CN112387305A - 一种核壳结构催化剂的合成及原位生成双氧水制备环氧氯丙烷的方法 - Google Patents
一种核壳结构催化剂的合成及原位生成双氧水制备环氧氯丙烷的方法 Download PDFInfo
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- CN112387305A CN112387305A CN202011276260.3A CN202011276260A CN112387305A CN 112387305 A CN112387305 A CN 112387305A CN 202011276260 A CN202011276260 A CN 202011276260A CN 112387305 A CN112387305 A CN 112387305A
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Images
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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Abstract
本发明提供了一种高稳定性的表面疏水改性核壳结构催化剂TS‑1@Au‑Pd/Silicalite‑1原位生成双氧水合成环氧氯丙烷的方法,催化剂核层为纳米片型TS‑1分子筛,催化剂壳层为Au‑Pd/Silicalite‑1纯硅分子筛,通过在双金属Au‑Pd/Silicalite1催化剂表面原位生成双氧水,产生的双氧水在TS‑1分子筛壳层与氯丙烯反应制得环氧氯丙烷,该催化剂可有效富集产生的双氧水,大幅提高氢气和氧气的利用率,具有较好的工业化前景。
Description
技术领域
本发明提供了一种高稳定性的表面疏水改性的纳米片核壳结构催化剂TS-1@Au-Pd/Silicalite-1原位生成双氧水合成环氧氯丙烷的方法,催化剂壳层为纳米薄片结构的TS-1,催化剂核层为包覆Au-Pd合金的纯硅分子筛Silicalite-1。通过在双金属Au-Pd/Silicalite-1催化剂贵金属纳米合金表面原位生成双氧水,并通过构建的疏水围栏将产生的双氧水分子富集于分子筛催化剂孔道之中,富集的的双氧水扩散至钛硅分子筛壳层的氯丙烯反应制得环氧氯丙烷,该催化剂可有效提高贵金属催化剂稳定性和氢气利用率,属于精细化工领域。
背景技术
TS-1钛硅分子筛是上世纪八十年代开发的一种新型的沸石分子筛材料,最早由意大利Enichem公司将钛元素引入具有ZSM-5结构的分子筛骨架形成的具有优良定向氧化性能的钛硅分子筛。TS-1催化剂在以H2O2为氧化剂的低温氧化反应中表现出优异的催化性能,如反应条件温和、催化活性和选择性高、工艺流程简单,可克服传统工艺路线长、副产多、反应条件苛刻的缺点,在推动化学工艺的绿色化进程方面具有积极的作用。其独特的催化性能使TS-1广泛应用于诸如烯烃环氧化、苯酚羟基化、醛酮的肟化以及醇醛的氧化反应中间。常规过氧化氢、氯丙烯制备环氧氯丙烷需配套蒽醌法过氧化氢工艺,经过蒽醌氢化、蒽醌氢化液氧化、低浓度过氧化氢膜浓缩等一系列步骤制得高浓度过氧化氢(35~60wt.%),过氧化氢工段占地面积大、制备工艺复杂,通过氢气和氧气原位合成环氧化合物可以解决环氧
环氧氯丙烷是一种重要的有机化工原料和中间体,广泛用于合成环氧树脂、氯醇橡胶、表面活性剂、离子交换树脂、涂料和增塑剂。目前,环氧氯丙烷是丙烯为原料生产的,生产的方法主要是高温氯丙烯法和甘油法,这两种合成方法均需要通过皂化反应步骤,均涉及到固废氯盐和大量有机废水的后处处理。固废和含氯废水的闭环及资源化过程不可避免会造成工艺流程复杂化、设备腐蚀和三废治理的问题。开发原位生成双氧水制环氧氯丙烷技术,可有效地解决环氧氯丙烷生产过程中的腐蚀和环保问题。专利U.S.Pat.No.4410501公开了一种以硅源、钛源、模板剂合成TS-1钛硅分子筛的合成方法,所合成的TS-1分子筛可以用于烷基化、歧化、催化裂化、重整等一系列反应。专利U.S.Pat.No.US4833260公开了一种以钛硅分子筛为催化剂,用过氧化氢直接对氯丙烯环氧化生产环氧氯丙烷的方法,该专利使用水热法合成钛硅分子筛作催化剂,使用浓度为10~70wt.%过氧化氢作氧化剂,可以高效氧化包括乙烯、丙烯、氯丙烯、环己烯等一系列烯烃化合物制备相应环氧化合物。