CN106669743A - 一种重整制氢催化剂及其制备方法 - Google Patents
一种重整制氢催化剂及其制备方法 Download PDFInfo
- Publication number
- CN106669743A CN106669743A CN201611177788.9A CN201611177788A CN106669743A CN 106669743 A CN106669743 A CN 106669743A CN 201611177788 A CN201611177788 A CN 201611177788A CN 106669743 A CN106669743 A CN 106669743A
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- Prior art keywords
- catalyst
- active component
- reforming hydrogen
- carrier
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000002407 reforming Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229950000845 politef Drugs 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 3
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 3
- 229940073769 methyl oleate Drugs 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 33
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 15
- 239000012047 saturated solution Substances 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229960004106 citric acid Drugs 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 238000001802 infusion Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种重整制氢催化剂及其制备方法，该催化剂以Ni、Fe、Cu、Zn、Ce、La或Co的金属氧化物中的一种或多种为活性组分，以NaCl、MgCl2、KCl、MgSO4、或Na2SO4中的一种为载体；以载体质量为基准，活性组分负载的质量百分含量为0.05～30％。其制备方法为浸渍法、柠檬酸络合法、溶胶凝胶法或超临界高温高压合成法，优选超临界高温高压合成法。本发明的催化剂适用于多种有机化合物的重整制氢反应，具有H2选择性高，使用寿命长、活性组分负载少、成本低、可再生等优点，应用前景广阔。本发明催化剂还可将地沟油等有机污染物转化为氢气，具有环境保护、变废为宝等重大社会和经济效益。
Description
技术领域：
本发明涉及一种重整制氢催化剂及其制备方法，属于新材料、工业催化和新能源技术领域。
背景技术：
随着全球性能源短缺和环境污染问题的日趋严峻，清洁能源的开发与利用迫在眉睫。氢气作为一种清洁、高效、可再生能源，正受到全球科研工作者的广泛关注。
商业制氢的工艺主要有电解水制氢、煤气化制氢和催化重整制氢三大类，其中催化重整制氢是最具发展潜力的制氢工艺之一。目前，催化重整制氢工艺的氢源主要是甲烷、乙醇、甲醇等，这些氢源本身具有可燃烧性，其能源转化途径并不具备附加值增益，因此，开发低品质有机物催化重整制氢技术具有变废为宝、高附加值等重大意义。催化剂是催化重整制氢工艺的核心。目前公开的催化剂主要是用于乙醇重整制氢反应。专利CN200610130277.1A公开了一种在三氧化二铝和二氧化硅复合载体上负载Ni基氧化物等活性组分的催化剂，300℃时乙醇转化率达到100％。不足的是催化剂的副产物CH4选择性较高。专利CN20061013084.7公开的以过渡金属混合氧化物为活性组分，以三氧化二铝与氧化镁为复合载体的催化剂，也具有较高的乙醇转化率，H2选择性达到60％。专利CN96100965.9A公开了一种将汽油转化成富氢气体的铂钯催化剂，催化剂的Ni含量为40～60％，制备的富氢气体中，氢气17％，甲烷62％。