CN102557908B - 2-(环己-1'-烯基)环己酮的制备方法 - Google Patents
2-(环己-1'-烯基)环己酮的制备方法 Download PDFInfo
- Publication number
- CN102557908B CN102557908B CN201110099723.8A CN201110099723A CN102557908B CN 102557908 B CN102557908 B CN 102557908B CN 201110099723 A CN201110099723 A CN 201110099723A CN 102557908 B CN102557908 B CN 102557908B
- Authority
- CN
- China
- Prior art keywords
- pimelinketone
- cyclohexanone
- reaction
- cyclohex
- hexamethylene
- 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.)
- Active
Links
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006482 condensation reaction Methods 0.000 claims abstract description 11
- 239000011973 solid acid Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000005494 condensation Effects 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 5
- 235000010292 orthophenyl phenol Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UOBQDYFTAJKQAL-UHFFFAOYSA-N O=C(CCCC1)C1C1CCCCC1 Chemical compound O=C(CCCC1)C1C1CCCCC1 UOBQDYFTAJKQAL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- -1 W are formed Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XAOPJZTWCMKPRB-UHFFFAOYSA-N octadecanoic acid;vanadium Chemical compound [V].CCCCCCCCCCCCCCCCCC(O)=O XAOPJZTWCMKPRB-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明披露一种2-(环己-1’-烯基)环己酮的制备方法，该方法使用特定的固体酸性催化剂，在特定温度条件下，由环己酮进行自缩合反应而制备2-(环己-1’-烯基)环己酮。该固体酸性催化剂具有化学式：AlxSyOz，其中x、y、z表示原子比，且x为1至4，y为1至3，z为可满足存在于该催化剂内呈氧化态的Al与S的价需求的数值。本发明的制备方法可在相对温和的反应条件下由环己酮自缩合制备2-(环己-1’-烯基)环己酮；可提高2-(环己-1’-烯基)环己酮的产率；并可减少对生产设备的腐蚀。
Description
技术领域
本发明涉及一种2-(环己-1’-烯基)环己酮的制备方法，其通过使用特定的催化剂，在特定温度条件下，由环己酮进行缩合反应而制备2-(环己-1’-烯基)环己酮。
背景技术
2-(环己-1’-烯基)环己酮是一种重要的化工产品，其用途广泛，除可作为环氧树酯的改性剂、塑料增塑剂、聚合物的交联剂外，还是合成重要精细有机化学品邻苯基苯酚的中间体。邻苯基苯酚的应用十分广泛，可用于合成染料、表面活性剂、阻燃剂、塑料稳定剂和医药产品等，并随着其用途的不断开发，其市场需求量也持续增长。
邻苯基苯酚的生产方式有六种：一、环己酮缩合脱氢法，二、联苯磺化或卤化水解法，三、氨基联苯重氮化水解法，四、氯苯高压水解法，五、二苯并呋喃(dibenzofuran)法，六、氯苯和苯酚偶合法。上述合成方法中，目前最广泛使用之制程为环己酮缩合脱氢法。环己酮缩合脱氢制程可分为两阶段反应，第一阶段是将环己酮置于酸或碱性催化剂下，进行缩合反应，得到二聚物2-(环己-1’-烯基)环己酮，第二阶段则以含有Pt等金属之催化剂，进行2-(环己-1’-烯基)环己酮的脱氢反应，制得邻苯基苯酚。
如上所述，2-(环己-1’-烯基)环己酮是由环己酮于酸或碱的催化下，在环己酮分子之间发生缩合反应而生成，其反应式如下：
环己酮自缩合反应通常会生成两种共振异构物(I)和(II)，但通常以2-(环己-1’-烯基)环己酮(II)为主，此两种化合物均能再进行后续的脱氢反应，以制备邻苯基苯酚。
目前已发表有关使用于环己酮自缩合以生产2-(环己-1’-烯基)环己酮的催化剂专利，大致可分为无机强酸强碱、有机酸、有机金属化合物和固体酸催化剂四大类。
美国第4,002,693号专利采用硫酸作为催化剂，2-(环己-1’-烯基)环己酮产率约为37％。然而，以硫酸作为催化剂存在着许多弊端。其一，硫酸的腐蚀性较大，对反应设备的投资较高；其二，若使用浓硫酸作为催化剂，其强氧化性及强脱水性会使反应的副产物增多，如使用较稀的硫酸虽可降低副反应的发生，但会导致反应体系中存在过多的水，进而降低反应的转化率；其三，催化剂硫酸无法重复使用，工艺成本耗费高，且反应废水易造成环保间题。
美国第3,980,716号专利披露可使用脂肪族羧酸、环烷酸、杂多酸、乙二胺四乙酸及乙酰丙酮与Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Mo、Cd、Sn、W等金属所形成的化合物，或以上金属的醇盐，作为环己酮自缩合产生二聚物反应的催化剂，其中以硬脂酸钒作为催化剂的效能较 佳，其环己酮转化率可达71％，二聚物选择性则为89％，但此反应须在无空气的状态下进行，且反应温度需高达190℃，才有较高的转化率。
美国第3,880,930号专利以磺酸型阳离子交换树酯、苯磺酸或对甲苯磺酸，催化环己酮自缩合生产二聚物，转化率最高可达59.9％，选择性90％，但酸性树酯的最大缺点是耐热性较差，须减压进行反应以降低反应温度，否则催化剂容易失活，设备投资成本与能源的损耗较高，而苯磺酸及对甲苯磺酸属于有机强酸，也存在着与硫酸相同的缺点，容易对设备造成腐蚀。
中国科学院山西煤化研究所的研究显示以5％NaNO2-稀土元素/γ-Al2O3作为环己酮双聚催化剂，使用固定床反应器在反应温度350℃下进行反应，环己酮转化率为52.4％，二聚物选择性为99.2％，然而其转化率较低，反应温度过高，能源耗用大，在工艺上不具优势[精细化工，1994，第11卷，第5期，第42-45页]。
中国第101205170号专利提出了改良后的催化剂，以假软水铝石(假勃姆石，pseudo-boehmite)前驱物锻烧后得到的Al2O3作为催化剂，于批式反应器中进行环己酮自缩合反应，其产率可达七成以上。
发明内容
有鉴于前述环己酮自缩合生产二聚物的工艺技术的缺点，本发明的目的在于提供一种2-(环己-1’-烯基)环己酮的制备方法，其可在相对温和的反应条件下，由环己酮自缩合制备2-(环己-1’-烯基)环己酮。
本发明的另一目的在于提供一种可以提高2-(环己-1’-烯基)环己酮产率的2-(环己-1’-烯基)环己酮的制备方法。
本发明的又一目的在于提供一种可减少生产设备腐蚀的2-(环己-1’-烯基)环己酮的制备方法。
根据本发明，使用一种新式固体酸性催化剂催化环己酮自缩合反应，以从环己酮制备得到2-(环己-1’-烯基)环己酮，其中该固体酸性催化剂的化学式为：
AlxSyOz
其中x、y、z表示原子比，且x为1至4，y为1至3，z为可满足存在于该催化剂内呈氧化态的Al与S的(化合)价需求的数值。根据本发明一个具体实施方式，其中，x为1至2，而y为1至2。
根据本发明一个优选的具体实施方式，该固体酸性催化剂可例如将Al(OH)3以浓度介于0.5至2.5M的硫酸溶液浸渍1小时，经干燥后以450℃以上温度煅烧而制得。此外，该固体酸性催化剂的添加量占反应液总重的2重量％以上；反应温度介于100至160℃之间，优选介于130至150℃之间。
本发明可应用于批次工艺及连续式工艺，包含连续搅拌反应器(Continuous Stirred Tank Reactor，CSTR)、固定床反应器(Packed Bed Reactor)、流化床反应器(Fluidized Bed Reactor)等。
以下通过具体实施例进一步说明本发明的特点与功效，但不以实施例说明限制本发明的范围。
具体实施方式
本说明书中所记载的转化率、选择率根据下列方程式计算：
转化率(％)＝{[环己酮添加浓度-环己酮剩余浓度](mol)/环己酮添加浓度(mol)}×100％
选择率(％)＝{2×产出的二聚物(mo1)/[环己酮添加浓度-环己酮剩余浓度](mol)}×100％
(实施例1-3)
(1)催化剂制备
将Al(OH)3以浓度0.6M的硫酸溶液浸渍，于室温下放置1小时后抽气过滤，干燥后经450℃以上温度煅烧，即得实验用催化剂。
(2)缩合反应测试
将568.2克环己酮和23.7克自制催化剂置于附有搅拌器的1L不锈钢制反应器中，控制反应温度分别为130℃、140℃、150℃，反应期间以反应物环己酮自身为带水剂，并另外通入氮气辅助移除反应所产生的水。于反应时间2小时、4小时及6小时取样，样品以气相层析仪及水分滴定仪分析，其结果列于表1中。
表1温度对2-(环己-1’-烯基)环己酮生成的影响
由表1实验结果可知，本发明生物催化剂可有效进行环己酮自缩合反应，并随着反应温度的升高，而提高反应速率与产率。
(实施例4-6)
(1)催化剂制备
以与实施例1-3相同的制备方法制备实验用催化剂。
(2)缩合反应测试
将568.2克环己酮及49.41克、77.48克、108.23克自制催化剂分别置于附有搅拌器的1L不锈钢制反应器中，控制反应温度为140℃，反应期间以反应物环己酮自身为带水剂，并另外通入氮气辅助移除反应所产生的水。于反应时间2小时、4小时及6小时取样，样品以气相层析仪及水分滴定仪分析，其实验结果列于表2中。
表2催化剂浓度对2-(环己-1’-烯基)环己酮生成的影响
由表2实验结果可知，增加催化剂添加量可有效提高反应速率，并在维持7成以上产率的前提下，可有效缩短反应时间。
Claims (1)
1.一种2-(环己-1’-烯基)环己酮的制备方法，所述方法使用固体酸性催化剂，在介于130至150℃的范围内的温度下，由环己酮进行自缩合反应而制备2-(环己-1’-烯基)环己酮，其中，所述固体酸性催化剂具有以下化学式：
AlxSyOz
其中，x、y、z表示原子比，且x为1至2，y为1至2，z为可满足存在于所述催化剂内呈氧化态的Al与S的价需求的数值，
其中，所述固体酸性催化剂占反应液总重的2重量％以上。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW099146246 | 2008-12-28 | ||
| TW099146246A TW201226379A (en) | 2010-12-28 | 2010-12-28 | Method of producing 2-(cyclohex-1'-enyl) cyclohexanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102557908A CN102557908A (zh) | 2012-07-11 |
| CN102557908B true CN102557908B (zh) | 2015-09-23 |
Family
ID=45771175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110099723.8A Active CN102557908B (zh) | 2010-12-28 | 2011-04-20 | 2-(环己-1'-烯基)环己酮的制备方法 |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US8519192B2 (zh) |
| CN (1) | CN102557908B (zh) |
| TW (1) | TW201226379A (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437558B (zh) * | 2014-11-19 | 2017-03-01 | 济南大学 | 一种用于环己酮自缩合反应的新型绿色固体超强酸催化剂及其应用 |
| TWI549749B (zh) * | 2015-05-07 | 2016-09-21 | China Petrochemical Dev Corp Taipei Taiwan | A catalyst composition for preparing o-phenylphenol and a process for preparing o-phenylphenol using the catalyst composition |
| CN106632387B (zh) * | 2016-12-13 | 2018-08-10 | 浙江华贝药业有限责任公司 | 一种工业合成中间体季戊四醇双缩二苯酮的合成工艺 |
| TWI759615B (zh) | 2019-07-22 | 2022-04-01 | 中國石油化學工業開發股份有限公司 | 2-環己烷基環己醇之製法 |
| TWI755626B (zh) * | 2019-09-03 | 2022-02-21 | 中國石油化學工業開發股份有限公司 | 一種環己酮二聚物之製備方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3880930A (en) * | 1972-05-29 | 1975-04-29 | Ruetgerswerke Ag | Process for the production of 1-{8 cyclohexene-(1-YL{9 )-cyclohexanone-(2) by condensation of cyclohexanone |
| US4002693A (en) * | 1974-02-28 | 1977-01-11 | Laporte Industries Limited | Process for the production of o-phenylphenol |
| CN1371897A (zh) * | 2001-02-23 | 2002-10-02 | 南京理工大学 | 用环己酮合成邻苯基苯酚的方法 |
| CN101074187A (zh) * | 2007-05-15 | 2007-11-21 | 盐城市华业医药化工有限公司 | 邻苯基苯酚的制备工艺 |
| CN101205170A (zh) * | 2007-11-08 | 2008-06-25 | 中国石油大学(华东) | 一种固体催化剂用于环己酮自缩合反应的使用方法 |
| CN101538196A (zh) * | 2008-03-18 | 2009-09-23 | 中国石油化工集团公司 | 一种制备2-(1-环己烯基)环己酮的方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3980716A (en) | 1968-03-15 | 1976-09-14 | Imperial Chemical Industries Limited | Production of ortho-phenylphenol from cyclohexanone |
| NL7500549A (nl) * | 1975-01-17 | 1976-07-20 | Stamicarbon | Werkwijze voor de bereiding van 2-(1-cyclo- hexenyl)-cyclohexanon. |
| CA2068489A1 (en) * | 1991-05-16 | 1992-11-17 | Masaru Ishino | Aldol condensation dehydration catalyst, a process for preparing the same and a process for preparing an aldol condensation dehydrate using the process |
-
2010
- 2010-12-28 TW TW099146246A patent/TW201226379A/zh unknown
-
2011
- 2011-04-20 CN CN201110099723.8A patent/CN102557908B/zh active Active
