CN111036216B - 通过高温焙烧得到高性能甲醇合成催化剂的方法 - Google Patents
通过高温焙烧得到高性能甲醇合成催化剂的方法 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 124
- 239000012298 atmosphere Substances 0.000 claims abstract description 46
- 239000003381 stabilizer Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 66
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 4
- 241001424392 Lucia limbaria Species 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 34
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 230000032683 aging Effects 0.000 description 13
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
- B01J23/80—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 zinc, cadmium or mercury
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
本发明涉及一种甲醇合成催化剂的制备方法,属于催化技术领域。包括以下步骤:a)采用共沉淀法制备得到含有铜、锌的碳酸盐混合物;b)碳酸盐混合物经过洗涤、干燥、焙烧后得到前驱体1;c)将前驱体1浸没在稳定剂溶液中处理后,移至惰性气氛保护炉中焙烧得到前驱体2;然后将前驱体2在空气中焙烧得到前驱体3;d)将前驱体3与载体混合后得到前驱体4,将前驱体4成型后得到甲醇合成催化剂。本发明方法制备得到的甲醇合成催化剂与传统方法相比较,铜晶粒尺寸小、甲醇时空收率高,粗醇中甲酸甲酯含量低,催化剂热稳定性高。
Description
技术领域
本发明属于催化技术领域,具体涉及一种甲醇合成催化剂的制备方法。
背景技术
随着MTO、MTP、MTA和MTG,以及作为新能源汽车制氢的原料等甲醇下游产品技术的迅速发展,带动了整个甲醇行业的大发展,同时也推动了大甲醇技术的开发热潮。甲醇合成催化剂是甲醇生产的核心技术,随着甲醇合成原料气、工艺和产品甲醇的具体应用要求,对甲醇合成催化剂提出了诸多苛刻要求,其中,甲醇合成催化剂需要持续改进的不足中,提高甲醇合成催化剂的热稳定性,主要是提高活性组分金属铜的抗烧结性能是至关重要的,一些相关研究也陆续被报道。
中国专利CN102950001A公开了一种耐高温甲醇催化剂及其制备方法,由铜锌氧化物作为活性组分,由碱土金属改性的氧化铝作为载体,由碱土金属和稀土金属氧化物作为稳定剂,采用分步沉淀、打浆的方法制备而成。
中国专利CN106390978A公开了一种耐高温二氧化碳加氢合成甲醇催化剂及其制备和应用方法,催化剂标记为AOxBOy,其中A为Zn、Cd、In,B为Zr、Cr。在5MPa、330℃、24000mL/g/h条件下,ZnOZrO2催化剂上甲醇选择性可达80%。
中国专利CN106540700A公开了一种耐高温甲醇催化剂的制备方法,以富铝型尖晶石作为载体,铜锌氧化物作为活性母体,采用分步沉淀、打浆的方法制得催化剂。
综上,现有技术在解决甲醇合成催化剂稳定性问题时,主要从两个方面入手,一是引入助剂和提高载体性能,从而提高活性组分,主要是铜元素的分散度,进而一定程度抑制在热(或热和水汽共存)驱使下铜的烧结长大;二是用热稳定性较好的氧化物替代活性组分铜,克服铜易热烧结失活的不足。前者能够起到一定程度的积极作用,但由于组分较多,给催化剂产品的均匀性和质量稳定性提出了较高的要求。此外,由于组分较多,存在诸多协同效应,对催化剂机理以及元素组成对催化剂性能的影响的分析,以及基于这些分析结果,指导催化剂更新换代等一系列深入、系统的研究带来了复杂性。后者的确可以起到提高催化剂耐热性能的作用,甲醇选择性也基本可以满足生产要求,但催化剂的活性较低,原料单程转化率低,在生产中需要加大循环量才能满足产能要求,能量消耗较大,经济性较差。
发明内容
本发明的目的是提供一种甲醇时空收率高、粗醇中甲酸甲酯含量低、热稳定性好的甲醇合成催化剂。
本发明的主要特点是利用稳定剂的特殊结构对催化剂活性位的保护作用,提高催化剂热处理过程的稳定性。
本发明一种甲醇合成催化剂的制备方法包括以下步骤:a)采用共沉淀法制备得到含有铜、锌的碳酸盐混合物;b)碳酸盐混合物经过洗涤、干燥、焙烧后得到前驱体1;c)将前驱体1浸没在稳定剂溶液中处理后,移至惰性气氛保护炉中焙烧得到前驱体2;然后将前驱体2在空气中焙烧得到前驱体3;d)将前驱体3与载体混合后得到前驱体4,将前驱体4成型后得到甲醇合成催化剂。