专利U.S.Pat.No.US5235111公开了一种以氢气、氧气、正己烷为原料在酸性条件下使用贵金属负载于TS-1分子筛催化剂上原位合成双氧水氧化链烷烃的方法。专利CN 101544620 B公开了一种以空心钛硅分子筛负载贵金属催化剂将环己烯、氢气、氧气、稀释气、溶剂和催化剂混合后,使用原位合成的双氧水作氧化剂,可有效减少开环、过度氧化等副反应的发生,可高活性、高选择性地制得环氧环己烷。“J.Catal.,1998,176:376-386和J.Mol.Catal.,A:Chem.2016,423:478-488”分别发表了以贵金属催化剂Pt-Pd/TS-1、Au-Pd/TS-1原位生成双氧水制环氧丙烷的方法。中国专利CN101434586 B公开了一种氯丙烯、氢气、氧气、稀释气、溶剂和负载贵金属的TS-1催化剂混合后,在氢气存在下,以氧气作氧化剂一步制取环氧氯丙烷的合成路线,该方案反应在空速为50000h-1,反应温度为120℃,反应压力为2.5Mpa条件下,转化率为5.2%,环氧氯丙烷选择性为93%,催化剂活性还需要进一步提高。
常规方法通过将贵金属直接负载于钛硅分子筛制成催化剂直接合成环氧氯丙烷,理论上可以通过在贵金属表面合成双氧并扩散至钛催分子筛孔道与不饱和烃类发生环氧化反应。但其不足之处在于:1、贵金属活性位上产生的双氧水极易扩散至反应体系,导致TS-1催化剂表面双氧水浓度极低不利于发生环氧化反应致使转化率降低。2、催化剂制备过程中贵金属晶粒易在分子筛表面发生聚集,难以实现高分散制备,贵金属利用率较低;3、贵金属负载于TS-1钛硅分子筛表面反应产物和原料接触极易发生深度氧化导致选择性下降。
发明内容
本发明通过构建一种核壳结构表面疏水改性的纳米薄片型TS-1@Au-Pd/Silicalite-1催化剂,可有效构建分子围栏将产生的H2O2富集于构建的分子筛之中,实现双氧水的高效利用;通过TS-1@Au-Pd/Silicalite-1分子筛核壳结构的设计,可以有效提高TS-1@Au-Pd/Silicalite-1催化剂的稳定性。
本发明的目的在于提供一种通过氢气、氧气、氯丙烯、溶剂、TS-1@Au-Pd/Silicalite-1催化剂制备环氧氯丙烷的方法。通过制备核壳结构表面疏水改性的TS-1@Au-Pd/Silicalite-1催化剂,分别构建了负载有贵金属Au-Pd/Silicalite-1惰性二氧化硅核层以及具有催化环氧化活性的TS-1分子筛壳层,通过催化剂的表面疏水改性构建分子围栏富集H2O2,可有效提高催化剂的催化活能和稳定性。
环氧氯丙烷的合成于反应温度为0~200℃和压力为0.1~5Mpa条件下,氯丙烯:甲醇:氢气:氧气:平衡气摩尔比为1:(0.5~10):(0.1~10):(0.1~10):(0~2000),反应液总质量空速为5~50000h-1。本发明提供了一种TS-1@Au-Pd/Silicalite-1催化剂的制备方法,所合成贵金属纳米粒子的方法包括常规浸渍法、负载法、原位生长等方法。
1、取一定比例的氯金酸(HAuCl4)和氯钯酸(H2PdCl4)溶于水中,配成水溶液,加入一定量的聚乙烯吡咯烷酮(PVP)作稳定剂,其中HAuCl4:H2PdCl4:PVP摩尔比范围为1:1:0.00875-1:5:0.04375;
2、冰水浴冷条件冷却至0℃下搅拌0.5h,加入一定量NaBH4或柠檬酸钠还原,加完继续搅拌2h得到Au-Pd纳米溶胶;其中HAuCl4:H2PdCl4:NaBH4=1:1:0.1-1:5:0.5;
3、向溶胶中加入HAuCl4:H2PdCl4:十六三甲氧基硅烷摩尔比范围为1:1:0.14-1:5:0.7,搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶。其中十六三甲氧基硅烷可用相同摩尔比的十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种替代作为分子筛生长结构导向剂。
4、继续加入Silicalite-1预水解液摩尔比为TEOS:TPAOH:H2O=1:0.35:237.5。于65℃水解3h,随后移至四氟水热釜中于170℃水热48h后得分子筛母液;
5、分子筛母液经冷却、离心、洗涤、干燥后得到制得Au-Pd/Silicalite-1;
6、取1-5g Au-Pd/Silicalite-1晶种,加入制得的摩尔比为Au:Pd:TEOS:TPAOH:H2O=1:1:1:0.35:237.5-1:5:5:1.75:1187.5预水解液,于50℃下搅拌1h;
