CN114950535B - 一种固体酸催化剂的制备方法及其在不饱和酮合成中的应用 - Google Patents
一种固体酸催化剂的制备方法及其在不饱和酮合成中的应用 Download PDFInfo
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- CN114950535B CN114950535B CN202210542870.6A CN202210542870A CN114950535B CN 114950535 B CN114950535 B CN 114950535B CN 202210542870 A CN202210542870 A CN 202210542870A CN 114950535 B CN114950535 B CN 114950535B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J2229/10—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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J2229/10—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明提供一种固体酸催化剂的制备方法,并应用于Saucy‑Marbet反应制备不饱和酮。固体酸催化剂的制备方法包括以下步骤:在低共熔溶剂中将SBA‑15与氨水和锑金属盐搅拌、干燥得到主体催化剂Sb‑SBA‑15;再通过浸渍法将铌作为助剂引入主体催化剂中,并进一步干燥、煅烧制得Nb‑Sb‑SBA‑15固体酸催化剂。Nb‑Sb‑SBA‑15是一种温和的酸催化剂,其具有优异的催化性能,且对设备无腐蚀、环境污染小、易于回收,可代替液体酸催化剂催化不饱和醇发生Saucy‑Marbet反应生产不饱和酮,有效抑制副反应的发生,反应转化率高达99.8%,产品纯度高达99.8%。
Description
技术领域
本发明属于有机合成领域,具体涉及一种用于催化Saucy-Marbet反应制备不饱和酮的固体酸催化剂的合成及应用。
背景技术
在香料和医药合成领域,不饱和酮是一种重要的精细化工中间体,如假紫罗兰酮(6,10-二甲基-3,5,9-十三碳烯-2-酮)、6-甲基-5-庚烯-2-酮、香叶基丙酮(2,6-二甲基-2,6-十一碳二烯-10-酮)等,是合成维生素A、胡萝卜素、芳樟醇、橙花叔醇等的重要中间体。目前,已报道的不饱和酮合成方法主要有三种:双乙烯酮法、乙酰乙酸乙酯法(卡洛重排反应)和甲基异丙烯基醚法(Saucy-Marbet反应)。
以芳樟醇(3,7-二甲基-1,6-辛二烯-3-醇)合成香叶基丙酮为例,双乙烯酮法是以芳樟醇和双烯酮为原料合成得到香叶基丙酮和橙花基丙酮的混合物,但由于此反应使用的双烯酮本身很不稳定,且没有成本优势,不利于工业生产。乙酰乙酸乙酯重排法是以芳樟醇和乙酰乙酸乙酯为原料,乙醇钠/异丙基锑为催化剂,产物中顺式与反式异构体的比例从92:8~3:2不等,但此合成方法所采用的乙酰乙酸乙酯不但单耗大、成本也高,且原子经济性差,使得该方法竞争力较弱。甲基异丙烯基醚法,即以不饱和醇和甲基异丙烯基醚为原料,在布朗斯特酸催化剂作用下发生Saucy-Marbet反应,然后异构反应得到不饱和酮产品。该方法最早由Saucy和Marbet等人报道(US3029287,US6184420),他们使用对甲苯磺酸、甲磺酸、硫酸等强酸催化可以高收率的得到目标产物,该反应的起始原料甲基异丙烯基醚简单易得,价格低廉,反应条件温和可控,因而具有较好的经济前景,但是,目前已知专利报道中,该反应主要使用甲苯磺酸、甲磺酸、硫酸等催化,酸催化剂用量大(5~10mol%),对设备腐蚀性强、反应放热剧烈,不可避免的产生部分脱水副产物,且反应完成后,酸催化剂和产品混溶在一起,难于回收套用;此外,在产品提纯过程中,还需将残留的酸催化剂中和,不但消耗碱中和剂,还产生多余的三废(CN1293181A,CN1817841A,EP1092700)。