一般地,a)步骤中,所述共沉淀法沉淀剂为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵、碳酸氢铵中的一种水溶液。
b)步骤中,所述干燥的温度为90~120℃,干燥时间为4~10h;焙烧温度为250~400℃,焙烧时间为0.5~1h。
c)步骤中,所述稳定剂结构为:
其中,(CH2)n中的n=1~6。
c)步骤中,所述稳定剂溶液的pH=7.5~9.0。
c)步骤中,所述的稳定剂溶液中处理的温度为20~50℃,时间为4~30h。
c)步骤中,所述的惰性气氛包括氮气、氩气、氦气中的一种。
c)步骤中,所述焙烧为首先在100℃下处理2h,然后在温度400~1000℃下处理1~10h。
c)步骤中,所述空气中焙烧温度为500~800℃,焙烧时间为2~6h。
d)步骤中,所述载体包含氧化铝、氧化锆、氧化钛、氧化硅、分子筛中的至少一种。
本发明方法制备得到的甲醇合成催化剂与传统方法相比较,铜晶粒尺寸小、甲醇时空收率高,粗醇中甲酸甲酯含量低,催化剂热稳定性高。
具体实施方式
以下的实施例仅用于进一步解释本发明的内容和效果,而不是对本发明的限制。
实施例1
称取3mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将0.5mol/L碳酸钠溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于90℃下干燥10h,再在空气气氛中于250℃下焙烧1h,得到前驱体1;配制1L 1mol/L的稳定剂溶液B(稳定剂分子中n=1,溶剂为水/乙醇体积比=1/1),用1mol/L碳酸钠溶液调节B的pH=7.5,在20℃下将前驱体1浸没在B中30h,然后置于惰性气氛保护炉中,在氮气气氛下,先在100℃下处理2h,然后在400℃下处理10h,得到前驱体2,将前驱体2在空气气氛中在500℃下焙烧6h得到前驱体3;将前驱体3与0.5mol氧化铝粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat1。
实施例2
称取2mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢钠溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于100℃下干燥6h,再在空气气氛中于350℃下焙烧40min,得到前驱体1;配制1L0.5mol/L的稳定剂溶液B(稳定剂分子中n=1,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=8,在25℃下将前驱体1浸没在B中20h,然后置于惰性气氛保护炉中,在氮气气氛下,先在100℃下处理2h,然后在500℃下处理6h,得到前驱体2,将前驱体2在空气气氛中在600℃下焙烧4h得到前驱体3;将前驱体3与0.5mol氧化铝粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat2。
实施例3
称取1mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢钠溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L0.5mol/L的稳定剂溶液B(稳定剂分子中n=2,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=8.5,在30℃下将前驱体1浸没在B中10h,然后置于惰性气氛保护炉中,在氮气气氛下,先在100℃下处理2h,然后在600℃下处理5h,得到前驱体2,将前驱体2在空气气氛中在600℃下焙烧6h得到前驱体3;将前驱体3与0.5mol氧化铝粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat3。
实施例4
称取1mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸钾溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L0.5mol/L的稳定剂溶液B(稳定剂分子中n=2,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=8.5,在40℃下将前驱体1浸没在B中8h,然后置于惰性气氛保护炉中,在氩气气氛下,先在100℃下处理2h,然后在700℃下处理4h,得到前驱体2,将前驱体2在空气气氛中在700℃下焙烧4h得到前驱体3;将前驱体3与0.5mol氧化锆粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat4。
实施例5
