CN108295890A - 一种ZSM-5@t-ZrO2核壳结构催化剂的制备方法 - Google Patents
一种ZSM-5@t-ZrO2核壳结构催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 230000002045 lasting effect Effects 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
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- 239000011259 mixed solution Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 46
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
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- 238000003786 synthesis reaction Methods 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- -1 soda acids Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000019647 acidic taste Nutrition 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
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
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Abstract
本发明公开了一种ZSM‑5@ t‑ZrO2核壳结构催化剂的制备方法,包括:ZSM‑5前驱液配制:常温下,按核壳质量比t‑ZrO2:ZSM‑5为4:1‑8:1,将t‑ZrO2粉末投入到步骤(1)制得的ZSM‑5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105℃烘干6 h、于500‑600℃温度下焙烧3 h,制得。本发明制得的催化剂能同时提高甲醇转化率及甲硫醇选择性,使用寿命长。
Description
技术领域
本发明属化工技术领域,具体来说涉及一种ZSM-5@t-ZrO2核壳结构催化剂的制备方法。
背景技术
ZSM-5分子筛是由SiO4和AlO4四面体单元交错排列成三维交叉孔道结构的微孔硅铝分子筛。因其具有丰富可调B酸性质、较高比表面积及独特微孔产物择形功能等特点,被广泛用于甲醇催化裂化制烃工艺、硫化氢甲醇法制甲硫醇工艺等。但在硫化氢甲醇法制甲硫醇工艺中,因其独特的酸碱催化机制要求催化剂需同时具有酸碱两性,致使单一分子筛催化剂催化效果不佳,不能有效解决如何协调甲醇和甲硫醇要求不同解离转化和反应生成环境条件的矛盾问题。
针对上述问题,现有研究主要集中在催化剂酸碱性质调变,但基于活性组分和各类助剂的单一氧化物或分子筛浸渍负载改性,新产生的活性中心会牺牲或覆盖催化剂原有部分活性中心,甚至还会堵塞部分孔道,致使催化剂催化性能提升不明显,且寿命较短。
发明内容
本发明的目的在于克服上述缺点而提供一种能同时提高甲醇转化率及甲硫醇选择性,使用寿命长的核壳结构催化剂的制备方法。
本发明的目的是通过下述技术方案实现的。
本发明的一种ZSM-5@ t-ZrO2核壳结构催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为4:1-8:1,将t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105℃烘干6 h、于500-600 ℃温度下焙烧3 h,制得ZSM-5@t-ZrO2核壳催化剂。
其中:第(2)步所述的t-ZrO2粉末粒度为200-400目。
本发明与现有技术相比,具有明显的有益效果,从以上技术方案可知:鉴于分子筛ZSM-5和过渡金属氧化物t-ZrO2分别在甲醇解离吸附和甲硫醇选择性生成表现出优异性能,结合反应酸碱催化机制,据此,本发明提出一种ZSM-5@ t-ZrO2核壳结构催化剂及其制备方法,提出构造基于微-介孔体系的核壳结构催化剂的思路,即制备一种以微孔ZSM-5为核相、介孔t-ZrO2为壳相新型催化剂,形成适宜L-B酸协同催化中心,增强甲醇较低温度下的解离吸附;构造核(B酸)壳(L酸碱)特殊反应路径增强甲硫醇选择性,抑制副产物生成;微-介孔体系的层级结构构造减弱分子的扩散限制,缓解积碳形成,延长催化剂寿命。
当反应混合气体进入催化剂时,一方面作为壳的t-ZrO2表面具有L碱性位,反应气体H2S在t-ZrO2的L碱活性中心吸附解离形成HS-;另一方面作为核的ZSM-5分子筛表面具有B酸位,甲醇在ZSM-5的B酸中心吸附解离形成甲氧基,H2S解离形成的HS-攻击甲氧基形成甲硫醇;同时以对目标产物甲硫醇具有较高选择性的t-ZrO2为壳层充分发挥核壳结构的限制效应,大大提高目标产物选择性;另外,壳层t-ZrO2的介孔与核层ZSM-5的微孔能形成特殊层级结构,进而减弱分子的扩散限制,缓解ZSM-5分子筛积碳形成,延长催化剂寿命。即以本发明制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺,既保证较高甲醇转化率,又有较高甲硫醇选择性,又获得较长寿命。
下面通过具体实施例对本发明作进一步说明。
具体实施方式
实施例1
一种ZSM-5@t-ZrO2核壳催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为4:1,将200目t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于500 ℃温度下焙烧3 h,制得ZSM-5@ t-ZrO2核壳结构催化剂。
使用例:制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺中(反应压力:1.0 MPa,反应温度:370 ℃,重时空速:1.5 h-1,氮气流速:89 mL·min-1,H2S/CH3OH摩尔比2.0:1.0),测得甲醇转化率90.25%,甲硫醇选择性89.75%,寿命22h,与单一催化剂相比(寿命≤4h)寿命延长至少18h。
实施例2
一种ZSM-5@t-ZrO2核壳催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为8:1,将200目t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于500 ℃温度下焙烧3 h,制得ZSM-5@ t-ZrO2核壳结构催化剂。
使用例:制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺中(反应压力:1.0 MPa,反应温度:370 ℃,重时空速:1.5 h-1,氮气流速:89 mL·min-1,H2S/CH3OH摩尔比2.0:1.0),测得甲醇转化率91.88%,甲硫醇选择性90.3%,寿命23h,与单一催化剂相比(寿命≤4h)寿命延长至少19h。
实施例3
一种ZSM-5@t-ZrO2核壳催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为4:1,将400目t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于500 ℃温度下焙烧3 h,制得ZSM-5@ t-ZrO2核壳结构催化剂。
使用例:制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺中(反应压力:1.0 MPa,反应温度:370 ℃,重时空速:1.5 h-1,氮气流速:89 mL·min-1,H2S/CH3OH摩尔比2.0:1.0),测得甲醇转化率92.25%,甲硫醇选择性88.95%,寿命20h,与单一催化剂相比(寿命≤4h)寿命延长至少16h。
实施例4
一种ZSM-5@t-ZrO2核壳催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为8:1,将400目t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于500 ℃温度下焙烧3 h,制得ZSM-5@ t-ZrO2核壳结构催化剂。
使用例:制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺中(反应压力:1.0 MPa,反应温度:370 ℃,重时空速:1.5 h-1,氮气流速:89 mL·min-1,H2S/CH3OH摩尔比2.0:1.0),测得甲醇转化率93.1%,甲硫醇选择性90.2%,寿命21h,与单一催化剂相比(寿命≤4h)寿命延长至少17h。
实施例5
一种ZSM-5@t-ZrO2核壳催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为8:1,将400目t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于600 ℃温度下焙烧3 h,制得ZSM-5@ t-ZrO2核壳结构催化剂。
使用例:制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺中(反应压力:1.0 MPa,反应温度:370 ℃,重时空速:1.5 h-1,氮气流速:89 mL·min-1,H2S/CH3OH摩尔比2.0:1.0),测得甲醇转化率92.58%,甲硫醇选择性92.76%,寿命23h,与单一催化剂相比(寿命≤4h)寿命延长至少19h。
实施例6
一种ZSM-5@t-ZrO2核壳催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为4:1,将200目t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于600 ℃温度下焙烧3 h,制得ZSM-5@ t-ZrO2核壳结构催化剂。
使用例:制得ZSM-5@t-ZrO2核壳催化剂应用在甲醇-硫化氢合成甲硫醇工艺中(反应压力:1.0 MPa,反应温度:370 ℃,重时空速:1.5 h-1,氮气流速:89 mL·min-1,H2S/CH3OH摩尔比2.0:1.0),测得甲醇转化率93.47%,甲硫醇选择性90.83%,寿命21h,与单一催化剂相比(寿命≤4h)寿命延长至少17h。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (2)
1.一种ZSM-5@ t-ZrO2核壳结构催化剂的制备方法,包括以下步骤:
(1)ZSM-5前驱液配制:按原料摩尔配比SiO2:Al2O3:TPAOH:H2O=360:1:10:800,常温下将偏铝酸钠加入去离子水中,持续搅拌下依次加入四丙基氢氧化铵和正硅酸乙酯混合溶液,搅拌24h 形成溶胶体系;
(2)ZSM-5@t-ZrO2核壳催化剂的制备:常温下,按核壳质量比t-ZrO2:ZSM-5为4:1-8:1,将t-ZrO2粉末投入到步骤(1)制得的ZSM-5前驱液中,继续搅拌均匀后转入反应釜中,180℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105℃烘干6 h、于500-600℃温度下焙烧3 h,制得ZSM-5@t-ZrO2核壳催化剂。
2.如权利要求1所述的ZSM-5@ t-ZrO2核壳结构催化剂的制备方法,其中:第(2)步所述的t-ZrO2粉末粒度为200-400目。
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