虽然均相酸催化剂催化活性高,但是会产生大量的工业废水,造成环境污染。作为均相酸催化剂的替代品,非均相酸催化剂易于分离、回收,优势明显,更适合应用于工业生产。固体酸催化剂具有独特的酸性位点,催化活性较高,一直以来都受到研究人员的重视。目前,用于有机合成领域的固体酸催化剂包括硫酸化金属氧化物(如SO2-4/NbO2,SO2-4/Ta2O5,SO2-4/Nb2O5和SO2-4/Ti O2)、H-型沸石、磺酸离子交换树脂、磺酸改性的介孔二氧化硅、磺化碳基催化剂、杂多酸(HPAs)和酸性离子液体(ILs)等。应用固体酸催化剂可以避免液体酸催化剂的许多缺点,与液体酸催化剂相比,固体酸催化剂具有容易存储、对设备无腐蚀作用、可以实现生产过程连续化、并可消除废酸污染等优点,此外,固体酸催化剂某些特殊结构可赋予其更高的活性和选择性。
发明内容
本发明的目的在于提供一种固体酸催化剂的制备方法,以硅酸钠为基体材料制得的SBA-15为载体,将Sb元素负载在SBA-15载体中得到主体酸催化剂Sb-SBA-15,此外Nb作为助剂被引入主体催化剂中制得Nb-Sb-SBA-15固体酸催化剂。制得的Nb-Sb-SBA-15是一种温和的酸催化剂,其在宽温度范围内具有优异的催化性能,且易于回收,可催化Saucy-Marbet反应生产不饱和酮,并有效抑制副反应的发生,提高产物收率。
为实现上述目的,本发明采用的技术方案具体包括如下内容:
一种固体酸催化剂的制备方法,包括以下步骤:
(1)将SBA-15载体与氨水和锑金属盐置于低共熔溶剂中,在氮气氛围中水热搅拌10~80h,并经干燥,焙烧4~6h处理得到具有催化活性的主体催化剂Sb-SBA-15;
(2)再以有机铌盐为铌源,通过浸渍法将过渡金属Nb作为助剂引入步骤(1)制得的主体催化剂中,并进一步干燥、煅烧制得掺杂Nb的固体酸催化剂Nb-Sb-SBA-15。
介孔二氧化硅材料具有规整的孔道结构、优异的表面物理化学性质及良好的水热稳定性,经常被用于各类催化剂的载体,然而纯硅介孔材料自身不包含酸性位点,不能直接催化反应,对介孔二氧化硅材料的研究大多是通过引入金属杂原子或者接枝加以改性。SBA-15介孔二氧化硅材料具有孔道结构均匀、比表面积大和稳定性好等特点,在催化领域显示出优越的性能。SBA-15的改性与材料表面丰富的Si-OH基密切相关,这些Si-OH基的存在形式主要有自由Si-OH键、双羟基Si-OH键和水合Si-OH键三种。这里的自由Si-OH键与双羟基Si-OH键具有较高的反应活性,可以在反应过程中与活性金属进行反应,将大量的活性位点引入骨架或孔道,从而改变骨架和孔道结构,改善分子筛的催化性能。将金属离子Sb引入其中会对载体骨架中电子结构产生影响,形成多种Sb配合物,从而生成酸性位点,通过这种金属掺杂的方法可以控制分子筛酸量的大小和酸性的强弱。此外铌属于过渡金属,在催化反应时提供活性中心,提高催化性能,它不仅可以作为催化剂助剂,也可以作为催化剂或其载体。
优选的,所述步骤(1)中,锑金属盐包括硝酸锑、硫酸锑、磷酸锑和乙酸锑中的一种或多种,所述锑金属盐以溶液的形式使用,溶液的摩尔浓度为0.2~0.8mol/L;
优选的,步骤(1)SBA-15载体与锑金属盐的质量比为1:1-5;使用氨水的浓度为2~20wt%;
优选的,所述步骤(1)中,水热合成温度为30~70℃,所述焙烧温度为400~600℃;
优选的,步骤(1)所述低共熔溶剂为有机酸和胆碱类化合物通过共热法制备的低共熔溶剂,其中有机酸和胆碱类化合物的摩尔比例为1~4:1;
