CN110498731A - The method and device of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid - Google Patents
The method and device of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid Download PDFInfo
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- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexane-carboxaldehyde Natural products O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 title claims abstract description 107
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 63
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- -1 methyl cyclohexane alkoxide Chemical class 0.000 title claims abstract description 25
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000007670 refining Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 289
- 239000007792 gaseous phase Substances 0.000 claims description 78
- 238000010992 reflux Methods 0.000 claims description 76
- 238000009833 condensation Methods 0.000 claims description 32
- 230000005494 condensation Effects 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 32
- 230000008676 import Effects 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 24
- 239000004366 Glucose oxidase Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000004365 Protease Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 7
- BISUKPSBCCXDRR-UHFFFAOYSA-N [Mo].[Zr].[Co] Chemical class [Mo].[Zr].[Co] BISUKPSBCCXDRR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- INEAOAIPCQTMJL-UHFFFAOYSA-N cobalt manganese molybdenum Chemical compound [Mn][Co][Mo] INEAOAIPCQTMJL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical group [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000686 essence Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 description 13
- 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 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000005457 optimization Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000008901 benefit Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 235000019640 taste Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- GKJIOBYKGJQUEQ-UHFFFAOYSA-N formic acid;methylcyclohexane Chemical compound OC=O.CC1CCCCC1 GKJIOBYKGJQUEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- BIDNLKIUORFRQP-XYGFDPSESA-N (2s,4s)-4-cyclohexyl-1-[2-[[(1s)-2-methyl-1-propanoyloxypropoxy]-(4-phenylbutyl)phosphoryl]acetyl]pyrrolidine-2-carboxylic acid Chemical compound C([P@@](=O)(O[C@H](OC(=O)CC)C(C)C)CC(=O)N1[C@@H](C[C@H](C1)C1CCCCC1)C(O)=O)CCCC1=CC=CC=C1 BIDNLKIUORFRQP-XYGFDPSESA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 229960002490 fosinopril Drugs 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- DKWNMCUOEDMMIN-PKOBYXMFSA-N melagatran Chemical compound C1=CC(C(=N)N)=CC=C1CNC(=O)[C@H]1N(C(=O)[C@H](NCC(O)=O)C2CCCCC2)CC1 DKWNMCUOEDMMIN-PKOBYXMFSA-N 0.000 description 2
- 229960002137 melagatran Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FSVJFNAIGNNGKK-UHFFFAOYSA-N 2-[cyclohexyl(oxo)methyl]-3,6,7,11b-tetrahydro-1H-pyrazino[2,1-a]isoquinolin-4-one Chemical compound C1C(C2=CC=CC=C2CC2)N2C(=O)CN1C(=O)C1CCCCC1 FSVJFNAIGNNGKK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- SXFSQZDSUWACKX-UHFFFAOYSA-N 4-methylthio-2-oxobutanoic acid Chemical compound CSCCC(=O)C(O)=O SXFSQZDSUWACKX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 208000014644 Brain disease Diseases 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 241001442514 Schistosomatidae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CNFMJLVJDNGPHR-UKTHLTGXSA-N Triapenthenol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1CCCCC1 CNFMJLVJDNGPHR-UKTHLTGXSA-N 0.000 description 1
- 238000005902 aminomethylation reaction Methods 0.000 description 1
- 239000003416 antiarrhythmic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000013595 glycosylation Effects 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 208000024691 pancreas disease Diseases 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229960002957 praziquantel Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940121649 protein inhibitor Drugs 0.000 description 1
- 239000012268 protein inhibitor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- 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
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to the method and devices of a kind of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, using hexahydrotoluene as raw material, using air as oxidant, prepare cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid by liquid-phase catalytic oxidation；Including reaction process, hexahydrotoluene removal process and cyclohexanemethanol subtractive process；The device of the invention is that reaction unit includes reactor R1101, directional decomposition device A1101；Hexahydrotoluene recyclable device includes an effect rectifying column T2101, two effect rectifying column T2201, three-effect rectification tower T2301 and quadruple effect rectifying column T2401；Refining plant includes lightness-removing column T3101, cyclohexanecarboxaldehyde tower T3201 and cyclohexanemethanol tower T3301.Hexahydrotoluene utilization rate >=99.99% prepares cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid purity >=99.99%, and yield is more than or equal to 99%.
Description
Technical field
The present invention relates to a kind of methods for preparing cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, and in particular to a kind of methyl
The method and device of cyclohexane oxidation coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid.
