CN112403476B - 一种甲醇水蒸气裂解高效金属催化剂及其应用 - Google Patents
一种甲醇水蒸气裂解高效金属催化剂及其应用 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 title claims description 11
- 239000002184 metal Substances 0.000 title claims description 11
- 238000002352 steam pyrolysis Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 14
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000003245 coal Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000004230 steam cracking Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000005336 cracking Methods 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 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 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 238000004523 catalytic cracking Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000003980 solgel method Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000007233 catalytic pyrolysis Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- -1 copper-nickel-aluminum Chemical compound 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J23/76—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
- B01J23/83—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 rare earths or actinides
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Abstract
本发明属于甲醇水蒸气裂解制氢催化剂及其制备方法和应用条件领域。本发明所述所述的甲醇水蒸气制氢高效催化剂,该催化剂的粒径为50‑60nm,其组成的质量百分比为:铜50‑60%、镍20‑40%、三氧化二铝3‑8%、氧化钾3‑8%、氧化铈2‑6%。该催化剂应用与甲醇水蒸气裂解制氢过程中时,其裂解反应温度为200‑300°C,所用原料甲醇是我国目前生产过剩的煤化工产品。本发明催化剂不采用贵重金属,大幅度降低了甲醇裂解制氢的成本。
Description
技术领域
本发明涉及甲醇制氢技术,特别涉及一种甲醇水蒸气裂解高效金属催化剂及其在水蒸气裂解甲醇制氢过程中的应用。
背景技术
能源是人类生存和社会经济可持续发展的重要支柱。随着能源需求和环境保护的压力迅速增长,寻找稳定的新的清洁能源势在必行。氢气是目前最理想的清洁能源,而精彩为煤化工产品其资源丰富、环境友好、等优点而成为一种很有前途的制氢原材料。甲醇是煤化工产品,我国目前产能还有一半以上没有发挥,甲醇通过水蒸气催化裂解更容易获得更高的氢产率。
