CN114073990A - 一种无需焙烧的铜基加氢催化剂制备方法 - Google Patents
一种无需焙烧的铜基加氢催化剂制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 title abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 24
- 229910052802 copper Inorganic materials 0.000 title abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title description 6
- 239000007789 gas Substances 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000002161 passivation Methods 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 229910002651 NO3 Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 nitrate ions Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 238000003483 aging Methods 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 20
- 238000006386 neutralization reaction Methods 0.000 description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 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 4
- 238000005516 engineering process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 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 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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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
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Abstract
本发明属于催化材料制备技术领域，具体涉及一种无需焙烧的铜基催化剂制备方法：铜基催化剂采用共沉淀法制备，将含有铜及其它助剂的可溶性盐水溶液与可溶性碳酸盐水溶液混合，控制温度和pH值，得到沉淀，沉淀经过老化、洗涤和干燥后，置于加热炉中，在含有氢气的混合气体中进行还原处理，然后在含有氧气的混合气体中进行钝化处理，最后成型，得到催化剂。本发明方法制备的铜基催化剂活性组分分散度高，晶粒尺寸小，活性和稳定性好；催化剂中碳酸盐含量低，尾气中碳氧化物含量低；催化剂制备过程中碳氧化物排放小，可富产低浓度甲醇水溶液。
Description
技术领域
本发明属于催化材料制备技术领域，具体涉及一种无需焙烧的铜基加氢催化剂制备方法。
背景技术
铜基催化剂作为优异的加氢、脱氢催化剂，被广泛应用于石油化工、有机化工、煤化工、环保等催化转化技术领域，如用作甲醇合成催化剂、醛（酮）加氢催化剂、醇脱氢催化剂、变换催化剂等等。铜基催化剂的制备方法决定了最终催化剂的微观组成、物化结构和特定性质，进而直接影响其催化剂性能的发挥。目前，工业用含铜催化剂大都采用共沉淀法制备，用廉价的碳酸盐或氢氧化物作为沉淀剂，因此，焙烧过程是目前工业用铜基催化剂必不可少的催化剂处理单元。焙烧过程决定着催化剂的孔结构、比表面积、活性组分分散度以及活性组分与助剂、载体之间的相互作用的形成，从这个角度考虑，焙烧过程又是十分关键的处理单元。工业上焙烧催化剂是在空气气氛下进行的，为了保证大部分碳酸盐分解，铜基催化剂焙烧温度一般要高于350℃。由于铜基催化剂的热稳定性较差，焙烧过程温度和时间如控制不当极易引起催化剂的烧结，进而影响铜基催化剂的活性和稳定性。因此，开发一种无需焙烧处理的铜基催化剂制备方法具有重要的现实意义。
发明内容
发明目的：本发明的目的是针对焙烧过程对铜基催化剂性能的不利影响的问题，提出一种无需焙烧的铜基催化剂制备方法，抑制铜基催化剂在制备过程中引起的烧结。
