CN106311207A - 一种硅胶基固体碱的制备方法 - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000007787 solid Substances 0.000 title claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 title abstract 3
- 238000000034 method Methods 0.000 title abstract 2
- 239000000741 silica gel Substances 0.000 claims abstract description 69
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 69
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims 17
- 239000003054 catalyst Substances 0.000 abstract description 35
- 239000002585 base Substances 0.000 abstract description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005642 Oleic acid Substances 0.000 abstract description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 5
- 238000006000 Knoevenagel condensation reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 238000005882 aldol condensation reaction Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 235000005513 chalcones Nutrition 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NNDLQUNWZOIESH-UHFFFAOYSA-N 8-hydroxy-7-[[7-[(8-hydroxy-5-sulfoquinoline-7-carbonyl)amino]-4-[3-[(8-hydroxy-5-sulfoquinoline-7-carbonyl)amino]propyl]heptyl]carbamoyl]quinoline-5-sulfonic acid Chemical compound C1=CC=NC2=C(O)C(C(=O)NCCCC(CCCNC(=O)C=3C(=C4N=CC=CC4=C(C=3)S(O)(=O)=O)O)CCCNC(=O)C3=C(C4=NC=CC=C4C(=C3)S(O)(=O)=O)O)=CC(S(O)(=O)=O)=C21 NNDLQUNWZOIESH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
本发明公开了一种硅胶基固体碱的制备方法,步骤为:(1)向反应瓶中加入大孔硅胶载体;(2)加热大孔硅胶载体到200~320℃;(3)加入大孔硅胶载体质量5~20%的可溶性强碱,进行反应;(4)保温,脱水2~5小时,冷却,即得到白色粉末状硅胶基固体碱催化剂。本发明以大孔硅胶作为载体,制得的硅胶基固体碱催化剂满足了成本低廉、比表面积大、孔径及孔容大、碱强度适中的优点,实际测试结果:孔径为15~20nm,孔容为1.0~1.5ml/g,比表面积为400~600m2/g,碱强度H‑=17~19。该催化剂在油酸与甘油的酯化反应、Knoevenagel缩合反应和羟醛缩合反应中都表现出了良好的催化活性。
Description
技术领域
本发明涉及化学化工技术领域,具体是一种硅胶基固体碱的制备方法。
背景技术
固体碱催化剂具有高活性、高选择性、反应条件温和、产物易于分离、经济环保、设备腐蚀小等优点,在工业生产中引起了广泛的关注。但相对于固体酸催化剂而言,固体碱催化剂起步晚,发展慢。随着碱性催化剂在非均相催化反应领域的大范围应用,对于固体碱的需求量越来越大,如何开发出制备简单、成本低廉的新型固体碱催化剂就成为了研究的热点。
目前研究最多且有工业化可能的固体碱主要是负载型固体碱,负载型固体碱的载体主要有三氧化铝、分子筛和活性炭三种,负载的前驱体物种主要为碱金属、碱金属氢氧化物、碳酸盐、氟化物、硝酸盐、醋酸盐、氨化物和叠氮化物等。γ-A12O3是最常见的固体碱载体,田部浩三在触媒1985,27(3):198中最先制备了Na/γ-A12O3、K/γ-A12O3等固体碱;Fraile等人开发了KF/Al2O3应用于具有不同的吸电子基团手性D-甘油醛的烯烃环氧化,保持了50%的非对映异构体。沸石分子筛因其高比表面积和独特的择形性而被广泛用作负载型固体碱的载体,Davis R J等研究了Cs/CsX、Cs/CsY、CsOx/CsX、CsOx/CsY这几种催化剂的碱性及催化活性,并深入探讨了催化剂中活性物质对催化活性的影响;Barrault J等研究了在碱性催化剂Mg/MCM-41的催化作用下用富甲基酯和甘油合成甘油甲酸酯,所得产率达到80%,其选择性远高于均相催化剂。活性炭(C)因其具有较大的比表面积,也常用作固体碱催化剂的载体,魏彤等人将KI、K2CO3、KOH浸渍于介孔活性炭(C)载体上,制备了KI/C、K2CO3/C、KOH/C催化剂,用于碳酸丙烯酯和甲醇酯交换反应。