优选的,制备低共熔溶剂所使用的胆碱类化合物包括乙酰胆碱和/或氯化胆碱,所述有机酸包括丙二酸、乳酸、戊二酸和琥珀酸中的一种或多种;
优选的,步骤(2)中,有机铌盐包括草酸铌、硝酸铌酰、乙酸铌、乙氧醇铌中的一种或多种;
优选的,所述有机铌盐与主体催化剂Sb-SBA-15的质量比为1:2~5;
浸渍温度为20~80℃,浸渍时间为24~48h;煅烧温度为500~600℃;
优选的,制备的固体酸催化剂Nb-Sb-SBA-15酸强度H0≤-3,酸量为1.8~5.0mmol/gcat。
进一步地,本发明提供了一种固体酸催化剂Nb-Sb-SBA-15的应用,所述固体酸催化剂可应用于催化Saucy-Marbet反应得到不饱和酮,所述合成不饱和酮的原料为不饱和醇和甲基异丙烯基醚,反应方程式如下:
进一步地,所述的不饱和醇选自2-甲基-3-丁烯-2-醇、3-甲基-1-戊烯-3-醇、3,7-二甲基-1,6-辛二烯-3-醇或其他碳四到碳十脂肪族不饱和醇中的至少一种。
进一步地,所述Saucy-Marbet反应在高压反应釜中进行,固体酸催化剂Nb-Sb-SBA-15置于高压釜内循环利用;所述反应原料不饱和醇和甲基异丙烯基醚的摩尔比为1:2~5,反应空速为2.0~16.0h-l。
本发明的积极效果在于:
(1)以SBA-15作为固体酸载体孔道结构均匀、稳定性好,可以在将大量的活性位点引入骨架或孔道,从而改变骨架和孔道结构,赋予分子筛优异的催化性能。
(2)以SBA-15载体负载Sb的主体催化剂Sb-SBA-15结构稳定,负载酸量高,催化活性高,能适应苛刻的反应条件,且环境友好。
(3)本发明所制备的固体酸催化剂Nb-Sb-SBA-15可以用于催化Saucy-Marbet反应,并且能有效抑制不饱和醇生成脱水副产物,转化率可以高达99.8%,产品选择性高达99.8%,后处理简单并能循环多次使用。
具体实施方式
下面通过具体实施例对本发明催化剂的合成及催化剂的应用作进一步说明,但本发明并不限于下述的实施例。
实施例1
固体酸催化剂Nb-Sb-SBA-15-1的制备
选用SBA-15作为载体制备主体催化剂,首先将氨水(浓度5wt%)滴加到0.4mol/L硝酸锑溶液(200mL)中,出现白色沉淀后继续滴加至出现白色溶液。然后将其加入低共熔溶剂中,该低共熔溶剂的氢键供体和受体分别为氯化胆碱和戊二酸(摩尔比例1:2),并倾入5gSBA-15,在装有磁力搅拌器、尾气吸收装置和氮气保护装置的500mL反应瓶中70℃搅拌2h,再降温至30℃反应10h。最后,洗涤过滤以去除反应溶剂及小分子寡聚物并在室温下干燥,并在550℃下焙烧4h制得主体催化剂Sb-SBA-15。
将3.20g主体催化剂Sb-SBA-15浸渍到50mL摩尔浓度为0.1mol/L的乙氧醇铌溶液中,将溶液在20℃水浴上搅拌24h后再蒸干,转移至100℃烘箱中干燥4h,最后在500℃下煅烧2h,制得Nb-Sb-SBA-15固体酸催化剂。制备的固体酸催化剂Nb-Sb-SBA-15负载酸量为3.2mmol/gcat。
实施例2
固体酸催化剂Nb-Sb-SBA-15-2的制备
选用SBA-15作为载体制备主体催化剂,首先将氨水(浓度5wt%)滴加到0.25mol/L乙酸锑溶液(200mL)中,出现白色沉淀后继续滴加至出现白色溶液。然后将其加入低共熔溶剂中,该低共熔溶剂的氢键供体和受体分别为氯化胆碱和丙二酸(摩尔比例1:3),并倾入5gSBA-15,在装有磁力搅拌器、尾气吸收装置和氮气保护装置的500mL反应瓶中70℃搅拌1h,再降温至40℃反应10h。最后,洗涤过滤以去除反应溶剂及小分子寡聚物并在室温下干燥,并在500℃下焙烧6h制得主体催化剂Sb-SBA-15。
将5.43g主体催化剂Sb-SBA-15浸渍到50mL摩尔浓度为0.05mol/L的草酸铌溶液中,将溶液在40℃水浴上搅拌24h后再蒸干,转移至100℃烘箱中干燥4h,最后在500℃下煅烧2h,制得Nb-Sb-SBA-15固体酸催化剂。制备的固体酸催化剂Nb-Sb-SBA-15负载酸量为4.1mmol/gcat。
