱体的制备方法，通过喷雾成型方案制备催化剂，较浸渍法制备催化剂，活性组分分散更均匀，得到的产品孔道更大，有利于反应原料的扩散，制备流程简单、加工成本低，产生的三废少。The second object of the present invention is to provide a method for preparing the above-mentioned nickel-based catalyst precursor. The catalyst is prepared through a spray molding scheme. Compared with the catalyst prepared by the impregnation method, the active components are dispersed more evenly, and the resulting product has larger pores, which is beneficial to the reaction raw materials. Diffusion, the preparation process is simple, the processing cost is low, and the three wastes are produced less.
本发明还提供了一种采用上述镍系催化剂前驱体或制备的镍系催化剂用于脱除苯中的硫的用途，可在温和条件下高效除去苯中的硫，使得处理后的苯中硫含量低于10ppb，满足企业实际需求。The present invention also provides a use of the above-mentioned nickel-based catalyst precursor or the prepared nickel-based catalyst for removing sulfur from benzene, which can efficiently remove sulfur from benzene under mild conditions, so that the sulfur in the treated benzene can be removed The content is less than 10ppb, meeting the actual needs of enterprises.
实现本发明目的之一的技术方案是：一种镍系催化剂前驱体，包括活性组分、粘接剂、复合载体，所述活性组分为镍和氧化镁的混合物，所述复合载体为氧化硅、氧化铝、氧化铈、氧化锆、分子筛中的一种或几种，通过喷雾成型得到。The technical solution to achieve one of the objectives of the present invention is: a nickel-based catalyst precursor, including an active component, a binder, and a composite carrier. The active component is a mixture of nickel and magnesium oxide, and the composite carrier is an oxidized catalyst. One or more of silicon, alumina, cerium oxide, zirconium oxide, and molecular sieves are obtained by spray molding.
进一步的，还包括复合助剂，所述复合助剂为镧、铈、镨、钕、钐、钕稀土氧化物中的一种或几种。Furthermore, a composite additive is included, and the composite additive is one or more of lanthanum, cerium, praseodymium, neodymium, samarium, and neodymium rare earth oxides.
优选的，所述活性组分中的镍和氧化镁的质量比为30-80：1-30，活性组分中的镍和复合载体的质量比为30-80：30-60，活性组分中的镍和复合助剂的质量比为30-80：1-30。Preferably, the mass ratio of nickel and magnesium oxide in the active component is 30-80:1-30, and the mass ratio of nickel and composite carrier in the active component is 30-80:30-60. The mass ratio of nickel and composite additives is 30-80:1-30.
优选的，所述粘接剂为阿拉伯胶、田菁粉、淀粉和柠檬酸中的一种或几种。Preferably, the adhesive is one or more of gum arabic, sesbania powder, starch and citric acid.
优选的，所述分子筛为ZSM-5、MCM-22、USY、β分子筛、MCM-41和SBA-15中的一种或几种。Preferably, the molecular sieve is one or more of ZSM-5, MCM-22, USY, β molecular sieve, MCM-41 and SBA-15.
进一步的，镍的前驱体为硫酸镍、氯化镍、碳酸镍、醋酸镍、硝酸镍中的一种或几种，氧化镁的前驱体为轻质氧化镁和重质氧化镁中的一种或几种，复合助剂的前驱体为硝酸盐、氢氧化物、氧化物中的一种或多种。Further, the precursor of nickel is one or more of nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, and nickel nitrate, and the precursor of magnesium oxide is one of light magnesium oxide and heavy magnesium oxide. Or several kinds, the precursor of the composite additive is one or more of nitrate, hydroxide, and oxide.
本发明还提供了一种镍系催化剂，采用任一上述镍系催化剂前驱体，经挤条、烘干、成型、还原和钝化制备得到镍系催化剂。The invention also provides a nickel-based catalyst, which is prepared by using any of the above-mentioned nickel-based catalyst precursors through extrusion, drying, shaping, reduction and passivation.
实现本发明目的之二的技术方案是：任一上述镍系催化剂前驱体的制备方法，包括以下步骤：The technical solution to achieve the second object of the present invention is: the preparation method of any of the above-mentioned nickel-based catalyst precursors, including the following steps:
1)按比例取料，将除粘接剂的其他组分于去离子水中搅拌混匀，得到悬浊液A，悬浊液A的固含量为30-50wt％；1) Take the materials according to the proportion, stir and mix the other components except the adhesive in deionized water to obtain suspension A. The solid content of suspension A is 30-50wt%;
2)悬浊液A在冷水浴条件下均质分散1-3h；2) Suspension A is homogeneously dispersed in a cold water bath for 1-3 hours;
3)加入粘接剂，粘接剂的加入量为1-5％，形成悬浊液B；3) Add adhesive, the amount of adhesive added is 1-5%, to form suspension B;
4)悬浊液B在冷水浴条件下均质分散1-3h；4) Disperse suspension B homogeneously in a cold water bath for 1-3 hours;
5)悬浊液B喷雾成型，得到镍系催化剂前驱体。5) Spray molding of suspension B to obtain a nickel-based catalyst precursor.
本发明还提供了任一上述镍系催化剂前驱体或镍系催化剂在用于除去苯中硫的用途。The present invention also provides the use of any of the above-mentioned nickel-based catalyst precursors or nickel-based catalysts for removing sulfur from benzene.
进一步的，所述除去的方法为，40-200℃，在0.2MPa-1.5MPa压力下，与镍系催化剂前驱体或镍系催化剂接触0.1h-10h。Further, the removal method is to contact the nickel-based catalyst precursor or nickel-based catalyst at 40-200°C for 0.1h-10h under a pressure of 0.2MPa-1.5MPa.
采用上述技术方案具有以下有益效果：Adopting the above technical solution has the following beneficial effects:
1、本发明镍系催化剂前驱体，通过复合载体提供微孔和介孔孔道，通过粘结剂提供大孔及堆积孔孔道，形成了多孔道分布的镍系催化剂前驱体，可有效满足不同硫含量，尤其是噻吩的苯溶液的除硫目的。1. The nickel-based catalyst precursor of the present invention provides micropores and mesopores through the composite carrier, and macropores and stacked pores through the binder, forming a nickel-based catalyst precursor with multi-pore distribution, which can effectively meet the needs of different sulfur content, especially for the purpose of sulfur removal in benzene solutions of thiophene.
2、本发明镍系催化剂前驱体，还添加有复合助剂，使催化剂的活性位更稳定，活性镍微晶颗粒不容易聚集长大，使催化剂的脱硫活性保持稳定。2. The nickel-based catalyst precursor of the present invention is also added with a composite additive to make the active sites of the catalyst more stable, and the active nickel microcrystalline particles are not easy to aggregate and grow, so that the desulfurization activity of the catalyst remains stable.
3、本发明镍系催化剂前驱体，采用喷雾成型的方法制备得到，使得活性金属镍微晶尺寸更小、分散更均匀，使得具有脱硫性能的活性位点更多，可高效、稳定的除去原料苯中的硫，且吸附苯中的硫，尤其是噻吩的浓度更高、硫容更大，还具有可吸附温度更低、单位重量催化剂除硫价格更低的优势。3. The nickel-based catalyst precursor of the present invention is prepared by spray molding, which makes the active metal nickel crystallites smaller and more uniformly dispersed, resulting in more active sites with desulfurization performance and efficient and stable removal of raw materials. It also has the advantages of lower adsorption temperature and lower sulfur removal price per unit weight of catalyst.
4、本发明镍系催化剂前驱体，限定了各组分的含量及配比，，若镍和氧化镁活性组分含量过低，将导致活性位点较少，吸附硫的性能就越差；复合助剂需要达到限定的比例才能完全阻隔镍微晶的聚集，以此保证催化剂的初活性和长时间的活性；复合载体、粘接剂特定配比提供的微孔、介孔和大孔比例均衡，能更好的分散活性位，若采用其他配比，将导致活性位分散不均匀，脱硫活性降低。4. The nickel-based catalyst precursor of the present invention limits the content and ratio of each component. If the content of the active components of nickel and magnesium oxide is too low, there will be fewer active sites and the worse the sulfur adsorption performance will be; The composite additive needs to reach a limited ratio to completely block the aggregation of nickel crystals to ensure the initial activity and long-term activity of the catalyst; the specific ratio of the composite carrier and binder provides the ratio of micropores, mesopores and macropores Balanced, it can better disperse the active sites. If other ratios are used, the active sites will be unevenly dispersed and the desulfurization activity will be reduced.
5、本发明镍系催化剂前驱体的制备方法，通过喷雾成型方案制备得到，较浸渍法制备催化剂，该方法制备的催化剂前驱体，活性金 属分散更均匀，得到的产品孔道更大，有利于反应原料的扩散；较沉淀法制备催化剂前驱体，该方法制备流程更简单、加工成本更低，产生的三废更少。5. The preparation method of the nickel-based catalyst precursor of the present invention is prepared by spray molding. Compared with the preparation of catalysts by the impregnation method, the catalyst precursor prepared by this method has more uniform dispersion of active metals, and the resulting product has larger pores, which is conducive to the reaction. Diffusion of raw materials; compared with the precipitation method for preparing catalyst precursors, this method has a simpler preparation process, lower processing costs, and produces less three wastes.
经申请人试验验证，采用本发明制备的镍系催化剂前驱体或镍系催化剂，在40-200℃，在0.2MPa-1.5MPa压力条件下，可有效除去苯中的硫至含量达到10ppb以下，满足企业实际需求。It has been verified by the applicant's experiments that the nickel-based catalyst precursor or nickel-based catalyst prepared by the present invention can effectively remove sulfur in benzene to a content below 10 ppb at 40-200°C and under a pressure of 0.2MPa-1.5MPa. Meet the actual needs of enterprises.
下面结合附图和具体实施方式作进一步的说明。Further description will be given below with reference to the accompanying drawings and specific embodiments.
本发明中，未标明具体结构的设备或零部件，通常为化工领域常规的设备或零部件，未标明具体连接方式的，通常为化工领域常规的连接方式或厂家建议的连接方式。使用的原料满足相关的国家或行业标准要求。In the present invention, the equipment or parts whose specific structure is not indicated are usually conventional equipment or parts in the chemical industry. If the specific connection method is not indicated, they are usually the conventional connection methods in the chemical industry or the connection methods recommended by the manufacturer. The raw materials used meet relevant national or industry standard requirements.
实施例1Example 1
称取101.1g碳酸镍,5g氧化镁、2.99g硝酸镧、3.83g硝酸镨和24gγ-Al
2O
3，加入到150g去离子水中，在冷水浴下，在均质机中搅拌3h；然后加入20g分子筛MCM-22,2.5g田菁粉和2.5g柠檬酸，在均质机中继续搅拌3h，再在喷雾成型机中喷雾成型，得到镍系催化剂前驱体。得到的镍系前驱体通过捏合、挤条、烘干、整型、焙烧、还原和钝化，得到颗粒型镍系催化剂。
Weigh 101.1g nickel carbonate, 5g magnesium oxide, 2.99g lanthanum nitrate, 3.83g praseodymium nitrate and 24g γ-Al 2 O 3 , add to 150g deionized water, stir in a homogenizer for 3 hours under a cold water bath; then add 20g molecular sieve MCM-22, 2.5g sesbania powder and 2.5g citric acid were stirred in a homogenizer for 3 hours, and then spray-molded in a spray molding machine to obtain a nickel catalyst precursor. The obtained nickel-based precursor is kneaded, extruded, dried, shaped, roasted, reduced and passivated to obtain a granular nickel-based catalyst.
实施例2Example 2
采用实施例1制备得到的镍系前驱体或颗粒型镍系催化剂，在120℃，0.5Mpa的条件下，采用常规脱硫塔，脱除噻吩浓度为10ppm的原料苯，停留时间为0.1h-10h，在塔底得到分离苯，噻吩的浓度为<10ppb。镍系前驱体或颗粒型镍系催化剂的硫容为12.5g/kg。Using the nickel-based precursor or granular nickel-based catalyst prepared in Example 1, under the conditions of 120°C and 0.5Mpa, a conventional desulfurization tower is used to remove the raw material benzene with a thiophene concentration of 10ppm, and the residence time is 0.1h-10h. , the separated benzene is obtained at the bottom of the tower, and the concentration of thiophene is <10ppb. The sulfur capacity of the nickel-based precursor or particulate nickel-based catalyst is 12.5 g/kg.
实施例3Example 3
称取60.66g碳酸镍,10g氧化镁、2.99g硝酸镧、3.83g硝酸镨 和33gγ-Al
2O
3，加入到150g去离子水中，在冷水浴下，在均质机中搅拌3h；然后加入26g分子筛MCM-22,3.5g田菁粉和3.5g柠檬酸，在均质机中继续搅拌3h，再在喷雾成型机中喷雾成型，得到镍系催化剂前驱体。得到的镍系前驱体通过捏合、挤条、烘干、整型、焙烧、还原和钝化，得到颗粒型镍系催化剂。
Weigh 60.66g nickel carbonate, 10g magnesium oxide, 2.99g lanthanum nitrate, 3.83g praseodymium nitrate and 33g γ-Al 2 O 3 , add them to 150g deionized water, stir in a homogenizer for 3 hours under a cold water bath; then add 26g of molecular sieve MCM-22, 3.5g of sesbania powder and 3.5g of citric acid were stirred in a homogenizer for 3 hours, and then spray-molded in a spray molding machine to obtain a nickel-based catalyst precursor. The obtained nickel-based precursor is kneaded, extruded, dried, shaped, roasted, reduced and passivated to obtain a granular nickel-based catalyst.
实施例4Example 4
采用实施例1制备得到的镍系催化剂前驱体或颗粒型镍系催化剂，在120℃，0.5Mpa压力条件下，采用常规脱硫塔，脱除噻吩浓度为10ppm的原料苯，停留时间为0.1h-10h，在塔底得到分离苯，噻吩的浓度为<10ppb。镍系催化剂前驱体或颗粒型镍系催化剂的硫容为5.5g/kg。The nickel-based catalyst precursor or granular nickel-based catalyst prepared in Example 1 is used to remove raw material benzene with a thiophene concentration of 10 ppm using a conventional desulfurization tower at 120°C and a pressure of 0.5 MPa. The residence time is 0.1h- 10h, separated benzene is obtained at the bottom of the tower, and the concentration of thiophene is <10ppb. The sulfur capacity of the nickel-based catalyst precursor or particulate nickel-based catalyst is 5.5 g/kg.
对照例1Comparative example 1
采用工业应用中直接打片的镍系催化剂，采用实施例2的脱硫条件，脱除噻吩浓度为10ppm的原料苯，停留时间为0.1h-10h，在塔底得到分离苯，最终硫容为0.3g/kg。Using a nickel-based catalyst that is directly flaked in industrial applications, using the desulfurization conditions of Example 2, the raw material benzene with a thiophene concentration of 10 ppm is removed, the residence time is 0.1h-10h, and benzene is separated at the bottom of the tower, with a final sulfur capacity of 0.3 g/kg.
对照例2Comparative example 2
采用工业应用中直接挤条的镍系催化剂，采用实施例2中脱硫条件，脱除噻吩浓度为10ppm的原料苯，停留时间为0.1h-10h，在塔底得到分离苯，最终硫容为0.4g/kg。Using a nickel-based catalyst that is directly extruded in industrial applications, using the desulfurization conditions in Example 2, the raw material benzene with a thiophene concentration of 10 ppm is removed, the residence time is 0.1h-10h, and benzene is separated at the bottom of the tower, with a final sulfur capacity of 0.4 g/kg.
Claims (10)
- 一种镍系催化剂前驱体，其特征在于：包括活性组分、粘接剂、复合载体，所述活性组分为镍和氧化镁的混合物，所述复合载体为氧化硅、氧化铝、氧化铈、氧化锆、分子筛中的一种或几种，通过喷雾成型得到。A nickel-based catalyst precursor, characterized by: including an active component, a binder, and a composite carrier. The active component is a mixture of nickel and magnesium oxide. The composite carrier is silicon oxide, alumina, and cerium oxide. , zirconia, and molecular sieves, obtained by spray molding.
- 根据权利要求1所述的镍系催化剂前驱体，其特征在于，还包括复合助剂，所述复合助剂为镧、铈、镨、钕、钐、钕稀土氧化物中的一种或几种。The nickel-based catalyst precursor according to claim 1, further comprising a composite additive, which is one or more of lanthanum, cerium, praseodymium, neodymium, samarium, and neodymium rare earth oxides. .
- 根据权利要求1或2所述的镍系催化剂前驱体，其特征在于，所述活性组分中的镍和氧化镁的质量比为30-80：1-30，活性组分中的镍和复合载体的质量比为30-80：30-60，活性组分中的镍和复合助剂的质量比为30-80：1-30。The nickel-based catalyst precursor according to claim 1 or 2, characterized in that the mass ratio of nickel and magnesium oxide in the active component is 30-80:1-30, and the nickel and composite in the active component The mass ratio of the carrier is 30-80:30-60, and the mass ratio of nickel and composite additives in the active component is 30-80:1-30.
- 根据权利要求1所述的镍系催化剂前驱体，其特征在于：所述粘接剂为阿拉伯胶、田菁粉、淀粉和柠檬酸中的一种或几种。The nickel-based catalyst precursor according to claim 1, wherein the binder is one or more selected from gum arabic, sesbania powder, starch and citric acid.
- 根据权利要求1所述的镍系催化剂前驱体，其特征在于：所述分子筛为ZSM-5、MCM-22、USY、β分子筛、MCM-41和SBA-15中的一种或几种。The nickel-based catalyst precursor according to claim 1, characterized in that the molecular sieve is one or more of ZSM-5, MCM-22, USY, β molecular sieve, MCM-41 and SBA-15.
- 根据权利要求1或2所述的镍系催化剂前驱体，其特征在于：镍的前驱体为硫酸镍、氯化镍、碳酸镍、醋酸镍、硝酸镍中的一种或几种，氧化镁的前驱体为轻质氧化镁和重质氧化镁中的一种或几种，复合助剂的前驱体为硝酸盐、氢氧化物、氧化物中的一种或多种。The nickel catalyst precursor according to claim 1 or 2, characterized in that: the nickel precursor is one or more of nickel sulfate, nickel chloride, nickel carbonate, nickel acetate, and nickel nitrate, and the magnesium oxide is The precursor is one or more of light magnesium oxide and heavy magnesium oxide, and the precursor of the composite additive is one or more of nitrate, hydroxide, and oxide.
- 一种镍系催化剂，其特征在于，采用权利要求1-5任一镍系催化剂前驱体，经挤条、烘干、成型、还原和钝化制备得到镍系催化剂。A nickel-based catalyst, characterized in that the nickel-based catalyst is prepared by using any nickel-based catalyst precursor according to claims 1 to 5 through extrusion, drying, shaping, reduction and passivation.
- 权利要求1-6任一镍系催化剂前驱体的制备方法，其特征在于，包括以下步骤：The preparation method of any nickel-based catalyst precursor according to claims 1 to 6, characterized in that it includes the following steps:1)按比例取料，将除粘接剂的其他组分于去离子水中搅拌混匀，得到悬浊液A，悬浊液A的固含量为30-50wt％；1) Take the materials according to the proportion, stir and mix the other components except the adhesive in deionized water to obtain suspension A. The solid content of suspension A is 30-50wt%;2)悬浊液A在冷水浴条件下均质分散1-3h；2) Suspension A is homogeneously dispersed in a cold water bath for 1-3 hours;3)加入粘接剂，粘接剂的加入量为1-5％，形成悬浊液B；3) Add adhesive, the amount of adhesive added is 1-5%, to form suspension B;4)悬浊液B在冷水浴条件下均质分散1-3h；4) Disperse suspension B homogeneously in a cold water bath for 1-3 hours;5)悬浊液B喷雾成型，得到镍系催化剂前驱体。5) Spray molding of suspension B to obtain a nickel-based catalyst precursor.
- 权利要求1-6镍系催化剂前驱体或权利要求7镍系催化剂在用于除去苯中硫的用途。The use of the nickel-based catalyst precursor according to claims 1 to 6 or the nickel-based catalyst according to claim 7 for removing sulfur from benzene.
- 根据权利要求9所述的用途，所述除去的方法为，含硫苯预热至40-200℃，在0.2MPa-1.5MPa压力下，与镍系催化剂前驱体或镍系催化剂接触0.1h-10h。According to the use according to claim 9, the removal method is to preheat the sulfur-containing benzene to 40-200°C, and contact it with the nickel-based catalyst precursor or nickel-based catalyst for 0.1h-under a pressure of 0.2MPa-1.5MPa. 10h.
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