CN114436794A - 一种合成甲基异戊基酮的方法 - Google Patents
一种合成甲基异戊基酮的方法 Download PDFInfo
- Publication number
- CN114436794A CN114436794A CN202011199013.8A CN202011199013A CN114436794A CN 114436794 A CN114436794 A CN 114436794A CN 202011199013 A CN202011199013 A CN 202011199013A CN 114436794 A CN114436794 A CN 114436794A
- Authority
- CN
- China
- Prior art keywords
- palladium
- phosphonic acid
- acid resin
- resin catalyst
- acetone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 49
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 38
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 230000005494 condensation Effects 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000009833 condensation Methods 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000005194 fractionation Methods 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920006342 thermoplastic vulcanizate Polymers 0.000 claims 1
- 230000001588 bifunctional effect Effects 0.000 abstract description 5
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002587 enol group Chemical group 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C07C45/61—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
- 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
- C07C45/68—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
- 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
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C45/61—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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种一步法合成甲基异戊基酮的方法。该方法包括以下内容：丙酮、异丁醛与氢气混合后，通过含有钯/膦酸树脂催化剂的固定床反应器，在酮醛缩合工艺条件下，进行缩合和加氢反应，反应流出物经气液分离和分馏，得到甲基异戊基酮；其中，所述的钯/膦酸树脂催化剂以钯为金属组分，以膦酸树脂为载体和酸性组分。本发明中采用双功能钯/膦酸树脂催化剂，提高了MIAK的选择性，且将两步反应合为一步，使得一步法生产MIAK的工业应用成为可能。
Description
技术领域
本发明涉及一种甲基异戊基酮的合成方法。
背景技术
甲基异戊基酮（简称MIAK），是一种无色透明液体, 其溶解力强、挥发速率低且速率稳定，可用于高固体份涂料。还可用于合成丙烯酸树脂等有机物的合成。
目前MIAK的生产方法为两步法：第一步在酸或碱的条件下，缩合脱水生成5-甲基-3-烯-2-己酮；第二步用烯烃饱和催化剂，把5-甲基-3-烯-2-己酮加氢反应成MIAK。如果是第一步反应后先把5-甲基-3-烯-2-己酮提纯出来再加氢，这种方法的缺点是操作流程复杂，能耗高；如果是第一步反应后直接把反应物加氢，然后再分离出MIAK，这种方法的缺点是操作副产物较多，原料损耗大。
发明内容
本发明所要解决的技术问题是提供一种一步法合成甲基异戊基酮（MIAK）的方法。
本发明的方法包括以下内容：
丙酮、异丁醛与氢气混合后，通过含有钯/膦酸树脂催化剂的反应器，在酮醛缩合工艺条件下，进行缩合和加氢反应，反应流出物经气液分离和分馏，得到甲基异戊基酮；其中，所述的钯/膦酸树脂催化剂以钯为金属组分，以膦酸树脂为载体和酸性组分。
进一步的，所述钯/膦酸树脂催化剂的钯含量为1.0～3.0 Kg·m-3(湿基)。催化剂的含水量（率）一般为40～60wt%。催化剂的总酸为（90℃，NH3TPD测定）1.0～4.0 mmol/g；酸分布（NH3TPD测定）：90～110℃为3%～10%；110～120℃为3%～15%；120～140℃为5%～30%；>140℃为40%～90%。
更进一步的，所述的钯/膦酸树脂催化剂优选为：钯含量为2.0～2.5 Kg·m-3(湿基)；催化剂的含水量（率）为45～55wt%；总酸(90℃，NH3TPD测定) 1.5～3.0mmol/g，酸分布（NH3TPD测定）为：90～110℃为4%～9%；110～120℃为4%～10%；120～140℃为6%～15%；>140℃为50%～90%。