目前国内外制备的固体碱主要存在以下问题:
(1)以γ-A12O3为载体,成体较低,但是难以获得大的比表面和孔容积,比表面一般小于200m2/g,孔径小于5nm,孔容小于0.7ml/g,对大分子的反应催化剂效果一般较差;
(2)以分子筛作为载体,比表面积和孔容积有了较大提高,所得催化剂比表面积大于300m2/g,孔径最大可达到15nm,孔容0.7~1.0ml/g,但是分子筛成本较高,所得催化剂成本偏高;
(3)以活性炭作为载体,活性组分为物理吸附,容易从催化剂载体上脱落,催化剂不稳定,容易失活。
因此有必要开发一种比表面积大、孔容和孔径大、碱强度适中、成本低廉,催化活性好的固体碱催化剂,以适应大分子的碱性催化反应,满足市场的需要。
发明内容
本发明的目的在于提供一种成本低廉、比表面积及孔容大、碱强度适中、催化效果好的硅胶基固体碱的制备方法。
为实现上述目的,本发明提供如下技术方案:
一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到200~320℃;
(3)加入大孔硅胶载体质量5~20%的可溶性强碱,进行反应;
(4)待反应完全后,保温,脱水2~5小时,冷却,即得到白色粉末状硅胶基固体碱催化剂。
作为本发明进一步的方案:所述的步骤(1)中,大孔硅胶载体属非晶态物质,其化学分子式为mSiO2·nH2O,其比表面为400~600m2/g,孔径为15~25nm,孔容为1.0~2.0ml/g。
作为本发明进一步的方案:所述的步骤(2)中,常压下将反应瓶中的大孔硅胶载体加热至200~320℃。
作为本发明进一步的方案:所述的步骤(2)中,加热温度为250~300℃。
作为本发明进一步的方案:所述的步骤(2)中,加热温度为280~300℃。
作为本发明进一步的方案:所述的步骤(2)中,加热温度为280℃。
作为本发明进一步的方案:所述的步骤(3)中,所述的可溶性强碱为氢氧化钠或氢氧化钾。
作为本发明进一步的方案:所述的步骤(3)中,可溶性强碱的加入方式为滴加,滴加完毕继续反应30~40min。
作为本发明进一步的方案:所述的步骤(3)中,可溶性强碱的加入量为硅胶质量的10~20%。
作为本发明进一步的方案:所述的步骤(3)中,可溶性强碱的加入量为硅胶质量的15%。
作为本发明进一步的方案:所述的步骤(4)中,保温,在真空度为0.09MPa条件下脱水,具体操作为:采用三口烧瓶作为反应瓶,该三口烧瓶的三个口分别连接真空泵、温度计、搅拌装置,在保温和0.09MPa真空条件下,配合不断搅拌进行脱水。
作为本发明进一步的方案:所述的步骤(4)中,脱水时间为3~5小时。
与现有技术相比,本发明的有益效果是:本发明所得到的硅胶基固体碱,是以成本低廉的大孔硅胶作为载体,所得到的催化剂满足了成本低廉,比表面积大,孔径及孔容大,碱强度适中的优点,实际测试结果:孔径为15~20nm,孔容为1.0~1.5ml/g,比表面积为400~600m2/g,碱强度H-=17~19。该催化剂在油酸与甘油的酯化反应、Knoevenagel缩合反应和羟醛缩合反应中都表现出了良好的催化活性。
附图说明
图1是本发明涉及的化学反应示意图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
请参阅图1,本发明实施例中,一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到200~320℃;
(3)加入大孔硅胶载体质量5~20%的可溶性强碱,进行反应;
(4)待反应完全后,保温,脱水2~5小时,冷却,即得到白色粉末状硅胶基固体碱催化剂。
其中,步骤(1)中,大孔硅胶载体属非晶态物质,其化学分子式为mSiO2·nH2O,其比表面为400~600m2/g,孔径为15~25nm,孔容为1.0~2.0ml/g。步骤(3)中,所述的可溶性强碱为氢氧化钠或氢氧化钾。
实施例1
本发明实施例中,一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到280℃;
(3)加入大孔硅胶载体质量10%的固体NaOH,进行反应;
(4)待反应完全后,保温脱水5小时即得到白色粉末状硅胶基固体碱催化剂,孔径为17nm,孔容为1.2ml/g,比表面积为450m2/g,碱强度H-=17.4。
向反应瓶中加入油酸73.6g,甘油7.27g,上述催化剂0.22g,保持真空度≥0.09MPa,于230℃反应5小时,酸值可降至20.9mgKOH/g,反应转化率为98.6%。
实施例2
本发明实施例中,一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到300℃;
(3)加入大孔硅胶载体质量20%的固体KOH,进行反应;
(4)待反应完全后,保温脱水4小时即得到白色粉末状硅胶基固体碱催化剂,孔径为15nm,孔容为1.4ml/g,比表面积为550m2/g,碱强度H-=18.7。
