CN113731385B - 固定床蒽醌法制双氧水用催化剂载体及催化剂的制备方法 - Google Patents
固定床蒽醌法制双氧水用催化剂载体及催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 22
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 5
- 239000001923 methylcellulose Substances 0.000 claims abstract description 5
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 26
- 239000004480 active ingredient Substances 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 241000219782 Sesbania Species 0.000 abstract 2
- 238000000748 compression moulding Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 11
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 239000002245 particle Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
本发明提供了一种固定床蒽醌法制双氧水用催化剂载体及催化剂的制备方法，载体包括按重量份计的以下原料：改性氧化铝粉100份；田箐粉或甲基纤维素中的一种，用量为8~15份；酸溶液1.9~4份、水100~140份。所述酸溶液包括有有机酸、硝酸和磷酸，用量比为1.3~2：0.1~1.0：0.5~1.0。制备时，将改性氧化铝粉与田箐粉或甲基纤维素混合，加入酸溶液混合均匀，经过碾压、压模成型，烘干、焙烧得到催化剂载体；将载体负载活性组份以及助剂，经还原、烘干、焙烧，得到催化剂成品。本发明制备得到的载体强度较高，催化剂具有较高的活性。
Description
技术领域
本发明涉及双氧水制备技术领域，具体涉及一种固定床蒽醌法制双氧水用催化剂载体及催化剂的制备方法。
背景技术
蒽醌法制双氧水的催化剂能促进反应过程、加快反应速度，而且提高反应效率和生产效率，得到了广泛应用。载体的制备和催化剂的制备也比较成熟。载体的孔结构，形状、工作液与催化剂接触面等，都会影响到催化剂的催化效果。现有的催化剂存在强度低，堆积密度高等问题。
发明内容
本发明提供一种固定床蒽醌法制双氧水用催化剂载体及催化剂的制备方法，该载体具有较高强度，催化剂具有较高的活性。
本发明的技术方案是，一种固定床蒽醌法制双氧水用催化剂载体，包括按重量份计的以下原料：改性氧化铝粉100份，扩孔剂8～15份，混酸1.9～4份、水100～140份；其中扩孔剂为田箐粉或甲基纤维素；混酸为有机酸、硝酸和磷酸按质量比1.3～2：0.1～1.0：0.5～1.0混合配制。
进一步地，所述改性氧化铝粉是将氧化铝用硝酸锆水溶液进行预处理，具体处理时，氧化铝和硝酸锆的水溶液按重量比1：3～8进行混合，60-80℃处理2-5小时，过滤烘干，粉碎成粉即得改性氧化铝粉。
进一步地，硝酸锆溶液的质量浓度为1-8％，后期烘干温度为110～120℃，粉碎后过200目筛。
进一步地，所述有机酸为草酸、丁二酸、乙酸、苹果酸、柠檬酸中的一种或者几种。
进一步地，载体成形为条形、球形、片状形、齿轮形或中孔齿轮形。其中，球形粒径为2.0～6.0mm；条形尺寸为(2.0～5.0)×2～10mm；片状形尺寸为(2～4)×2mm；齿轮形尺寸为2.5～5.0mm。
进一步地优选，载体成形为中孔齿轮形，其外径尺寸为￠(3-6)×6mm，中间孔洞尺寸为0.5-1.5mm。
本发明还涉及制备所述固定床蒽醌法制双氧水用催化剂载体的方法，具体步骤为：将改性氧化铝粉加入扩孔机混合均匀，然后加入混酸，碾压均匀；再进行成型，最后经烘干(温度为100～200℃)和600-900℃焙烧后得到固定床蒽醌法制双氧水用催化剂载体。
本发明还涉及采用所述载体制备的固定床蒽醌法制双氧水用催化剂，该载体中负载金属活性成分，负载量为载体质量的0.10％-5.0％，优选0.25％-5.0％；活性成分为钌、铑、钯、铂、铱中的任意一种或几种。活性组份的前体为对应的硝酸盐或碳酸盐或氯化物。
进一步地，所述催化剂中还负载有金属助剂，负载量为载体质量的0.02％-20％，助剂为镍、钼、钴、锰、锆、铜、锌、钍、钛、铁、镁中的至少两种。助剂的前体为对应的硝酸盐或碳酸盐或氯化物。
本发明还涉及制备所述催化剂的方法，具体步骤为：将载体负载有活性组份及助剂后的催化剂，用0.1-20％甲醛或水合肼或硼氢化钾还原后，于80-200℃烘干，400-800℃焙烧得到催化剂成品。
本发明具有以下有益效果：
1、本发明制备催化剂载体时，采用改性氧化铝粉为原料，氧化铝粉经过硝酸锆的处理，不仅发挥了锆具有活性助剂的作用，同时也通过氧化锆来提高载体的机械强度。通过扩孔剂的使用，增加后期催化剂与工作液的接触面积，提高孔容和孔径。将载体成型为中孔齿轮形，拓展了载体的表面积，增加了催化剂与工作液的接触面积，有利于提高催化剂的催化能力，同时可以防止载体的堆积密度过高，提供了强度高、堆重低的载体。
2、本发明载体制备时，加入了混酸；尤其是有机酸，利用其酸性柔和的特点，既可以起到粘结作用，同时可以改善催化剂粉化，防止活性组份的流失，延长催化剂的使用寿命。
3、制备催化剂过程中，通过助剂的合理使用，在提高催化剂的活性的同时，增加活性的稳定性。
4、本发明制备的催化剂用于固定床蒽醌法制双氧水的生产装置上，氢效可以达到8-11g/l，活性7-9KgH2O2100％/KgCat.d.。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。
以下实施例中所用到的改性氧化铝粉的制备：
将氧化铝用硝酸锆溶液进行预处理，硝酸锆溶液的质量浓度为6％，氧化铝和硝酸锆溶液按重量比1：5进行混合，70℃处理4小时，过滤，110～120℃烘干，粉碎后过200目筛，即得改性氧化铝粉。
所用的酸均为工业级。
实施例1：
1、载体制备
称取改性氧化铝粉1000g于混料机中，加田箐粉82g，开启混料机混匀；然后将10g柠檬酸、10g草酸、1g硝酸、6g磷酸混合，加水1000g制成混合酸液，加入到混料机中碾压均匀，取一部分挤条成￠3.5mm×(4-10)mm三叶草条，另一部分压合成￠3.0mm球形载体。然后在120℃烘干，900℃焙烧2小时，分别得到催化剂的载体A和载体B。
2、催化剂的制备
该250克载体A和250克载体B均负载金属活性成分和助剂，金属活性成分负载量为载体质量的0.3％，活性成分为硝酸钯和硝酸铱，硝酸钯和硝酸铱的质量比为5:1；助剂负载量为载体质量的5％，助剂为硝酸镍、硝酸锆和硝酸钍，三者的质量比为10:100:1。负载时将载体A、载体B分别投入上述溶液制备的中，浸渍20分钟，120℃烘干、400℃焙烧后得到催化剂A1、B1。
实施例2：
1、称取改性氧化铝粉1000g于混料机中，加甲基纤维素140g，开启混料机混匀；然后将23g柠檬酸、8g草酸、2g硝酸、5g磷酸混合，加水1000g制成混合酸液，加入到混料机中碾压均匀，压合成￠3.5mm齿轮形载体，于120℃烘干，850℃焙烧2小时，即可得到催化剂的载体C。
2、催化剂的制备
该载体C，250克负载金属活性成分和助剂，金属活性成分负载量为载体质量的0.3％，活性成分为氯化钯；助剂负载量为载体质量的3％，助剂为硝酸镍和硝酸锰，质量比为1:1。负载时将载体C投入采用上述金属活性成分和助剂制备的溶液中，浸渍40分钟，取出还原、烘干、焙烧后得到催化剂C1。
实施例3：
1)载体制备
称取改性氧化铝粉500g于混料机中，加田箐粉60g，开启混料机混匀；然后将4g丁二酸、8g柠檬酸、5g硝酸、3g磷酸混合，加水700g制成混合酸液，加入到混料机中碾压均匀，压成￠3.0×2mm片状载体，于120℃烘干，800℃焙烧3小时，即可得到催化剂的载体D。
2)该载体D，250克置于含有金属活性成分和助剂的溶液中进行负载，金属活性成分负载量为载体质量的0.3％，活性成分为氯化钯和硝酸铱；助剂负载量为载体质量的3％，助剂为醋酸钴和硝酸锰。浸渍负载时间为30分钟，取出还原、烘干、焙烧后得到催化剂D1。
实施例4：
1)载体制备
称取改性氧化铝粉1公斤于混料机中，加田箐粉120g，开启混料机；然后将20g苹果酸、4g硝酸、5g混合，加水1.2公斤制成混合酸液，加入到混料机中碾压均匀。碾合后压成￠4×6mm中孔￠1mm的中孔齿轮形载体，于120℃烘干，800℃焙烧3小时，即可得到催化剂的载体E。
2)催化剂的制备
该载体E，取250克置于含有金属活性成分和助剂的溶液中进行负载，金属活性成分负载量为载体质量的0.3％，活性成分为氯化钯和硝酸铱；助剂负载量为载体质量的5％，助剂为醋酸钴和硝酸锰。浸渍负载时间为30分钟，取出还原、烘干、焙烧后得到催化剂E1。
