CN112892598A - 一种仲丁醇脱氢mof催化剂的制备方法 - Google Patents
一种仲丁醇脱氢mof催化剂的制备方法 Download PDFInfo
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 21
- 239000012918 MOF catalyst Substances 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910017518 Cu Zn Inorganic materials 0.000 claims abstract description 12
- 229910017752 Cu-Zn Inorganic materials 0.000 claims abstract description 12
- 229910017943 Cu—Zn Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 alkali metal salt Chemical class 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000003607 modifier Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 239000012266 salt solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
-
- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种仲丁醇脱氢MOF催化剂的制备方法,包括如下步骤:1)向配位体溶液中先加入Al盐,加热,先生成Al的预配位化合物,保持加热,再同时加入Cu盐和Zn盐,持续反应,生成Al‑Cu‑Zn多元素MOF;2)将步骤1)所得Al‑Cu‑Zn多元素MOF在低氧气氛的条件下进行碳化处理,制得骨架碳支撑体;3)将步骤2)所得骨架碳支撑体与碱金属盐催化改性剂混合均匀,即得。本发明采用溶剂热法合成Cu、Zn、Al多元素共生的具有金属有机骨架结构的有机配位化合物,通过分步加入金属盐的方法将金属离子分布在不同的节点位置,调变溶剂热条件可以非常和缓的生成MOF,保证了金属离子的分布可控,所得催化剂具有较高的活性稳定性和产物选择性。
Description
技术领域
本发明涉及有机合成领域,尤其涉及一种仲丁醇脱氢MOF催化剂的制备方法。
背景技术
甲乙酮是一种十分重要的化工原料和有机溶剂,用途非常广泛。目前生产甲乙酮的主要方法是仲丁醇脱氢制备甲乙酮,该方法中采用CuO、ZnO、Al2O3催化剂。例如公开号分别为CN100360228C和CN1101262C的中国发明专利中分别公开了CuO、ZnO、Al2O3仲丁醇脱氢制备甲乙酮催化剂。中国专利CN105709752A首先配制锌盐的乙二胺配合物,配制铜盐和稀土盐的混合水溶液,在一定pH值下进行共沉淀,得到含有稀土元素的CuO、ZnO、Al2O3催化剂。中国专利CN107597125B公开了一种含固态钾的CuO、ZnO、Al2O3催化剂,也是采用共沉淀法制备。中国专利CN105056958A公开了一种含有氧化钴和氧化钡的CuO、ZnO、Al2O3催化剂,采用尿素和三乙醇胺作为沉淀剂。以上CuO、ZnO、Al2O3催化剂都是采用沉淀法制备。由于沉淀过程速度极快,很难控制催化剂中各个组分的排列,对催化剂活性以及产物选择性难以有效调节。因此,开发高性能的仲丁醇脱氢催化剂就显得非常重要。
金属有机骨架结构配合物(MOF)是一种具有独特孔道分布和比面积高达1000m2/g以上的金属元素与配位体形成的固体配合物。通常,MOF中的金属都是以离子态存在,主要是作为吸附剂。并且,大部分MOF化合物都是单一金属离子与配体形成的配合物,与实际使用的催化剂中多组分共存的情况不同,不能作为脱氢催化剂。如何制备一种多种金属元素共存的MOF化合物,保证各个元素有序排列,并且结构稳定;经过适当处理将金属离子转化为对应的氧化物,并且仍然保持MOF化合物的结构形态不变是将其应用于催化领域的关键所在。
发明内容
本发明针对上述问题,提供一种仲丁醇脱氢MOF催化剂的制备方法,包括以下步骤:
1)制备Al-Cu-Zn多元素MOF
向配位体的有机溶液中加入Al盐,加热,生成Al的预配位化合物,保持加热,同时加入Cu盐和Zn盐,持续反应,生成Al-Cu-Zn多元素MOF;
2)碳化制备骨架碳支撑体
将步骤1)所得Al-Cu-Zn多元素MOF在低氧气氛的条件下进行碳化处理,制得骨架碳支撑体;
3)制备MOF催化剂
将步骤2)所得骨架碳支撑体与碱金属盐催化改性剂混合均匀,即得。
进一步,步骤1)中,所述Al盐、Cu盐和Zn盐分别为对应的硝酸盐、硫酸盐、醋酸盐或氯化物;所述Al盐、Cu盐和Zn盐的重量比为1:(2-8):(1-5);所述配位体为对苯二甲酸、均苯三甲酸、对苯二甲酸酯、均苯三甲酸酯以及上述化合物的苯环烃基取代衍生物之一;有机溶剂为无水乙醇或DMF;加热温度为100-300℃,反应时间为1-100h。步骤2)中,碳化处理条件为:温度300-600℃,时间2-50h,惰性气体中氧含量<10%。步骤3)中,所述碱金属盐为碳酸钾、碳酸钠、碳酸镁或碳酸钙中的一种,用量为所述Al盐、Cu盐和Zn盐总量的1-2.5%。
本发明采用溶剂热法合成Cu、Zn、Al多元素共生的具有金属有机骨架结构的有机配位化合物,通过分步加入金属盐的方法将金属离子分布在不同的节点位置,调变溶剂热条件可以非常和缓的生成MOF,保证了金属离子的分布可控,尤其多元素离子之间的分布可控;将生成的MOF化合物进行限氧碳化,配位体的苯环转变成碳骨架提供孔道和保证催化剂具有大的比表面积,同时,金属离子转变成相应的氧化物被锚定在特定的位置上,既保证了各组分之间的协同效应,又能阻止金属晶粒在使用情况下长大,保证催化剂具有较高的活性稳定性和产物选择性。尤其用作仲丁醇脱氢制备甲乙酮的催化剂,不但大幅度的提高了仲丁醇的转化率,而且明显的提高了甲乙酮的选择性。
简言之,首先采用溶剂热法合成Cu、Zn、Al多元素共生的MOF的有机配位化合物,向配位体溶液中分步加入盐溶液,先加入Al盐溶液生成Al的预配位化合物,再加入Cu-Zn混盐溶液,最终生成Cu、Zn、Al混杂的金属有机配位化合物。经过过滤、干燥、碳化处理得到一种以骨架碳为支撑,以CuO、ZnO、Al2O3为主要活性组分,以重量百分比为基准,各组分含量为:CuO 20-60%,ZnO 5-35%,Al2O3 1-25%,C 1-50%,碱金属盐催化改性剂0.5-10%的脱氢催化剂。
具体实施方式
以下结合实例对本发明进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种仲丁醇脱氢MOF催化剂的制备方法,其步骤为:称取Cu(NO3)2·3H2O 25g和Zn(NO3)2·6H2O 15g混溶于200ml二甲基甲酰胺中并加热至80℃,称取Al(NO3)3·9H2O 3g溶于100mL二甲基甲酰胺中并加热至80℃,称取对苯二甲酸65g溶于500ml 80℃的二甲基甲酰胺中,在剧烈搅拌下将Al盐溶液缓缓加入对苯二甲酸溶液中,加完后继续搅拌2h;将Cu-Zn混盐溶液加入上述溶液中,加完后继续搅拌2h,将上述物料移入高压釜中在150℃反应20h,得到一种蓝色的物质,过滤,固体物料在120℃真空干燥10h,放入管式炉中在450℃用5%O2/95%N2碳化处理5h,得到一种黑色物质,加入1g K2CO3混合均匀,即得。
实施例2
一种仲丁醇脱氢MOF催化剂的制备方法,其步骤为:称取Cu(NO3)2·3H2O 60g和Zn(NO3)2·6H2O 15g混溶于500mL无水乙醇中并加热至70℃,称取Al(NO3)3·9H2O 10g溶于100mL无水乙醇中并加热至70℃,称取均苯三甲酸139g溶于700ml 70℃的无水乙醇中,在剧烈搅拌下将Al盐溶液缓缓加入均苯三甲酸无水乙醇溶液中,加完后继续搅拌1h;将Cu-Zn混盐溶液加入上述溶液中,加完后继续搅拌2h,将上述物料移入高压釜中在250℃反应10h,得到一种蓝色的物质,过滤,固体物料在110℃真空干燥15h,放入管式炉中在500℃用5%O2/95%N2碳化处理3h,得到一种黑色物质,加入1.5g Na2CO3混合均匀,即得。
实施例3