7、加入摩尔比为TEOS:PAOH:TBOT:乙醇=1:0.31:0.06:1.53-5:1.65:0.3:7.65混合液,于60℃下预水解3h后转入水热釜170℃下水热48h制得含结构导向剂的TS-1@Au-Pd/Silicalite-1分子筛;
8、将分子筛母液过滤、离心洗涤、干燥,将其转入马弗炉以℃/min的速率升温至550℃高温焙烧4h后制得催化剂TS-1@Au-Pd/Silicalite-1;
9、取45-50g TS-1@Au-Pd/Silicalite-1分子筛,加入摩尔比为TPAOH:H2O=1:7.683-5:38.415混合液,于170℃水热48h,得分子筛母液;
10、分子筛母液经冷却、离心、洗涤、干燥后,将其转入马弗炉以5℃/min的速率升温至550℃焙烧4h得TS-1@Au-Pd/Silicalite-1分子筛;
11、取45-50g TS-1@Au-Pd/Silicalite-1分子筛,加入摩尔比为TPAOH:CMC:H2O=1:0.06:10.01-5:0.3:50混捏挤条成型干燥后;
12、将其转入马弗炉以5℃/min的速率升温至550℃焙烧4~8h得TS-1@Au-Pd/Silicalite-1分子筛;
13、取45-50gTS-1@Au-Pd/Silicalite-1分子筛催化剂,加入摩尔比为1:1-1:5的TS-1@Au-Pd/Silicalite-1:包含硅烷的乙醇混合液;所述硅烷为十六烷基三甲氧基硅烷、十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种与乙醇的摩尔比为1:100-1:200;
14、在室温下搅拌24h,得到表面疏水改性的TS-1@Au-Pd/Silicalite-1催化剂。
15、将分子筛催化剂装入固定床反应器或直接将原粉加入淤浆床反应器通入氢气和氧气在核壳分子筛催化剂核层Au-Pd/Sililicate-1原位产生双氧水,产生的双氧水内扩散至TS-1分子筛Ti活性位与氯丙烯反应得到环氧氯丙烷。
与现有技术相比,本发明的有益效果为:
(1)本发明中提供了一种表面疏水改性的纳米薄片型TS-1@Au-Pd/Silicalite-1催化剂,通过表面疏水改性,其贵金属表面产生的过氧化氢可以通过构建的分子围栏有效富集,提高氢气利用效率
(2)本发明TS-1@Au-Pd/Silicalite-1催化剂Au-Pd原子在分子筛表面均匀分布,粒径为2-3nm。
(3)本发明中提供的合成路线,反应条件温和,氢气利用率高,通过氢气和氧气原位合成H2O2高效氧化氯丙烯制得环氧氯丙烷。
(4)本发明中提供合成路线合成环氧氯丙烷的收率60%,选择性>95%,具有较好的产业化前景。
附图说明
图1为固定床微反评价装置的整体流程图。
图2为实施例1TS-1@Au-Pd/Silicalite-1催化剂A SEM图。
图3为实施例1TS-1@Au-Pd/Silicalite-1催化剂A分子筛催化剂HR-TEM图。
图4为实施例1TS-1@Au-Pd/Silicalite-1催化剂A分子筛催化剂XRD图像。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
通过常规负载方法或常规核壳催化剂制备方法对比实施例验证本方法制备催化剂的技术优势。
实施例1-3为发明催化剂的制备
实施例1
本实施例中贵金属和载体的摩尔比为1Au:1Pd:65.68SiO2:3.55TiO2。
(1)取0.8625g(0.002538mol)的HAuCl4和0.6351g(0.004697mol)的H2PdCl4固体,配成100ml水溶液),加入1.111g聚乙烯吡咯烷酮(PVP)作保护剂,冰水浴冷条件冷却至0℃下搅拌0.5小时,然后加入3.783g(0.1mol)的硼氢化钠(NaBH4)还原剂,继续搅拌2h得到PVP稳定的Au-Pd纳米溶胶,其中贵金属摩尔比为1Au:1Pd。其中硼氢化钠可用相同摩尔比柠檬酸钠替代,PVP可用相同摩尔比三乙醇胺(TEA)替代。
(2)往溶胶溶液中加入0.1300g(0.0007255mol)(3-氨基丙基)三甲氧基硅烷(APS)作为表面接枝偶联剂,继续搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶。