本发明的主要特点是通过控制催化剂还原和钝化条件，实现催化剂的活化，同时在较低的温度下完成前驱体碳酸盐的完全分解，无需额外的焙烧环节。
技术方案：本发明目的通过下述技术方案实现：
本发明提供一种无需焙烧的铜基催化剂制备方法，铜基催化剂采用共沉淀法制备，将含有铜及其它助剂的可溶性盐水溶液与可溶性碳酸盐水溶液混合，控制温度和pH值，得到沉淀，沉淀经过老化、洗涤和干燥后，置于加热炉中，在含有氢气的混合气体中进行还原处理，然后在含有氧气的混合气体中进行钝化处理，最后成型，得到催化剂。
一般地，铜基催化剂中Cu元素的质量百分含量为10%~60%。
所述可溶性碳酸盐为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵和碳酸氢氨中的一种。
所述控制温度在25℃~80℃；pH值在6.8~9.0。
所述洗涤，每次用为滤饼3倍体积的去离子水进行洗涤，洗涤至洗涤液中钠离子低于100ppm，硝酸根离子低于10ppm。
所述含有氢气的混合气体为，除氢气之外，还含有氮气、氦气、氩气中的一种，氢气的体积含量为5%~30%。
所述还原处理温度为150℃~250℃；含有氢气的混合气空速为2000h-1~20000h-1。
所述含有氧气的混合气体为，除了氧气之外，还含有氮气、氦气、氩气中的一种，氧气的体积含量为0.5%~5%。
所述钝化处理温度为25℃~60℃；含有氧气的混合气空速为1000h-1~5000h-1。
所述还原处理，尾气经过水吸收，得到甲醇水溶液。
有益效果：
本发明方法制备的铜基催化剂活性组分分散度高，晶粒尺寸小，活性和稳定性好；催化剂中碳酸盐含量低，用于脱氢反应中时尾气中碳氧化物含量低；催化剂制备过程中碳氧化物排放小，可富产低浓度甲醇水溶液。
具体实施方式
以下的实施例用于进一步解释本发明的内容，并不是对本发明的限制。
实施例1
取0.4mol硝酸铜、0.5mol硝酸锌和1.1mol硝酸铝溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液并预热至50℃；配制1mol/L碳酸钠水溶液并预热至50℃；将混合硝酸盐溶液和碳酸钠水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为6.8；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为80ppm，硝酸根离子为5ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至加热炉中进行还原处理。加热炉气氛为含氢气5%的氢气-氮气混合气，混合气空速为2000h-1，加热炉以5℃/min的升温速率从室温升至200℃，然后在200℃下维持30min后，降温至25℃，整个还原处理过程尾气采用水吸收后排空，得到稀甲醇水溶液。然后将气氛切换为含氧气0.5%的氧气-氮气混合气进行钝化处理，混合气空速为1000h-1，维持30min。钝化处理后，进行打片成型，制得φ5×5mm圆柱型催化剂C1。
实施例2
取0.2mol硝酸铜、0.6mol硝酸锌、1.0mol硝酸铝和0.2mol硝酸锆溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液；配制1mol/L碳酸钠水溶液；将混合硝酸盐溶液和碳酸钠水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为7.0；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为90ppm，硝酸根离子为8ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至加热炉中进行还原处理。加热炉气氛为含氢气10%的氢气-氮气混合气，混合气空速为5000h-1，加热炉以5℃/min的升温速率从室温升至150℃，然后在150℃下维持60min后，降温至25℃，整个还原处理过程尾气采用水吸收后排空，得到稀甲醇水溶液。然后将气氛切换为含氧气1.0%的氧气-氮气混合气进行钝化处理，混合气空速为1500h-1，维持10min。钝化处理后，进行打片成型，制得φ5×5mm圆柱型催化剂C2。
实施例3
取0.6mol硝酸铜、0.4mol硝酸锌和1.0mol硝酸铝溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液；配制1mol/L碳酸氢钠水溶液；将混合硝酸盐溶液和碳酸氢钠水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为7.5；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为70ppm，硝酸根离子为6ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至加热炉中进行还原处理。加热炉气氛为含氢气15%的氢气-氮气混合气，混合气空速为10000h-1，加热炉以5℃/min的升温速率从室温升至230℃，然后在230℃下维持10min后，降温至25℃，整个还原处理过程尾气采用水吸收后排空，得到稀甲醇水溶液。然后将气氛切换为含氧气2.0%的氧气-氮气混合气进行钝化处理，混合气空速为2000h-1，维持5min。钝化处理后，进行打片成型，制得φ5×5mm圆柱型催化剂C3。
