CN108409541B - 用于间甲酚合成2,3,6-三甲基苯酚的催化剂及其制备方法 - Google Patents
用于间甲酚合成2,3,6-三甲基苯酚的催化剂及其制备方法 Download PDFInfo
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- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 6
- 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 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 9
- 238000005804 alkylation reaction Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000000520 microinjection Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019261 food antioxidant Nutrition 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 230000011987 methylation Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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Abstract
用于间甲酚合成2,3,6‑三甲基苯酚的催化剂及其制备方法,涉及催化剂及其制备方法。所述用于间甲酚合成2,3,6‑三甲基苯酚的催化剂的组成为Fe2O3、SiO2和CuO。制备时,将Fe(NO3)3·9H2O溶解于去离子水中,然后依次加入Na2SiO3·9H2O和Cu(NO3)2·3H2O,溶解后得混合物A;向混合物A中加入氨水,搅拌老化,然后冷却至室温后抽滤,将滤饼干燥后煅烧,即得用于间甲酚合成2,3,6‑三甲基苯酚的催化剂。催化剂不含贵金属和有毒重金属,成本低廉,环保,制备方法简单,催化活性好和选择性高,间甲酚转化率可达100%,2,3,6‑三甲基苯酚的选择性可达97.9%。
Description
技术领域
本发明涉及一种催化剂及其制备方法,尤其是涉及一种用于间甲酚合成2,3,6-三甲基苯酚的催化剂及其制备方法。
背景技术
2,3,6-三甲基苯酚是一种重要的化工中间体,主要用于合成维生素E的中间体2,3,5-三甲基氢醌。除此之外,2,3,6-三甲基苯酚还广泛应用于材料、农药、化妆品、食品抗氧化剂和消毒剂的生产等领域,市场需求前景较好。
根据原料的不同,工业上合成2,3,6-三甲基苯酚的方法主要有三种:一种是以苯酚和甲醇为原料,在催化剂作用下,运用气固相反应二段合成法合成2,3,6-三甲基苯酚,专利CN 102976903B公开了一种以苯酚为原料,通过磺化、酯化、付克烷基化以及脱磺酰基等反应合成2,3,6-三甲基苯酚的工艺,其中烷基化反应所用催化剂为Mn、Si、Cr等掺杂的铁系催化剂,该工艺存在的缺陷是工艺复杂以及目的产物选择性低。第二种是以2,5-二甲酚和甲醇为原料,直接甲基化合成2,3,6-三甲基苯酚,中国专利CN 106582699A公开了一种以2,5-二甲酚和甲醇为原料,以Mn、Si、K掺杂的铁系氧化物为催化剂,直接气相烷基化合成2,3,6-三甲基苯酚的工艺。该工艺存在的主要缺点是原料昂贵。第三种是以间甲酚和甲醇为原料,中国专利CN 102974354A公开了一种以间甲酚为原料,甲醇为甲基化剂,以Si、Al及碱金属掺杂的铁系复合氧化物催化合成2,3,6-三甲基苯酚的工艺,该工艺具有转化率高、目标产物选择性高等优点,是目前工业化生产应用最广泛的一种合成2,3,6-三甲基苯酚的路径。对于烷基化反应催化剂的研究主要经历了三代:第一代是活性氧化铝催化剂,该催化剂可以在较低温度下催化烷基化反应,但副反应较多导致目的产物选择性低,美国专利US4283574公开了一种以γ-Al2O3催化苯酚烷基化反应的工艺;第二代是氧化镁催化剂,该催化剂具有活性好,选择性高的特点,但是需要在较高的温度下进行反应,导致能耗高、催化剂易结碳、使用寿命短等,美国专利US 3446856公开了一种以MgO催化苯酚烷基化的工艺;第三代是近年来开发的铁系复合氧化物催化剂,该类催化剂具有反应温度低、活性好以及选择性高等特点,如中国专利CN 101844968A公开了一种以Ge、Cr、In等掺杂的铁系复合氧化物催化2,5-二苯酚合成2,3,6-三甲基苯酚的工艺,专利US 4406824公开了一种Ge、Cr、La掺杂的铁系复合氧化物催化间甲酚合成2,3,6-三甲基苯酚的工艺,该工艺有待改进之处在于催化剂中往往涉及贵金属以及有毒金属的使用,导致催化剂生产成本较高或催化剂在使用中存在安全隐患。
发明内容
本发明的目的是解决上述2,3,6-三甲基苯酚制备过程中铁系复合氧化物催化剂成本太高以及使用有毒金属等问题,提供一种廉价、环保且具有高活性和高选择性的用于间甲酚合成2,3,6-三甲基苯酚的催化剂及其制备方法。
本发明所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的组成为Fe2O3、SiO2和CuO,各组成的摩尔比为Fe2O3∶SiO2∶CuO=100∶(5~10)∶(0.5~5)。
所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,包括以下步骤:
1)将Fe(NO3)3·9H2O溶解于去离子水中,然后依次加入Na2SiO3·9H2O和Cu(NO3)2·3H2O,溶解后得混合物A;
2)向混合物A中加入氨水,搅拌老化,然后冷却至室温后抽滤,将滤饼干燥后煅烧,即得用于间甲酚合成2,3,6-三甲基苯酚的催化剂。
在步骤1)中,所述去离子水的温度可为40~70℃。
在步骤1)和2)中,所述Fe(NO3)3·9H2O、去离子水、Na2SiO3·9H2O、Cu(NO3)2·3H2O、氨水的配比可为(16~18)∶(69~73)∶(0.2~0.8)∶(0.02~0.3)∶(8~13)。
在步骤2)中,所述氨水可采用25%的氨水;所述搅拌老化的温度可为40~70℃,搅拌老化的时间可为1~5h;所述干燥的温度可为80~120℃,干燥的时间可为10~24h;所述煅烧的温度可为450~650℃,煅烧的时间可为3~6h。
本发明制备的催化剂主要用于催化间甲酚气相烷基化反应合成2,3,6-三甲基苯酚,催化剂装填在固定床反应器中,间甲酚、甲醇和水按摩尔比1∶(4~7)∶(0~2)的比例混合后,以0.3~1.2h-1的液时空速进入反应器,反应器温度320~380℃,反应在常压下进行。
与现有技术相比,本发明的催化剂不含贵金属和有毒重金属,成本低廉,环保,制备方法简单,催化活性好和选择性高,间甲酚转化率可达100%,2,3,6-三甲基苯酚的选择性可达97.9%。
具体实施方式
以下实施例将对本发明作进一步说明。
实施例1:
将36.36g Fe(NO3)3·9H2O溶解于温度60℃的150g去离子水中,再依次加入0.639gNa2SiO3·9H2O和0.109g Cu(NO3)2·3H2O,待其溶解后,向该溶液中加入25%氨水溶液25g,保持温度60℃,继续搅拌1h将其老化。冷却至室温后进行抽滤,将滤饼置于100℃干燥12h。将干燥后的固体在550℃下煅烧5h即得催化剂。该催化剂各组分摩尔比为Fe2O3∶SiO2∶CuO=100∶5∶1。低温氮吸附-脱附法测定催化剂的比表面积为53m2/g,孔容为0.180cm3/g。
将制得的催化剂(20~40)目装填于内径8mm的固定床反应器,催化剂装填量3.5ml,将间甲酚、甲醇和水以摩尔比1∶5∶1.5的比例混合,通过微量注射泵注入反应器中,在常压、340℃和液时空速0.7h-1的条件下进行反应,结果表明,间甲酚转化率为100%,2,3,6-三甲酚选择性为97.9%。
实施例2:
将36.36g Fe(NO3)3·9H2O溶解于温度40℃的150g去离子水中,再依次加入1.279gNa2SiO3·9H2O和0.545g Cu(NO3)2·3H2O,待其溶解后,向该溶液中加入25%氨水溶液20.3g,保持温度40℃,继续搅拌3h将其老化。冷却至室温后进行抽滤,将滤饼置于100℃干燥12h。将干燥后的固体在500℃下煅烧5h即得催化剂。该催化剂各组分摩尔比为Fe2O3∶SiO2∶CuO=100∶10∶5。所述催化剂的比表面积为54m2/g,孔容为0.183cm3/g。
将制得的催化剂(20~40)目装填于内径8mm的固定床反应器,催化剂装填量3.5ml,将间甲酚、甲醇和水以摩尔比1∶4∶1的比例混合,通过微量注射泵注入反应器中,在常压、320℃和液时空速0.5h-1的条件下进行反应,结果表明,间甲酚转化率为100%,2,3,6-三甲酚选择性为96.4%。
实施例3:
将36.36g Fe(NO3)3·9H2O溶解于温度60℃的150g去离子水中,再依次加入1.023gNa2SiO3·9H2O和0.0545g Cu(NO3)2·3H2O,待其溶解后,向该溶液中加入25%氨水溶液27.5g,保持温度60℃,继续搅拌5h将其老化。冷却至室温后进行抽滤,将滤饼在100℃干燥12h。将干燥后的固体在600℃下煅烧3h即得催化剂。该催化剂各组分摩尔比为Fe2O3∶SiO2∶CuO=100∶8∶0.5。所述催化剂的比表面积为50m2/g,孔容为0.170cm3/g。
将制得的催化剂(20~40)目装填于内径8mm的固定床反应器,催化剂装填量3.5ml,将间甲酚、甲醇和水以摩尔比1∶7∶2的比例混合,通过微量注射泵注入反应器中,在常压、360℃和液时空速0.9h-1的条件下进行反应,结果表明,间甲酚转化率为100%,2,3,6-三甲酚选择性为97.2%。
Claims (8)
1.用于间甲酚合成2,3,6-三甲基苯酚的催化剂,其特征在于其组成为Fe2O3、SiO2和CuO,各组成的摩尔比为Fe2O3∶SiO2∶CuO=100∶(5~10)∶(0.5~5);
所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法包括以下步骤:
1)将Fe(NO3)3·9H2O溶解于去离子水中,然后依次加入Na2SiO3·9H2O和Cu(NO3)2·3H2O,溶解后得混合物A;
2)向混合物A中加入氨水,搅拌老化,然后冷却至室温后抽滤,将滤饼干燥后煅烧,即得用于间甲酚合成2,3,6-三甲基苯酚的催化剂。
2.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于包括以下步骤:
1)将Fe(NO3)3·9H2O溶解于去离子水中,然后依次加入Na2SiO3·9H2O和Cu(NO3)2·3H2O,溶解后得混合物A;
2)向混合物A中加入氨水,搅拌老化,然后冷却至室温后抽滤,将滤饼干燥后煅烧,即得用于间甲酚合成2,3,6-三甲基苯酚的催化剂。
3.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于在步骤1)中,所述去离子水的温度为40~70℃。
4.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于在步骤1)和2)中,所述Fe(NO3)3·9H2O、去离子水、Na2SiO3·9H2O、Cu(NO3)2·3H2O、氨水的配比为(16~18)∶(69~73)∶(0.2~0.8)∶(0.02~0.3)∶(8~13)。
5.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于在步骤2)中,所述氨水采用25%的氨水。
6.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于在步骤2)中,所述搅拌老化的温度为40~70℃,搅拌老化的时间为1~5h。
7.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于在步骤2)中,所述干燥的温度为80~120℃,干燥的时间为10~24h。
8.如权利要求1所述用于间甲酚合成2,3,6-三甲基苯酚的催化剂的制备方法,其特征在于在步骤2)中,所述煅烧的温度为450~650℃,煅烧的时间为3~6h。
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