目前甲醇水蒸气裂解制氢催化剂大部分采用贵重金属,其生产成本高,不宜在甲醇水蒸气裂解制氢中推广使用。在贵重金属以外的催化剂大部分采用铜镍锌等组合催化剂,不但反应温度高,而且转化率低。
鉴于上述情况,如何克服现有的技术缺陷,降低能耗与生产成本,仍然是目前甲醇制氢过程中的一个核心难题。
发明内容
本发明的目的在于解决现有技术的不足,提供一种甲醇水蒸气裂解高效金属催化剂,在原来铜镍铝混合催化剂的基础上添加氧化钾和氧化铈,其能够在低温条件下,大幅度提高甲醇裂解制氢的效率,并且有较长的使用寿命的混合催化剂,及其在甲醇水蒸气裂解制氢过程中的应用。
为了实现上述目的,本发明采取如下技术方案:
一种甲醇水蒸气裂解高效金属催化剂,其形状是粒径为50-60nm的细小颗粒,其组成包括铜、镍、三氧化二铝、氧化钾、氧化铈;所述的各组分的重量百分比是铜50-60%、镍20-40%、三氧化二铝3-8%、氧化钾3-8%、氧化铈2-6%。
上述催化剂使用溶胶凝胶法制备得到,具体制备方法如下:
(a)载体的制备
载体采用三氧化二铝,首先将其球状研磨为60-80目,在500°C活化4小时,得到三氧化二铝粉末。
(2)催化剂的制备
按所述比例,称取的三氧化二铝粉末(SB粉)放入三颈瓶中,加入少量水,70°C恒温水浴磁力搅拌溶解30分钟,加入硝酸溶液,继续搅拌4小时,加入硝酸铜、硝酸镍、硝酸钾和硝酸铈混合溶液搅拌1小时,80°C水浴锅里缓慢蒸干,110°C烘箱干燥过夜,在马弗炉空气气氛350°C焙烧3小时,制得催化剂。
本发明所述的催化剂,能够有效地应用于水蒸气甲醇裂解制氢过程:首先将该催化剂均匀填充在甲醇水蒸气裂解反应罐内通过反应罐加热将催化剂加热,再将原料甲醇和水蒸气通入到反应罐进口管的预热区内,二者混合、预热后进入反应罐中,使甲醇在水蒸气气氛和定温环境下快速进行裂解反应,将甲醇的碳-氢-氧有机质转化为氢气和二氧化碳的富氢混合气;该反应后的混合气体经过包括冷凝器、二氧化碳化学吸收氢、干燥器在内的尾气收集提纯系统后得到纯氢气,所述裂解反应温度为300-500°C;每小时水蒸气和甲醇进料量的比为1-2/1;每小时甲醇和水蒸气总的进料量与醇基的质量比为10-30/1。
实测表明,将本催化剂使用在甲醇水蒸气裂解制氢反应罐时,在200-300°C的温度下可获得很高的甲醇转化率,即甲醇转化率为95%以上。
本发明所述的催化剂,通过各种活性组分的协同作用,大幅度提高了低温甲醇裂解制氢过程中的转化率、甲醇制氢产率和催化剂的使用寿命。其中,铜组分主要用于拓展低温端的甲醇裂解制氢起始反应活性,镍组分主要用于加强较高温区的甲醇裂解制氢反应活性,氧化钾组分主要用于降低甲醇水蒸气裂解制氢过程中催化剂表面的积碳,同时起到加强较高温区的甲醇催化裂解反应活性作用,提高甲醇裂解制氢反应氢的产率,氧化铈主要用于提高甲醇裂解制氢反应中目标产物氢的选择性,同时增强甲醇裂解过程中催化剂表面的电子吸附,拓展低温端的甲醇催化裂解制氢起始反应活性的作用;三氧化二铝组分用于催化剂中活性组分的载体,起到提高催化剂中活性组分的分散度和催化剂的机械强度的作用。本发明所述的催化剂在温度为450°C条件下连续工作24小时后,氢气产率和原料甲醇转化率几乎没有变化,而不添加氧化钾和氧化铈组分的催化剂连续工作24小时和则会产生积碳。由此可见,添加氧化钾和氧化铈组分有利于降低甲醇催化裂解制取氢气过程中催化剂表面的积碳,提高产率和催化剂的使用寿命。
本发明所述的催化剂,使用在水蒸气裂解甲醇制氢过程中时,由于在进行催化水蒸气裂解甲醇制氢反应过程中催化剂表面积碳和结焦很少,因而有效地延长了催化剂使用寿命。
本发明所述的催化剂,可以适用于各种醇类为原料的催化裂解制氢反应。实现了资源-能源-环境一体化的可持续性的循环利用。
具体实施方式
为了进一步说明本发明,下面通过具体实施例对本发明进行进一步的详细说明。
实施例1 采用溶胶凝胶法制备催化剂1
(a)按铜50-60%、镍20-40%、三氧化二铝3-8%、氧化钾3-8%、氧化铈2-6%的重量百分比分别称量分析纯的三水硝酸铜、六水硝酸镍、六水硝酸铈、硝酸钾和三氧化二铝。