将80g环己酮、2.5%(占环己酮质量百分比)上述催化剂加入到装有搅拌器、控温装置和分水器的250ml三颈烧瓶中,控制温度在210℃,使环己酮回流,水与环己酮共沸蒸出,反应5h后,抽滤溶液并回收催化剂,GC分析环己酮的转化率为99.5%。
实施例3
本发明实施例中,一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到280℃;
(3)加入大孔硅胶载体质量15%的固体NaOH,进行反应;
(4)待反应完全后,保温脱水3小时即得到白色粉末状硅胶基固体碱催化剂,孔径为19nm,孔容为1.5ml/g,比表面积为490m2/g,碱强度H-=17.3。
在带有搅拌的三颈瓶中依次加入4g上述催化剂、0.2mol苯乙酮和0.2mol苯甲醛、50ml无水乙醇,控温40℃反应3h。反应结束后,加热溶解查尔酮,过滤并回收催化剂,将滤液在旋转蒸发仪中蒸干,得浅黄色固体缩合物查尔酮粗产品,以95%乙醇重结晶得到淡黄色针状晶体,收率为94.5%。
实施例4
本发明实施例中,一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到200℃;
(3)加入大孔硅胶载体质量5%的固体NaOH,进行反应;
(4)待反应完全后,保温脱水2小时即得到白色粉末状硅胶基固体碱催化剂,孔径为15nm,孔容为1.0ml/g,比表面积为400m2/g,碱强度H-=17.0。
向反应瓶中加入油酸73.6g,甘油7.27g,上述催化剂0.22g,保持真空度≥0.09MPa,于230℃反应5小时,酸值可降至21.0mgKOH/g,反应转化率为98.1%。
实施例5
本发明实施例中,一种硅胶基固体碱的制备方法,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到320℃;
(3)加入大孔硅胶载体质量20%的固体KOH,进行反应;
(4)待反应完全后,保温脱水4小时即得到白色粉末状硅胶基固体碱催化剂,孔径为20nm,孔容为1.4ml/g,比表面积为600m2/g,碱强度H-=19.0。
在带有搅拌的三颈瓶中依次加入4g上述催化剂、0.2mol苯乙酮和0.2mol苯甲醛、50ml无水乙醇,控温40℃反应3h。反应结束后,加热溶解查尔酮,过滤并回收催化剂,将滤液在旋转蒸发仪中蒸干,得浅黄色固体缩合物查尔酮粗产品,以95%乙醇重结晶得到淡黄色针状晶体,收率为94.9%。
本发明所得到的硅胶基固体碱,是以成本低廉的大孔硅胶作为载体,所得到的催化剂满足了成本低廉,比表面积大,孔径及孔容大,碱强度适中的优点,实际测试结果:孔径为15~20nm,孔容为1.0~1.5ml/g,比表面积为400~600m2/g,碱强度H-=17~19。该催化剂在油酸与甘油的酯化反应、Knoevenagel缩合反应和羟醛缩合反应中都表现出了良好的催化活性。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (10)
1.一种硅胶基固体碱的制备方法,其特征在于,由以下步骤组成:
(1)向反应瓶中加入大孔硅胶载体;
(2)加热大孔硅胶载体,使之温度升到200~320℃;
(3)加入大孔硅胶载体质量5~20%的可溶性强碱,进行反应;
(4)待反应完全后,保温,脱水2~5小时,冷却,即得到白色粉末状硅胶基固体碱催化剂。
2.根据权利要求1所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(1)中,大孔硅胶载体属非晶态物质,其化学分子式为mSiO2·nH2O,其比表面为400~600m2/g,孔径为15~25nm,孔容为1.0~2.0ml/g。
3.根据权利要求1所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(2)中,加热温度为250~300℃。
4.根据权利要求3所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(2)中,加热温度为280~300℃。
5.根据权利要求4所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(2)中,加热温度为280℃。
6.根据权利要求1所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(3)中,所述的可溶性强碱为氢氧化钠或氢氧化钾。
7.根据权利要求6所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(3)中,可溶性强碱的加入量为硅胶质量的10~20%。
8.根据权利要求7所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(3)中,可溶性强碱的加入量为硅胶质量的15%。
9.根据权利要求1所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(4)中,在真空度为0.09MPa条件下脱水。
10.根据权利要求1所述的硅胶基固体碱的制备方法,其特征在于,所述的步骤(4)中,脱水时间为3~5小时。
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