实施例4
取0.8mol硝酸铜、0.2mol硝酸锌、0.8mol硝酸铝和0.2mol硝酸镁溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液并预热至80℃；配制1mol/L碳酸钾水溶液并预热至80℃；将混合硝酸盐溶液和碳酸钾水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为8.0；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为85ppm，硝酸根离子为9ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至加热炉中进行还原处理。加热炉气氛为含氢气20%的氢气-氮气混合气，混合气空速为12000h-1，加热炉以5℃/min的升温速率从室温升至250℃，然后在250℃下维持5min后，降温至25℃，整个还原处理过程尾气采用水吸收后排空，得到稀甲醇水溶液。然后将气氛切换为含氧气3%的氧气-氮气混合气进行钝化处理，混合气空速为3000h-1，维持5min。钝化处理后，进行打片成型，制得φ5×5mm圆柱型催化剂C4。
实施例5
取1.0mol硝酸铜、0.2mol硝酸锌和0.8mol硝酸铝溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液；配制1mol/L碳酸氢钾水溶液；将混合硝酸盐溶液和碳酸氢钾水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为8.0；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为92ppm，硝酸根离子为7ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至加热炉中进行还原处理。加热炉气氛为含氢气25%的氢气-氮气混合气，混合气空速为18000h-1，加热炉以5℃/min的升温速率从室温升至250℃，然后在250℃下维持5min后，降温至25℃，整个还原处理过程尾气采用水吸收后排空，得到稀甲醇水溶液。然后将气氛切换为含氧气4%的氧气-氮气混合气进行钝化处理，混合气空速为4000h-1，维持5min。钝化处理后，进行打片成型，制得φ5×5mm圆柱型催化剂C5。
实施例6
取1.2mol硝酸铜、0.2mol硝酸锌、0.4mol硝酸铝和0.2mol硝酸铈溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液；配制1mol/L碳酸铵水溶液；将混合硝酸盐溶液和碳酸铵水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为8.5；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为85ppm，硝酸根离子为6ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至加热炉中进行还原处理。加热炉气氛为含氢气30%的氢气-氮气混合气，混合气空速为20000h-1，加热炉以5℃/min的升温速率从室温升至250℃，然后在250℃下维持5min后，降温至25℃，整个还原处理过程尾气采用水吸收后排空，得到稀甲醇水溶液。然后将气氛切换为含氧气5%的氧气-氮气混合气进行钝化处理，混合气空速为5000h-1，维持5min。钝化处理后，进行打片成型，制得φ5×5mm圆柱型催化剂C6。
实施例7
取1.2mol硝酸铜、0.2mol硝酸锌、0.4mol硝酸铝和0.2mol硝酸铈溶于去离子水，配成总盐浓度为1mol/L的混合硝酸盐溶液并预热至25℃；配制1mol/L碳酸铵水溶液并预热至25℃；将混合硝酸盐溶液和碳酸铵水溶液并流加入到盛有200mL去离子水的中和桶中并不断搅拌，控制桶中溶液pH值为8.5；中和结束后用去离子水洗涤滤饼，每次用水量为滤饼体积的3倍，洗涤至洗涤液中钠离子浓度为85ppm，硝酸根离子为6ppm结束洗涤；将洗涤好的滤饼放在干燥箱中于100℃下干燥10h后，转移至马弗炉中焙烧。马弗炉气氛为空气，空气空速为20000h-1，加热炉以5℃/min的升温速率从室温升至350℃，然后在350℃下维持30min后，降温至25℃，整个焙烧处理过程尾气排空；然后进行打片成型，制得φ5×5mm圆柱型催化剂C-1。
实施例8
将催化剂C1、C2、C3、C6和C-1五个催化剂用于甲醇合成反应中，甲醇合成反应在不锈钢固定床反应器中进行，反应管内径为35mm，催化剂填装量为50mL。还原条件：还原气为含氢气体积分数为5%的氢气-氮气混合气，空速为1000h-1，还原温度为250℃，常压，还原时间为4h。甲醇合成反应条件：合成气体积组成为5%CO2、15%CO、65%H2，余量为N2；空速为10000h-1；温度为250℃；压力为5MPa。反应结果见表1所示。
实施例9
将催化剂C4、C5、C6和C-1四个催化剂用于环己醇脱氢制环己酮反应中，环己醇脱氢反应在不锈钢固定床反应器中进行，反应管内径为35mm，催化剂填装量为50mL。还原条件：还原气为含氢气体积分数为5%的氢气-氮气混合气，空速为1000h-1，还原温度为220℃，常压，还原时间为4h。环己醇脱氢反应条件：环己醇空速为0.8h-1，反应温度为220℃；常压。反应结果见表2所示。
表1 催化剂在甲醇合成反应中的催化效果
| 催化剂 | 还原态催化剂Cu晶粒尺寸（nm） | CO转化率（%） | CO<sub>2</sub>转化率（%） | 甲醇选择性（%） | 乙醇含量（ppm） |
| C1 | 10 | 65.5 | 55.9 | 99.2 | 500 |
| C2 | 9 | 68.9 | 61.2 | 99.7 | 310 |
| C3 | 12 | 69.9 | 68.1 | 99.8 | 240 |
| C6 | 8 | 68.4 | 67.1 | 99.4 | 380 |
| C-1 | 15 | 55.2 | 45.9 | 98.7 | 1100 |
表2 催化剂在环己醇脱氢制环己酮反应中的催化效果
| 催化剂 | 环己醇转化率（%） | 环己酮选择性（%） | 重组分含量（ppm） | 尾氢中COx含量（ppm） |
| C4 | 51.4 | 99.5 | 260 | 9 |
| C5 | 52.6 | 99.5 | 310 | 8 |
| C6 | 53.8 | 99.7 | 280 | 9 |
| C-1 | 49.6 | 98.8 | 1000 | 85 |
从表1数据可以看出，与传统技术比较，采用本发明技术制备的铜基催化剂具有活性组分Cu晶粒尺寸小的优势，在甲醇合成反应中具有优越的催化性能，催化剂活性、选择性以及对重要杂质的控制能力都显著增强。从表2数据同样能够看出，本专利技术制备的催化剂较传统方法催化剂，在环己醇脱氢制环己酮反应中具有明显的优势，除了具有较高的活性和环己酮选择性之外，重组分含量大大降低，尾氢中的COx含量大大降低，从而保证了尾氢的纯度和使用要求，尤其是对氢气中CO含量有高要求的加氢反应中，本专利技术的优势更加明显。
Claims (10)
1.一种无需焙烧的铜基加氢催化剂制备方法，其特征在于铜基催化剂采用共沉淀法制备，将含有铜及其它助剂的可溶性盐水溶液与可溶性碳酸盐水溶液混合，控制温度和pH值，得到沉淀，沉淀经过老化、洗涤和干燥后，置于加热炉中，在含有氢气的混合气体中进行还原处理，然后在含有氧气的混合气体中进行钝化处理，最后成型，得到催化剂。
2.根据权利要求1所述的制备方法，其特征在于所述铜基催化剂中Cu元素占金属阳离子物质的量的百分含量为10%~60%。
3.根据权利要求1所述的制备方法，其特征在于所述可溶性碳酸盐为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵和碳酸氢铵中的一种。
4.根据权利要求1所述的制备方法，其特征在于控制温度在25℃~80℃；pH值在6.8~9.0。
5.根据权利要求1所述的制备方法，其特征在于所述洗涤，每次用为滤饼3倍体积的去离子水进行洗涤，洗涤至洗涤液中钠离子低于100ppm，硝酸根离子低于10ppm。
6.根据权利要求1所述的制备方法，其特征在于所述含有氢气的混合气体为，除氢气之外，还含有氮气、氦气、氩气中的一种，氢气的体积含量为5%~30%。
7.根据权利要求1所述的制备方法，其特征在于所述还原处理温度为150℃~250℃；含有氢气的混合气空速为2000h-1~20000h-1。
8.根据权利要求1所述的制备方法，其特征在于所述含有氧气的混合气体为，除了氧气之外，还含有氮气、氦气、氩气中的一种，氧气的体积含量为0.5%~5%。
9.根据权利要求1所述的制备方法，其特征在于所述钝化处理温度为25℃~60℃；含有氧气的混合气空速为1000h-1~5000h-1。
10.根据权利要求1所述的制备方法，其特征在于所述还原处理，尾气经过水吸收，得到甲醇水溶液。
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