进一步的，所述的钯/膦酸树脂催化剂的比表面积一般为 8～15 m2/g，平均孔直径60～140 Å，孔容为0.01～0.04 mL/g；优选：比表面积为10～13 m2/g，平均孔直径80～110 Å，孔容为0.02～0.03 mL/g。
所述钯/膦酸树脂催化剂，可以采用本领域的常规方法制备。典型的制备方法如下：将膦酸树脂浸入到钯盐水溶液中，浸渍处理后过滤出树脂催化剂，用去离子水水洗至中性即可。其中，所述膦酸树脂及其制备方法均为本领域技术人员熟知的知识。
进一步的，所述的酮醛缩合工艺条件为：反应压力为2.0MPa～8.0MPa，优选为2.5MPa～5.0MPa；反应温度为80℃～160℃，优选为90℃～140℃；丙酮与异丁醛（混合物）的体积空速为0.2h-1～5.0h-1，优选为0.5h-1～3.0h-1；氢液体积比为100～400，优选为150～300；丙酮与异丁醛摩尔比为0.5:1～4:1，优选1:1～3:1。
进一步的，气液分离后反应液的分馏，可以采用本领域内熟知的蒸馏操作。原料进行缩合脱水及加氢反应后，经气-液分离器，将氢气与反应液分开，氢气可循环使用。反应液通过轻组分塔，将过度加氢的烷烃分出后，再依次分出水、丙酮、异丁醛、甲基异丁基酮，最后在产品塔顶得到MIAK，塔釜得到重组分。
进一步的，所述反应器可以为任何反应器形式，如流化床、沸腾床、移动床、或固定床反应器， 优选固定床反应器。
现有的两步法流程复杂、能耗高、操作繁琐。如果使用双功能催化剂，让缩合、脱水及加氢反应在一个催化剂上完成，就可以用一步法生产MIAK，进而可以大幅度减轻操作难度、提高生产效率。但是，目前使用的树脂类双功能催化剂为载钯的磺酸型树脂，酮醛缩合时，用磺酸型树脂催化剂会发生大量的丙酮与丙酮自身缩合以及异丁醛与异丁醛自身缩合的产物，使得副产物含量较大，而导致目的产物的选择性不高。所以用载钯磺酸型树脂一步法生产MIAK，经济性较差，难以工业化。
针对以上问题，本发明基于对酮醛缩和反应原理的研究，选择一种特殊的树脂——膦酸树脂，然后在该树脂上负载金属Pd，得到了一种钯/膦酸树脂催化剂。利用该催化剂，使得丙酮与异丁醛的脱水加氢能同时进行，即通过一步反应合成MIAK。
一步反应合成MIAK的反应式见式（1）。
与现有技术相比较，本发明的一步法合成甲基异戊基酮的方法具有以下有益效果：
1、本申请的发明人通过研究发现，膦酸树脂中含有能直接和金属配位的P=O基，而P=O基很容易和金属Pd配位。同时，丙酮被活化成烯醇式结构后，烯醇式结构中的烯基亦极易与活性金属Pd进行配位。所以，膦酸树脂中的P=O基团、活性金属Pd以及丙酮烯醇式结构可以形成大π键结构。研究还发现，要生成MIAK，关键是体系中要能够长时间、稳定生成大量的丙酮烯醇式结构。而这个大π键的存在，正好满足了这一要求。因此采用载钯的膦酸树脂催化剂，可以从催化机理上提高MIAK中间产物的稳定性，抑制了副产物的生成，进而提高了MIAK的选择性。
2、目前使用的树脂类双功能催化剂为载钯的磺酸型树脂。在用于酮醛缩合反应时，用磺酸型树脂催化剂会发生大量的丙酮与丙酮自身缩合以及异丁醛与异丁醛自身缩合，使得副产物含量增加较多，而导致目的产物的选择性不高。所以用载钯磺酸型树脂一步法生产MIAK，经济性较差，难以工业化。而本发明中基于催化原理上的发现，采用双功能钯/膦酸树脂催化剂，用于酮醛缩合加氢的方法来生产MIAK，可以将两步反应合为一步，简化了反应流程及操作步骤。尤其是所选择的载钯膦酸树脂催化剂，提高了MIAK的选择性，使得一步法生产MIAK的工业应用成为可能。
附图说明
图1为本发明方法的流程示意图。
其中，1-丙酮，2-丁醛，3-反应器，4-新鲜氢气，5-气液分离器，6-循环氢气，7.反应液。
具体实施方式
以下结合具体实施例，对本发明的技术方案作更详细的描述。
如图1所示，本发明的合成MIAK方法包括：将原料丙酮1、丁醛2分别用泵送入反应器3，同时将新鲜氢气4与循环氢气6用氢气压缩机送入反应器3，反应后将反应液送入气液分离器5，经过气液分离后，气液分离器上部得到循环氢气6，气液分离器下部得到反应液7。
实施例中所用载钯膦酸树脂催化剂的物化性质列于表1，反应条件和结果列于表2。
表1 催化剂性质
表2 反应条件及反应结果
注：转化率及选择性的计算方法为：
丙酮摩尔转化率=(原料中丙酮的摩尔数－产品中丙酮的摩尔数)/原料中丙酮的摩尔数；
异丁醛摩尔转化率=(原料中异丁醛的摩尔数－产品中异丁醛的摩尔数)/原料中异丁醛的摩尔数；
MIBK摩尔选择性=(产品中MIBK的摩尔数×2)/(原料中丙酮的摩尔数－产品中丙酮的摩尔数)；
MIAK摩尔选择性=(产品中MIAK的摩尔数×2)/(原料中异丁醛的摩尔数－产品中异丁醛的摩尔数)。
比较例1-5
比较例中所用催化剂为载钯磺酸树脂催化剂，物化性质为表3所示。比较例的反应条件及结果如表4所示。
与实施例相比，比较例催化剂的主要性质应当基本相当，如Pd，含水量，总酸，平均孔直径。只有这样，才更能体现本发明中选择Pd/膦酸树脂催化剂的的优点和效果。
表3 催化剂性质
表4 比较例反应条件及反应结果
在相同的工艺条件下，从实施例及比较例的结果可以看出，本发明的合成甲基异戊基酮的方法，能够大幅度提高MIAK的选择性，从而实现一步法制备MIAK。
Claims (10)
1.一种一步法合成甲基异戊基酮的方法，包括以下内容：
丙酮、异丁醛与氢气混合后，通过含有钯/膦酸树脂催化剂的反应器，在酮醛缩合工艺条件下，进行缩合和加氢反应，反应流出物经气液分离和分馏，得到甲基异戊基酮；其中，所述的钯/膦酸树脂催化剂以钯为金属组分，以膦酸树脂为载体和酸性组分。
2.按照权利要求1所述的方法，其特征在于，所述钯/膦酸树脂催化剂的钯含量为1.0～3.0 Kg·m-3，含水量为40～60 wt%。