(3)往溶胶中直接加入3.47g(0.0167mol)正硅酸四乙酯TEOS,4.75g(0.0058mol)25wt%四丙基氢氧化铵溶液与67.8g H2O,溶液65℃水解3h后移入四氟水热釜170℃下水热48h后分子筛母液冷却、离心、洗涤、干燥后得到Au-Pd@Silicalite-1,Silicalite-1晶化原料摩尔比为1TEOS:0.35TPAOH:237.5H2O,其中贵金属和载体的摩尔比为1Au:1Pd:65.68SiO2。
(4)取1g Au-Pd/Silicalite-1晶种,加入31.2g(0.15mol)正硅酸四乙酯(TEOS)与38.8g(0.047mol)25wt%四丙基氢氧化铵(TPAOH),在50℃下搅拌1h后加入3.06g(0.009mol)钛酸四正丁酯(TBOT)与10.56g(0.229mol)乙醇的混合溶液,60℃下预水解3小时后转入水热釜170℃下水热48h,将二次晶化分子筛母液离心、洗涤、干燥后在550℃马弗炉焙烧4h得TS-1@Au-Pd/Silicalite-1,其中贵金属和载体的摩尔比为1Au:1Pd:65.68SiO2:3.55TiO2。
(5)将TS-1@Au-Pd/Silicalite-1催化剂45g加入650g水,再加入3.8g(0.0047mol)25wt.%四丙基氢氧化铵(TPAOH),进行水热2天。水热后离心出TS-1@Au-Pd/Silicalite-1分子筛,进行550℃马弗炉焙烧4h。
(6)取45g TS-1@Au-Pd/Silicalite-1分子筛,加入12.5g 40wt.%的硅溶胶,0.5g羟甲基纤维素,15g H2O混捏成型后挤条成型干燥后,转入马弗炉550℃焙烧4h得TS-1@Au-Pd/Silicalite-1分子筛。
(7)取50g TS-1@Au-Pd/Silicalite-1分子筛催化剂加入0.866g(0.0025mol)十六烷基三甲氧基硅烷和16.32g无水乙醇,在室温下搅拌24h表面硅烷化得到表面疏水改性的TS-1@Au-Pd/Silicalite-1催化剂A。其中十六烷基三甲氧基硅烷可用相同摩尔比的十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种替代。
实施例2
本实施例中贵金属和载体的摩尔比为1Au:1.185Pd:65.68SiO2:3.55TiO2。
(1)取1.725g(0.005076mol)的HAuCl4和2.764g(0.009394mol)的H2PdCl4固体,配成100ml水溶液),加入1.111g聚乙烯吡咯烷酮(PVP)作保护剂,冰水浴冷条件冷却至0℃下搅拌0.5小时,然后加入3.783g(0.1mol)的硼氢化钠(NaBH4)还原剂,继续搅拌2h得到PVP稳定的Au-Pd纳米溶胶,其中贵金属摩尔比为1Au:1.85Pd。其中贵金属摩尔比为1Au:1Pd。其中硼氢化钠可用相同摩尔比柠檬酸钠替代,PVP可用相同摩尔比三乙醇胺(TEA)替代。
(2)往溶胶溶液中加入0.1300g(0.0007255mol)(3-氨基丙基)三甲氧基硅烷(APS)作为表面接枝偶联剂,继续搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶。
(3)往溶胶中直接加入3.47g(0.0167mol)正硅酸四乙酯TEOS,4.75g(0.0058mol)25wt%四丙基氢氧化铵溶液与67.8g H2O,溶液65℃水解3h后移入四氟水热釜170℃下水热48h后分子筛母液冷却、离心、洗涤、干燥后得到Au-Pd@Silicalite-1,Silicalite-1晶化原料摩尔比为1TEOS:0.35TPAOH:237.5H2O,其中贵金属和载体的摩尔比为1Au:1.85Pd:65.68SiO2。
(4)取1g Au-Pd/Silicalite-1晶种,加入31.2g(0.15mol)正硅酸四乙酯(TEOS)与38.8g(0.047mol)25wt%四丙基氢氧化铵(TPAOH),在50℃下搅拌1h后加入3.06g(0.009mol)钛酸四正丁酯(TBOT)与10.56g(0.229mol)乙醇的混合溶液,60℃下预水解3小时后转入水热釜170℃下水热48h,将二次晶化分子筛母液离心、洗涤、干燥后在550℃马弗炉焙烧4h得TS-1@Au-Pd/Silicalite-1,其中贵金属和载体的摩尔比为1Au:1.85Pd:65.68SiO2:3.55TiO2。