称取3mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢钾溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于100℃下干燥6h,再在空气气氛中于350℃下焙烧30min,得到前驱体1;配制1L0.1mol/L的稳定剂溶液B(稳定剂分子中n=3,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=9,在50℃下将前驱体1浸没在B中4h,然后置于惰性气氛保护炉中,在氩气气氛下,先在100℃下处理2h,然后在800℃下处理3h,得到前驱体2,将前驱体2在空气气氛中在800℃下焙烧2h得到前驱体3;将前驱体3与0.5mol氧化锆粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat5。
实施例6
称取1mol硝酸铜和2mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸钾溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L 2mol/L的稳定剂溶液B(稳定剂分子中n=2,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=8.5,在45℃下将前驱体1浸没在B中8h,然后置于惰性气氛保护炉中,在氩气气氛下,先在100℃下处理2h,然后在900℃下处理2h,得到前驱体2,将前驱体2在空气气氛中在800℃下焙烧3h得到前驱体3;将前驱体3与0.5mol氧化钛粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat6。
实施例7
称取3mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸铵溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L0.5mol/L的稳定剂溶液B(稳定剂分子中n=4,溶剂为水/乙醇体积比=1/1),用1mol/L碳酸钠溶液调节B的pH=8.5,在45℃下将前驱体1浸没在B中8h,然后置于惰性气氛保护炉中,在氦气气氛下,先在100℃下处理2h,然后在1000℃下处理1h,得到前驱体2,将前驱体2在空气气氛中在800℃下焙烧3h得到前驱体3;将前驱体3与0.5mol氧化钛粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat7。
实施例8
称取3mol硝酸铜和2mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将0.5mol/L碳酸氢铵溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L0.2mol/L的稳定剂溶液B(稳定剂分子中n=5,溶剂为水/乙醇体积比=1/1),用1mol/L碳酸钠溶液调节B的pH=8.5,在50℃下将前驱体1浸没在B中6h,然后置于惰性气氛保护炉中,在氦气气氛下,先在100℃下处理2h,然后在800℃下处理2h,得到前驱体2,将前驱体2在空气气氛中在500℃下焙烧3h得到前驱体3;将前驱体3与1mol氧化钛粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat8。
实施例9
称取3mol硝酸铜和2mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢铵溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L0.4mol/L的稳定剂溶液B(稳定剂分子中n=6,溶剂为水/乙醇体积比=1/1),用1mol/L碳酸铵溶液调节B的pH=8.5,在50℃下将前驱体1浸没在B中6h,然后置于惰性气氛保护炉中,在氦气气氛下,先在100℃下处理2h,然后在800℃下处理2h,得到前驱体2,将前驱体2在空气气氛中在500℃下焙烧3h得到前驱体3;将前驱体3与1mol氧化硅粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat9。
实施例10
称取3mol硝酸铜和2mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢铵溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于120℃下干燥4h,再在空气气氛中于400℃下焙烧30min,得到前驱体1;配制1L1mol/L的稳定剂溶液B(稳定剂分子中n=2,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=9,在50℃下将前驱体1浸没在B中6h,然后置于惰性气氛保护炉中,在氦气气氛下,先在100℃下处理2h,然后在800℃下处理2h,得到前驱体2,将前驱体2在空气气氛中在500℃下焙烧3h得到前驱体3;将前驱体3与1mol ZSM-5分子筛粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat10。
对比例1