3.按照权利要求1所述的方法，其特征在于，所述钯/膦酸树脂催化剂的总酸1.0～4.0mmol/g；酸分布为：90～110℃为3%～10%；110～120℃为3%～15%；120～140℃为5%～30%；>140℃为40%～90%，总酸及酸分布于90℃下，NH3TPD测定。
4.按照权利要求3所述的方法，其特征在于，所述钯/膦酸树脂催化剂的总酸为 1.5～3.0mmol/g：酸分布为：90～110℃为4%～9%；110～120℃为4%～10%；120～140℃为6%～15%；>140℃为50%～90%。
5.按照权利要求3所述的方法，其特征在于，所述钯/膦酸树脂催化剂的比表面积为 8～15 m2/g，平均孔直径60～140 Å，孔容为0.01～0.04 mL/g。
6.按照权利要求4所述的方法，其特征在于，所述的钯/膦酸树脂催化剂比表面积为10～13 m2/g，平均孔直径为80～110 Å，孔容为0.02～0.03 mL/g。
7.按照权利要求1所述的方法，其特征在于，所述钯/膦酸树脂催化剂的制备方法如下：将膦酸树脂浸入到钯盐水溶液中，浸渍处理后过滤出树脂催化剂，用去离子水洗涤至中性即可。
8.按照权利要求1所述的方法，其特征在于，所述的酮醛缩合工艺条件为：反应压力为2.0MPa～8.0MPa，反应温度为80℃～160℃，丙酮与异丁醛混合物的体积空速为0.2h-1～5.0h-1，氢液体积比为100～400，丙酮与异丁醛摩尔比为0.5:1～4:1。
9.按照权利要求8所述的方法，其特征在于，所述的酮醛缩合工艺条件为：反应压力为2.5MPa～5.0MPa，反应温度为90℃～140℃，丙酮与异丁醛混合物的体积空速为0.5h-1～3.0h-1，氢液体积比为150～300，丙酮与异丁醛摩尔比为1:1～3:1。
10.按照权利要求2所述的方法，其特征在于，所述钯/膦酸树脂催化剂的钯含量为2.0～2.5 Kg·m-3，催化剂的含水量为45～55wt%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011199013.8A CN114436794A (zh) | 2020-10-31 | 2020-10-31 | 一种合成甲基异戊基酮的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011199013.8A CN114436794A (zh) | 2020-10-31 | 2020-10-31 | 一种合成甲基异戊基酮的方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114436794A true CN114436794A (zh) | 2022-05-06 |
Family
ID=81357993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011199013.8A Pending CN114436794A (zh) | 2020-10-31 | 2020-10-31 | 一种合成甲基异戊基酮的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114436794A (zh) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0227868A1 (en) * | 1984-09-25 | 1987-07-08 | Sumitomo Chemical Company, Limited | Process for production of methyl isobutyl ketone |
| US4739122A (en) * | 1985-10-18 | 1988-04-19 | Union Carbide Corporation | Preparation of ketones |
| CN1080564A (zh) * | 1993-05-04 | 1994-01-12 | 中国石油化工总公司抚顺石油化工研究院 | 合成甲基异丁基酮的催化剂及其制备方法 |
| US5583263A (en) * | 1995-08-30 | 1996-12-10 | Shell Oil Company | Process of making ketones |
| CN1457927A (zh) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | 一种钯／树脂催化剂的制备方法 |
| CN1488617A (zh) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | 一种合成甲基异丁基酮／甲基异丁基醇的方法 |
| US20040122261A1 (en) * | 2002-12-23 | 2004-06-24 | Mccusker-Orth Jennifer Ellen | Processes for the preparation of higher molecular weight ketones |
| CN100998953A (zh) * | 2006-01-09 | 2007-07-18 | 中国石油化工股份有限公司 | 一种Pd/树脂催化剂的制备方法 |
| CN103228603A (zh) * | 2010-11-30 | 2013-07-31 | 罗狄亚聚酰胺特殊品有限公司 | 制备dibk的方法 |
-
2020
- 2020-10-31 CN CN202011199013.8A patent/CN114436794A/zh active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0227868A1 (en) * | 1984-09-25 | 1987-07-08 | Sumitomo Chemical Company, Limited | Process for production of methyl isobutyl ketone |