(5)将TS-1@Au-Pd/Silicalite-1催化剂45g加入650g水,再加入3.8g(0.0047mol)25wt.%四丙基氢氧化铵(TPAOH),进行水热2天。水热后离心出TS-1@Au-Pd/Silicalite-1分子筛,进行550℃马弗炉焙烧4h。
(6)取45g TS-1@Au-Pd/Silicalite-1分子筛,加入12.5g 40wt.%的硅溶胶,0.5g羟甲基纤维素,15g H2O混捏成型后挤条成型干燥后,转入马弗炉550℃焙烧8h得TS-1@Au-Pd/Silicalite-1分子筛。
(7)取50g TS-1@Au-Pd/Silicalite-1分子筛催化剂加入0.866g(0.0025mol)十六烷基三甲氧基硅烷和16.32g无水乙醇,在室温下搅拌24h表面硅烷化得到表面疏水改性的TS-1@Au-Pd/Silicalite-1催化剂B。其中十六烷基三甲氧基硅烷可用相同摩尔比的十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种替代。
实施例3
本实施例中贵金属和载体的摩尔比为1Au:5Pd:65.68SiO2:3.55TiO2。
(1)取0.8625g(0.01269mol)的HAuCl4和3.1755g(0.023485mol)的H2PdCl4固体,配成100ml水溶液),加入1.111g聚乙烯吡咯烷酮(PVP)作保护剂,冰水浴冷条件冷却至0℃下搅拌0.5小时,然后加入3.783g(0.1mol)的硼氢化钠(NaBH4)还原剂,继续搅拌2h得到PVP稳定的Au-Pd纳米溶胶,其中贵金属摩尔比为1Au:5Pd。其中硼氢化钠可用相同摩尔比柠檬酸钠替代,PVP可用相同摩尔比三乙醇胺(TEA)替代。
(2)往溶胶溶液中加入0.1300g(0.0007255mol)(3-氨基丙基)三甲氧基硅烷(APS)作为表面接枝偶联剂,继续搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶。
(3)往溶胶中直接加入3.47g(0.0167mol)正硅酸四乙酯TEOS,4.75g(0.0058mol)25wt%四丙基氢氧化铵溶液与67.8g H2O,溶液65℃水解3h后移入四氟水热釜170℃下水热48h后分子筛母液冷却、离心、洗涤、干燥后得到Au-Pd@Silicalite-1,Silicalite-1晶化原料摩尔比为1TEOS:0.35TPAOH:237.5H2O,其中贵金属和载体的摩尔比为1Au:5Pd:65.68SiO2。
(4)取1g Au-Pd/Silicalite-1晶种,加入31.2g(0.15mol)正硅酸四乙酯(TEOS)与38.8g(0.047mol)25wt%四丙基氢氧化铵(TPAOH),在50℃下搅拌1h后加入3.06g(0.009mol)钛酸四正丁酯(TBOT)与10.56g(0.229mol)乙醇的混合溶液,60℃下预水解3小时后转入水热釜170℃下水热48h,将二次晶化分子筛母液离心、洗涤、干燥后在550℃马弗炉焙烧4h得TS-1@Au-Pd/Silicalite-1,其中贵金属和载体的摩尔比为5Au:1Pd:65.68SiO2:3.55TiO2。
(5)将TS-1@Au-Pd/Silicalite-1催化剂45g加入650g水,再加入3.8g(0.0047mol)25wt.%四丙基氢氧化铵(TPAOH),进行水热2天。水热后离心出TS-1@Au-Pd/Silicalite-1分子筛,进行550℃马弗炉焙烧4h。
(6)取45g TS-1@Au-Pd/Silicalite-1分子筛,加入12.5g 40wt.%的硅溶胶,0.5g羟甲基纤维素,15g H2O混捏成型后挤条成型干燥后,转入马弗炉550℃焙烧8h得TS-1@Au-Pd/Silicalite-1分子筛。
(7)取50g TS-1@Au-Pd/Silicalite-1分子筛催化剂加入0.866g(0.0025mol)十六烷基三甲氧基硅烷和16.32g无水乙醇,在室温下搅拌24h表面硅烷化得到表面疏水改性的TS-1@Au-Pd/Silicalite-1催化剂C。其中十六烷基三甲氧基硅烷可用相同摩尔比的十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种替代。
常规负载方法对比例1
(1)称取0.86g(0.0025310moL)氯金酸和1.38g(0.0055151moL)氯钯酸溶解于20mL去离子水中形成混合溶液,等体积浸渍于100g TS-1后转移至80℃烘箱干燥12h,分子筛载体干燥后冷却至室温加入计量1%的NaOH:Na2CO3=2:1的混合碱液至最终体系pH为10使沉淀完全,加入去离子水洗涤至电导率50S/m,然后在110℃烘箱中干燥;