一种仲丁醇脱氢MOF催化剂的制备方法,其步骤为:称取Cu(NO3)2·3H2O 27g和Zn(NO3)2·6H2O 20g混溶于500ml二甲基甲酰胺中并加热至80℃,AlCl3 10g溶于200mL二甲基甲酰胺中并加热至80℃,称取对苯二甲酸85g溶于500ml 80℃的二甲基甲酰胺中,在剧烈搅拌下将Al盐溶液缓缓加入对苯二甲酸溶液中,加完后继续搅拌1h;将Cu-Zn混盐溶液加入上述溶液中,加完后继续搅拌2h,将上述物料移入高压釜中在200℃反应20h,得到一种蓝色的物质,过滤,固体物料在120℃真空干燥10h,放入管式炉中在450℃用5%O2/95%N2碳化处理5h,得到一种黑色物质,加入1.5g K2CO3混合均匀,即得。
对比例1
一种仲丁醇脱氢催化剂的制备方法,其步骤为:分别称取Cu(NO3)2·3H2O 25g,Zn(NO3)2·6H2O 25g,Al(NO3)3·9H2O 9g混溶于500mL去离子水中并加热至80℃,在剧烈搅拌下用1M Na2CO3水溶液滴定至pH为7,加完后继续搅拌2h,得到一种蓝色的物质,过滤,水洗至中性,在120℃干燥10h,放入管式炉中在450℃焙烧处理5h,得到一种黑色物质,加入1gK2CO3混合均匀,即得。
将实施例1至3所得MOF催化剂和对比例1所得催化剂用常压评价装置评价其反应活性。评价方法为:先将催化剂粉碎至40-60目,量取5ml装入反应器中,先用H2进行程序升温还原,然后在反应温度200℃和250℃,液体空速为5h-1的条件下进行活性评价。结果如表1所示。
表1.实施例1-3和对比例1性能对比
表1中数据说明,本发明仲丁醇脱氢MOF催化剂的反应活性和选择性明显优于现有CuO、ZnO、Al2O3催化剂。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种仲丁醇脱氢MOF催化剂的制备方法,其特征在于,包括如下步骤:
1)制备Al-Cu-Zn多元素MOF
向配位体的有机溶液中加入Al盐,加热,生成Al的预配位化合物,保持加热,同时加入Cu盐和Zn盐,持续反应,生成Al-Cu-Zn多元素MOF;
2)碳化制备骨架碳支撑体
将步骤1)所得Al-Cu-Zn多元素MOF在低氧气氛的条件下进行碳化处理,制得骨架碳支撑体;
3)制备MOF催化剂
将步骤2)所得骨架碳支撑体与碱金属盐催化改性剂混合均匀,即得。
2.根据权利要求1所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤1)中,所述Al盐、Cu盐和Zn盐分别为对应的硝酸盐、硫酸盐、醋酸盐或氯化物。
3.根据权利要求1或2所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤1)中,所述Al盐、Cu盐和Zn盐的重量比为1:(2-8):(1-5)。
4.根据权利要求1或2所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤1)中,所述配位体为对苯二甲酸、均苯三甲酸、对苯二甲酸酯、均苯三甲酸酯以及上述化合物的苯环烃基取代衍生物之一;有机溶剂为无水乙醇或DMF。
5.根据权利要求1或2所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤1)中,加热温度为100-300℃,反应时间为1-100h。
6.根据权利要求1或2所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤2)中,碳化处理条件为:温度300-600℃,时间2-50h,惰性气体中氧含量<10%。
7.根据权利要求1或2所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤3)中,所述碱金属盐为碳酸钾、碳酸钠、碳酸镁或碳酸钙中的一种。
8.根据权利要求1-7任一项所述的仲丁醇脱氢MOF催化剂的制备方法,其特征在于,步骤3)中,所述碱金属盐的用量为所述Al盐、Cu盐和Zn盐总量的1-2.5%。
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