(b)载体采用三氧化二铝,首先将其球状研磨为60-80目,在500°C活化4小时,得到SB粉。称取一定量的SB粉放入三颈瓶中,加入少量水,70°C恒温水浴磁力搅拌溶解30分钟,加入一定量的硝酸溶液,继续搅拌4小时,加入硝酸铜、硝酸镍、硝酸钾和硝酸铈混合溶液搅拌1小时,80°C水浴锅里缓慢蒸干,110°C烘箱干燥过夜,在马弗炉空气气氛350°C焙烧3小时,制得催化剂。
实施例2 采用沉淀沉积法制备催化剂2
沉淀沉积法是把普通浸渍法和沉淀法结合起来,浸渍一段时间后,再加入沉淀剂,使待沉淀组分沉积在载体上。用碳酸钠做沉淀剂,PH=10情况下采用沉淀沉积法制备了3%Pd/CeO2,反应温度在160-220°C,与传统浸渍法相比显示了很好的催化活性,在220°C甲醇转化率提升近20个百分点。
实施例3由甲醇为原料,并利用实施例1 得到的催化剂在反应罐中进行催化裂解制氢反应装置为甲醇水蒸气催化制氢反应罐:它包括一个带有保温层的筒形催化裂解反应器及连接在两端部的反应物(甲醇和水蒸气)通入管道和催化裂解尾气输出管道,甲醇存储罐、水蒸气发生器分别与通入管道接通,并分别设有控制阀和反应物流量控制器,通入管道外壁上设有用于预热的外加热装置;在输出管道上依次连接有包括水蒸气冷凝器、二氧化碳化学反应吸收器和干燥器在内的尾气收集提纯系统;在筒形催化裂解反应器的内腔中设置有陶瓷绝缘层与外接电源连通的电炉丝,电炉丝的功率由所需催化裂解反应温度和催化裂解反应器体积选择。制氢方法:首先将本发明所述催化剂在280氢气气氛中还原后填充在内置电炉丝周围并与电炉丝表面均匀接触,催化剂用量由每小时甲醇进料量决定,然后接通预热区电加热带电源,使预热区的温度在200°C左右;接通用于内加热的电炉丝电源,使电炉丝的电流分别在I=1.0A、2.0A、3.0A、4.0A不变,通过调节反应器外加热炉的功率,使催化裂解反应器内腔的温度在200-300°C范围内调节。最后开启甲醇原料存储罐出口管上的液体进样泵以及水蒸气发生器的阀门,调节甲醇和水蒸气的流量,经预热后的甲醇蒸汽和水蒸气的混合气,在催化裂解反应器内腔中发生甲醇裂解反应、甲醇催化水蒸气裂解反应,得到产品氢气。
实施例4 制氢效果
测试本发明催化剂中载体铝源、催化剂的焙烧温度、制备催化剂的反应时间对甲醇水蒸气催化裂解制氢效果的影响。为测试本发明催化剂中各条件对甲醇水蒸气催化裂解制氢效果的影响,在本实施例中,测试的原料为煤制甲醇,使用装置和方法均与实施例3相同,不同的是:改变催化剂中的载体、焙烧温度及制备催化剂的反应温度等对水蒸气催化裂解制氢效果的影响,测试条件是水蒸气流量60g/h,甲醇35g/h,催化剂用量是8g,粒径50nm,甲醇水蒸气催化裂解制氢的反应温度为280°C,在利用不同组分催化剂的情况下,测量所得氢气量和甲醇用量。并计算氢气产率和甲醇转化率。
(a)载体不同铝源的影响
经测试,不同铝源催化剂的活性测试数据,铝溶胶即先由SB粉出发按溶胶凝胶方法制备出载体,经350°C焙烧,再同传统浸渍法相似浸渍活性组分铜镍,浸渍在铝溶胶催化剂上的铜镍催化剂活性最差,原料转化率仅为31%,可能该温度焙烧的载体没有具备三氧化二铝的晶型,用溶胶凝胶方法制备的催化剂表现很好的反应活性,甲醇转化率达65%,表现出良好的催化性能,溶胶凝胶方法优于其他制备方法。可能与该方法制备的催化剂能够得到高均一和高比表面积,金属组分高度分散在载体上,使催化剂具有很高的反应活性关。溶胶凝胶方法制备的催化剂在220-280°C温度区间反应活性最佳。从而利于反应的进行。
(b)焙烧温度的影响
溶胶凝胶法不同焙烧温度催化剂的活性测试,焙烧温度分别为350°C、450°C、500°C、550°C和600°C,焙烧温度对催化性能有显著影响,在450°C焙烧催化活性最佳,原因为铜系催化剂以浸渍法和共沉淀等传统方法制备时,铜的焙烧条件为350°C,但在溶胶凝胶方法中,由于铝源由SB粉出发,在该温度焙烧尚未形成良好晶型,增加焙烧温度有利于氧化铝晶型的形成,在450°C达到最佳甲醇转化率,进一步增加焙烧温度500°C以上,虽然有利于晶型生长,但铜系催化剂属于非耐高温催化剂,在高温焙烧时很容易烧结,综合两方面因素在450°C使原料转化率最佳。
