CN112742403B - Natural gas hydrodesulfurization catalyst and preparation method and application thereof - Google Patents
Natural gas hydrodesulfurization catalyst and preparation method and application thereof Download PDFInfo
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- CN112742403B CN112742403B CN201911052388.9A CN201911052388A CN112742403B CN 112742403 B CN112742403 B CN 112742403B CN 201911052388 A CN201911052388 A CN 201911052388A CN 112742403 B CN112742403 B CN 112742403B
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- China
- Prior art keywords
- catalyst
- natural gas
- hydrodesulfurization catalyst
- hydrodesulfurization
- reaction
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- 239000003345 natural gas Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000001099 ammonium carbonate Substances 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 18
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- ZJXWFPDCTMSVIS-UHFFFAOYSA-N [Mn].[Co].[Zr] Chemical compound [Mn].[Co].[Zr] ZJXWFPDCTMSVIS-UHFFFAOYSA-N 0.000 description 1
- XQYCUFOSMOQDCI-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Co+2].[Al+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Co+2].[Al+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] XQYCUFOSMOQDCI-UHFFFAOYSA-N 0.000 description 1
- VVUILVMDMIIETB-UHFFFAOYSA-K [Ti].Cl[Al](Cl)Cl Chemical compound [Ti].Cl[Al](Cl)Cl VVUILVMDMIIETB-UHFFFAOYSA-K 0.000 description 1
- GJAROXYKDRBDBI-UHFFFAOYSA-J [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJAROXYKDRBDBI-UHFFFAOYSA-J 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 1
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/40—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
A natural gas hydrodesulfurization catalyst and its preparation method and application are disclosed. The natural gas hydrodesulfurization catalyst comprises raspberry type particles composed of an active component a, a structural auxiliary agent b and other auxiliary agents c, wherein the raspberry type particles are hollow microspheres with a large hole on the surface, hollow structures are arranged in the hollow microspheres, and the large hole is communicated with the hollow structures to form a cavity with an opening at one end; w is based on the weight of the corresponding oxide a ：W b ：W c = (45 to 90): (10-50): (0 to 15). This application is through regulation and control catalyst composition and morphological characteristics, obtains this application natural gas hydrodesulfurization catalyst that has raspberry type structure, can improve organic sulfur conversion efficiency by a wide margin, even can still keep the high conversion rate to organic sulfur in the natural gas under higher airspeed. And this application catalyst particle size is less, can be applicable to microchannel reactor, can realize that the device equipment is miniaturized.
Description
Technical Field
The invention belongs to the field of gas purification, and particularly relates to a natural gas hydrodesulfurization catalyst, a preparation method thereof and a hydrodesulfurization reaction method.
Background
Natural gas is an important fossil energy source and a hydrocarbon resource, the main component of the natural gas is methane, and the natural gas contains a small amount of low-carbon alkane. Natural gas typically contains some amount of inorganic and organic sulfur compounds that tend to poison subsequent conversion catalysts. Typically, the metal catalyst has a sulfide tolerance of no greater than 20ppb. Therefore, it is of great significance to remove sulfides in natural gas. The inorganic sulfur in the natural gas is mainly hydrogen sulfide and can be removed by using a zinc oxide desulfurizer, but the effect of removing the organic sulfur by dry-method zinc oxide adsorption is poor. Therefore, organic sulfur is usually converted into hydrogen sulfide by hydrogenation and then removed by using a zinc oxide desulfurizer.
Patent CN101722006 discloses a bifunctional hydrogenation catalyst, which adopts a titanium oxide-alumina supported Co-Mo-Ni-Cu-RE catalyst to effectively hydrogenate organic sulfur in gas, and the content of the organic sulfur after treatment is less than 0.5ppm. The catalyst is in the form of pellets of 3-5 mm, and no specific reaction space velocity is given.
The conventional organic sulfur hydrogenation catalyst has low space velocity and low organic sulfur conversion rate, and cannot realize the high-efficiency utilization of the catalyst and the miniaturization of equipment.
Disclosure of Invention
The application provides a natural gas hydrodesulfurization catalyst, a preparation method and an application thereof.
In a first aspect, the application provides a natural gas hydrodesulfurization catalyst, which comprises raspberry-shaped particles composed of an active component a, a structural assistant b and other assistants c, wherein the raspberry-shaped particles are hollow microspheres with a large pore on the surface, hollow structures are arranged in the hollow microspheres, and the large pore and the hollow structures are communicated to form a cavity with one open end;
the metal elements of the active component a are Co and Mo; the structural auxiliary agent b is one or more selected from alumina, silica, titanium oxide and zirconia; the metal elements of the other auxiliary agents c are one or more selected from W, mn and Zn;
w is based on the weight of the corresponding oxide a ：W b ：W c = (45 to 90): (10-50): (0 to 15) in which W a Denotes the weight percentage of active component a in relation to the corresponding oxide, W b Denotes the weight percentage of the structural auxiliary b based on the corresponding oxide in the catalyst, W c The other auxiliary c represents the weight percentage of the catalyst, calculated as the corresponding oxide.
In one embodiment, the active component is Co — Mo.
In one embodiment, the composition of each component in terms of the corresponding oxide is preferably W a ：W b ：W c ＝(45～85)：(15～45)：(0～10)。
In one embodiment, the catalyst has a size in the range of 60 μm to 600 μm and a cavity size in the range of 10 μm to 200 μm. Preferably, the size of the catalyst is in the range of 80 μm to 500 μm, and the size of the cavity is in the range of 20 μm to 150 μm.
In one embodiment, the natural gas hydrodesulfurization catalyst is used in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm.
In a second aspect, the present application provides a method of preparing a natural gas hydrodesulfurization catalyst comprising the steps of:
(1) Uniformly dispersing soluble salts or colloid particles of active components, soluble salts or colloid particles of structural auxiliaries and soluble salts or colloid particles of other auxiliaries into a solvent, and precipitating by using a precipitator to obtain a catalyst precursor;
(2) Mixing the catalyst precursor obtained in the step (1) with a pore-forming agent and/or an explosive to prepare slurry;
(3) And (3) carrying out spray drying and forming on the slurry obtained in the step (2) to obtain the catalyst.
In one embodiment, the soluble salt is selected from one or more of inorganic salts selected from one or more of chlorides, nitrates, acetates, sulfates and organic materials selected from metal alkoxides.
In one embodiment, the pore-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactant.
In one embodiment, the synthetic cellulose is one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxyl cellulose fatty alcohol; the polymer alcohol is one or more of polyethylene glycol, polypropylene alcohol, polyvinyl alcohol and polypropylene alcohol; the surfactant is one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, acrylic acid copolymer with molecular weight of 200-20000 and maleic acid copolymer.
In one embodiment, the blasting agent is selected from one or more of nitric acid, nitrate, picric acid, trinitrotoluene (TNT), nitroglycerin, nitrocotton, danner explosive, hexogen, lead azide and C4 plastic explosive.
In one embodiment, the pore former is used in an amount of 1.0 to 100.0% on a dry basis of the oxide and the blasting agent is used in an amount of 0.5 to 100.0% on a dry basis of the oxide.
In one embodiment, the inlet temperature of the spray drying air is 400 to 1200 ℃, preferably 450 to 700 ℃; the air outlet temperature is 70-300 ℃. In one embodiment, the method comprises a further roasting treatment after spray drying and forming, wherein the roasting temperature is 300-600 ℃, and is preferably 350-500 ℃; the roasting time is 1-24 h, preferably 2-16 h.
In one embodiment, the solvent is selected from water, an organic solvent or a mixture of water and an organic solvent.
In one embodiment, the organic solvent is one of alcohols, ketones, acids, or a mixture of two or more thereof.
In one embodiment, the precipitant is an alkaline substance, such as one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, ammonium bicarbonate, and urea.
In another aspect, the present application relates to the use of the natural gas hydrodesulfurization catalyst of the present application in catalyzing the hydrodesulfurization of natural gas.
In another aspect, the present application relates to a method for hydrodesulfurization of natural gas comprising:
the sulfur-containing compound is used as the catalyst for the hydrodesulfurization of the natural gas in the application for activation treatment,
and (3) introducing a feed gas into the reactor to contact with the activated catalyst to carry out hydrodesulfurization reaction, wherein the feed gas comprises hydrogen and natural gas containing organic sulfide.
In one embodiment, the hydrodesulfurization reaction is carried out in a microchannel reactor, which is a reactor having reaction channels with at least one dimension less than 1000 μm.
In one embodiment, the feed gas has an organic sulfide content of 1 to 600ppm, preferably 10 to 500ppm; the reaction temperature is 280-360 ℃, and preferably 300-340 ℃; the reaction pressure is 0.1MPa to 6MPa, preferably 1MPa to 5MPa; the volume fraction of hydrogen in the feed gas is 0.5-20%, preferably 1.0-15%; the volume space velocity of the feed gas is 1000h -1 ～50000h -1 Preferably 2000h -1 ～40000h -1 。
We find that the natural gas hydrodesulfurization catalyst with a raspberry structure is obtained by regulating and controlling the composition and morphological characteristics of the catalyst, so that the organic sulfur conversion efficiency can be greatly improved, and the high conversion rate of organic sulfur in natural gas can be still maintained even at a higher airspeed. And this application catalyst particle size is less, can be applicable to the microchannel reactor, can realize that the device equipment is miniaturized.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst obtained in example 1;
FIG. 2 is a scanning electron micrograph of the catalyst obtained in example 3.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
In a first aspect, the application provides a natural gas hydrodesulfurization catalyst, which comprises raspberry-shaped particles composed of an active component a, a structural assistant b and other assistants c, wherein the raspberry-shaped particles are hollow microspheres with a large pore on the surface, hollow structures are arranged in the hollow microspheres, and the large pore and the hollow structures are communicated to form a cavity with one open end;
the metal elements of the active component a are Co and Mo; the structural auxiliary agent b is one or more selected from alumina, silica, titanium oxide and zirconia; the metal elements of the other auxiliary agents c are one or more selected from W, mn and Zn;
w is based on the weight of the corresponding oxide a ：W b ：W c = (45 to 90): (10-50): (0 to 15) wherein W a Denotes the weight percentage of active component a in relation to the corresponding oxide, W b Denotes the weight percentage of the structural auxiliary b based on the corresponding oxide in the catalyst, W c Expressed in terms of the corresponding oxideAnd the other auxiliary agent c accounts for the weight percentage of the catalyst.
Fig. 1 and 2 show the morphology of the catalysts of the present application. The catalyst is raspberry type particles, the raspberry type particles are hollow microspheres with a large hole in the surface, hollow structures are arranged inside the hollow microspheres, and the large hole is communicated with the hollow structures to form a cavity with an opening at one end. The size range of the catalyst is 60-600 mu m, and the size range of the cavity is 10-200 mu m; preferably, the size range of the catalyst is 80-500 μm, and the size range of the cavity is 20-150 μm. The pore diameter of the surface macropores is 0.5-200 μm. The catalyst has a shell layer surrounding the cavity and having a thickness of 20-200 μm. The appearance is close to spherical, and the sphericity is 0.85-0.99, preferably 0.90-0.98.
The sphericity of the green microbead is calculated by the following formula:
σ＝4πA/L 2
wherein σ is sphericity; a is the projected area of the microsphere in m 2 (ii) a L is the projection perimeter of the microsphere, and the unit is m; a and L are obtained from SEM pictures of microspheres and processed by Image processing software Image-Pro Plus.
The raspberry type microsphere particle has the breakage rate of 0-1%, the breakage rate is measured according to a method provided by a similar strength standard number Q/SH 3360-2010, and the specific method comprises the following steps:
firstly, selecting sieves S1 and S2 with the mesh numbers of M1 and M2 respectively, wherein M1 is less than M2, enabling microspheres to be detected to firstly pass through the sieve S1 with the mesh number of M1, then enabling the sieved microsphere powder to pass through the sieve S2 with the mesh number of M2, and finally enabling the microsphere powder intercepted by the sieve S2 to be used as a sample to be detected.
Adding a sample to be tested with a certain mass into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure to microspheres through a cylinder for a certain time, screening the pressed microsphere powder by using a screen S2 with the mesh number of M2, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the total mass of the added microspheres to obtain the breaking rate of the microspheres.
In the present invention, M1 may be 100 mesh, M2 may be 150 mesh, the pressure may be 100N, and the time may be 10s.
The strength of the microspheres can be evaluated by using the breakage rate; when the breakage rate is smaller, the strength of the microspheres is higher.
Under the condition of pressurization, the raspberry type microsphere particle has low breakage rate and obviously higher strength than the existing known oxide microspheres, such as the apple-shaped hollow molecular sieve microsphere disclosed by CN108404970A, which is determined by the difference of raw materials and preparation methods thereof. The raspberry type microsphere particles have higher porosity due to higher strength, greatly reduced pressure drop, excellent processing performance and loss resistance, short reaction diffusion distance when being applied to a catalytic reaction, and wide application prospect.
The catalyst of the present application has the advantages that: the micron ball with raspberry structure may be filled into micro channel reactor and has high conversion rate to organic sulfur in natural gas maintained at high airspeed.
In one embodiment, the metal elements of active component a are Co and Mo. The metal element of the active component a in the catalyst of the present application may be present in various forms. For example, the metal element of the active component a in the catalyst of the present application may be present in the form of a metal oxide, may also be present in the form of a metal sulfide, may even be present in a reduced state, and may also be present in the form of the above three forms together. These forms may be interconverted, for example, the metal oxide may be sulfided and converted to the metal sulfide form, or reduced and converted to the reduced form. The skilled person can select and transform accordingly according to the use requirement. For example, when desulfurization is performed, it may be activated to convert it into a sulfide form and then used for the catalytic reaction of desulfurization.
In one embodiment, the structural assistant b is one or more selected from alumina, silica, titania and zirconia.
In another embodiment, the metal element of the other auxiliary agent c is one or more selected from W, mn and Zn. The metal element of the other assistant c exists in an oxidized state or a sulfurized state, and these existing forms can be mutually converted, for example, a metal oxide can be converted into a metal sulfide form after being sulfurized, and the metal sulfide can also be converted into a metal oxide through oxidation.
W based on the weight of the corresponding oxide a ：W b ：W c = (45 to 90): (10-50): (0 to 15), preferably, W a ：W b ：W c = (45 to 85): (15-45): (0-10); wherein W a Denotes the weight percentage of active component a in relation to the corresponding oxide, W b Denotes the weight percentage of the structural auxiliary b, calculated as the corresponding oxide, in relation to the catalyst, W c The other auxiliary agents c are expressed as a percentage by weight of the catalyst, calculated on the corresponding oxides.
In one embodiment, the natural gas hydrodesulfurization catalyst is used in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm. The microchannel reactor is an active reactor type in recent years, generally refers to a reactor with at least one dimension of a reaction channel being less than 1000 microns, has the characteristics of mass transfer enhancement, heat transfer enhancement, easiness in miniaturization and the like, and is applied to the field of intense heat release such as FT synthesis and the like.
In a second aspect, the present application provides a method of preparing the natural gas hydrodesulfurization catalyst comprising the steps of:
(1) Uniformly dispersing soluble salts or colloid particles of active components, soluble salts or colloid particles of structural auxiliaries and soluble salts or colloid particles of other auxiliaries into a solvent, and precipitating by using a precipitator to obtain a catalyst precursor;
(2) Mixing the catalyst precursor obtained in the step (1) with a pore-forming agent and/or an explosive to prepare slurry;
(3) And (3) carrying out spray drying and forming on the slurry obtained in the step (2) to obtain the catalyst.
In one embodiment, the soluble salt is selected from one or more of inorganic salts selected from one or more of chlorides, nitrates, acetates, sulfates and organic materials selected from metal alkoxides.
Examples of soluble salts of the active component include, but are not limited to, co, mo hydrochloride, nitrate, acetate, sulfate, and the like, such as cobalt chloride, cobalt nitrate, cobalt acetate, cobalt sulfate; nickel chloride, nickel nitrate, nickel acetate and nickel sulfate; molybdenum chloride, molybdenum nitrate, molybdenum acetate, molybdenum sulfate, and molybdates such as ammonium molybdate, sodium molybdate, potassium molybdate, and the like.
Examples of soluble salts of the structural adjunct include, but are not limited to, one or more of an aluminum source selected from the group consisting of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a zirconium source selected from one or more of silicate, sodium silicate, water glass, and silica sol, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium hydroxycarbonate, and tetrabutoxy zirconium, and a titanium source selected from one or more of titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium aluminum chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate, and tetra-isopropyl titanate.
Examples of soluble salts of other adjuvants include, but are not limited to, hydrochlorides of W, mn, zn, nitrates, acetates, sulfates, etc., and may include, for example, tungsten chloride, manganese chloride, zinc chloride, manganese nitrate, zinc nitrate, tungsten acetate, manganese acetate, zinc acetate, tungsten sulfate, manganese sulfate, zinc sulfate, etc.
In another embodiment, the active ingredient, structural assistant and other assistant colloidal particles refer to nanoparticles containing the active ingredient, structural assistant and other assistant, such as commonly used aluminum sol, silica sol, titanium solvent and the like.
In one embodiment, the active ingredient, the structural adjuvants and the further adjuvants are used in a ratio of (45 to 90): (10-50): (0 to 15). In this application, the desired components are dispersed in a solvent and precipitated with a precipitant to obtain a catalyst precursor. In one embodiment, the solvent may comprise water, an organic solvent, or a mixture of an organic solvent and water. In one embodiment, the organic solvent may be one of alcohols, ketones (e.g., acetone, butanone, etc.), acids (e.g., formic acid, acetic acid, propionic acid, etc.), or a mixture of two or more thereof. In one embodiment, the precipitant is generally a basic substance, such as one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, ammonium bicarbonate, and urea. After the precipitation, the aging treatment may be carried out at 0 to 90 ℃ for 0.1 to 24 hours, preferably 0.5 to 2 hours.
As described above, the obtained catalyst precursor is mixed with a pore-forming agent and/or a blasting agent to prepare slurry. In the present application, the pore-forming agent and the blasting agent may be used individually or together.
In one embodiment, the pore-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactant. In another embodiment, the synthetic cellulose is one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy cellulose fatty alcohol; the polymer alcohol is one or more of polyethylene glycol, polypropylene alcohol, polyvinyl alcohol and polypropylene alcohol; the surfactant is one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, acrylic acid copolymer with molecular weight of 200-20000 and maleic anhydride copolymer. The pore-forming agent is used in an amount of 1.0 to 200.0%, preferably 2 to 150%, and more preferably 5 to 100% based on the total dry weight of the catalyst precursor.
In one embodiment, the blasting agent is selected from one or more of nitric acid, nitrate, picric acid, trinitrotoluene (TNT), nitroglycerin, nitrocotton, danner explosive, hexogen, lead azide, and C4 plastic explosive. The amount of the blasting agent used may be 0.5 to 200.0%, preferably 1.0 to 100%, and more preferably 2.0 to 50% of the total dry weight of the catalyst precursor.
The slurry obtained was spray-dried and shaped as described above to obtain the catalyst. The spray drying apparatus used in the present invention is a conventional apparatus in the existing flow path, and the present invention is not particularly limited thereto. In the spray-drying process, a spray-drying tower is used comprising: the device comprises a feeding system, a hot air system, a drying tower system, a receiving system and a sealing system. The feeding system is connected with the drying tower system in the middle of the top end, the hot air system is connected with the side face of the top end of the drying tower system, the receiving system is connected with the bottom end of the drying tower system, and the sealing system is connected with the hot air system. In the spray drying process, it is essentially necessary to have a spray of the stock solution; drying the tiny droplets in the spray; three functions of separating and recovering fine powder products. In the spray drying apparatus, an atomizer, a drying chamber, and a fine powder recoverer corresponding to the above functions are generally equipped.
In the application, the slurry is fed into a spray drying device, drying and forming are carried out at the air inlet temperature of 400-1200 ℃, preferably 450-700 ℃, the air outlet temperature is 50-300 ℃, preferably 120-200 ℃, the pressure in a spray tower is similar to that of conventional spraying, and raspberry type microsphere particles can be obtained.
Because of the many control parameters and complex factors in the spray drying process, the particle size and the particle shape after spray drying are very complex. The size range of the product is generally in micron order, and the product is generally a mixture of shapes including a sphere, a disc, an apple shape, a grape shape, a cavity shape, a meniscus shape and the like, and how to selectively form an ideal single shape, such as a cavity shape, is a difficulty in the formation of the product.
One method in the prior art is to form spherical emulsion under the action of surface tension of a surfactant, then at the moment of spray forming at a lower temperature, a pore-forming agent is vaporized or pyrolyzed in the spherical emulsion, and the gas generated by vaporization and pyrolysis can cause the inner cavity of the microsphere emulsion; and (3) slowly releasing gas to form macropores on the surface to be communicated with the internal hollow structure, forming secondary stacking holes on the molecular sieve particles in the spray forming process to form mesopores on the surface of the molecular sieve microspheres, and combining the subsequent roasting process to obtain the large-particle hollow molecular sieve microspheres.
Under the high temperature of 400-1200 ℃, the oxide and the reducing agent in the slurry have strong oxidation-reduction self-propagating combustion reaction to instantly generate a large amount of gas; meanwhile, the liquid drops enter a high-temperature area for spraying, the liquid drops are strongly evaporated, and the surface tension formed by the thickened slurry causes the liquid drops to shrink rapidly. The strong explosion of the inside and the strong contraction of the outside form a raspberry type hollow material with good strength. The prepared raspberry type microsphere has high particle strength, high sphericity and high yield.
In one embodiment, the method comprises a further roasting treatment after spray drying and forming, wherein the roasting temperature is 300-600 ℃, and is preferably 350-500 ℃; the roasting time is 1-24 h, preferably 2-16 h.
The catalyst has a raspberry type structure, has high strength and smaller particle size, and has excellent processing performance and loss resistance rate, and the pressure drop is greatly reduced due to the special structure and high strength; the small particle size enables the catalyst to be applied to miniaturized devices such as microchannel reactors. Such high strength and small particle size are brought about by the raw materials and the preparation method thereof.
In another aspect, the application also relates to the application of the catalyst in the catalytic hydrodesulfurization of natural gas, and a method for the hydrodesulfurization reaction of natural gas.
The method for the hydrodesulfurization reaction of natural gas comprises the following steps:
the sulfur-containing compound is used for activating the natural gas hydrodesulfurization catalyst,
and (3) introducing a feed gas into the reactor to contact with the activated catalyst to carry out hydrodesulfurization reaction, wherein the feed gas comprises hydrogen and natural gas containing organic sulfide.
The natural gas hydrodesulfurization catalyst has small particle size, can be suitable for a micro-channel reactor, and can realize the miniaturization of equipment. In one embodiment, the hydrodesulfurization reaction is carried out in a microchannel reactor, which is a reactor having reaction channels with at least one dimension less than 1000 μm. The natural gas hydrodesulfurization reaction can be carried out in a microchannel reactor as follows: the natural gas hydrodesulfurization catalyst is filled in a microchannel reactor, a sulfur-containing compound is firstly introduced for sulfuration activation treatment, and then natural gas containing organic sulfide and hydrogen are introduced into the microchannel reactor to contact with the natural gas hydrodesulfurization catalyst for hydrodesulfurization reaction under the condition of hydrodesulfurization reaction.
In the present application, the method of activating the catalyst is not particularly limited, and the activation pressure is 0.1 to 2MPa, preferably 0.2 to 1.8MPa; the activation temperature is 100-800 ℃, preferably 200-600 ℃, and more preferably 250-450 ℃; the activation time is 0.5 to 72 hours, preferably 1 to 48 hours, and more preferably 2 to 36 hours; the space velocity of the activated gas is 2000-40000 h -1 Preferably 2500 to 30000h -1 (ii) a Wherein, the sulfur-containing compound used for the vulcanization activation treatment is at least one of carbon disulfide, hydrogen sulfide and dimethyl disulfide.
In one embodiment, the feed gas has an organic sulfide content of 1 to 600ppm, preferably 10 to 500ppm; the reaction temperature is 280-360 ℃, and preferably 300-340 ℃; the reaction pressure is 0.1MPa to 6MPa, preferably 1MPa to 5MPa; the volume fraction of hydrogen in the feed gas is 0.5-20%, preferably 1.0-15%; the volume space velocity of the feed gas is 1000h -1 ～50000h -1 Preferably 2000h -1 ～40000h -1 。
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
Examples
Reagents, instruments and tests
In the following examples and comparative examples, the starting materials used are, without specific reference, commercially available products, some of which are as follows:
polyethylene glycol PEG4000 powder (Wenzhou Shuanghoi rubber and plastic materials Co., ltd.);
methylcellulose (Hubei Jiangtiantai chemical Co., ltd.).
The breakage of the catalyst can be measured as follows:
the microspheres to be measured firstly pass through a 100-mesh sieve, then the sieved microsphere powder passes through a 150-mesh sieve, and finally the microsphere powder intercepted by the 150-mesh sieve is used as a sample to be measured. Adding microspheres with a certain mass (the granularity is 100-150 meshes) into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure (100N) to the microspheres through a cylinder for a certain time (10 seconds), screening the pressed microsphere powder by using a 150-mesh screen, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the total mass of the added microspheres to obtain the breaking rate of the microspheres.
Example 1
(1) Preparation of catalyst precursor
Dissolving 11.65kg of cobalt nitrate hexahydrate and 22.46kg of aluminum nitrate nonahydrate in 50L of deionized water; dissolving 43kg of ammonium carbonate in 50L of deionized water, adding 13.61kg of ammonium molybdate until the ammonium molybdate is completely dissolved, slowly adding the ammonium molybdate solution into the cobalt nitrate/aluminum nitrate solution, continuously adding the ammonium carbonate until the pH value of the solution is between 9.0 and 9.1, standing and aging at room temperature for 6 hours after complete precipitation, filtering, and washing twice with 75L of deionized water;
(2) Pulping
The filter cake was dispersed in 100L of deionized water, vigorously stirred and beaten, and 13.0kg of PEG4000 and 6.5kg of ammonium nitrate were added in this order, stirred and beaten at 30 ℃ for 2 hours.
(3) Spray drying and forming
And (3) forming the slurry by a Niro Bowen non Tower spray drying device with the spray drying pressure of 5.5-9.0 MPa, the initial air inlet temperature of drying of 465 ℃ and the air outlet temperature of drying termination of 148 ℃. And roasting the catalyst in air at 400 ℃ for 4 hours to obtain the raspberry-shaped catalyst with the average particle size of about 150 mu m and the average cavity size of 45 mu m, which is marked as C1. The content of active components is 65wt% and the content of structural auxiliary agent is 35wt% calculated by oxide. The scanning electron micrograph of the catalyst is shown in figure 1, the scale in the left figure of figure 1 is 100 μm, the morphology of a single raspberry-shaped catalyst particle is shown, and the morphology of a plurality of raspberry-shaped catalyst particles is shown in the right figure. The degree of crushing was 0.5% and the sphericity was 0.96.
Comparative example 1
The process of example 1 was followed except that step (2) was as follows:
dispersing the filter cake into 100L of deionized water, and stirring and pulping for 2h at 30 ℃.
A spherical catalyst having an average particle diameter of about 140 μm was obtained and was designated as DB1. The content of active components is 65wt% and the content of structural auxiliary agent is 35wt% calculated by oxide. The degree of crushing was 2.6% and the sphericity was 0.94.
Comparative example 2
The process of example 1 is followed except that steps (2) and (3) are as follows:
and fully mixing 800g of methylcellulose and 700g of sesbania powder with the filter cake, uniformly kneading by a strip extruder, extruding and molding, and roasting in air at 400 ℃ for 4 hours to obtain a butterfly-shaped strip catalyst with the outer diameter of about 1.6mm, wherein the butterfly-shaped strip catalyst is recorded as DB2. The content of active components is 65wt% and the content of structural auxiliary agent is 35wt% calculated by oxide.
Comparative example 3
(1) Catalyst precursor preparation
Dissolving 2.33kg of cobalt nitrate hexahydrate and 52.63kg of aluminum nitrate nonahydrate in 50L of deionized water, dissolving 45kg of ammonium carbonate in 50L of deionized water, adding 4.08kg of ammonium molybdate until the ammonium nitrate is completely dissolved, slowly adding the ammonium molybdate solution into the cobalt nitrate aluminum solution, continuously adding the ammonium carbonate until the pH value of the solution is between 9.0 and 9.1, standing at room temperature after complete precipitation, aging for 6 hours, filtering, and washing twice with 75L of deionized water;
steps (2) and (3) were the same as example 1, and calcined in air at 400 ℃ for 4 hours to obtain a raspberry catalyst with an average particle size of about 155 μm and an average cavity size of 50 μm, which was designated as DB3. The content of active components calculated by oxide is 18wt%, and the content of structural auxiliary agent is 82wt%. The degree of crushing was 0.7% and the sphericity was 0.92.
Comparative example 4
(1) Preparation of catalyst precursor
Dissolving 19.42kg of cobalt nitrate hexahydrate in 40L of deionized water, dissolving 32kg of ammonium carbonate in 60L of deionized water, adding 20.43kg of ammonium molybdate till the ammonium molybdate is completely dissolved, slowly adding the ammonium molybdate solution into the cobalt nitrate solution, continuously adding the ammonium carbonate until the pH value of the solution is between 9.0 and 9.1, standing and aging at room temperature for 6 hours after complete precipitation, filtering, and washing twice with 75L of deionized water;
the steps (2) and (3) are the same as the example 1, and roasting is carried out for 4 hours in the air at the temperature of 400 ℃, so as to obtain the raspberry-shaped catalyst with the average grain diameter of about 146 mu m and the average cavity size of 40 mu m, which is marked as DB4. The content of active components is 100wt% and the content of structural auxiliary agent is 0wt% in terms of oxide. The degree of crushing was 0.8% and the sphericity was 0.91.
Comparative example 5
5.5kg of HZSM-5 molecular sieve with the grain size of 300-350 nm, 3kg of kaolin, 1kg of cement and 0.5kg of ammonium carbonate are added into 20kg of deionized water, and shearing emulsification is carried out for 2 hours at 2000rpm by a homogenizing emulsifier to form uniform colloidal slurry, wherein the solid content of the colloidal slurry is 31.7%.
And adding 300g of P123 surfactant into the colloidal slurry, and continuously stirring for 1h to obtain the microsphere slurry.
And (3) conveying the microsphere slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.8Mpa, the inlet temperature of the spray dryer is 280 ℃, the outlet temperature of the spray dryer is 120 ℃, and the microsphere slurry flows out of the outlet of the spray dryer for 2-5 seconds to obtain microsphere particles, wherein the crushing rate of the microsphere particles is 37.2%, and the sphericity of the microsphere particles is 0.82.
Example 2
(1) Preparation of catalyst precursor
Dissolving 7.77kg of cobalt nitrate hexahydrate, 28.88kg of aluminum nitrate nonahydrate and 7.31kg of zinc nitrate hexahydrate in 50L of deionized water; dissolving 38kg of sodium carbonate in 50L of deionized water, adding 9.53kg of ammonium molybdate until the ammonium molybdate is completely dissolved, slowly adding the ammonium molybdate solution into a cobalt nitrate, aluminum nitrate and zinc nitrate solution, continuously adding the sodium carbonate until the pH value of the solution is 9.5-9.6, standing at room temperature after complete precipitation, aging for 6 hours, filtering, and washing with 150L of deionized water for four times;
(2) Pulping
Dispersing the filter cake into 50L of deionized water, stirring vigorously and pulping, adding 10.0kg of PEG4000 and 6.5kg of ammonium nitrate in sequence, and stirring and pulping for 2h at 30 ℃.
(3) Spray drying and forming
The slurry was formed by a Niro Bowen non Nozzle Tower model spray dryer at a spray drying pressure of 7.0 to 9.0MPa, an inlet temperature of 500 ℃ or less and an outlet temperature of about 160 ℃. And roasting the mixture for 4 hours in air at 450 ℃ to obtain the raspberry-shaped catalyst with the average particle size of about 230 mu m and the average cavity size of 60 mu m, which is marked as C2. The content of active components calculated by oxide is 45wt%, the content of structural auxiliary agent is 45wt%, and the content of other auxiliary agents is 10wt%. The degree of crushing was 0.3% and the sphericity was 0.92.
Example 3
(1) Catalyst precursor preparation
15.54kg of cobalt nitrate hexahydrate and 9.63kg of aluminum nitrate nonahydrate were dissolved in 50L of deionized water, and 8.23kg of manganese nitrate solution (50 wt%) was added; dissolving 38kg of ammonium carbonate in 50L of deionized water, adding 14.97kg of ammonium molybdate, dissolving completely, slowly adding the ammonium molybdate solution into a cobalt nitrate, aluminum nitrate and manganese nitrate solution, continuously adding ammonium carbonate until the pH value of the solution is 9.5-9.6, standing at room temperature after complete precipitation, aging for 6 hours, filtering, and washing twice with 80L of deionized water;
(2) Pulping
Dispersing the filter cake into 120L of deionized water, stirring vigorously and pulping, adding 10.0kg of PEG4000 and 6.5kg of ammonium nitrate in sequence, and stirring and pulping for 2h at 30 ℃.
(3) Spray drying and forming
The slurry was formed by a Niro Bowen non Nozzle Tower model spray dryer at a spray drying pressure of 7.0 to 8.0MPa, an inlet temperature of 480 ℃ or less and an outlet temperature of about 145 ℃. And roasting the catalyst for 4 hours in air at 480 ℃ to obtain the raspberry-shaped catalyst with the average particle size of about 120 mu m and the average cavity size of 40 mu m, which is marked as C3. The scanning electron microscope photo of the active component, calculated by oxide, is shown in figure 2, wherein the scale is 100 μm, and the content of the active component is 75wt%, the content of the structural auxiliary agent is 15wt%, and the content of the other auxiliary agent is 10wt%. The degree of crushing was 0.6% and the sphericity 0.94.
Example 4
(1) Preparation of catalyst precursor
Dissolving 15.54kg of cobalt nitrate hexahydrate and 16.67kg of silica sol containing 30wt% of silica in 40L of deionized water, dissolving 30kg of ammonium carbonate in 50L of deionized water, adding 14.97kg of ammonium molybdate till complete dissolution, slowly adding the ammonium molybdate solution into the mixed nitrate solution, continuously adding ammonium carbonate till the pH value of the solution is 9.0-9.2, standing at room temperature after complete precipitation, aging for 12 hours, filtering, and washing twice by 80L of deionized water;
(2) Pulping
Dispersing the filter cake into 120L of deionized water, stirring vigorously and pulping, adding 10.0kg of PEG4000 and 6.5kg of ammonium nitrate in sequence, and stirring and pulping for 2h at 30 ℃.
(3) Spray drying and forming
The slurry was formed by a Niro Bowen non Nozzle Tower model spray dryer at a spray drying pressure of 7.0 to 8.0MPa, an inlet temperature of 480 ℃ or less and an outlet temperature of about 145 ℃. And roasting the catalyst for 4 hours in air at 480 ℃ to obtain the raspberry-shaped catalyst with the average particle size of about 120 mu m and the average cavity size of 40 mu m, which is marked as C4. The content of active components calculated by oxide is 75wt%, and the content of structural auxiliary agent is 25wt%. The degree of crushing was 0.8% and the sphericity was 0.96.
Example 5
(1) Preparation of catalyst precursor
Slowly dissolving 15.54kg of cobalt nitrate hexahydrate and 9.50kg of titanium tetrachloride in 50L of deionized water, dissolving 30kg of ammonium carbonate in 60L of deionized water, and adding 14.97kg of ammonium molybdate and 1.10kg of ammonium metatungstate (containing WO) 3 91 wt%), slowly adding the molybdenum-tungsten solution into the mixed cobalt-titanium solution, continuously adding ammonium carbonate until the pH value of the solution is between 9.0 and 9.2, standing at room temperature after complete precipitation, aging for 12 hours, filtering, and washing twice by 80L deionized water;
(2) Pulping
Dispersing the filter cake into 120L of deionized water, stirring vigorously and pulping, adding 10.0kg of PEG4000 and 6.5kg of ammonium nitrate in sequence, and stirring and pulping for 2h at 30 ℃.
(3) Spray drying and forming
The slurry was formed by a Niro Bowen Nozzle power model spray dryer at a spray drying pressure of 7.0 to 8.0MPa, an inlet temperature below 480 ℃ and an outlet temperature of about 145 ℃. And roasting the catalyst in air at 480 ℃ for 4 hours to obtain the raspberry-shaped catalyst with the average particle size of about 120 mu m and the average cavity size of 40 mu m, which is marked as C5. The content of active components calculated by oxide is 75wt%, the content of structural auxiliary agent is 20wt%, and the content of other auxiliary agents is 5wt%. The degree of crushing was 0.5% and the sphericity was 0.95.
Example 6
(1) Catalyst precursor preparation
15.54kg of cobalt nitrate hexahydrate and 11.01kg of zirconium nitrate pentahydrate were slowly dissolved in 100L of deionized water, and 4.11kg of manganese nitrate solution (50 wt%) was added. Dissolving 30kg of ammonium carbonate in 60L of deionized water, adding 14.97kg of ammonium molybdate until the ammonium molybdate is completely dissolved, slowly adding the molybdenum solution into the mixed cobalt-zirconium-manganese solution, continuously adding the ammonium carbonate until the pH value of the solution is between 9.0 and 9.2, standing and aging at room temperature for 12 hours after complete precipitation, filtering, and washing twice with 80L of deionized water;
(2) Pulping
Dispersing the filter cake into 120L of deionized water, stirring vigorously and pulping, adding 10.0kg of PEG4000 and 6.5kg of ammonium nitrate in sequence, and stirring and pulping for 2h at 30 ℃.
(3) Spray drying and forming
The slurry was formed by a Niro Bowen non Nozzle Tower model spray dryer at a spray drying pressure of 7.0 to 8.0MPa, an inlet temperature of 480 ℃ or less and an outlet temperature of about 145 ℃. And roasting the catalyst in air at 480 ℃ for 4 hours to obtain the raspberry-shaped catalyst with the average particle size of about 120 mu m and the average cavity size of 40 mu m, which is marked as C6. The content of active components is 75wt% calculated by oxide, 20wt% of structural auxiliary agent and 5wt% of other auxiliary agent. The degree of crushing was 0.4% and the sphericity was 0.91.
Example 7
A mini-microchannel reactor (channel cross-section minimum dimension 1000 μm), mini-reactor module with 16 reaction channels and 36 cooling channels, reaction channel length 200mm, catalyst maximum loading 6mL. Evaluation of the catalyst with the larger part size was carried out under the same conditions in a fixed-bed microreactor having a diameter of 6 mm.
The specific operation comprises the following steps: taking 2.0ml of the catalyst, diluting with 4.0ml of 100-micron quartz sand, filling into a constant temperature area of a reactor, controlling the reaction pressure to be 2.5MPa, introducing 3.0vol% hydrogen sulfide hydrogen, gradually heating to 320 ℃, and feedingSulfurizing and activating, and introducing natural gas mixture of 20-40L/h at the temperature (for reaction space velocity of 10000) -1 ～20000h -1 ) Carrying out hydrodesulfurization reaction, wherein the content of COS in the reaction raw material is 200ppm, the content of hydrogen sulfide is 50ppm, the content of hydrogen is 1vol%, and the residual gas is methane. The tail gas composition analysis was performed by using a gas chromatograph equipped with a sulfur detector (SCD) to analyze the organic sulfur content and the organic sulfur desulfurization rate. The reaction results are shown in table 1.
It can be seen from the results of the above examples, comparative examples and table 1 that the hydrodesulfurization catalyst provided by the present invention can efficiently convert organic sulfur in natural gas at a high space velocity, and is suitable for microchannel reactors. The results show that the raspberry type microspherical particle catalyst provided by the embodiment of the invention is significantly superior to a comparative example in comprehensive performance of sphericity, strength and catalytic performance.
The research shows that the organic sulfur conversion efficiency can be greatly improved by regulating and controlling the composition and the morphological characteristics of the catalyst, and the high organic sulfur conversion rate can be still maintained even at a higher airspeed. And the catalyst has small particle size, can be suitable for a microchannel reactor, and can realize the miniaturization of equipment.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (19)
1. A natural gas hydrodesulfurization catalyst comprises raspberry type particles formed by an active component a, a structural auxiliary agent b and other auxiliary agents c, wherein the raspberry type particles are hollow microspheres with a large hole on the surface, hollow structures are arranged in the hollow microspheres, and the large hole is communicated with the hollow structures to form a cavity with one open end;
the metal elements of the active component a are Co and Mo; the structural auxiliary agent b is one or more selected from alumina, silica, titanium oxide and zirconia; the metal elements of the other auxiliary agents c are one or more selected from W, mn and Zn;
w based on the weight of the corresponding oxide a ：W b ：W c = (45 to 90): (10 to 50): (0 to 15) wherein W a Denotes the weight percentage of active component a based on the corresponding oxide, W, of the catalyst b Denotes the weight percentage of the structural auxiliary b based on the corresponding oxide in the catalyst, W c Represents the weight percentage of other auxiliary agents c in the corresponding oxides in the catalyst;
the size range of the catalyst is 60-600 mu m, and the size range of the cavity is 10-200 mu m;
the preparation method of the catalyst comprises the following steps:
(1) Uniformly dispersing soluble salts or colloidal particles of active components, soluble salts or colloidal particles of structural auxiliaries and soluble salts or colloidal particles of other auxiliaries into a solvent, and precipitating by using a precipitator to obtain a catalyst precursor;
(2) Mixing the catalyst precursor obtained in the step (1) with a pore-forming agent and/or an explosive to prepare slurry;
(3) Carrying out spray drying and forming on the slurry obtained in the step (2) to obtain the catalyst;
the blasting agent is selected from one or more of nitric acid, nitrate, picric acid, trinitrotoluene (TNT), nitroglycerin, nitrocotton, dana explosive, hexogen, lead azide and C4 plastic explosive;
the dosage of the pore-forming agent is 1.0-200.0% of the dry basis of the oxide, and the dosage of the blasting agent is 0.5-200.0% of the dry basis of the oxide.
2. The natural gas hydrodesulfurization catalyst of claim 1, wherein the active component is Co-Mo.
3. The natural gas hydrodesulfurization catalyst of claim 1, which isIn the formula (I), the composition of each component in terms of the corresponding oxide is W a ：W b ：W c =（45~85）：（15~45）：（0~10）。
4. The natural gas hydrodesulfurization catalyst of claim 1 wherein the catalyst has a size range of 80 to 500 μm and a cavity size range of 20 to 150 μm.
5. The natural gas hydrodesulfurization catalyst of any one of claims 1-4 wherein the natural gas hydrodesulfurization catalyst is used in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm.
6. The natural gas hydrodesulfurization catalyst of claim 1, wherein the soluble salts are selected from one or more of inorganic salts selected from one or more of chlorides, nitrates, acetates, sulfates and organic salts selected from metal alkoxides.
7. The natural gas hydrodesulfurization catalyst of claim 1 wherein the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactants.
8. The natural gas hydrodesulfurization catalyst of claim 7, wherein the synthetic cellulose is one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxy cellulosic fatty alcohol; the polymer alcohol is one or more of polyethylene glycol, polypropylene alcohol, polyvinyl alcohol and polypropylene alcohol; the surfactant is one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, acrylic acid copolymer with molecular weight of 200-20000 and maleic acid copolymer.
9. The natural gas hydrodesulfurization catalyst of claim 1 wherein the spray drying inlet air temperature is 400 to 1200 ℃; the air outlet temperature is 70 to 300 ℃.
10. The natural gas hydrodesulfurization catalyst of claim 9, wherein the spray drying inlet air temperature is from 450 ℃ to 700 ℃.
11. The natural gas hydrodesulfurization catalyst of claim 1, wherein the method comprises the step of further roasting after spray drying and forming, and the roasting temperature is 300-600 ℃; the baking time is 1 to 24h.
12. The natural gas hydrodesulfurization catalyst of claim 11, wherein the calcination temperature is from 350 to 500 ℃; the roasting time is 2 to 169h.
13. The natural gas hydrodesulfurization catalyst of claim 1, wherein the solvent is selected from water, an organic solvent, or a mixture of water and an organic solvent.
14. The natural gas hydrodesulfurization catalyst of claim 1 wherein the precipitant is a basic material selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, ammonium bicarbonate, and urea.
15. Use of a natural gas hydrodesulphurisation catalyst as defined in any one of claims 1 to 14 in catalysing the hydrodesulphurisation of natural gas.
16. A process for the hydrodesulfurization of natural gas which comprises:
activating a natural gas hydrodesulphurisation catalyst according to any one of claims 1-14 with sulphur-containing compounds,
and (3) introducing a feed gas into the reactor to contact with the activated catalyst to carry out hydrodesulfurization reaction, wherein the feed gas comprises hydrogen and natural gas containing organic sulfide.
17. The process of claim 16 wherein the hydrodesulfurization reaction is carried out in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm.
18. The method according to claim 16, wherein the content of organic sulfide in the feed gas is 1 to 600ppm; the reaction temperature is 280-360 ℃; the reaction pressure is 0.1MPa to 6MPa; the volume fraction of hydrogen in the feed gas is 0.5 to 20 percent; the volume space velocity of the feed gas is 1000h -1 ～50000h -1 。
19. The method according to claim 18, wherein the content of the organic sulfide in the feed gas is 10 to 500ppm; the reaction temperature is 300-340 ℃; the reaction pressure is 1 MPa-5 MPa; the volume fraction of hydrogen in the feed gas is 1.0 to 15 percent; the volume space velocity of the feed gas is 2000h -1 ～40000h -1 。
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| US4548912A (en) * | 1980-04-14 | 1985-10-22 | Ashland Oil, Inc. | Microspherical catalysts |
| CN1272398A (en) * | 1999-04-30 | 2000-11-08 | 北京海顺德钛催化剂有限公司 | Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application |
| CN108144613A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of fischer-tropsch synthetic catalyst of hollow microsphere shape and preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4548912A (en) * | 1980-04-14 | 1985-10-22 | Ashland Oil, Inc. | Microspherical catalysts |
| CN1272398A (en) * | 1999-04-30 | 2000-11-08 | 北京海顺德钛催化剂有限公司 | Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application |
| CN108144613A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of fischer-tropsch synthetic catalyst of hollow microsphere shape and preparation and application |
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