(2)将负载后的0.5%Pd-0.5%Au/TS-1转入管式炉,设置氢气流速为100mL/min,以5℃/min的速度程序升温至350℃,在350℃下保温2h得0.5%Pd-0.5%Au/Silicalite-1@TS-1催化剂,还原后的催化剂冷却至室温后通入0.5%稀释氧氮混合气进行钝化处理30min得0.5%Pd-0.5%Au/TS-1催化剂101g。
对比例2
(1)取100ml的四氯金酸(HAuCl4)和氯钯酸钠(Na2PdCl4)溶液(其中金钯原子比为1:1,共加入0.8625g(0.002538mol)的HAuCl4和0.7467g(0.002538mol)的Na2PdCl4固体,配成100ml水溶液),加入1.111g聚乙烯吡咯烷酮(PVP)作为保护,在0℃下搅拌0.5小时。然后加入3.783g(0.1mol)的硼氢化钠(NaBH4),继续搅拌2h得到PVP稳定的Au-Pd纳米溶胶。
(2)往溶胶溶液中加入0.1300g(0.0007255mol)(3-氨基丙基)三甲氧基硅烷(APS)作为表面接枝偶联剂,继续搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶。
(3)往Au-Pd溶胶中加入31.2g(0.15mol)正硅酸四乙酯(TEOS)与38.8g(0.047mol)25wt%四丙基氢氧化铵(TPAOH),在50℃下搅拌1h后加入3.06g(0.009mol)钛酸四正丁酯(TBOT)与10.56g(0.229mol)乙醇的混合溶液,60℃下预水解3小时后转入水热釜170℃下水热48h,将二次晶化分子筛母液离心、洗涤、干燥后在550℃马弗炉焙烧4h得TS-1@Au-Pd。
对比例3
(1)取0.8625g(0.002538mol)的HAuCl4和1.382g(0.004697mol)的H2PdCl4固体,配成100ml水溶液),加入1.111g聚乙烯吡咯烷酮(PVP)作保护剂,冰水浴冷条件冷却至0℃下搅拌0.5小时,然后加入3.783g(0.1mol)的硼氢化钠(NaBH4)还原剂,继续搅拌2h得到PVP稳定的Au-Pd纳米溶胶。
(2)往溶胶溶液中加入0.1300g(0.0007255mol)(3-氨基丙基)三甲氧基硅烷(APS)作为表面接枝偶联剂,继续搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶。
(3)往溶胶中直接加入3.47g(0.0167mol)正硅酸四乙酯TEOS,4.75g(0.0058mol)25wt%四丙基氢氧化铵溶液与67.8g H2O,溶液65℃水解3h后移入四氟水热釜170℃下水热48h后分子筛母液冷却、离心、洗涤、干燥后得到Au-Pd@Silicalite-1,Silicalite-1晶化原料摩尔比为1TEOS:0.35TPAOH:237.5H2O。将分子筛母液离心、洗涤、干燥后在550℃马弗炉焙烧4h得Au-Pd/Silicalite-1。
实施例4-9为实施例1-3与对比例1-3所制备催化活性进行验证的过程。
催化活性活性的装置所采用的是固定床反应器,该固定床反应器为长度2.1m,管径为2cm。催化剂的装填方式过程中采用焙烧后的石英砂作为装填的封料物。
实施例4
将氯丙烯、氧气、氢气、氮气、溶剂和催化剂A按照氯丙烯与氧气、氢气、氮气的摩尔比为1:2:2:5,溶剂甲醇与催化剂的质量比为200,在温度为30℃压力为0.2MPa下,在总气体体积空速为500h-1下进行反应。
反应24小时后的结果如下:氯丙烯收率为45%;环氧氯丙烷选择性为95%;二氯丙醇+缩醚2%;
实施例5
将氯丙烯、氧气(10%体积,其余为氮气)、氢气、二氧化碳、溶剂和催化剂B按照氯丙烯与氧气、氢气的摩尔比为2:1:2:3,溶剂甲醇与催化剂的质量比为500,在温度为60℃压力为1MPa下,在总气体体积空速为600h-1下进行反应。
反应24小时后的结果如下:氯丙烯收率为48%;环氧氯丙烷选择性为96%;二氯丙醇+缩醚4%;
实施例6
将氯丙烯、氧气、氢气、溶剂和催化剂C按照氯丙烯与氧气、氢气的摩尔比为1:1:1,溶剂甲醇与催化剂的质量比为100,在温度为120℃压力为2.5MPa下,在总气体体积空速为1000h-1下进行反应。
反应24小时后的结果如下:氯丙烯收率为38%;环氧氯丙烷选择性为95%;二氯丙醇+缩醚5%;
实施例7
将氯丙烯、氧气、氢气、氮气、溶剂和Au-Pd/TS-1分子筛催化剂,按照氯丙烯与氧气、氢气、氮气的摩尔比为1:2:2:5,溶剂甲醇与催化剂的质量比为200,在温度为30℃压力为0.2MPa下,在总气体体积空速为500h-1下进行反应。
反应24小时后的结果如下:氯丙烯收率为20%;环氧氯丙烷选择性为85%;二氯丙醇+缩醚14%;
实施例8
将氯丙烯、氧气、氢气、氮气、溶剂和TS-1@Au-Pd核壳结构催化剂,按照氯丙烯与氧气、氢气、氮气的摩尔比为1:2:2:5,溶剂甲醇与催化剂的质量比为200,在温度为30℃压力为0.2MPa下,在总气体体积空速为500h-1下进行反应。
反应24小时后的结果如下:氯丙烯收率为30%;环氧氯丙烷选择性为75%;二氯丙醇+缩醚25%;
实施例9
将氯丙烯、氧气、氢气、氮气、溶剂和Silicalite-1@Au-Pds核壳结构催化剂,按照氯丙烯与氧气、氢气、氮气的摩尔比为1:2:2:5,溶剂甲醇与催化剂的质量比为200,在温度为30℃压力为0.2MPa下,在总气体体积空速为500h-1下进行反应。
反应24小时后的结果如下:氯丙烯收率为5%;环氧氯丙烷选择性为86%,收率为85.7%;二氯丙醇+缩醚14%;
产物通过气相色谱的内标法进行分析,来监测氯丙烯的收率、环氧氯丙烷和二氯丙醇及缩醚的选择性。采用装备HP-5毛细管色谱柱(35m×0.32nm×0.30μm)和AgilentGC8890型气相色谱仪,用氮气作为载体,进样口7.5spi,250℃,色谱柱为220℃,进样为0.8ml/min,后FID为300℃。用乙腈作为溶剂,正丁醇作为内标。催化剂的性能指标:
环氧氯丙烷的选择性%=环氧氯丙烷的收率/(环氧氯丙烷的收率+二氯丙醇的收率+缩醚的收率)×100
剩余双氧水用碘量法进行检测:其方法为取0.5g的反应液,加入1g的碘化钾,避光5分钟后,再加入1g钼酸铵,然后用硫代硫酸钠进行滴定。滴定至溶液的颜色发生变化的时候,加入淀粉指示剂,当溶液的颜色为透明色时候即为滴定的终点。
表1实施例1-3与对比例1-3所制得催化剂中Au与Pd的含量
表2实施例1-3与对比例1-3催化活性验证结果
申请人声明,以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,所属技术领域的技术人员应该明了,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,均落在本发明的保护范围和公开范围之内。
HITACHI S-4800型场发射扫描电镜测定TS-1@Au-Pd/Silicalite-1催化剂形貌:从图2中可看催化剂晶粒尺寸为200nm附近,晶粒大小均匀。用JEM-2010型透射电镜观测催化剂形貌,电子束电压200kV;从图3中可看到Au-Pd纳米合金尺寸为2~3nm附近;且合金纳煽米粒子均匀分散于分子筛体相。
X-射线粉末衍射(XRD)所用仪器为Philips X’pert pro X射线衍射仪,测试条件为Cu靶(λ=0.15418nm),Ni滤波片,管压40KV,管流40mA;从图4可观察到15°附近TS-1 002,102,301,322晶面族衍射峰,25°附近的三组峰分别对应着TS-1 501,151,303晶面族衍射峰,特征衍射峰表明所合成分子筛是MFI晶型TS-1分子筛,且未观察到Au-Pd金属对应衍射峰,贵金属组分呈高分散状态。
Claims (10)
1.一种TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,包括以下步骤
(1)取一定比例的氯金酸(HAuCl4)和氯钯酸(H2PdCl4)溶于水中,配成水溶液,加入一定量的聚乙烯吡咯烷酮(PVP)作稳定剂;
(2)冰水浴冷条件冷却至0℃下搅拌0.5h,加入一定量还原剂,加完继续搅拌2h得到Au-Pd纳米溶胶;
(3)向溶胶中加入HAuCl4,H2PdCl4,十六三甲氧基硅烷,搅拌2h后得到硅烷偶联剂接技的Au-Pd溶胶;
(4)继续加入Silicalite-1预水解液TEOS,TPAOH,H2O,于65℃水解3h,随后移至四氟水热釜中于170℃水热48h后得分子筛母液;
(5)分子筛母液经冷却、离心、洗涤、干燥后得到制得Au-Pd/Silicalite-1;
(6)取1-5g Au-Pd/Silicalite-1晶种,加入Au,Pd,TEOS,TPAOH,H2O的预水解液,于50℃下搅拌1h;
(7)加入TEOS,PAOH,TBOT,乙醇混合液于60℃下预水解3h后转入水热釜170℃下水热48h制得含结构导向剂的TS-1@Au-Pd/Silicalite-1分子筛;
(8)将分子筛母液过滤、离心洗涤、干燥,将其转入马弗炉以℃/min的速率升温至550℃高温焙烧4h后制得催化剂TS-1@Au-Pd/Silicalite-1;
(9)取45-50g TS-1@Au-Pd/Silicalite-1分子筛,加入TPAOH,H2O混合液,于170℃水热48h,得分子筛母液;
(10)分子筛母液经冷却、离心、洗涤、干燥后,将其转入马弗炉以5℃/min的速率升温至550℃焙烧4h得TS-1@Au-Pd/Silicalite-1分子筛;
(11)取45-50g TS-1@Au-Pd/Silicalite-1分子筛,加入TPAOH,CMC,H2O混捏挤条成型干燥后;
(12)将其转入马弗炉以5℃/min的速率升温至550℃焙烧4~8h得TS-1@Au-Pd/Silicalite-1分子筛;
(13)取45-50gTS-1@Au-Pd/Silicalite-1分子筛催化剂,加入含硅烷的乙醇混合液;
(14)在室温下搅拌24h,得到表面疏水改性的TS-1@Au-Pd/Silicalite-1催化剂;
(15)将分子筛催化剂装入固定床反应器或直接将原粉加入淤浆床反应器通入氢气和氧气在核壳分子筛催化剂核层Au-Pd/Sililicate-1原位产生双氧水,产生的双氧水内扩散至TS-1分子筛Ti活性位与氯丙烯反应得到环氧氯丙烷。
2.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤1中,HAuCl4:H2PdCl4:PVP摩尔比范围为1:1:0.00875-1:5:0.04375。
3.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤2中,还原剂为NaBH4或柠檬酸钠,其中HAuCl4:H2PdCl4:还原剂=1:1:0.1-1:5:0.5。
4.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤3中,HAuCl4:H2PdCl4:十六三甲氧基硅烷摩尔比范围为1:1:0.14-1:5:0.7;十六三甲氧基硅烷可用相同摩尔比的十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种替代。
5.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤4中,Silicalite-1预水解液摩尔比为TEOS:TPAOH:H2O=1:0.35:237.5。
6.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤6中,Au:Pd:TEOS:TPAOH:H2O=1:1:1:0.35:237.5-1:5:5:1.75:1187.5摩尔比的预水解液。
7.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤7中,摩尔比为TEOS:PAOH:TBOT:乙醇=1:0.31:0.06:1.53-5:1.65:0.3:7.65混合液。
8.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤9中,摩尔比为TPAOH:H2O=1:7.683-5:38.415混合液。
9.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤11中,摩尔比为TPAOH:CMC:H2O=1:0.06:10.01-5:0.3:50。
10.根据权利要求1所述的TS-1@Au-Pd/Silicalite-1催化剂的制备方法,其特征在于,步骤13中,TS-1@Au-Pd/Silicalite-1:含硅烷的乙醇混合液摩尔比为1:1-1:5;所述硅烷为十六烷基三甲氧基硅烷、十八烷基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、三甲基氯硅烷中的一种或多种与乙醇的摩尔比为1:100-1:200。
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