| US4739122A (en) * | 1985-10-18 | 1988-04-19 | Union Carbide Corporation | Preparation of ketones |
| CN1080564A (zh) * | 1993-05-04 | 1994-01-12 | 中国石油化工总公司抚顺石油化工研究院 | 合成甲基异丁基酮的催化剂及其制备方法 |
| US5583263A (en) * | 1995-08-30 | 1996-12-10 | Shell Oil Company | Process of making ketones |
| CN1457927A (zh) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | 一种钯／树脂催化剂的制备方法 |
| CN1488617A (zh) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | 一种合成甲基异丁基酮／甲基异丁基醇的方法 |
| US20040122261A1 (en) * | 2002-12-23 | 2004-06-24 | Mccusker-Orth Jennifer Ellen | Processes for the preparation of higher molecular weight ketones |
| CN100998953A (zh) * | 2006-01-09 | 2007-07-18 | 中国石油化工股份有限公司 | 一种Pd/树脂催化剂的制备方法 |
| CN103228603A (zh) * | 2010-11-30 | 2013-07-31 | 罗狄亚聚酰胺特殊品有限公司 | 制备dibk的方法 |
Non-Patent Citations (2)
| Title |
|---|
| 冯亚凯 等: "P／Pd树脂的合成及催化加氢性能", 天津大学学报, vol. 29, no. 04, pages 521 - 526 * |
| 卞克建，丁龙福，高炬，顾海翔: "用离子交换树脂－Pd催化丙酮和氢气一步法合成甲基异丁基酮的研究", 南京大学学报(自然科学版), vol. 31, no. 01, pages 63 - 67 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8212070B2 (en) | Method for preparing acrylic acid from glycerol | |
| JP5339904B2 (ja) | 混合アルコールの脱水のための反応性蒸留 | |
| CN104926657B (zh) | 草酸酯气相加氢合成乙醇酸酯的方法 | |
| CN104355975B (zh) | 一种丙酮两步法合成甲基异丁基酮的方法 | |
| TW201427933A (zh) | 一種聯產環己醇和鏈烷醇的方法和裝置 | |
| CN102453002A (zh) | 一种环氧丙烷的制备方法 | |
| JP2022538679A (ja) | アルキルメタクリレートおよび任意にメタクリル酸の製造方法 | |
| Wang et al. | Butadiene production from ethanol | |
| CN103212437A (zh) | 一种制备钛基催化剂及合成环氧丙烷和过氧化二异丙苯的方法 | |
| CN102452934A (zh) | 一种乙酸仲丁酯的制备方法 | |
| CN114436794A (zh) | 一种合成甲基异戊基酮的方法 | |
| WO2000024700A1 (en) | PROCESS FOR THE MANUFACTURE OF α,α-BRANCHED CARBOXYLIC ACIDS | |
| CN111763143A (zh) | 一种合成丙烯酸的方法 | |
| JP2007533608A (ja) | アルキレンオキシドの調製方法 | |
| US10087131B2 (en) | Process for the production of glycolic acid | |
| CN114685257B (zh) | 一种合成甲基异戊基酮的方法 | |
| CN107501053A (zh) | 一种由烯烃一步制醇醚的绿色合成方法 | |
| CN109809973B (zh) | 一种制备2-乙基己醛的方法 | |
| CN102452890A (zh) | 一种将甲基环己醇氢解为甲基环己烷的方法 | |
| JPS60233024A (ja) | 第３級ブチルアルコ−ルの製造方法 | |
| CN110776389B (zh) | 一种制备苯乙烯的复配型催化剂及方法 | |
| CN111978151B (zh) | 一种3-甲基-2-丁烯醇的制备方法 | |
| CN112958074B (zh) | 一种用于制备3-羟基丙醛的催化剂及其制备方法和应用 | |
| CN102329222A (zh) | 一步法氧化环己烷制备己二酸的方法及其使用的催化剂 | |
| WO2012017447A2 (en) | Method for selective hydration of aroma olefins to alcohols in continuous solid catalyst column reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240102 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |