CN114105741A - Preparation method of large cycloalkanolone - Google Patents
Preparation method of large cycloalkanolone Download PDFInfo
- Publication number
- CN114105741A CN114105741A CN202111542886.9A CN202111542886A CN114105741A CN 114105741 A CN114105741 A CN 114105741A CN 202111542886 A CN202111542886 A CN 202111542886A CN 114105741 A CN114105741 A CN 114105741A
- Authority
- CN
- China
- Prior art keywords
- reaction
- oxidation
- hydrogenation
- catalyst
- macrocyclic
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 73
- 230000003647 oxidation Effects 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 230000008569 process Effects 0.000 claims abstract description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 alcohol ketone Chemical class 0.000 claims abstract description 27
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 6
- 238000010924 continuous production Methods 0.000 claims abstract description 6
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 6
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 25
- 239000004913 cyclooctene Substances 0.000 description 19
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 17
- 239000004914 cyclooctane Substances 0.000 description 17
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 8
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000006735 epoxidation reaction Methods 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VXPFEVUAMVPPQU-UHFFFAOYSA-N dioxosilane nickel Chemical compound [Ni].O=[Si]=O VXPFEVUAMVPPQU-UHFFFAOYSA-N 0.000 description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001925 cycloalkenes Chemical class 0.000 description 3
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SGJUFIMCHSLMRJ-UHFFFAOYSA-N 2-hydroperoxypropane Chemical group CC(C)OO SGJUFIMCHSLMRJ-UHFFFAOYSA-N 0.000 description 2
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 2
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 2
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical group [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FBMMEHJLWTZKOR-SOFGYWHQSA-N (1e)-cycloocten-1-ol Chemical compound O\C1=C\CCCCCC1 FBMMEHJLWTZKOR-SOFGYWHQSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003060 catalysis inhibitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003681 vanadium Chemical class 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Abstract
The invention provides a preparation method of macrocyclic alkanol ketone, which comprises three continuous processes of oxidation, separation and hydrogenation in series: 1) and (3) an oxidation process: the reaction raw material comprises one or the combination of large cycloalkane, mono-olefin and multi-olefin, and the precursor of large cycloalkanone is generated by introducing oxidizing gas under the action of an oxidation catalyst and an initiator; 2) the separation process comprises the following steps: rectifying a precursor generated in the oxidation process; 3) and (3) hydrogenation process: introducing hydrogen and nitrogen into the separated precursor, and obtaining a macrocyclic alkanol ketone mixture under the action of a hydrogenation catalyst and an inhibitor; in the oxidation process, the carbon number of the macrocycloalkane is 8-16, and the precursor is a macrocyclic epoxy product and an alcohol ketone mixture. The method can obtain the target product with higher selectivity, reduce the generation of side reactions, is simple and convenient to operate and improves the product yield.
Description
Technical Field
The invention belongs to the field of fine chemical engineering and new material preparation, and particularly relates to a preparation method of large cycloalkanolone.
Background
The synthesis method of macrocyclic alkanol ketone is a key process for preparing essence and flavor, high-grade lubricating oil and long-carbon polyamide, the macrocyclic alkanol ketone is produced by an air oxidation method at present, ketone/alcohol and a large amount of naphthenic hydroperoxide are produced in a reaction system, and the naphthenic hydroperoxide can be catalyzed and decomposed into ketone/alcohol mixture by molybdenum series, chromium series and vanadium series metal salt or complex; another production process employs an olefin oxidation scheme that employs a common oxidant comprising t-butyl hydroperoxide, cumene hydroperoxide, cyclohexyl hydroperoxide to form an oxa-ternary cyclic product, which is hydrogenated over different types of catalysts to form a ketone/alcohol mixture or a single product.
US3419615 discloses a cyclododecane oxidation method which can use boric acid, metaboric acid, cobalt and manganese salts as catalysts, and can prepare a mixture of cyclododecanol and cyclododecanone from cyclododecane under air conditions, but the conversion rate is only 5% -25%, and the raw materials need to idle in large quantity in a reaction system, so that the energy consumption is high; meanwhile, the high-temperature reaction in which oxygen participates has strict requirements on reaction conditions and has higher reaction risk.
EP0950659 describes a product of synthesis of epoxy twelve-membered ring structure, the catalyst is a combination of quaternary ammonium salt or pyridinium salt and a tungstate, dodecyl tungstate, heteropoly acid containing tungsten or its salt, which can realize multistage series reaction, and the reaction is operated in the range of room temperature to 120 ℃. In the embodiment, the conversion rate of the effluent liquid of the reactor is controlled to be 21.5-22.1%, and the selectivity can reach 91.2-94.2%. The technology uses corrosive heteropoly acid salt, and has a strict restrictive condition for material selection in industrial production; in addition, the process has the advantages of low conversion rate of the large cycloolefin raw material, low reaction efficiency and high energy consumption, and a large amount of raw materials need to be recovered.
The traditional epoxidation process of organic hydrogen peroxide or hydrogen peroxide and cycloolefin comprises the following three difficulties. The first and the large alkyl epoxy products are mainly realized by hydrogen peroxide and alkyl hydrogen peroxide, in order to improve the conversion rate and the feeding coefficient of a single reactor in the reaction process, high-concentration peroxide raw materials are needed in the system, and the storage risk of the hydrogen peroxide or the alkyl hydrogen peroxide is high; secondly, the peroxide concentration in the reaction system is higher, disordered initiation side reaction is generated, about 15% of carboxylic acid, ester and unsaturated alcohol ketone byproducts are generated, and the product selectivity and yield are lower; thirdly, the byproducts of the oxidation reaction, namely carboxylic acid, ester and unsaturated alcohol ketone, are decomposed in the rectification process, and no effective means is provided for realizing waste utilization.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a macrocyclic cycloalkanone, so as to solve the disadvantages of the conventional process.
According to the invention, three processes of oxidation, separation and hydrogenation are connected in series, so that the atom economy is improved, the reaction risk is reduced, the generation of byproducts is inhibited, and the preparation of the large cycloalkanone ketone by a green process can be realized.
The reaction principle of the invention is as follows: one or a combination of large cycloalkane, mono-olefin and multi-olefin is used as a raw material, the intermediate generated cycloalkene hydrogen peroxide is used for continuously reacting with the raw material, one molecule of oxygen can react with two molecules of cycloolefins, and the conversion efficiency of the raw material per unit time is doubled compared with that of the traditional alkane oxidation process. The intentional result is that the peroxide concentration is reduced in the reaction process, the risk is controllable, and the industrial production is safe to control.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
firstly, the reaction raw material of the oxidation process comprises one or the combination of large cycloalkane, mono-olefin and polyene, and the precursor of large cycloalkanone is generated by introducing oxidation gas under the action of oxidation catalyst and initiator.
Experiments show that in the oxidation process, the carbon number of the large cycloalkane is 8-16, the oxidation process has good effect and practical value, and the precursor of the large cycloalkanone is a mixture of a large ring epoxy product and an alcohol ketone.
The oxidation process adopts oxidizing gas to realize macrocyclic alkoxylation, the source of the used oxidizing gas (namely oxidant) is green and convenient, explosion caused by accumulation in a hydrogen peroxide and alkyl peroxide hydroxide reaction system is avoided, peroxide generated in the reaction system directly reacts with olefin under the condition of a catalyst to generate epoxide, and the peroxide is decomposed into an alcohol ketone mixture.
Further, the oxidation catalyst is any one salt containing molybdenum, chromium and vanadium, and the salt can be one of nitrate, sulfate, phosphate, halogen salt, organic carboxylate and organic sulfonate; preferably an organic carboxylate or organic sulfonate; most preferred is an organic carboxylate having 2 to 16 carbon atoms.
Furthermore, the dosage of the oxidation catalyst is 0.01-5% of the mass of the raw materials, the preferable dosage of the oxidation catalyst is 0.05-1%, and the most preferable dosage is 0.1-0.5%.
Further, the initiator is alkyl hydrogen peroxide, preferably alkyl hydrogen peroxide with 4-16 carbon atoms; the dosage of the initiator is 0.1-1% of the mass of the raw materials, preferably 0.2-0.9%, and most preferably 0.5-0.8%.
The oxidizing gas plays a role in the reaction in a flowing mode, the volume ratio of the introduced oxidizing gas to the material per minute is 1-100: 1, the preferable volume ratio is 20-50: 1, and the most preferable volume ratio is 25-40: 1; the oxidizing gas is either air or oxygen.
Further, the reaction temperature of the oxidation reaction is 75-250 ℃, the preferable reaction temperature is 80-150 ℃, and the most preferable temperature is 100-125 ℃; the reaction pressure is 0.1-2.0 MPa, the preferable reaction pressure is 0.5-1.6 MPa, and the most preferable pressure is 0.8-1.0 MPa; the reaction time is 0.5-6 h, preferably 1.0-5 h, and most preferably 1.5-4 h.
And secondly, the separation process is to rectify the precursor generated in the oxidation process, and the oxidation product is subjected to simple rectification separation and enters a hydrogenation process, so that the operation is simple and convenient.
And finally, the hydrogenation process is to introduce hydrogen and nitrogen into the separated precursor, and obtain a macrocyclic alkanol ketone mixture under the action of a hydrogenation catalyst and an inhibitor.
The hydrogenation process adopts a nitrogen and hydrogen mixed system, and avoids the side hydrogenolysis reaction of the generated macrocyclic alcohol in a pure hydrogen atmosphere by reducing the hydrogen concentration; and the catalyst and the inhibitor are used together, so that the activity of the catalyst is reduced, the reaction of materials under mild conditions is realized, and the hydrogenolysis side reaction caused by the catalyst with higher activity is avoided.
Further, in the hydrogenation process, the main metal of the hydrogenation catalyst is any one or more of nickel, platinum group, copper and cobalt, preferably the main metal is nickel and/or copper; the dosage of the added hydrogenation catalyst is 0.1-5% of the mass of the raw materials, and the preferred addition amount of the hydrogenation catalyst is 0.5-2%; most preferably 1% to 1.5%.
Further, the hydrogenation catalyst support mayIs selected from one of alumina, molecular sieve, silicon dioxide, diatomite, titanium dioxide and hydrotalcite, preferably silicon dioxide and titanium dioxide; most preferably silicon dioxide, and the specific surface area of the silicon dioxide is 350-600 m2The pore diameter is 20 to 50nm, and the pore volume is 0.87 to 1.5 ml/g.
Further, in the hydrogenation process, the ratio of nitrogen to hydrogen is 1-10: 1, preferably 2-8: 1; the most preferable ratio is 4-5: 1.
Furthermore, in the hydrogenation process, the dosage of the inhibitor is 0.1-50% of the mass of the hydrogenation catalyst, and the inhibitor is one of organic amine, pyridine and pyrrole derivatives; preferably pyridines or pyrroles; most preferred are pyridines.
Further, in the hydrogenation process, the reaction temperature is 60-240 ℃, and the preferable reaction temperature is 120-220 ℃; the most preferable temperature is 150-190 ℃; the reaction pressure is 0.1-10 MPa, and the preferable pressure is 0.5-8 MPa; the most preferable pressure is 4-6 MPa; the reaction time is 0.25-2 h, preferably 0.5-1.5 h, and most preferably 0.75-1.25 h.
Furthermore, the reactor used in the oxidation process and the hydrogenation process is one of a fixed bed, a fluidized bed, a reaction kettle and a circulating pipe; preferably one of a fixed bed reactor, a circulating tube reactor and a reaction kettle reactor; most preferably a circulating tube reactor.
The invention adopts the combination of the oxidation process and the hydrogenation process, and the lipid, carboxylic acid and unsaturated byproducts generated by transitional oxidation in the oxidation process can generate the alcohol ketone target product through hydrogenation, thereby improving the product yield, reducing the intermediate material treatment process, finally realizing the reduction of carbon emission and improving the technical innovation and the process competitiveness.
Advantageous effects
In conclusion, the preparation method of the macrocyclic alkanol ketone provided by the invention avoids the accumulation of alkyl hydroperoxide through reaction cascade, greatly reduces the process risk, allows the low-concentration alkyl hydroperoxide to mainly participate in the epoxidation reaction, and greatly improves the epoxidation yield by 93.7-97.5%, compared with the traditional method for preparing the alkanol ketone by air oxidation of cyclohexane, the yield by 80% is greatly improved, and the side reaction is converted into carboxylic acid, ester and unsaturated alkanol ketone by only 2.5-6.3%.
In addition, the oxidation process and the hydrogenation process are connected in series, so that the material cooling and heating operation is avoided, the separation is simplified, the material storage is reduced, the transfer transportation frequency is reduced, and the like, so that the production energy consumption and the equipment investment are reduced, and the product economy is improved; the side reaction product is converted into a product with economic value, the atom economy is improved, and the waste is changed into valuable; the double-carbon policy tightly withstands the large trend of chemical development, and the reaction series connection and the process series connection reduce carbon emission and improve the technical competitiveness of the production process.
Drawings
FIG. 1: the reaction principle diagram for preparing cyclooctanol and cyclooctanone by the cyclooctene oxidation and hydrogenation process of the invention
FIG. 2: reaction schematic diagram for preparing cyclooctanol and cyclooctanone by cyclooctane oxidation process in prior art
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific examples, specifically, examples 1 to 3 are descriptions of the overall three-stage continuous process of the present invention, examples 4 to 6 are descriptions of the oxidation process of the present invention, and examples 7 to 8 are descriptions of the hydrogenation process of the present invention; it is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The three-stage continuous process of the present invention is illustrated below with reference to FIG. 1, using cyclooctene as the reaction material.
And (3) an oxidation process: adding raw material cyclooctene into a circulating tube reactor, adding 0.01-5% of oxidation catalyst and 0.1-1% of initiator by mass of raw material, and introducing air or oxygen at a volume ratio of 1-100: 1 per minute. The reaction temperature is 75-250 ℃, the reaction pressure is 0.1-2.0 MPa, and the reaction time is 0.5-6 h;
the separation process comprises the following steps: rectifying and separating the product, removing unreacted cyclooctene, and directly adding the residual raw materials in the tower kettle into a hydrogenation reactor;
and (3) hydrogenation process: adding a hydrogenation catalyst into the residual raw materials (substances such as cyclooctene peroxide, cyclooctenol, cyclooctanone, bridged products and the like) in the tower kettle, wherein the dosage of the hydrogenation catalyst is 0.1-5% of the mass of the raw materials, the ratio of nitrogen to hydrogen is adjusted to be 1-10: 1, and the dosage of a catalyst inhibitor is 0.1-50% of the mass of the catalyst. The reaction temperature is 60-240 ℃, the reaction pressure is 0.1-10 MPa, and the reaction time is 0.25-2 h.
Example 2
This example describes the three-stage continuous process of the present invention using cyclododecane as the starting material.
And (3) an oxidation process: adding raw materials into a circulating reactor, and introducing air, wherein the volume ratio of the air to the materials is 25: 1, the reaction temperature is 180 ℃, the reaction pressure is 0.8MPa, the reaction time is 4 hours, the oxidation catalyst is molybdenum acetate, the using amount of the molybdenum acetate is 1.0 percent of the mass of the raw materials, and the initiator is isopropyl hydroperoxide;
the separation process comprises the following steps: rectifying and separating the product, removing unreacted cyclododecane, and directly adding the residual raw materials in the tower kettle into a hydrogenation reactor;
and (3) hydrogenation process: introducing hydrogen and nitrogen into the substances subjected to the separation process, wherein the ratio of the hydrogen to the nitrogen is 1: and 4, the reaction temperature is 160 ℃, the reaction pressure is 4.5MPa, the reaction time is 1.5h, the hydrogenation catalyst is 40% of nickel-silicon dioxide, the dosage of the hydrogenation catalyst is 5% of the mass of the raw materials, the inhibitor is triethylamine, and the dosage of the inhibitor is 5% of the mass of the raw materials.
After the reaction, the total selectivity of the alcohol ketone was 91.3% and the conversion was 16.7%.
Comparative example 1
Conventional alkane oxidation processes: adding cyclododecane into a circulating reactor, and introducing oxygen, wherein the volume ratio of the oxygen to the materials is 25: 1, the reaction temperature is 180 ℃, the reaction pressure is 0.8MPa, the reaction time is 4h, the boric acid accounts for 4.0 percent of the weight of the cyclododecane, the total selectivity of the alcohol ketone after the reaction is finished is 76.3 percent, and the conversion rate is 15.6 percent.
The conventional alkane oxidation process was compared to the process of the present invention and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the conversion rate and the product yield of the alcohol ketone in the three-stage oxidation, separation and hydrogenation process of the invention are improved compared with the conventional oxidation process by using cyclododecane as a raw material, and especially the final alcohol ketone product yield of the invention is improved by 15%.
Example 3
In this example, the three-stage continuous process of the present invention is described using cyclododecene as a raw material.
And (3) an oxidation process: adding raw materials into a circulating reactor, and introducing oxygen, wherein the volume ratio of the oxygen to the materials is 50:1, the reaction temperature is 110 ℃, the reaction pressure is 0.8MPa, the reaction time is 4 hours, the oxidation catalyst is molybdenum naphthenate, the using amount of the molybdenum naphthenate is 0.75 percent of the mass of the raw material, and the initiator is isopropyl hydroperoxide;
the separation process comprises the following steps: rectifying and separating the product to remove unreacted cyclododecene, and directly adding the residual material into a hydrogenation reactor;
and (3) hydrogenation process: introducing hydrogen and nitrogen into the substances subjected to the separation process, wherein the ratio of the hydrogen to the nitrogen is 1: the method comprises the following steps of 1, wherein the reaction temperature is 200 ℃, the reaction pressure is 9MPa, the reaction time is 1.5h, the hydrogenation catalyst is 40% of nickel-silicon dioxide, the dosage of the hydrogenation catalyst is 0.5% of the mass of the raw materials, the inhibitor is triethylamine, and the dosage of the inhibitor is 0.5% of the mass of the raw materials.
Comparative example 2
The experimental procedure is as in example 3, and the epoxidation process (i.e. without isolation) is compared with the process of the present invention under the same reaction conditions as in example 3, and the results are shown in Table 2.
TABLE 2
The comparison of the oxidation process, the hydrogenation process and the separation process shows that the yield of the comprehensive product of the technology can be 3.9 percent higher than that of the epoxidation process after the intermediate product is not separated. Part of carboxylic acid, lipid and unsaturated alcohol ketone generated in the oxidation process are easy to generate aggregation in the rectification process, and high-boiling point byproducts are taken as waste materials to be discharged from the tower bottom. The technology separates unreacted raw materials and catalyst by rectification, the mixed system is directly hydrogenated, and partial oxidation by-products are converted into cyclododecanol.
Example 4
The example introduces an oxidation process in a reaction for preparing cyclooctanol by taking cyclooctane and cyclooctene as raw materials:
the mass ratio of the raw materials of cyclooctane and cyclooctene is 1: 1, taking air as an oxidant, and introducing air and a material in a volume ratio of 20: the method comprises the following steps of 1, wherein the temperature of an oxidation reaction is 120 ℃, the reaction pressure is 1.0MPa, the reaction time is 4 hours, the oxidation catalyst is molybdenum acetylacetonate, the dosage of the molybdenum acetylacetonate is 0.05% of the mass of a raw material, the initiator is tert-butyl hydroperoxide, the dosage of the tert-butyl hydroperoxide is 0.5% of the mass of the raw material, the yield of an obtained product is 93.5%, and the conversion rate is 20.5%.
Comparative example 3
This comparative example is shown in fig. 2, the experimental procedure is the same as that of example 4, the raw materials cyclooctane and cyclooctene described in example 4 are mixed and replaced by single cyclooctane, other reaction conditions are not changed, and the results of comparing example 4 with comparative example 3 are shown in table 3.
TABLE 3
By comparison, the conversion rate is doubled and the product yield is improved by 17.3% compared with the reaction using cyclooctane as a raw material only by mixing cyclooctane and cyclooctene as the raw materials; the alkyl hydroperoxide generated in the oxidation process continuously reacts with the cyclooctene, thereby indirectly improving the conversion rate and the yield.
Example 5
The example introduces an oxidation process in a reaction for preparing cyclooctanol by taking cyclooctane and cyclooctene as raw materials:
taking cyclooctane and cyclooctene as raw materials, wherein the mass ratio of the cyclooctane to the cyclooctene is 1: 1, taking oxygen as an oxidant, and introducing oxygen and a material in a volume ratio of 20: the method comprises the following steps of 1, wherein the temperature of an oxidation reaction is 105 ℃, the reaction pressure is 0.5MPa, the reaction time is 1h, the oxidation catalyst is molybdenum acetylacetonate, the using amount of the molybdenum acetylacetonate is 0.05% of the mass of a raw material, the initiator is tert-butyl hydroperoxide, the using amount of the tert-butyl hydroperoxide is 0.5% of the mass of the raw material, the yield of an obtained product is 96.7%, and the conversion rate is 15.6%.
Comparative example 4
The experimental procedure was the same as in example 5, except that the raw materials cyclooctane and cyclooctene described in example 5 were mixed and replaced with cyclooctane alone, the reaction conditions were not changed, and the results of comparing example 5 with comparative example 4 are shown in table 4.
TABLE 4
By comparison, the reaction conversion rate is doubled and the product yield is increased by 23.6% when the cyclooctane and the cyclooctene are mixed and compared with the single cyclooctane by using oxygen as an oxidant. Pure oxygen reacts faster than air and the time is shortened to 1/4. The alkyl hydroperoxide generated in the oxidation process continuously reacts with the cyclooctene, thereby indirectly improving the conversion rate and the yield.
Example 6
The example introduces an oxidation process in a reaction for preparing cyclooctanol by taking cyclooctane and cyclooctene as raw materials:
taking cyclooctane and cyclooctene as raw materials, wherein the mass ratio of the cyclooctane to the cyclooctene is 1: 1, taking oxygen as an oxidant, and introducing oxygen and a material in a volume ratio of 10: the method comprises the following steps of 1, wherein the temperature of an oxidation reaction is 105 ℃, the reaction pressure is 0.5MPa, the reaction time is 1h, the oxidation catalyst is molybdenum acetylacetonate, the using amount of the molybdenum acetylacetonate is 0.05% of the mass of a raw material, the initiator is tert-butyl hydroperoxide, the using amount of the tert-butyl hydroperoxide is 0.5% of the mass of the raw material, the yield of an obtained product is 96.7%, and the conversion rate is 15.6%.
Comparative example 5
The experimental procedure was the same as that of example 6, except that no oxidation catalyst was used in this comparative example, and other reaction conditions were not changed, and the results of comparing example 6 with comparative example 5 are shown in Table 5.
TABLE 5
By comparison, it can be seen that the oxidation catalyst and no catalyst comparison: whether the oxidation catalyst is used or not has great influence on a reaction system, the epoxidation reaction cannot be carried out without the catalyst, and the conversion rate and the selectivity of the product are obviously reduced.
Comparative example 6
The experimental procedure was the same as that of example 6 except that no initiator was used and the other reaction conditions were not changed, and the results of comparing example 6 with comparative example 6 are shown in Table 6.
TABLE 6
Through comparison, the following results are found: the use or non-use of the initiator has larger influence on a reaction system, the free radical reaction is slower without initiation, the required time is longer, the influence on the conversion rate of the corresponding product is obvious, and the selectivity change is not obvious.
Example 7
The example describes a hydrogenation process using cycloxynonane as a raw material:
introducing hydrogen and nitrogen into epoxy cyclononane serving as a raw material, wherein the ratio of the hydrogen to the nitrogen is 1: 1, the reaction temperature is 210 ℃, the reaction pressure is 6MPa, the reaction time is 1.5h, the hydrogenation catalyst is 10% of nickel-silicon dioxide, the dosage of the hydrogenation catalyst is 0.5% of the mass of the raw material, the inhibitor is pyridine, and the dosage of the inhibitor is 0.2% of the mass of the raw material.
Comparative example 7
The experimental procedure was the same as in example 7, and the other conditions were the same as in example 7 in the case where no inhibitor was added, and the results are shown in Table 7.
TABLE 7
The comparison shows that whether the inhibitor is used or not has great influence on the reaction, the hydrogenolysis side reaction of the reaction system without the addition of the inhibitor is obviously improved, and the reaction selectivity is reduced. The invention adds inhibitor to improve the reaction yield greatly. The conclusion of controlling the activity of the hydrogenation catalyst and improving the reaction selectivity can be seen from the following table.
Example 8
The example describes a hydrogenation process using cycloxynonane as a raw material:
introducing hydrogen and nitrogen into epoxy cyclononane serving as a raw material, wherein the ratio of the hydrogen to the nitrogen is 1: 1, the reaction temperature is 210 ℃, the reaction pressure is 6MPa, the reaction time is 1.5h, the hydrogenation catalyst is 10% of nickel-silicon dioxide, the dosage of the hydrogenation catalyst is 0.5% of the mass of the raw material, the inhibitor is pyridine, and the dosage of the inhibitor is 0.2% of the mass of the raw material.
Comparative example 8
The experimental procedure was the same as in example 8 except that the gas was introduced in the presence of the inhibitor in the same manner as in example 8, and the results are shown in Table 8.
TABLE 8
The comparison shows that the reaction is greatly influenced by the mixing of the hydrogen and the nitrogen, and the hydrogenolysis in the pure hydrogen environment is obvious. The reaction selectivity is reduced from 99.4% to 85.3%, and the pure hydrogen atmosphere is not beneficial to the reaction.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents and the like included in the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the large cycloalkanol ketone is characterized by comprising three continuous processes of oxidation, separation and hydrogenation which are connected in series:
1) and (3) an oxidation process: the reaction raw material comprises one or the combination of large cycloalkane, mono-olefin and multi-olefin, and the precursor of large cycloalkanone is generated by introducing oxidizing gas under the action of an oxidation catalyst and an initiator;
2) the separation process comprises the following steps: rectifying a precursor generated in the oxidation process;
3) and (3) hydrogenation process: introducing hydrogen and nitrogen into the separated precursor, and obtaining a macrocyclic alkanol ketone mixture under the action of a hydrogenation catalyst and an inhibitor;
in the oxidation process, the carbon number of the large cycloalkane is 8-16, and the precursor of the large cycloalkanone is a mixture of a large ring epoxy product and an alcohol ketone.
2. The method for preparing macrocycloalcanolone according to claim 1, wherein in the oxidation process, the oxidation catalyst is any one salt containing molybdenum, chromium and vanadium, and the salt is one of nitrate, sulfate, phosphate, halogen salt, organic carboxylate and organic sulfonate; preferably an organic carboxylate or organic sulfonate; most preferably organic carboxylate with 2-16 carbon atoms; the dosage of the oxidation catalyst is 0.01-5% of the mass of the raw materials, the preferable dosage of the oxidation catalyst is 0.05-1%, and the most preferable dosage is 0.1-0.5%.
3. The preparation method of the large cycloalkanone ketone as claimed in claim 1, wherein in the oxidation process, the initiator is alkyl hydroperoxide, preferably alkyl hydroperoxide with carbon number of 4-16; the dosage of the initiator is 0.1-1% of the mass of the raw materials, preferably 0.2-0.9%, and most preferably 0.5-0.8%.
4. The preparation method of the macrocyclic cycloalkanone as claimed in claim 1, wherein in the oxidation process, a volume to material volume ratio of the oxidation gas introduced per minute is 1-100: 1, preferably 20-50: 1, and most preferably 25-40: 1.
5. The preparation method of a macrocyclic cycloalkanone as claimed in claim 1, wherein in the oxidation process, the reaction temperature is 75-250 ℃, preferably the reaction temperature is 80-150 ℃, and most preferably the temperature is 100-125 ℃; the reaction pressure is 0.1-2.0 MPa, the preferable reaction pressure is 0.5-1.6 MPa, and the most preferable pressure is 0.8-1.0 MPa; the reaction time is 0.5-6 h, preferably 1.0-5 h, and most preferably 1.5-4 h.
6. The method for preparing a macrocyclic alkanone according to claim 1, wherein in the hydrogenation process, the main metal of the hydrogenation catalyst is any one or more of nickel, platinum group, copper and cobalt, preferably the main metal is nickel and/or copper; the dosage of the added hydrogenation catalyst is 0.1-5 percent of the mass of the raw materials, and the preferred addition amount of the hydrogenation catalyst is 0.5-2 percent; most preferably 1 to 1.5 percent; the hydrogenation catalyst carrier is alumina, molecular sieve, silicon dioxide, diatomite, titanium dioxide and hydrotalcite, preferably silicon dioxide and titanium dioxide; most preferred is silica.
7. The preparation method of the large cycloalkanolone according to claim 1, wherein in the hydrogenation process, the ratio of nitrogen to hydrogen is 1-10: 1, preferably 2-8: 1; the most preferable ratio is 4-5: 1.
8. The method for preparing a macrocyclic alkylol ketone as claimed in claim 1, wherein in the hydrogenation process, the amount of the inhibitor is 0.1-50% of the mass of the hydrogenation catalyst, and the inhibitor is one of organic amine, pyridine and pyrrole derivatives; preferably pyridines or pyrroles; most preferred are pyridines.
9. The preparation method of a macrocyclic cycloalkanone as claimed in claim 1, wherein in the hydrogenation process, the reaction temperature is 60-240 ℃, preferably 120-220 ℃; the most preferable temperature is 150-190 ℃; the reaction pressure is 0.1-10 MPa, and the preferable pressure is 0.5-8 MPa; the most preferable pressure is 4-6 MPa; the reaction time is 0.25-2 h, preferably 0.5-1.5 h, and most preferably 0.75-1.25 h.
10. The method for preparing macrocycloalcolone according to claim 1, wherein the reactor used in the oxidation process and the hydrogenation process is one of a fixed bed, a fluidized bed, a reaction kettle and a circulating pipe; preferably one of a fixed bed reactor, a circulating tube reactor and a reaction kettle reactor; most preferably a circulating tube reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111542886.9A CN114105741A (en) | 2021-12-16 | 2021-12-16 | Preparation method of large cycloalkanolone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111542886.9A CN114105741A (en) | 2021-12-16 | 2021-12-16 | Preparation method of large cycloalkanolone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114105741A true CN114105741A (en) | 2022-03-01 |
Family
ID=80366008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111542886.9A Pending CN114105741A (en) | 2021-12-16 | 2021-12-16 | Preparation method of large cycloalkanolone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114105741A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1064167A (en) * | 1963-08-19 | 1967-04-05 | Exxon Research Engineering Co | Preparation of cyclic alkanols |
| US5859301A (en) * | 1993-12-23 | 1999-01-12 | Dsm N.V. | Process for preparing alkanones and alkanols |
| US6335472B1 (en) * | 1998-12-28 | 2002-01-01 | Ube Industries, Ltd. | Method of hydrogenating epoxidized C6—C12 cyclohydrocarbon compounds |
| JP2002047221A (en) * | 2000-07-27 | 2002-02-12 | Ube Ind Ltd | Method for producing cyclododecanone and cyclododecanol |
| CN105237345A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Method for preparing cyclooctanol and cyclooctanone through cyclooctane oxidation |
| CN112661620A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Preparation method of cyclopentanone |
-
2021
- 2021-12-16 CN CN202111542886.9A patent/CN114105741A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1064167A (en) * | 1963-08-19 | 1967-04-05 | Exxon Research Engineering Co | Preparation of cyclic alkanols |
| US5859301A (en) * | 1993-12-23 | 1999-01-12 | Dsm N.V. | Process for preparing alkanones and alkanols |
| US6335472B1 (en) * | 1998-12-28 | 2002-01-01 | Ube Industries, Ltd. | Method of hydrogenating epoxidized C6—C12 cyclohydrocarbon compounds |
| JP2002047221A (en) * | 2000-07-27 | 2002-02-12 | Ube Ind Ltd | Method for producing cyclododecanone and cyclododecanol |
| CN105237345A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Method for preparing cyclooctanol and cyclooctanone through cyclooctane oxidation |
| CN112661620A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Preparation method of cyclopentanone |
Non-Patent Citations (1)
| Title |
|---|
| 曾崇余;崔咪芬;: "环十二烷空气催化氧化制环十二醇及酮", 南京工业大学学报(自然科学版), no. 1 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6479705B2 (en) | Process for preparing ketone, alcohol and hydroperoxide | |
| EP0659726B1 (en) | Process for preparing a cycloalkanone and/or a cycloalkanol | |
| JPS6257607B2 (en) | ||
| CN109336750A (en) | A kind of synthesis technology of isoamyl olefine aldehydr | |
| CN110560169A (en) | Cycloparaffin catalytic oxidation method promoted by iron porphyrin | |
| US4508923A (en) | Oxidation of hydrocarbons | |
| US6762319B1 (en) | Hydrocarbon, alcohol and/or ketone oxidation method | |
| CN110407680B (en) | Method for preparing isopentenal | |
| HU218302B (en) | Method for producing cyclohexyl-hydroperoxide | |
| CN114105741A (en) | Preparation method of large cycloalkanolone | |
| CN114105911B (en) | Preparation method for co-production of cyclododecene ether and cyclododecanol | |
| US7291755B2 (en) | Process for producing alcohol and/or ketone | |
| CN112358392B (en) | Method for efficiently synthesizing refined adipic acid by using tubular reactor | |
| US3987101A (en) | Process for preparing cycloalkanones and cycloalkanols | |
| CN107400038B (en) | Method for preparing cyclohexanone and cyclohexanol by decomposing cyclohexyl hydroperoxide | |
| CN109438175B (en) | Method for preparing cyclohexanol and cyclohexanone by decomposing cyclohexyl hydroperoxide | |
| CN112661618B (en) | Copper catalysis preparation method of cyclopentanone | |
| JPH049344A (en) | Production of cyclohexanone and cyclohexanol | |
| CN112661620A (en) | Preparation method of cyclopentanone | |
| CN113651685B (en) | Process for preparing dicarboxylic acids by two-stage oxidation of cyclic alkanes | |
| CN114075096B (en) | Cyclohexene synthesis process | |
| CN102941120A (en) | Catalytic system for preparing cyclohexanol and cyclohexanone by liquid-phase catalytic oxidation of cyclohexane and use method of catalytic system | |
| CN112142566B (en) | Method for producing cyclohexanol and cyclohexanone | |
| CN112661602B (en) | Preparation method of cyclopentanol based on copper catalyst | |
| CN112209816B (en) | Preparation method of adipic acid |
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 |
Effective date of registration: 20221223 Address after: No. 1 Jingjin Road, Beichen District, Tianjin City, 300400 Applicant after: CHINA TIANCHEN ENGINEERING Co.,Ltd. Applicant after: CHINA NATIONAL CHEMICAL ENGINEERING Co.,Ltd. Address before: No. 1 Jingjin Road, Beichen District, Tianjin City, 300400 Applicant before: CHINA TIANCHEN ENGINEERING Co.,Ltd. |
|
| TA01 | Transfer of patent application right |