称取2mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢钠溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于100℃下干燥6h,再在空气气氛中于350℃下焙烧40min,得到前驱体1;将前驱体1与0.5mol氧化铝粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat2-1。
对比例2
称取2mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢钠溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于100℃下干燥6h,再在空气气氛中于350℃下焙烧40min,得到前驱体1;配制1L0.5mol/L的稳定剂溶液B(稳定剂分子中n=1,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=8,在25℃下将前驱体1浸没在B中20h,然后置于空气中,先在100℃下处理2h,然后在500℃下处理6h,得到前驱体2;将前驱体2与0.5mol氧化铝粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat2-2。
对比例3
称取2mol硝酸铜和1mol硝酸锌溶于水配制成铜锌总离子浓度为1mol/L的水溶液A,将1mol/L碳酸氢钠溶液与A在60℃下并流加入到含有500mL的制样桶中并不断剧烈搅拌,维持桶中溶液pH=7.5,沉淀结束并老化后,得到碳酸盐混合物;碳酸盐混合物用去离子水洗涤后,于100℃下干燥6h,再在空气气氛中于350℃下焙烧40min,得到前驱体1;配制1L0.5mol/L的稳定剂溶液B(稳定剂分子中n=1,溶剂为水),用1mol/L碳酸钠溶液调节B的pH=8,在25℃下将前驱体1浸没在B中20h,然后置于惰性气氛保护炉中,在氮气气氛下,先在100℃下处理2h,然后在500℃下处理6h,得到前驱体2;将前驱体2与0.5mol氧化铝粉末充分混合,加入质量为0.2%的石墨,进行打片,得到φ5×5mm催化剂Cat2。
催化剂性能评价方法为:在固定床反应器中(反应管内径为32mm),装填催化剂50mL,催化剂首先在含5vol.%H2的H2/N2混合气中于230℃下还原3h,然后调至反应温度,将还原气切换成空速为10000h-1的原料气(CO/CO2/N2/H2=16/7/8.0/69)进行反应,反应压力为5MPa,反应10h后进行产物分析得到初始性能;然后将至常压,升温至450℃保持5h后,恢复初活性时的评价条件,反应10h后进行产物分析得到耐热后性能,结果见表1所示。
表1 催化剂评价结果
从上表可以看出,本发明专利技术制得的甲醇合成催化剂与传统方法(Cat2-1制法)比较,还原后催化剂中铜晶粒尺寸明显减小,初始性能和耐热后性能甲醇时空收率都很大程度提高,并且耐热后铜晶粒尺寸和甲醇时空收率变化幅度非常小,甲酸甲酯含量较低,催化剂热稳定性高。同时比较Cat2与Cat2-1性能可以发现,只采用稳定剂处理和惰性气氛焙烧,而不采用之后的空气气氛焙烧得到的催化剂,其综合性能较差。
Claims (9)
2.根据权利要求1所述的制备方法,其特征在于,a)步骤中所述共沉淀法沉淀剂为碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵、碳酸氢铵中的一种水溶液。
3.根据权利要求1所述的制备方法,其特征在于,b)步骤中所述干燥的温度为90~120℃,干燥时间为4~10h;焙烧温度为250~400℃,焙烧时间为0.5~1h。
4.根据权利要求1所述的制备方法,其特征在于,c)步骤中所述稳定剂溶液的pH=7.5~9.0。
5.根据权利要求1所述的制备方法,其特征在于,c)步骤中所述的稳定剂溶液中处理的温度为20~50℃,时间为4~30h。
6.根据权利要求1所述的制备方法,其特征在于,c)步骤中所述的惰性气氛包括氮气、氩气、氦气中的一种。
7.根据权利要求1所述的制备方法,其特征在于,c)步骤中所述惰性气氛保护焙烧为首先在100℃下处理2h,然后在400~1000℃下处理1~10h。
8.根据权利要求1所述的制备方法,其特征在于,c)步骤中所述空气中焙烧温度为500~800℃,焙烧时间为2~6h。
9.根据权利要求1所述的制备方法,其特征在于,d)步骤中所述载体包含氧化铝、氧化锆、氧化钛、氧化硅、分子筛中的至少一种。
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CN105067687B (zh) * | 2015-08-14 | 2018-11-06 | 首都师范大学 | 聚多巴胺-金属离子复合纳米颗粒及其制备方法和应用 |
CN108220645B (zh) * | 2017-12-06 | 2019-12-06 | 嘉兴厚亿纺织股份有限公司 | 一种紫杂铜复合液态精炼剂 |
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