- 2011-11-16 US US13/297,687 patent/US8519192B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3880930A (en) * | 1972-05-29 | 1975-04-29 | Ruetgerswerke Ag | Process for the production of 1-{8 cyclohexene-(1-YL{9 )-cyclohexanone-(2) by condensation of cyclohexanone |
| US4002693A (en) * | 1974-02-28 | 1977-01-11 | Laporte Industries Limited | Process for the production of o-phenylphenol |
| CN1371897A (zh) * | 2001-02-23 | 2002-10-02 | 南京理工大学 | 用环己酮合成邻苯基苯酚的方法 |
| CN101074187A (zh) * | 2007-05-15 | 2007-11-21 | 盐城市华业医药化工有限公司 | 邻苯基苯酚的制备工艺 |
| CN101205170A (zh) * | 2007-11-08 | 2008-06-25 | 中国石油大学(华东) | 一种固体催化剂用于环己酮自缩合反应的使用方法 |
| CN101538196A (zh) * | 2008-03-18 | 2009-09-23 | 中国石油化工集团公司 | 一种制备2-(1-环己烯基)环己酮的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102557908A (zh) | 2012-07-11 |
| US20120059193A1 (en) | 2012-03-08 |
| US8519192B2 (en) | 2013-08-27 |
| TWI460156B (zh) | 2014-11-11 |
| TW201226379A (en) | 2012-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102557908B (zh) | 2-(环己-1'-烯基)环己酮的制备方法 | |
| Kawabata et al. | Highly efficient esterification of carboxylic acids with alcohols by montmorillonite-enwrapped titanium as a heterogeneous acid catalyst | |
| CN101544548B (zh) | 一种氧气氧化醇制备醛或酮的方法 | |
| CN107376997B (zh) | 一种用于氧化苯甲醇制苯甲醛的催化剂制备及其应用 | |
| CN108250069B (zh) | 一种异辛酸的制备方法 | |
| CN107096551B (zh) | 一种2,2,4-三甲基-1,3-戊二醇双异丁酸酯酯化反应催化剂及制备方法和用途 | |
| CN103922931B (zh) | 一种一步催化合成乙二醇***乙酸酯的方法 | |
| CN108440463A (zh) | 一种用负载型金属分子筛催化剂催化制备5-羟甲基糠醛的方法 | |
| Barve et al. | Preparation of pure methyl esters from corresponding alkali metal salts of carboxylic acids using carbon dioxide and methanol | |
| CN101898946B (zh) | 一种催化甘油氢解的方法 | |
| CN106362776B (zh) | 用于合成十二碳醇酯的催化剂及其制备方法和应用 | |
| CN102757346A (zh) | 一种富马酸二甲酯的制备方法 | |
| CN110078601A (zh) | 多金属氧酸盐高效催化对二甲苯制备对甲基苯甲醛的方法 | |
| CN101830783B (zh) | 一种希夫碱配合物催化氧气氧化醇制备醛的方法 | |
| CN104262109A (zh) | 一种间苯二酚的合成方法 | |
| CN111747831A (zh) | 一种制备环戊酮的方法 | |
| CN106883087A (zh) | 一种气相光催化氧化乙醇制乙烯、乙醛和丙酮的Cu/TiO2催化剂及反应工艺 | |
| CN101817780B (zh) | 吡啶-2-甲醛的制备方法 | |
| CN101602014B (zh) | 负载型碳纳米纤维催化剂及其应用 | |
| CN108929224A (zh) | 一种利用双功能催化剂催化制备5-羟基戊酸甲酯的方法 | |
| CN106995463B (zh) | 一种油溶性铬酸异辛酯催化体系 | |
| CN107434767B (zh) | 一种利用环己烯和醋酸制备环己醇和醋酸环己酯的方法 | |
| CN104003971B (zh) | 一种催化氧化环己酮制备ε-己内酯的方法 | |
| CN104693023B (zh) | 一种生物质糖制备乙酰丙酸酯的方法 | |
| CN110105180A (zh) | 一种邻二甲苯催化制备2-甲基苯甲醛的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |