CN116832767B - Preparation method of platinum-series adsorbent for desulfurizing aromatic compounds - Google Patents
Preparation method of platinum-series adsorbent for desulfurizing aromatic compounds Download PDFInfo
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- CN116832767B CN116832767B CN202311127352.9A CN202311127352A CN116832767B CN 116832767 B CN116832767 B CN 116832767B CN 202311127352 A CN202311127352 A CN 202311127352A CN 116832767 B CN116832767 B CN 116832767B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 137
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 31
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000001035 drying Methods 0.000 claims abstract description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000008367 deionised water Substances 0.000 claims abstract description 39
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 39
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 29
- 239000003921 oil Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 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 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003349 gelling agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 229940024546 aluminum hydroxide gel Drugs 0.000 claims description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000010687 lubricating oil Substances 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
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 20
- 230000023556 desulfurization Effects 0.000 abstract description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 229910002844 PtNi Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFLJZFAEPPHUCU-UHFFFAOYSA-N benzene;thiophene Chemical compound C=1C=CSC=1.C1=CC=CC=C1 FFLJZFAEPPHUCU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 thiophene 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a preparation method of a platinum-series adsorbent for aromatic hydrocarbon compound desulfurization, which belongs to the technical field of aromatic hydrocarbon desulfurization chemical industry and comprises the following steps: step S1: preparing an alumina ball carrier; step S2: immersing the prepared alumina ball carrier in a platinum-containing precursor solution, and drying and roasting to obtain a platinum metal adsorbent preliminarily; step S3: continuously dipping the obtained platinum metal adsorbent in a nickel-containing precursor solution, and drying and roasting to obtain a platinum nickel adsorbent; step S4: the obtained platinum-nickel adsorbent is immersed in alkali metal solution with a certain concentration for micro-treatment and activation for a certain time; step S5: and washing the obtained treated adsorbent to be neutral by using deionized water with a certain temperature, and drying and roasting to finally obtain the platinum-series adsorbent for desulfurizing the aromatic compounds. The desulfurization adsorbent prepared by the invention has uniform particle size, high dispersity of metal Pt and Ni on the surface of the alumina ball carrier, strong stability and simple preparation method.
Description
Technical Field
The invention relates to a preparation method of a platinum-series adsorbent for aromatic hydrocarbon compound desulfurization, belonging to the technical field of aromatic hydrocarbon desulfurization chemical industry.
Background
Aromatic hydrocarbons are important organic chemical raw materials, and are mainly derived from coking aromatic hydrocarbons obtained by hydrofining crude aromatic hydrocarbons which are byproducts in coking processes in petroleum industry and coal chemical industry. With the shortage of petroleum resources and the rapid development of the organic synthesis industry, the demand of pure aromatic hydrocarbon in countries around the world is increasing year by year. Meanwhile, along with the increase of the environmental pressure facing the world, strict environmental protection standards are gradually put out, one of the very important standards is that sulfides in oil products need to be strictly controlled, and more domestic and foreign related researchers start to research a feasible desulfurization method.
In order to deeply remove thiophene sulfides in aromatic hydrocarbons, various methods such as adsorption separation method, extractive distillation method, freeze crystallization method, catalytic hydrogenation method, selective oxidation method, sulfuric acid refining method and the like have been studied. The adsorption desulfurization method has simple process, low investment cost and remarkable desulfurization effect, and is preferentially considered by researchers at home and abroad.
The adsorbent carrier is generally made of porous materials such as molecular sieve, metal oxide, active carbon and the like, and the desulfurization effect reaches ppm level at normal temperature and normal pressure. Physical adsorption is mainly used at normal temperature and normal pressure, and is superior to chemical adsorption; the high temperature and high pressure are generally mainly chemical adsorption, and the depth of chemical adsorption desulfurization is superior to physical adsorption.
The desulfurization adsorbent commonly used at present mainly uses alumina as a carrier, metal Pd as an active component, and the content is about 1.0 percent, so as to carry out deep desulfurization. Although the adsorbent has better desulfurization effect, the cost of benzene desulfurization is obviously increased due to the increase of the market price of metal Pd in recent years, which is unfavorable for the development of economy.
The Chinese patent with publication No. CN111804268B discloses a beaded Pd-Ni adsorbent for deep desulfurization of refined benzene, which is characterized in that Ni metal elements are introduced into a Pd-containing alumina carrier by hydrothermal reaction, so that the growth and agglomeration of Pd particles can be limited, the two metals interact to form beaded beads with uniform size, the sulfur content in thiophene-benzene solution can be reduced from 300ppb to below 10ppb, the desulfurization rate is as high as more than 97%, and compared with the adsorbent mainly comprising Pd active components, the cost is obviously increased.
Chinese patent application publication No. CN114471448A discloses a benzene refining desulfurizing adsorbent and its preparation method, using hydrothermal synthesis method to prepare acicular alumina carrier, and obtaining 200-300 m 2 The mesoporous with high specific area per gram and average pore diameter of 8-30 nm has the advantages of high dispersion of Pt particles, no agglomeration phenomenon and high sulfur capacity, but the invention introduces a certain content of Ni and Ag, and the preparation cost of the adsorbent is still higher.
The Chinese patent application publication No. CN112958082A discloses a catalyst for desulfurizing aromatic hydrocarbon and a preparation method thereof, wherein the catalyst is characterized in that palladium serving as an active metal component is uniformly distributed on the surface of a carrier and can be directly applied to a desulfurizing procedure in a cyclohexanol production process, the desulfurized aromatic hydrocarbon is directly partially hydrogenated to produce cycloolefin, and the catalyst has high sulfur capacity but still has high cost.
The adsorbent prepared by the method has the advantages that the desulfurization effect meets the industrial requirement, but the cost is relatively high, and the adsorbent has a certain inhibition effect on large-scale production, so that the development of the adsorbent with high sulfur capacity and low cost is a problem to be solved by the current technicians in the field.
Disclosure of Invention
The purpose of the invention is that: in order to overcome the defects in the prior art, the invention provides a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds.
The technical scheme for solving the technical problems is as follows:
a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: mixing an aluminum source, an acid source, a gelatinizing agent and deionized water according to a certain proportion, heating at the same time, stirring for a period of time to obtain aluminum hydroxide gel with certain viscosity, then forming in an oil column, and finally aging, washing, drying and roasting to obtain an alumina ball carrier;
step S2: immersing the prepared alumina ball carrier in a platinum-containing precursor solution for a period of time, drying and roasting to obtain a platinum metal adsorbent preliminarily;
step S3: continuously dipping the obtained platinum metal adsorbent in a nickel-containing precursor solution, drying and roasting after dipping for a period of time to obtain the platinum nickel adsorbent;
step S4: the obtained platinum-nickel adsorbent is immersed in alkali metal solution with a certain concentration for micro-treatment and activation for a certain time;
step S5: and washing the obtained treated platinum-nickel adsorbent to be neutral by using deionized water with a certain temperature, drying and roasting to finally obtain the platinum-series adsorbent for desulfurizing the aromatic compounds.
Further, in step S1, the mass ratio of the aluminum source, the acid source, the gelling agent and the deionized water is 1: (0.1-10): (0.001-2.5): (0.1 to 220), preferably 1: (0.5-8): (0.003-2): (0.5-180).
Further, in step S2, the platinum content in the platinum-containing precursor solution is 0.3wt% to 2.0wt%, the platinum dispersity is 80% to 95%, and the mass ratio of the alumina ball carrier to the platinum-containing precursor solution is 1: (0.5 to 5), preferably 1: (0.8-2.5).
Further, in the step S3, the nickel content in the nickel-containing precursor solution is 0.05wt% -1.5 wt%, and the mass ratio of the alumina ball carrier to the nickel-containing precursor solution is 1: (0.3 to 3.5), preferably 1: (0.5-2).
Further, in step S1, the aluminum source includes one or more of aluminum trichloride, aluminum powder, sodium metaaluminate, pseudo-boehmite, and aluminum nitrate; the acid source comprises one or more of hydrochloric acid, nitric acid, acetic acid and citric acid; the gelling agent comprises one or more of hexamethylenetetramine, ammonia water and urea; the oil in the oil column is one or more of lubricating oil, gasoline, methyl silicone oil and white oil.
Further, in step S2, the platinum-containing precursor solution includes one or more of a platinum nitrate solution, a chloroplatinic acid solution, a platinous chloride solution, a potassium platinous chloride solution, and a potassium chloroplatinate solution;
in step S3, the nickel-containing precursor solution includes one or more of a nickel nitrate solution, a nickel acetate solution, a nickel hydroxide solution, a nickel oxide solution, and a nickel dichloride solution.
Further, in step S4, the alkali metal solution includes one or more of sodium hydroxide solution, sodium carbonate solution, sodium chloride solution, potassium hydroxide solution, potassium carbonate solution, potassium chloride solution and potassium nitrate solution; the concentration of the alkali metal solution is 0.1-15%, preferably 0.3-12%; the activation time of the micro-treatment is 0.1 to 8 hours, preferably 0.5 to 5.5 hours.
Further, in step S1 and step S2, the selection conditions of the alumina ball carrier are: the specific surface area is 130-400 m 2 Per gram, pore volume of 0.45-1.5 cm 3 Per gram, the average pore diameter is 4-35 nm, and the bulk density is 0.5-0.8 g/cm 3 The diameter of the alumina ball carrier is 1.8-2.5 mm, and the selection conditions are preferably as follows: specific surface area of 150-340 m 2 Per gram, pore volume of 0.50-1.35 cm 3 Per gram, the average pore diameter is 6-28 nm, and the bulk density is 0.55-0.7 g/cm 3 The diameter of the alumina ball carrier is 2-2.3 mm.
Further, in step S1, the heating temperature after mixing the materials is 30-120 ℃, preferably 35-110 ℃; the stirring rate is 50-500 rad/min, preferably 100-350 rad/min; the stirring time is 0.1 to 6 hours, preferably 0.5 to 4 hours; the temperature of the oil column is 80-130 ℃, preferably 85-125 ℃; the aging temperature is 80-130 ℃, preferably 85-120 ℃; the aging time is 1 to 8 hours, preferably 2 to 6 hours; the water washing temperature is 40-120 ℃, preferably 50-110 ℃; the drying temperature is 70-200 ℃, preferably 95-160 ℃; the drying time is 8-24 h, preferably 10-18 h; the roasting temperature is 500-650 ℃, preferably 500-650 ℃; the calcination time is 1 to 8 hours, preferably 2 to 6 hours.
Further, in step S2, step S3 and step S5, the baking temperature is 350 to 700 ℃, preferably 380 to 650 ℃; the roasting time is 1 to 8 hours, preferably 2.5 to 5 hours; the drying is divided into two types, wherein the first type is drying under a reduced pressure state, the drying temperature is 40-95 ℃, preferably 45-85 ℃, and the drying time is 0.5-6 h, preferably 1-4 h; the second is drying under normal pressure, the drying temperature is 90-150 ℃, preferably 100-135 ℃, and the drying time is 12-36 h, preferably 15-30 h;
in the step S2 and the step S3, the soaking time of the alumina ball carrier or the platinum metal adsorbent in the two precursor solutions is 0.5 h-8 h, preferably 1-6 h;
in step S5, the deionized water temperature is 35-90 ℃, preferably 45-75 ℃.
The beneficial effects of the invention are as follows:
1. the alumina ball carrier prepared by the invention has a rich three-dimensional reticular mesoporous structure and a very large specific surface area, and can promote thiophene molecules to reach adsorption sites efficiently and rapidly to complete adsorption;
2. the desulfurization adsorbent prepared by the invention has uniform particle size, high dispersity of metal Pt and Ni on the surface of the alumina ball carrier, strong stability and simple preparation method;
3. the invention can reduce the cost by introducing cheap Ni metal and alkali metal, and simultaneously selects Pt as a main active component, compared with palladium adsorbent, the catalyst has the same or better desulfurization effect, promotes synergistic effect between metals, enhances the adsorption force between metals and sulfides such as thiophene, can efficiently remove the sulfides such as thiophene in aromatic hydrocarbon, has strong sulfur capacity which can reach 1.48g/Kg, has low cost, ensures the product quality, expands the product application, and can realize large-scale industrial production.
Drawings
FIG. 1 shows PtNiK/Al prepared in example 2 of the present invention 2 O 3 Isothermal desorption of the adsorbent;
FIG. 2 shows PtNiK/Al prepared in example 2 of the present invention 2 O 3 Pore size distribution of the adsorbent;
FIG. 3 is an SEM image of an alumina ball carrier prepared according to example 2 of the invention;
FIG. 4 shows PtNiK/Al prepared in example 2 of the present invention 2 O 3 SEM image of adsorbent.
Detailed Description
The principles and features of the present invention will be described below with reference to fig. 1 to 4, which are examples only for explaining the present invention and are not intended to limit the scope of the present invention, and the reagents used in the present invention are all commercially available.
Example 1: a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: dissolving 150g of aluminum nitrate and 250g of sodium metaaluminate in 600g of nitric acid, adding 1000g of deionized water, uniformly mixing and stirring at a stirring rate of 150rad/min, adding 8g of citric acid, uniformly stirring, adding 5.5g of ammonia water, stirring at 45 ℃ for 1h, molding the obtained gel in a white oil column at 100 ℃, sequentially aging for 2h at 120 ℃, washing with deionized water at 70 ℃, drying at 120 ℃ for 10h, and roasting at 580 ℃ for 4h to obtain an alumina ball carrier;
step S2: 180g of alumina ball carrier is weighed and placed in a flask, meanwhile 1.5545g of potassium platinous chloride is weighed and dissolved in 320g of deionized water to prepare a platinum-containing precursor solution, the solution is placed in the flask, immersed for 2 hours, then dried for 1.5 hours at 55 ℃ under a reduced pressure state, dried for 16 hours at 130 ℃ under a normal pressure state, and baked for 4 hours at 550 ℃ to obtain a platinum metal adsorbent preliminarily;
step S3: putting a platinum metal adsorbent into a flask, weighing 8.4049g of nickel nitrate, dissolving the nickel nitrate into 320g of deionized water, preparing a nickel-containing precursor solution, putting the solution into the flask, soaking for 2 hours, then drying at 55 ℃ for 1.5 hours under a reduced pressure state, continuously drying at 130 ℃ for 16 hours under a normal pressure state, and roasting at 550 ℃ for 4 hours to obtain the platinum nickel adsorbent;
step S4: micro-treating and activating the platinum-nickel adsorbent with 2.0wt% sodium carbonate solution for 2 hours;
step S5: washing the micro-treated activated adsorbent with 60 ℃ deionized water to be neutral and chlorine-free, drying at 120 ℃ for 12h, and roasting at 560 ℃ for 4h to obtain PtNiNa/Al 2 O 3 The adsorbent, wherein the platinum content is 0.5wt% of the mass of the adsorbent, the nickel content is 0.15wt% of the mass of the adsorbent, and the sodium content is 2.0wt% of the mass of the adsorbent.
Example 2: a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: dissolving 400g of pseudo-boehmite in 1000g of nitric acid solution, adding 1700g of deionized water and 3g of hexamethylenetetramine, mixing and stirring at a stirring rate of 150rad/min at 50 ℃, stirring for 1h, molding the obtained gel in a white oil column at 100 ℃, then sequentially aging for 2h at 120 ℃, washing with 70 ℃ deionized water, drying at 120 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain an alumina ball carrier;
step S2: 600g of alumina ball carrier is weighed and placed in a flask, meanwhile 15.9312g of chloroplatinic acid is weighed and dissolved in 1100g of deionized water to prepare a platinum-containing precursor solution, the solution is placed in the flask and immersed for 2 hours, then dried for 1.5 hours at 55 ℃ under a reduced pressure state, dried for 14 hours at 130 ℃ under a normal pressure state and baked for 4 hours at 550 ℃ to obtain a platinum metal adsorbent preliminarily;
step S3: putting a platinum metal adsorbent into a flask, weighing 28.0164g of nickel nitrate, dissolving the nickel nitrate into 1100g of deionized water, preparing a nickel-containing precursor solution, putting the solution into the flask, soaking for 2 hours, then drying at 55 ℃ for 1.5 hours under a reduced pressure state, continuously drying at 130 ℃ for 16 hours under a normal pressure state, and roasting at 550 ℃ for 4 hours to obtain the platinum nickel adsorbent;
step S4: micro-treating and activating the platinum-nickel adsorbent with 2.0wt% potassium hydroxide solution for 1.5h;
step S5: washing the micro-treated activated adsorbent with 60 ℃ deionized water to be neutral and chlorine-free, drying at 120 ℃ for 12h, and roasting at 580 ℃ for 4h to obtain PtNiK/Al 2 O 3 The adsorbent, wherein the platinum content is 1.0wt% of the mass of the adsorbent, the nickel content is 0.15wt% of the mass of the adsorbent, and the potassium content is 2.0wt% of the mass of the adsorbent.
As shown in FIGS. 1 to 4, ptNiK/Al prepared in this example 2 O 3 The adsorbent and alumina feature patterns are specifically analyzed as follows:
(1) As can be seen from FIG. 1, the temperature profile belongs to the type IV isotherm, and the temperature profile is measured at relative pressure (P/P 0 ) The wide H3 type hysteresis ring phenomenon is shown between 0.45 and 0.99, which indicates that the adsorbent has rich mesoporous structure;
(2) As seen from fig. 2, the mesoporous pore diameter is mainly distributed between 6-12 nm, and is consistent with the adsorption and desorption isothermal line structure, which shows that the adsorbent is a material with a mesoporous structure;
(3) FIG. 3 is an SEM image of an alumina sphere support, a fibrous morphology;
(4) FIG. 4 is an adsorbent PtNiK/Al 2 O 3 Through metal loadingAfter that, the carrier morphology is basically unchanged, the fibrous morphology is still maintained, and the metal is supported on the surface of the carrier, so that the distribution is relatively uniform, thiophene molecules can reach the adsorption sites efficiently and rapidly, and the adsorption effect is completed.
Comparative example 1: a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: dissolving 150g of aluminum nitrate and 250g of sodium metaaluminate in 1500g of nitric acid solution, uniformly mixing, adding 1400g of deionized water and 2g of hexamethylenetetramine, mixing and stirring at a stirring rate of 150rad/min at 50 ℃, stirring for 1h, molding the obtained gel in a white oil column at 100 ℃, sequentially aging for 2h at 120 ℃, washing with 70 ℃ of deionized water, drying at 120 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain an alumina ball carrier;
step S2: weighing 50g of alumina ball carrier, placing in a flask, simultaneously weighing 0.6638g of chloroplatinic acid, dissolving in 90g of deionized water, preparing a platinum-containing precursor solution, placing the solution in the flask, immersing for 2 hours, then drying at 55 ℃ for 1.5 hours under reduced pressure, continuing drying at 130 ℃ for 16 hours under normal pressure, and roasting at 550 ℃ for 4 hours to obtain the platinum metal adsorbent preliminarily;
step S3: washing the platinum metal adsorbent with 60 ℃ deionized water until the platinum metal adsorbent is neutral and free of chlorine, drying the platinum metal adsorbent at 120 ℃ for 12h, and roasting the platinum metal adsorbent at 550 ℃ for 4h to obtain Pt/Al 2 O 3 The content of platinum in the adsorbent is 0.5wt% of the mass of the adsorbent.
Comparative example 2: a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: dissolving 400g of pseudo-boehmite in 1000g of nitric acid solution, adding 1700g of deionized water and 3g of hexamethylenetetramine, mixing and stirring at a stirring rate of 150rad/min at 50 ℃, stirring for 1h, molding the obtained gel in a white oil column at 100 ℃, then sequentially aging for 2h at 120 ℃, washing with 70 ℃ deionized water, drying at 120 ℃ for 10h, and roasting at 600 ℃ for 4h to obtain an alumina ball carrier;
step S2: weighing 150g of alumina ball carrier, placing in a flask, simultaneously weighing 3.9830g of chloroplatinic acid, dissolving in 270g of deionized water, preparing a platinum-containing precursor solution, placing the solution in the flask, immersing for 2 hours, then drying at 55 ℃ for 1.5 hours under reduced pressure, continuing drying at 130 ℃ for 16 hours under normal pressure, and roasting at 550 ℃ for 4 hours to obtain the platinum metal adsorbent preliminarily;
step S3: washing the platinum metal adsorbent with 60 ℃ deionized water until the platinum metal adsorbent is neutral and free of chlorine, drying the platinum metal adsorbent at 120 ℃ for 12h, and roasting the platinum metal adsorbent at 550 ℃ for 4h to obtain Pt/Al 2 O 3 The content of platinum in the adsorbent is 1.0wt% of the mass of the adsorbent.
Comparative example 3: a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: dissolving 150g of aluminum nitrate and 250g of sodium metaaluminate in 600g of nitric acid, adding 1000g of deionized water, uniformly mixing and stirring at a stirring rate of 150rad/min, adding 8g of citric acid, uniformly stirring, adding 5.5g of ammonia water, stirring at 45 ℃ for 1h, molding the obtained gel in a white oil column at 100 ℃, sequentially aging for 2h at 120 ℃, washing with deionized water at 70 ℃, drying at 120 ℃ for 10h, and roasting at 580 ℃ for 4h to obtain an alumina ball carrier;
step S2: 100g of alumina ball carrier is weighed and placed in a flask, meanwhile 1.2458g of potassium chloroplatinate is weighed and dissolved in 180g of deionized water to prepare a platinum-containing precursor solution, the solution is placed in the flask and immersed for 2 hours, then dried for 1.5 hours at 55 ℃ under a reduced pressure state, dried for 16 hours at 130 ℃ under a normal pressure state and baked for 4 hours at 550 ℃ to obtain a platinum metal adsorbent preliminarily;
step S3: putting a platinum metal adsorbent into a flask, weighing 4.6694g of nickel nitrate, dissolving the nickel nitrate into 180g of deionized water, preparing a nickel-containing precursor solution, putting the solution into the flask, soaking for 2 hours, then drying at 55 ℃ for 1.5 hours under a reduced pressure state, continuously drying at 130 ℃ for 16 hours under a normal pressure state, and roasting at 550 ℃ for 4 hours to obtain the platinum nickel adsorbent;
step S4: washing the platinum-nickel adsorbent with 60 ℃ deionized water until the platinum-nickel adsorbent is neutral and free of chlorine, drying the platinum-nickel adsorbent at 120 ℃ for 12h, and roasting the platinum-nickel adsorbent at 550 ℃ for 4h to obtain PtNi/Al 2 O 3 An adsorbent, wherein the platinum comprisesThe amount was 0.5wt% based on the mass of the adsorbent, and the nickel content was 0.15wt% based on the mass of the adsorbent.
Comparative example 4: a preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds comprises the following steps:
step S1: dissolving 150g of aluminum nitrate and 250g of sodium metaaluminate in 600g of nitric acid, adding 1000g of deionized water, uniformly mixing and stirring at a stirring rate of 150rad/min, adding 8g of citric acid, uniformly stirring, adding 5.5g of ammonia water, stirring at 45 ℃ for 1h, molding the obtained gel in a white oil column at 100 ℃, sequentially aging for 2h at 120 ℃, washing with deionized water at 70 ℃, drying at 120 ℃ for 10h, and roasting at 580 ℃ for 4h to obtain an alumina ball carrier;
step S2: weighing 150g of alumina ball carrier, placing in a flask, simultaneously weighing 3.9830g of chloroplatinic acid, dissolving in 270g of deionized water, preparing a platinum-containing precursor solution, placing the solution in the flask, immersing for 2 hours, then drying at 55 ℃ for 1.5 hours under reduced pressure, continuing drying at 130 ℃ for 16 hours under normal pressure, and roasting at 550 ℃ for 4 hours to obtain the platinum metal adsorbent preliminarily;
step S3: putting a platinum metal adsorbent into a flask, weighing 7.0041g of nickel nitrate, dissolving the nickel nitrate into 270g of deionized water, preparing a nickel-containing precursor solution, putting the solution into the flask, soaking for 2 hours, then drying at 55 ℃ for 1.5 hours under a reduced pressure state, continuously drying at 130 ℃ for 16 hours under a normal pressure state, and roasting at 550 ℃ for 4 hours to obtain the platinum nickel adsorbent;
step S4: washing the platinum-nickel adsorbent with 60 ℃ deionized water until the platinum-nickel adsorbent is neutral and free of chlorine, drying the platinum-nickel adsorbent at 120 ℃ for 12h, and roasting the platinum-nickel adsorbent at 550 ℃ for 4h to obtain PtNi/Al 2 O 3 The content of platinum in the adsorbent is 1.0wt% of the mass of the adsorbent, and the content of nickel in the adsorbent is 0.15wt% of the mass of the adsorbent.
Comparative example 5: the palladium content of the palladium alumina ball adsorbent sold by a certain company in China is 1.0 weight percent of the mass of the adsorbent.
Comparative example 6: platinum alumina ball adsorbent is sold in certain company in China, and the platinum content is 1.0 weight percent of the mass of the adsorbent.
Comparative example 7: a commercially available extruded platinum alumina adsorbent of a certain company in China has a platinum content of 1.0 weight percent of the mass of the adsorbent.
The method for evaluating the performance of the adsorbent comprises the following steps: adopting a fixed bed reactor, reducing the adsorbent with 80g in the environment of 300-550 ℃ for 2-5 h before using, controlling the reaction temperature to 130-180 ℃, controlling the reaction pressure to 0.8-1.1 MPa and the volume airspeed to 0.5-3 h -1 And (3) collecting effluent liquid, cooling to room temperature, detecting the content of thiophene in aromatic hydrocarbon by a gas phase method, and calculating the sulfur capacity.
The adsorbents obtained in examples and comparative examples were evaluated according to the above methods, and sulfur capacities were calculated and summarized as shown in table 1:
table 1: examples and comparative examples corresponding data summary table
From the results, the alumina ball carrier prepared by the invention has a richer three-dimensional reticular mesoporous structure (6-28 nm) and a maximum specific surface area (150-340 m) 2 And/g), the thiophene molecule can be promoted to reach the adsorption site efficiently and quickly, the adsorption effect is completed, and meanwhile, the prepared desulfurization adsorbent is loaded with platinum-nickel metal and activated by alkali metal micro-treatment, the adsorbent has strong stability, the thiophene sulfur can be efficiently removed, the sulfur capacity can reach 1.48g/Kg, the preparation process of the adsorbent is simple, the cost is low, and the performances of the adsorbent are superior to those of other platinum adsorbents on the market, and the adsorbent has the effect of isofrigorism with the palladium adsorbent.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (15)
1. A preparation method of a platinum-series adsorbent for desulfurizing aromatic compounds is characterized by comprising the following steps: the method comprises the following steps:
step S1: mixing an aluminum source, an acid source, a gelatinizing agent and deionized water according to a certain proportion, heating at the same time, stirring for a period of time to obtain aluminum hydroxide gel with certain viscosity, then forming in an oil column, and finally aging, washing, drying and roasting to obtain an alumina ball carrier; the mass ratio of the aluminum source to the acid source to the gelling agent to the deionized water is 1: (0.1-10): (0.001-2.5): (0.1-220);
the aluminum source comprises one or more of aluminum trichloride, aluminum powder, sodium metaaluminate, pseudo-boehmite and aluminum nitrate; the acid source comprises one or more of hydrochloric acid, nitric acid, acetic acid and citric acid; the gelling agent comprises one or more of hexamethylenetetramine, ammonia water and urea; the oil in the oil column is one or more of lubricating oil, gasoline, methyl silicone oil and white oil;
step S2: immersing the prepared alumina ball carrier in a platinum-containing precursor solution for a period of time, drying and roasting to obtain a platinum metal adsorbent preliminarily;
step S3: continuously dipping the obtained platinum metal adsorbent in a nickel-containing precursor solution, drying and roasting after dipping for a period of time to obtain the platinum nickel adsorbent;
step S4: the obtained platinum-nickel adsorbent is immersed in alkali metal solution with a certain concentration for micro-treatment and activation for a certain time;
step S5: and washing the obtained treated platinum-nickel adsorbent to be neutral by using deionized water with a certain temperature, drying and roasting to finally obtain the platinum-series adsorbent for desulfurizing the aromatic compounds.
2. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in step S1, the mass ratio of the aluminum source, the acid source, the gelling agent and the deionized water is 1: (0.5-8): (0.003-2): (0.5-180).
3. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in the step S2, the platinum content in the platinum-containing precursor solution is 0.3 to 2.0 weight percent, the platinum dispersity is 80 to 95 percent, and the mass ratio of the alumina ball carrier to the platinum-containing precursor solution is 1: (0.5-5).
4. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 3, wherein: the mass ratio of the alumina ball carrier to the platinum-containing precursor solution is 1: (0.8-2.5).
5. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in the step S3, the nickel content in the nickel-containing precursor solution is 0.05 to 1.5 weight percent, and the mass ratio of the alumina ball carrier to the nickel-containing precursor solution is 1: (0.3-3.5).
6. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 5, wherein: the mass ratio of the alumina ball carrier to the nickel-containing precursor solution is 1: (0.5-2).
7. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in step S2, the platinum-containing precursor solution includes one or more of a platinum nitrate solution, a chloroplatinic acid solution, a platinous chloride solution, a potassium platinous chloride solution, and a potassium platinate solution;
in step S3, the nickel-containing precursor solution includes one or more of a nickel nitrate solution, a nickel acetate solution, a nickel hydroxide solution, a nickel oxide solution, and a nickel dichloride solution.
8. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in step S4, the alkali metal solution includes one or more of sodium hydroxide solution, sodium carbonate solution, sodium chloride solution, potassium hydroxide solution, potassium carbonate solution, potassium chloride solution and potassium nitrate solution; the concentration of the alkali metal solution is 0.1-15%, and the micro-treatment activation time is 0.1-8 h.
9. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 8, wherein: the concentration of the alkali metal solution is 0.3-12%, and the micro-treatment activation time is 0.5-5.5 h.
10. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in step S1 and step S2, the selection conditions of the alumina ball carrier are: the specific surface area is 130-400 m 2 Per gram, pore volume of 0.45-1.5 cm 3 Per gram, the average pore diameter is 4-35 nm, and the bulk density is 0.5-0.8 g/cm 3 The diameter of the alumina ball carrier is 1.8-2.5 mm.
11. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 10, wherein: the selection conditions of the alumina ball carrier are as follows: specific surface area of 150-340 m 2 Per gram, pore volume of 0.50-1.35 cm 3 Per gram, the average pore diameter is 6-28 nm, and the bulk density is 0.55-0.7 g/cm 3 The diameter of the alumina ball carrier is 2-2.3 mm.
12. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in the step S1, the heating temperature after the materials are mixed is 30-120 ℃; the stirring speed is 50-500 rad/min; stirring for 0.1-6 h; the temperature of the oil column is 80-130 ℃; the aging temperature is 80-130 ℃; aging time is 1-8 h; the water washing temperature is 40-120 ℃; the drying temperature is 70-200 ℃; the drying time is 8-24 hours; the roasting temperature is 500-650 ℃; the roasting time is 1-8 h.
13. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 12, wherein: in the step S1, the heating temperature after the materials are mixed is 35-110 ℃; the stirring speed is 100-350 rad/min; stirring for 0.5-4 h; the temperature of the oil column is 85-125 ℃; the aging temperature is 85-120 ℃; aging time is 2-6 h; the washing temperature is 50-110 ℃; the drying temperature is 95-160 ℃; the drying time is 10-18 h; the roasting temperature is 500-650 ℃; the roasting time is 2-6 h.
14. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 1, wherein: in the step S2, the step S3 and the step S5, the roasting temperature is 350-700 ℃; roasting time is 1-8 h; the drying is divided into two types, wherein the first type is drying under a reduced pressure state, the drying temperature is 40-95 ℃, and the drying time is 0.5-6 h; the second is drying under normal pressure, the drying temperature is 90-150 ℃ and the drying time is 12-36 h;
in the step S2 and the step S3, the soaking time of the alumina ball carrier or the platinum metal adsorbent in the two precursor solutions is 0.5-8 h;
in step S5, the deionized water temperature is 35-90 ℃.
15. The method for producing a platinum-series adsorbent for desulfurizing aromatic compounds according to claim 14, wherein: in the step S2, the step S3 and the step S5, the roasting temperature is 380-650 ℃; roasting time is 2.5-5 h; the drying is divided into two types, wherein the first type is drying under a reduced pressure state, the drying temperature is 45-85 ℃, and the drying time is 1-4 hours; the second is drying under normal pressure, the drying temperature is 100-135 ℃ and the drying time is 15-30 h;
in the step S2 and the step S3, the soaking time of the alumina ball carrier or the platinum metal adsorbent in the two precursor solutions is 1-6 h;
in step S5, the deionized water temperature is 45-75 ℃.
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| CN115872424A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | High-strength spherical alumina and preparation method thereof |
| CN116408104A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method and application thereof |
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2023
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| US3042628A (en) * | 1957-11-04 | 1962-07-03 | Engelhard Ind Inc | Production of alumina and catalyst containing same |
| ES264290A1 (en) * | 1960-01-25 | 1961-07-01 | Universal Oil Prod Co | Hydrogenation of aromatic hydrocarbons |
| CN108568290A (en) * | 2018-04-25 | 2018-09-25 | 福州大学 | The preparation method and application of the spherical adsorbent of efficient removal low concentration hydrogen sulphide |
| CN116408104A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Adsorption desulfurization catalyst and preparation method and application thereof |
| CN114471448A (en) * | 2021-12-30 | 2022-05-13 | 贵研工业催化剂（云南）有限公司 | Benzene refining desulfurization adsorbent and preparation method thereof |
| CN115872424A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | High-strength spherical alumina and preparation method thereof |
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