对比例1：
1)载体制备活性氧化铝粉滚球成型2.5-3.5毫米，50-150度密闭养生、烘干、800℃焙烧，得载体F。
2)催化剂制备
取250克载体F置于含有金属活性成分和助剂的溶液中进行负载，金属活性成分负载量为载体质量的0.3％，活性成分为氯化钯和硝酸铱；助剂负载量为载体质量的5％，助剂为醋酸钴和硝酸锰。浸渍负载时间为30分钟，取出还原、烘干、焙烧后得到催化剂F1。
对比例2：
1)载体制备
称取不作改性处理的氧化铝1公斤于混料机中，加田箐粉120g，开启混料机；然后将20g苹果酸、4g硝酸、5g磷酸混合，加水1.2公斤制成混合酸液，加入到混料机中碾压均匀。碾合后压成￠4×6mm中孔￠1mm的中孔齿轮形载体，于120℃烘干，800℃焙烧3小时，即可得到催化剂的载体G。
2)催化剂的制备
取250克该载体G置于含有金属活性成分和助剂的溶液中进行负载，金属活性成分负载量为载体质量的0.3％，活性成分为氯化钯和硝酸铱；助剂负载量为载体质量的5％，助剂为醋酸钴和硝酸锰。浸渍负载时间为30分钟，取出还原、烘干、焙烧后得到催化剂G1。
上述催化剂载体性能及催化剂性能见表1和表2。
表1
| 载体 | 强度N/颗 | 堆积密度g/ml | 比表面m2/g | 孔容cm3/g | 孔径nm |
| A | 168N/cm | 0.508 | 189.1325 | 0.6219 | 13.5747 |
| B | 42.6 | 0.461 | 181.3115 | 0.6779 | 13.8802 |
| C | 38.4 | 0.474 | 179.5744 | 0.6576 | 15.5113 |
| D | 42.6 | 0.451 | 177.8732 | 0.6489 | 14.3421 |
| E | 40.9 | 0.443 | 1795543 | 0.6473 | 14.5732 |
| F | 66.8 | 0.603 | 172.3578 | 0.5205 | 8.5441 |
| G | 36.2 | 0.437 | 175.3621 | 0.6338 | 14.762 |
表2
催化剂的活性7-9KgH2O2100％/KgCat.d，达到了预期。从催化剂的评价效果来分析，催化剂载体外表面与催化剂的活性有着正相关的关系。
Claims (8)
1.一种固定床蒽醌法制双氧水用催化剂载体，其特征在于，包括按重量份计的以下原料：改性氧化铝粉100份，扩孔剂8~15份，混酸1.9~4份、水100~140份；其中改性氧化铝粉是将氧化铝粉用硝酸锆溶液进行预处理，具体处理时，氧化铝粉和硝酸锆的水溶液按重量比1：3~8进行混合后，60-80℃处理2-5小时，过滤，110~120℃烘干，粉碎后过200目筛成粉即得；扩孔剂为田箐粉或甲基纤维素；混酸为有机酸、硝酸和磷酸按质量比1.3~2：0.1~1.0：0.5~1.0混合配制；
该催化剂载体制备时，将改性氧化铝粉加入扩孔剂混合均匀，然后加入混酸，碾压均匀；再进行成型，具体成型为条形、球形、片状形或齿轮形，最后经烘干和600-900℃焙烧后即得。
2.根据权利要求1所述的固定床蒽醌法制双氧水用催化剂载体，其特征在于：硝酸锆的水溶液质量浓度为1-8%。
3.根据权利要求1所述的固定床蒽醌法制双氧水用催化剂载体，其特征在于：所述有机酸为草酸、丁二酸、乙酸、苹果酸、柠檬酸中的一种或者几种。
4.根据权利要求1所述的固定床蒽醌法制双氧水用催化剂载体，其特征在于：所述齿轮形为中孔齿轮形。
5.根据权利要求4所述的固定床蒽醌法制双氧水用催化剂载体，其特征在于：载体成形为中孔齿轮形，其外径尺寸为￠3-6mm×6mm，中间孔洞尺寸为0.5-1.5mm。
6.采用权利要求1~5任意一项所述载体制备的固定床蒽醌法制双氧水用催化剂，其特征在于：该载体中负载金属活性成分，负载量为载体质量的0.10%-5.0%，活性成分为钌、铑、钯、铂、铱中的任意一种或几种。
7.根据权利要求6所述的催化剂，其特征在于：所述催化剂中还负载有金属助剂，负载量为载体质量的0.02%-20%，助剂为镍、钼、钴、锰、锆、铜、锌、钍、钛、铁、镁中的至少两种。
8.制备权利要求6或7所述催化剂的方法，其特征在于，具体步骤为：将载体负载有活性组份及助剂后的催化剂，用0.1-20%甲醛或水合肼或硼氢化钾还原后，于80-200℃烘干，400-800℃焙烧得到催化剂成品。
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