(c)反应时间的影响
溶胶凝胶催化剂在350°C焙烧,随反应时间的活性测试,反应经简短诱导期后从60min催化剂活性一直稳定,转化率维持在62%-66%之间,氢气的TOF值在115-125mmol/g-catal/h左右波动,360min后活性开始下降,说明催化剂在实验室阶段具有较好的初活性,但稳定性还需进一步改善。
(d)钾含量的影响
表1为催化剂中不同钾含量催化剂的活性测试结果,当加入1%的钾助剂时,对催化活性基本没有变化,随着钾含量的增加,催化剂的活性明显升高;甲醇转化率呈上升趋势,当钾含量接近5%时甲醇转化率达到最大值,继续增加催化剂中的钾含量,催化剂的活性明显下降,甲醇转化率达到最低,比不加钾助剂的催化剂活性还差。这说明在本实验条件下,钾的量有一个最佳范围。超过最佳范围后,催化活性呈迅速下降趋势,甚至劣于不加助剂的催化剂活性,这可能是由于钾属于碱金属,一定含量的钾会中和三氧化二铝载体的酸性,有一最佳值,一旦超过了这个最佳值,催化剂呈现碱性状态,不利于原料的转化。
反应条件:催化剂用量200mg,反应时间120min,,GHSV=8400h,反应温度:260°C
(d) 稀土助剂对催化剂性能的影响
不同的稀土金属氧化物(La2O3/CeO2和Y2O3)等助剂的加入,能够明显改善催化活性,原料甲醇转化率显著升高,产物中只有H2、CO,未检测到副产物的生成,其中La2O3和CeO2是甲醇裂解反应中较好的催化助剂。这里采用氧化铈,当氧化铈含量为3.0-5.0%时,催化剂的活性中心数目最多;氧化铈含量大于5%,催化剂的活性中心数量略有减少。
Claims (5)
1.一种甲醇水蒸气裂解高效金属催化剂,其形状是粒径为50-60nm的细小颗粒,其组成包括铜、镍、三氧化二铝、氧化钾、氧化铈;其特征在于所述的各组分的重量百分比是铜50-60%、镍20-40%、三氧化二铝3-8%、氧化钾3-8%、氧化铈2-6%,
所述甲醇水蒸气裂解高效金属催化剂通过如下步骤制备而成:
(a)载体的制备
载体采用三氧化二铝,首先将其球状研磨为60-80目,在500°C活化4小时,得到三氧化二铝粉末;
(b)催化剂的制备
按所述比例,称取的三氧化二铝粉末放入三颈瓶中,加入少量水,70℃恒温水浴磁力搅拌溶解30分钟,加入硝酸溶液,继续搅拌4小时,加入硝酸铜、硝酸镍、硝酸钾和硝酸铈混合溶液搅拌1小时,80℃水浴锅里缓慢蒸干,110℃烘箱干燥过夜,在马弗炉空气气氛350℃焙烧3小时,制得催化剂。
2.如权利要求1所述的甲醇水蒸气裂解高效金属催化剂,其特征在于,各组分的重量百分比为:铜为52-58%、镍25-35%、三氧化二铝4-7%、氧化钾4-7%、氧化铈3-5%。
3.如权利要求1所述甲醇水蒸气裂解高效金属催化剂在水蒸气制氢过程中的应用,其特征在于,包括首先将该催化剂均匀填充在甲醇水蒸气制氢反应罐内,通过对反应罐加热将催化剂加热,再将原来甲醇和水蒸气通入到反应罐进口管的预热区内,二者混合、预热后进入反应罐中,使甲醇在水蒸气气氛和定温环境下快速进行裂解反应,将甲醇中的含碳-氢-氧有机质转化为氢气和二氧化碳的富氢混合气;该反应后的混合气体经过包括冷凝器、二氧化碳化学吸收器、干燥器在内的尾气收集提纯系统后得到纯氢气,所述裂解反应温度为200-300℃,相对应的反应条件是:水蒸气的压力4-5个大气压,每小时水蒸气和甲醇进料量的质量比为1-2/1;每小时甲醇和水蒸气总的进料量与催化剂的质量比为10-30/1。
4.如权利要求3所述的甲醇水蒸气裂解高效金属催化剂在水蒸气裂解甲醇制氢过程中的应用,其特征在于,使用的反应罐时,所述的裂解反应温度是220-280℃。
5.如权利要求3所述的甲醇水蒸气裂解高效金属催化剂在水蒸气裂解甲醇制氢过程中的应用,其特征在于,所述原料甲醇是煤化工产品。
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