不足的是催化剂采用的贵金属成本较高，而且催化剂Ni含量偏高，氢气选择性偏低，CH4选择性高。专利CN01138906.0A公开了一种汽油氧化重整制氢催化剂，催化剂以RuO2为主催化成分，RuO2占催化剂总量的0.1-0.8wt％，以稀土元素的氧化物，碱土金属的氧化物，碱金属的氧化物之一种或多种为助催化成分，以Al2O3、ZrO2、TiO2、MgO、堇青石等的一种为催化剂载体。催化剂在820℃时，H2选择性达到1.5～1.7mol(H2+CO)/mol C。不足的是，反应温度偏高，选择性适中。因此，催化剂的设计目的在于提高催化剂的选择性，降低催化剂活性组分负载，提高催化剂的稳定性。
目前有机污染物，尤其是地沟油，其本身是会造成环境污染、危害人类身体健康的有害物质。因此，通过合适的工艺将其转化为具有高附加值的氢气，在经济、社会、环境领域均具有重大意义。因此，开发一种适用于地沟油重整制氢催化剂不仅能解决环境污染问题，还能促进能源的高效利用。
发明内容：
本发明的目的是为了改进现有技术的不足而提供一种重整制氢催化剂，本发明的另一目的是提供上述重整制氢催化剂的制备方法，并且创新性的将其应用于将地沟油、乙酸乙酯等有机化合物转化为富氢合成气。
本发明的技术方案为：一种重整制氢催化剂，其特征在于：催化剂以Ni、Fe、Cu、Zn、Ce、La或Co的金属氧化物中的一种或多种为活性组分，以NaCl、MgCl2、KCl、MgSO4、或Na2SO4中的一种为载体；以载体质量为基准，活性组分负载的质量百分含量为0.05～30％。
催化剂可通过浸渍法、柠檬酸络合法、溶胶凝胶法及超临界高温高压合成法制备，优选超临界高温高压合成法。
本发明所述的一种重整制氢催化剂，其制备方法包括浸渍法、柠檬酸络合法、溶胶凝胶法及超临界高温高压合成法，具体步骤为：
1)浸渍法：先按活性组分负载的质量百分含量0.05～30％，准确称取定量的Ni、或Fe、或Cu、或Zn、或Ce、或La、或Co的金属盐，滴加去离子水溶解配成饱和溶液；再称取定量的NaCl、MgCl2、KCl、MgSO4或Na2SO4中的一种，完全浸没于配制的饱和溶液中，采用恒温磁力搅拌器在20～90℃下搅拌10min～2h，使充分混匀；然后在60～120℃烘箱中烘干2～12h，500～800℃焙烧1～12h，得到目标催化剂；
2)柠檬酸络合法：先按活性组分负载的质量百分含量和活性组分金属元素摩尔比，准确称取一定量的Ni、或Fe、或Cu、或Zn、或Ce、或La、或Co的金属盐，定量的NaCl、MgCl2、KCl、MgSO4或Na2SO4中的一种，添加去离子水，配成饱和溶液；在恒温磁力搅拌器上搅拌并加热至60～90℃；按阳离子：柠檬酸摩尔比1：(0.5～2)加入定量的一水合柠檬酸；搅拌直至溶液变成凝胶；120～200℃烘干2～12h；500～800℃焙烧1～12h，得到目标催化剂；
3)溶胶凝胶法：先按活性组分负载的质量百分含量和活性组分金属元素摩尔比，准确称取一定量的Ni、或Fe、或Cu、或Zn、或Ce、或La、或Co的金属盐，定量的NaCl、MgCl2、KCl、MgSO4或Na2SO4中的一种，添加去离子水，配成饱和溶液；按拟薄水铝石与载体的质量比为(0.1～0.5)：1，称取一定质量的拟薄水铝石，加入溶液中，在恒温磁力搅拌器上搅拌并加热至60～90℃；滴加浓硝酸溶液，直至溶液透明形成胶体；80～150℃烘箱烘干2～12h成凝胶，500～800℃焙烧1～12h，得到目标催化剂；
本专利优选超临界高温高压合成法：优选超临界高温高压合成法的具体步骤为：先按活性组分负载的质量百分含量0.05～30％，准确称取Ni、Fe、Cu、Zn、Ce、La或Co的金属盐，和NaCl、MgCl2、KCl、MgSO4或Na2SO4中的一种，将上述原料混合后置于聚四氟乙烯消解罐中；按去离子水与载体的质量比为(0.01～0.5)：1，滴加去离子水；将消解罐密封不锈钢反应釜中，将反应釜置于120～250℃烘箱中保温6～24h；降温后取出，最后500～800℃焙烧1～12h，得到重整制氢催化剂。
优选所述的混合方式为研磨或球磨；优选上述的金属盐为可溶性的硝酸盐、硫酸盐、盐酸盐或醋酸盐。
本发明提供的上述的重整制氢催化剂可用于有机化合物重整制氢反应，适用的有机化合物的主要代表有：地沟油、油酸甲酯、乙酸乙酯、甲烷、甲醇、乙醇、丙烷、汽油、柴油或甘油。
有益效果：
1.创新地采用金属盐作为催化剂的载体，催化剂具有活性组分负载低、H2选择性高等优势；2.首次将地沟油、乙酸乙酯等有机化合物作为氢源，在催化剂作用下进行重整制氢反应制备氢气，能够同时解决环境污染和能源短缺问题；3.本发明催化剂制备工艺简单、成本低廉、催化效果好，具有较好的工业应用前景。
具体实施方式：
实施例1
浸渍法：先按活性组分负载的质量百分含量为1％，准确称取定量的硝酸镍粉体放于烧杯中，置于恒温磁力搅拌器上；滴加定量的去离子水，配成饱和溶液；再称取定量的MgCl2，浸没于上述饱和溶液中；打开磁力搅拌器，在20℃下搅拌20min，使充分混匀；然后将烧杯置于烘箱中80℃烘干4h，之后将干燥的粉末置于坩埚中，700℃焙烧12h；冷却后取出，得到目标催化剂。
实施例2
柠檬酸络合法：先按活性组分负载的质量百分含量为5％，准确称取定量的硫酸铁和氯化钠粉体放于烧杯中，添加去离子水，配成饱和溶液；打开恒温磁力搅拌器加热至90℃；按阳离子：柠檬酸摩尔比1:1加入定量的一水合柠檬酸，充分搅拌直至溶液标称凝胶；将上述凝胶120℃烘干12h；然后600℃焙烧6h，冷却后取出，得到目标催化剂。
实施例3
溶胶凝胶法：先按活性组分负载的质量百分含量为0.05％，准确称取定量的醋酸铜和氯化钾粉体放于烧杯中，添加去离子水，配成饱和溶液；打开恒温磁力搅拌器加热至90℃；按载体质量的30％称取定量的拟薄水铝石加入溶液中搅拌，然后滴加浓硝酸溶液直至液体透明形成胶体，搅拌2h；80℃，12h烘干成凝胶；最后800℃焙烧1h，冷却后取出，得到目标催化剂。
实施例4
超临界高温高压合成法：先按活性组分负载的质量百分含量为30％，准确称取一定量的氯化锌和硫酸镁粉体，球磨10min后放于聚四氟乙烯消解罐中，按去离子水与载体的质量比为0.5：1，加入适量的去离子水；将聚四氟乙烯消解罐密封于不锈钢反应釜中，120℃保温24h；降温后取出，然后800℃焙烧1h，冷却后取出，得到目标催化剂。
实施例5
浸渍法：先按活性组分负载的质量百分含量为10％和活性组分中金属元素摩尔比1：9，准确称取定量的硝酸铈和硝酸钴粉体放于烧杯中，置于恒温磁力搅拌器上；滴加定量的去离子水，配成饱和溶液；再称取定量的硫酸钠，浸没于上述饱和溶液中；打开磁力搅拌器，在50℃下搅拌10min，使充分混匀；然后将烧杯置于烘箱中60℃烘干12h，之后将干燥的粉末置于坩埚中，500℃焙烧5h；冷却后取出，得到目标催化剂。
实施例6
柠檬酸络合法：先按活性组分负载的质量百分含量为8％和活性组分中金属元素摩尔比5：5，准确称取定量的醋酸钴、醋酸铜和氯化钾粉体放于烧杯中，添加去离子水，配成饱和溶液；打开恒温磁力搅拌器加热至60℃；按阳离子：柠檬酸摩尔比1:0.5加入定量的一水合柠檬酸，充分搅拌直至溶液标称凝胶；将上述凝胶150℃烘干2h；然后500℃焙烧12h，冷却后取出，得到目标催化剂。
实施例7
溶胶凝胶法：先按活性组分负载的质量百分含量为12％和活性组分中金属元素摩尔比9：1，准确称取定量的硫酸锌、硫酸铁和氯化镁粉体放于烧杯中，添加去离子水，配成饱和溶液；打开恒温磁力搅拌器加热至60℃；按载体质量的50％称取定量的拟薄水铝石加入溶液中搅拌，然后滴加浓硝酸溶液直至液体透明形成胶体，搅拌2h；120℃，6h烘干成凝胶；最后900℃焙烧3h，冷却后取出，得到目标催化剂。
实施例8
超临界高温高压合成法：先按活性组分负载的质量百分含量为3％和活性组分中金属元素摩尔比3：7，准确称取一定量的硝酸镍、硝酸锌和氯化钠粉体，研磨30min后放于聚四氟乙烯消解罐中，按去离子水与载体的质量比为0.1：1，加入适量的去离子水；将聚四氟乙烯消解罐密封于不锈钢反应釜中，250℃保温6h；降温后取出，然后700℃焙烧4h，冷却后取出，得到目标催化剂。
实施例9
浸渍法：先按活性组分负载的质量百分含量为20％，准确称取定量的硝酸镧粉体放于烧杯中，置于恒温磁力搅拌器上；滴加定量的去离子水，配成饱和溶液；再称取定量的氯化钠，浸没于上述饱和溶液中；打开磁力搅拌器，在90℃下搅拌1h，使充分混匀；然后将烧杯置于烘箱中120℃烘干2h，之后将干燥的粉末置于坩埚中，800℃焙烧1h；冷却后取出，得到目标催化剂。
实施例10
柠檬酸络合法：先按活性组分负载的质量百分含量为15％，准确称取定量的氯化镍和硫酸镁粉体放于烧杯中，添加去离子水，配成饱和溶液；打开恒温磁力搅拌器加热至80℃；按阳离子：柠檬酸摩尔比1:2加入定量的一水合柠檬酸，充分搅拌直至溶液标称凝胶；将上述凝胶200℃烘干6h；然后800℃焙烧2h，冷却后取出，得到目标催化剂。
实施例11
溶胶凝胶法：先按活性组分负载的质量百分含量为0.5％，准确称取定量的氯化铜和硫酸钠粉体放于烧杯中，添加去离子水，配成饱和溶液；打开恒温磁力搅拌器加热至80℃；按载体质量的10％称取定量的拟薄水铝石加入溶液中搅拌，然后滴加浓硝酸溶液直至液体透明形成胶体，搅拌2h；120℃，6h烘干成凝胶；最后700℃焙烧6h，冷却后取出，得到目标催化剂。
实施例12
超临界高温高压合成法：先按活性组分负载的质量百分含量为6％，准确称取一定量的氯化镧和硫酸镁粉体球磨5h后放于聚四氟乙烯消解罐中，按去离子水与载体的质量比为0.01：1，加入适量的去离子水；将聚四氟乙烯消解罐密封于不锈钢反应釜中，180℃保温12h；降温后取出，然后500℃焙烧12h，冷却后取出，得到目标催化剂。
催化重整制氢性能：
实施例1～12的重整制氢性能在同一反应条件下的进行评价，实验条件为：催化剂3g，有机化合物：6ml/h，水：4ml/h，O2：10ml/min，预热温度300℃，反应温度300～750℃。
与现有技术相比，本发明提供的催化剂具有H2选择性高，氢源转化率较高，反应温度低等优点。
表1实施例样品的催化重整制氢性能
| 催化剂 | 氢源 | 温度/℃ | H2选择性/％ | 转化率/％ |
| 实施例1 | 甲烷 | 500 | 56.08 | 91 |
| 实施例2 | 甲醇 | 520 | 60.92 | 85 |
| 实施例3 | 乙醇 | 450 | 48.33 | 72 |
| 实施例4 | 丙烷 | 450 | 58.69 | 88 |
| 实施例5 | 乙酸乙酯 | 650 | 67.2 | 89 |
| 实施例6 | 地沟油 | 750 | 48.47 | 72 |
| 实施例7 | 油酸甲酯 | 750 | 61.29 | 80 |
| 实施例8 | 汽油 | 600 | 63.48 | 91 |
| 实施例9 | 柴油 | 600 | 58.66 | 74 |
| 实施例10 | 甘油 | 600 | 62.78 | 83 |
| 实施例11 | 地沟油酯 | 750 | 64.92 | 85 |
| 实施例12 | 乙酸乙酯 | 750 | 88.06 | 97 |
Claims (6)
1.一种重整制氢催化剂，其特征在于：催化剂以Ni、Fe、Cu、Zn、Ce、La或Co的金属氧化物中的一种或多种为活性组分，以NaCl、MgCl2、KCl、MgSO4、或Na2SO4中的一种为载体；以载体质量为基准，活性组分负载的质量百分含量为0.05～30％。
2.一种制备如权利要求1所述的重整制氢催化剂的方法，其具体步骤为：先按活性组分负载的质量百分含量0.05～30％，准确称取Ni、Fe、Cu、Zn、Ce、La或Co的金属盐，和NaCl、MgCl2、KCl、MgSO4或Na2SO4中的一种，将上述原料混合后置于聚四氟乙烯消解罐中；按去离子水与载体的质量比为(0.01～0.5)：1，滴加去离子水；将消解罐密封不锈钢反应釜中，将反应釜置于120～250℃烘箱中保温6～24h；降温后取出，最后500～800℃焙烧1～12h，得到重整制氢催化剂。
3.如权利要求2所述的方法，其特征在于：所述的金属盐为可溶性的硝酸盐、硫酸盐、盐酸盐或醋酸盐。
4.如权利要求2所述的方法，其特征在于：所述的混合方式为研磨或球磨。
5.如权利要求1所述的重整制氢催化剂在有机化合物重整制氢反应中的应用。
6.如权利要求5所述的应用，其特征在于：所述的有机化合物为地沟油、油酸甲酯、乙酸乙酯、甲烷、甲醇、乙醇、丙烷、汽油、柴油或甘油。
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| CN115069260A (zh) * | 2022-07-29 | 2022-09-20 | 南京工业大学 | 一种镍基分级多孔重整制氢催化剂及其制备方法和应用 |
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| CN114733535A (zh) * | 2022-04-01 | 2022-07-12 | 南京工业大学 | 一种可回收再造的钙钛矿型Ni基复合氧化物催化剂及其制备方法 |
| CN115069260A (zh) * | 2022-07-29 | 2022-09-20 | 南京工业大学 | 一种镍基分级多孔重整制氢催化剂及其制备方法和应用 |
| CN115069260B (zh) * | 2022-07-29 | 2023-05-05 | 南京工业大学 | 一种镍基分级多孔重整制氢催化剂及其制备方法和应用 |
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