实施例3
固体酸催化剂Nb-Sb-SBA-15-3的制备
选用SBA-15作为载体制备主体催化剂,首先将氨水(浓度7wt%)滴加到0.60mol/L磷酸锑溶液(150mL)中,出现白色沉淀后继续滴加至出现白色溶液。然后将其加入低共熔溶剂中,该低共熔溶剂的氢键供体和受体分别为氯化胆碱和戊二酸(摩尔比例1:2),并倾入5gSBA-15,在装有磁力搅拌器、尾气吸收装置和氮气保护装置的500mL反应瓶中50℃搅拌1h,再降温至30℃反应10h。最后,洗涤过滤以去除反应溶剂及小分子寡聚物并在室温下干燥,并在500℃下焙烧4h制得主体催化剂Sb-SBA-15。
将4.80g主体催化剂Sb-SBA-15浸渍到50mL摩尔浓度为0.1mol/L的乙氧醇铌溶液中,将溶液在30℃水浴上搅拌24h后再蒸干,转移至100℃烘箱中干燥4h,最后在550℃下煅烧2h,制得Nb-Sb-SBA-15固体酸催化剂。制备的固体酸催化剂Nb-Sb-SBA-15负载酸量为3.9mmol/gcat。
实施例4
固体酸催化剂Nb-Sb-SBA-15-4的制备
选用SBA-15作为载体制备主体催化剂,首先将氨水(浓度10wt%)滴加到0.25mol/L硫酸锑溶液(150mL)中,出现白色沉淀后继续滴加至出现白色溶液。然后将其加入低共熔溶剂中,该低共熔溶剂的氢键供体和受体分别为氯化胆碱和琥珀酸(摩尔比例1:3),并倾入5g SBA-15,在装有磁力搅拌器、尾气吸收装置和氮气保护装置的500mL反应瓶中70℃搅拌2h,再降温至40℃反应10h。最后,洗涤过滤以去除反应溶剂及小分子寡聚物并在室温下干燥,并在400℃下焙烧6h制得主体催化剂Sb-SBA-15。
将3.68g主体催化剂Sb-SBA-15浸渍到50mL摩尔浓度为0.05mol/L的硝酸铌酰溶液中,将溶液在30℃水浴上搅拌48h后再蒸干,转移至100℃烘箱中干燥4h,最后在500℃下煅烧2h,制得Nb-Sb-SBA-15固体酸催化剂。制备的固体酸催化剂Nb-Sb-SBA-15负载酸量为4.4mmol/gcat。
实施例5
以固体酸催化剂Nb-Sb-SBA-15催化不饱和酮的合成
以不饱和醇和甲基异丙烯基醚为原料,在固定床反应器上评价催化剂,其步骤是在固定床反应器中分别装填实施例1~4得到的固体酸催化剂Nb-Sb-SBA-15,使不饱和醇和甲基异丙烯基醚通过颗粒间隙流过固定床反应器中的催化剂床层,在固体酸催化剂的作用下,将不饱和醇和甲基异丙烯基醚(MOP)进行SM缩合重排反应,不饱和醇和甲基异丙烯基醚的摩尔比为1:2~5,反应空速为2.0h-l,SM反应的温度为140℃,停留时间为1小时,压力为1MPa。表1为实施例1~4制备的固体酸催化剂在几种不同的不饱和醇应用例中的催化活性测试结果。
表1固体酸催化剂催化剂活性评价
编号 | 不饱和醇 | 不饱和醇/MOP摩尔比 | 催化剂 | 不饱和醇转化率 | 选择性 |
1 | 2-甲基-3-丁烯-2-醇 | 1:3 | Nb-Sb-SBA-15-1 | 99.1% | 98.4% |
2 | 2-甲基-3-丁烯-2-醇 | 1:3 | Nb-Sb-SBA-15-3 | 99.2% | 99.6% |
3 | 2-甲基-3-丁烯-2-醇 | 1:4 | Nb-Sb-SBA-15-4 | 99.5% | 99.8% |
4 | 3,7-二甲基-1,6-辛二烯-3-醇 | 1:3 | Nb-Sb-SBA-15-2 | 99.8% | 93.6% |
5 | 3,7-二甲基-1,6-辛二烯-3-醇 | 1:4 | Nb-Sb-SBA-15-3 | 99.6% | 99.4% |
6 | 3-甲基-1-戊烯-3-醇 | 1:3 | Nb-Sb-SBA-15-1 | 99.7% | 97.1% |
7 | 3-甲基-1-戊烯-3-醇 | 1:2 | Nb-Sb-SBA-15-2 | 98.9% | 94.9% |
8 | 3-甲基-1-戊烯-3-醇 | 1:4 | Nb-Sb-SBA-15-3 | 99.8% | 99.8% |
对比例1
将摩尔比例为1:3的3-甲基-1-戊烯-3-醇和甲基异丙烯基醚加入500mL高压反应釜中,将反应釜闭合后用氮气置换3次,开启加热升温至160摄氏度后泵入0.5mol%(相对于3-甲基-1-戊烯-3-醇)的对甲基苯磺酸催化剂溶液,反应压力为1MPa,反应时间为3h,搅拌转速800rpm,反应转化率97.9%,选择性74.6%,催化剂不回收。
对比例2
以3,7-二甲基-1,6-辛二烯-3-醇和甲基异丙烯基醚为原料,在固定床反应器中装填实施例1得到的固体酸催化剂Sb-SBA-15,使3,7-二甲基-1,6-辛二烯-3-醇和甲基异丙烯基醚通过颗粒间隙流过固定床反应器中的催化剂床层,在固体酸催化剂的作用下,将3,7-二甲基-1,6-辛二烯-3-醇和甲基异丙烯基醚(MOP)进行SM缩合重排反应,3,7-二甲基-1,6-辛二烯-3-醇和甲基异丙烯基醚的摩尔比为1:3,反应空速为2.0h-l,SM反应的温度为140℃,停留时间为1小时,压力为1MPa,反应转化率为99.1%,选择性85.8%。
Claims (11)
1.一种固体酸催化剂的制备方法,包括:
(1)将SBA-15载体与氨水和锑金属盐置于低共熔溶剂中,进行水热反应,并经干燥,焙烧处理得到主体催化剂Sb-SBA-15;低共熔溶剂为有机酸和胆碱类化合物通过共热法制备,其中,胆碱类化合物包括乙酰胆碱、氯化胆碱中的一种或多种,有机酸包括丙二酸、乳酸、戊二酸和琥珀酸中的一种或多种,有机酸和胆碱类化合物的摩尔比例为1~4:1;水热温度为30~70℃,时间为10~80h;
(2)以有机铌盐为铌源,通过浸渍法将Nb引入步骤(1)制得的主体催化剂中,并进一步干燥、煅烧制得掺杂Nb的固体酸催化剂Nb-Sb-SBA-15。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中,锑金属盐包括硝酸锑、硫酸锑、磷酸锑和乙酸锑中的一种或多种。
3.根据权利要求1或2所述的制备方法,其特征在于,所述步骤(1)中,SBA-15载体与锑金属盐的质量比为1:1-5。
4.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中,所述焙烧温度为400~600℃,焙烧时间为4~6h。
5.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)中,有机铌盐与主体催化剂Sb-SBA-15的质量比为1:2~5。
6.根据权利要求5所述的制备方法,其特征在于,有机铌盐包括草酸铌、硝酸铌酰、乙酸铌、乙氧醇铌中的一种或多种。
7.根据权利要求1、5-6任一项所述的制备方法,其特征在于,所述步骤(2)中,浸渍温度为20~80℃,浸渍时间为24~48h;煅烧温度为500~600℃。
8.根据权利要求1-7任一项所述制备方法得到固体酸催化剂Nb-Sb-SBA-15在催化不饱和酮合成中的用途。
9.根据权利要求8所述的用途,合成不饱和酮的原料为不饱和醇和甲基异丙烯基醚。
10.根据权利要求9所述的用途,其中,所述的不饱和醇选自2-甲基-3-丁烯-2-醇、3-甲基-1-戊烯-3-醇、3,7-二甲基-1,6-辛二烯-3-醇或其他碳四到碳十脂肪族不饱和醇中的至少一种。
11.根据权利要求9或10所述的用途,其中,不饱和醇和甲基异丙烯基醚的摩尔比为1:2~5。
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