Background technique
Hexahydrobenzaldehyde is the intermediate of plant growth regulator triapenthenol, be mainly used for organic synthesis, pharmaceutical synthesis and
For nano magnesia catalysis and ethyl nitrine acetate alcohol aldehyde reaction, α-phenodiazine-beta-hydroxy esters (α-diazo- β-is generated
Hydroxyesters), pharmaceutically it is used for organic synthesis drug melagatran (Melagatran)/fosinopril
(Fosinopril) etc. it can treat high blood pressure disease.Cyclohexanemethanol and other alcohol have similar chemical property, can occur oxidation,
Esterification, etherificate, halogenation etc..Cyclohexanemethanol and 4- methyl mercapto -2-Oxobutyric acid can carry out esterification and generate 4- first sulphur
Base -2-Oxobutyric acid hexamethylene methyl esters can be used to treat liver, kidney, pancreas and brain disease；4-HBA and cyclohexanemethanol esterification
Reaction generates 4-HBA hexamethylene methyl esters, then can carry out aminomethylation reaction life with tetrahydropyrrole, formalin
At hydroxyl two (pyrrolidinylmethyl) benzoate methyl esters, which can be prepared into antiarrhythmic drug；Utilize ring
Own methanol can synthesize hydroxyl polyethoxy methylcyclohexyl normal octane, and the sodium salt of the substance is a kind of biodegrade washing
Agent can be used to administer sewage；Cyclohexanemethanol can also carry out glycosylation, and preparation is used as immunocyte protein inhibitor.Ring
Own formic acid is organic synthesis raw material, can be used for synthesizing resist pregnant 392 drug and treatment blood fluke new drug praziquantel drug, it is also possible to make
Vulcanized rubber expanding material, petroleum clarifying agent, pesticide, dyestuff and other organic compounds.
Chinese patent CN102951978A reports a kind of method that acid is reduced into alcohol by sodium borohydride, takes water as a solvent,
Cetyl trimethylammonium bromide is phase transfer catalyst, and using benzoic acid as raw material, cyclohexanemethanol has been prepared.
Currently, there is no patent by the method for raw material coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid of hexahydrotoluene
Report.
The invention proposes a kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid and
Device, with air (oxygen) for oxidant, prepares hexamethylene first by liquid-phase catalytic oxidation using hexahydrotoluene as raw material
Alcohol；The wherein conversion per pass 2%-20% of hexahydrotoluene, the selective 30%-60% of cyclohexanemethanol, other side reaction packets
The selective 20%-30% of hexahydrobenzaldehyde, the selective 10%-50% of hexahydrobenzoid acid are included, multi-effect distillation work is then passed through
Skill recycles unreacted hexahydrotoluene, so that the energy consumption in hexahydrotoluene removal process is greatlyd save, finally by coupling
The mode of rectifying refines cyclohexanemethanol, and the cyclohexanemethanol product of purity >=99.99% can be obtained, and makes full use of cyclohexanemethanol
The heat of different tastes greatly reduces energy consumption needed for distillation process by process optimization in purification process, which can
Energy consumption >=40% is reduced, condensation water consumption reduces >=50%.The process flow is simply easily achieved, it can be achieved that with hexahydrotoluene
Cyclohexanemethanol is continuously prepared for raw material, substantially increases the economic benefit and social benefit of enterprise.
Summary of the invention
The invention proposes a kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid and
Device, with air (oxygen) for oxidant, prepares hexamethylene first by liquid-phase catalytic oxidation using hexahydrotoluene as raw material
Aldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid.Wherein conversion per pass >=2-20% of hexahydrotoluene, the selectivity of cyclohexanemethanol
30%-60%, the selective 20%-30% of hexahydrobenzaldehyde, the selective 10%-50% of hexahydrobenzoid acid, then by more
It imitates rectification process and recycles unreacted hexahydrotoluene, to greatly save the energy consumption in hexahydrotoluene removal process, finally
Cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid are refined by way of coupling rectification, and the hexamethylene first of purity >=99.99% can be obtained
Aldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid product, and make full use of in purification process the heats of different tastes, by process optimization,
Energy consumption needed for distillation process is greatly reduced, which can reduce energy consumption >=40%, and condensation water consumption reduces >=50%.It should
Process flow is simply easily achieved, it can be achieved that continuously preparing cyclohexanecarboxaldehyde, cyclohexanemethanol and hexamethylene as raw material using hexahydrotoluene
Formic acid substantially increases the economic benefit and social benefit of enterprise.
The present invention adopts the following technical scheme that realize:
A kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, with hexahydrotoluene
Cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid are prepared by liquid-phase catalytic oxidation using air as oxidant for raw material；Its
It is characterized in including the following steps
(1) reaction process: reactor R1101 is added after hexahydrotoluene and catalyst mixing, air is filled with instead from bottom
Device is answered, unreacted gas enters after reactor head discharge and divides cooler E1101, condensed liquid returning reactor, no
Solidifying gas emptying；Material after the reaction was completed enters directional decomposition device A1101 after air heat exchanger E1102 and air heat-exchange,
The peroxide directional decomposition that A1101 generates reaction, material enters an effect rectifying column T2101 after decomposition；
(2) hexahydrotoluene removal process: the material from directional decomposition device A1101 enters an effect rectifying column T2101,
T2101 top gaseous phase enters T2101 heat exchanger E2101 and exchanges heat, and material a part flows back after heat exchange, and a part is used as product
Extraction, kettle material enter two effect rectifying column T2201；T2201 top gaseous phase enters T2201 heat exchanger E2201 and exchanges heat, and changes
Material a part flows back after heat, and a part is produced as product, and kettle material enters three-effect rectification tower T2301；T2301 tower overhead gas
Mutually enter T2301 heat exchanger E2301 exchange heat, after heat exchange material enter T2301 overhead condenser carry out condensation cooling it is latter
Partial reflux, a part are produced as product, and kettle material enters quadruple effect rectifying column T2401；T2401 top gaseous phase enters
T2401 overhead condenser E2401 carry out condensation it is cooling after partial reflux, partially produced as product, kettle material enters de- light
Tower T3101；
(3) cyclohexanemethanol subtractive process: the kettle material from T2401 enters lightness-removing column T3101, lightness-removing column T3101 tower
Top gas mutually enters T3101 overhead condenser E3101 and carries out after condensing cooling, and partial reflux is partially produced as light impurity, tower reactor
Material enter cyclohexanecarboxaldehyde tower T3201, T3201 top gaseous phase enter T3201 overhead condenser E3201 carry out condensation it is cooling after,
Partial reflux, partially produces as cyclohexanecarboxaldehyde product, and kettle material enters cyclohexanemethanol tower T3301, T3301 top gaseous phase portion
Divide after being exchanged heat into T3201 heat exchanger E3202, returns to T3301 as reflux, partially enter T3301 overhead condenser
After E3301 carries out condensation cooling, partial reflux part is produced as cyclohexanemethanol product, and tower reactor produces heavy seeds.
The reactor is tank reactor, and quantity is 1 or more series connection.
The reaction process operating pressure is 0.5-2MPa, and operation temperature is 150-300 DEG C.
The molar ratio of the hexahydrotoluene and oxygen is that 1:1-1:2 used catalyst is cobalt molybdenum, cobalt molybdenum manganese, cobalt molybdenum zirconium
Related salts or metalloporphyrin cobalt, manganese, Zr catalyst, total metal content is 50ug/g-200ug/g in reaction process.
The one effect rectifying column T2101 operating pressure 0.3-1MPa；Two effect rectifying column T2201 operating pressure 0.15-
0.8MPa；Two effect rectifying column T2301 operating pressure 0.1-0.5MPa；Two effect rectifying column T2401 operating pressure 0.01-0.1MPa；
Lightness-removing column T3101 operating pressure 0.01-0.1MPa；Cyclohexanecarboxaldehyde tower T3201 operating pressure 0.01-0.1MPa；Cyclohexanol tower
T3301 operating pressure 0.1-1MPa.
The device of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde of the invention, cyclohexanemethanol and cyclohexanecarboxylic acid, including reaction
Device, hexahydrotoluene recyclable device and refining plant；It is characterized in that reaction unit includes reactor R1101, directional decomposition dress
Set A1101；Hexahydrotoluene recyclable device includes an effect rectifying column T2101, two effect rectifying column T2201, three-effect rectification tower T2301
And quadruple effect rectifying column T2401；Refining plant includes lightness-removing column T3101, cyclohexanecarboxaldehyde tower T3201 and cyclohexanemethanol tower T3301.
The reactor R1101 of the reaction unit is equipped with material inlet, air intlet, air outlet slit and material outlet；
Wherein material inlet and air outlet slit are all connected with a point cooler E1101, and air intlet and material outlet are all connected with air heat exchanger
E1102, air heat exchanger E1102 material outlet connect directional decomposition device A1101；A1101 is equipped with material inlet, top gas phase
Outlet and material outlet, wherein material inlet connects E1102, and top gas phase outlet connects subsequent VOC processing unit, material outlet
Connect hexahydrotoluene recovery system.
The one effect rectifying column T2101 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction
Mouth and reboiler return tower mouth, and wherein material inlet connects A1101 material outlet, top gaseous phase outlet connection T2101 heat exchanger
E2101 thermal material import, reflux material inlet connect E2101 material outlet, and reboiler returns tower mouth connection reboiler E2102 object
Material outlet, tower reactor produce mouth connection E2102 material inlet and two effect rectifying column T2102；Two effect rectifying column T2201 be equipped with raw material into
Mouth, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connects T2101 tower
Kettle produces mouth, top gaseous phase outlet connection heat exchanger E2201 thermal material import, and reflux material inlet connection E2201 thermal material goes out
Mouthful, reboiler returns the outlet of tower mouth connection heat exchanger E2101 cold material, and tower reactor produces mouth connection E2101 cold material import and triple effect
Rectifying column T2301；Three-effect rectification tower T2301 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth
And reboiler returns tower mouth, wherein material inlet connection T2201 tower reactor produces mouth, top gaseous phase outlet connection heat exchanger E2301 heat
Material inlet, E2301 material outlet connect condenser E2302 material inlet, and reflux material inlet connection E2302 material goes out
Mouthful, reboiler returns the outlet of tower mouth connection heat exchanger E2201 cold material, and tower reactor produces mouth connection E2201 cold material import and quadruple effect
Rectifying column T2401；Quadruple effect rectifying column T2401 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth
And reboiler returns tower mouth, wherein material inlet connection T2301 tower reactor produces mouth, top gaseous phase outlet connection T2401 overhead condensation
Device E2401 material inlet, reflux material inlet connect E2401 material outlet, and reboiler returns the tower mouth connection cold object of heat exchanger E2301
Material outlet, tower reactor produce mouth connection E2301 cold material import and refining system.
The refining plant includes lightness-removing column T3101, cyclohexanecarboxaldehyde tower T3201 and cyclohexanemethanol tower T3301；Lightness-removing column
T3101 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and reboiler and returns tower mouth, wherein raw material
Import connects T2401 tower reactor and produces mouth, and top gaseous phase outlet connection T3101 overhead condenser E3101 material inlet, flow back material
Import connects E3101 material outlet, and reboiler returns the outlet tower mouth connection reboiler E3102, and tower reactor produces mouth and connects E3102 material
Import and cyclohexanecarboxaldehyde tower T3201；Cyclohexanecarboxaldehyde tower T3201 be equipped with material inlet, top gaseous phase outlet, reflux material inlet,
Tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connection T3101 tower reactor produces mouth, top gaseous phase outlet connection
T3201 overhead condenser E3201 material inlet, reflux material inlet connect E3201 material outlet, and reboiler returns the connection of tower mouth and changes
Hot device E3202 cold material outlet, tower reactor produce mouth connection E3102 cold material import and cyclohexanecarboxaldehyde tower T3102；Cyclohexanol tower
T3301 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, side take-off mouth tower reactor extraction mouth and reboiler and returns tower
Mouthful, wherein material inlet connection T3201 tower reactor produces mouth, and top gaseous phase outlet connects heat exchanger E3202 thermal material import,
E3202 material outlet connects T3301 overhead condenser E3301 material inlet, and reflux material inlet connection E3301 material goes out
Mouthful, side take-off mouth connecting side line cooler E3302 material inlet, reboiler returns tower mouth connection reboiler E3303 material outlet,
Tower reactor produces mouth and connects E3303 material inlet.
The invention proposes a kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid and
Device, with air (oxygen) for oxidant, prepares hexamethylene first by liquid-phase catalytic oxidation using hexahydrotoluene as raw material
Alcohol；Unreacted hexahydrotoluene is recycled by multi-effect distillation, refines cyclohexanecarboxaldehyde, hexamethylene finally by the mode of coupling rectification
Methanol and cyclohexanecarboxylic acid, and the heat of different tastes in purification process is made full use of to greatly reduce essence by process optimization
Energy consumption needed for process is evaporated, and realizes continuous production.
Beneficial achievement of the invention is:
1, using hexahydrotoluene as raw material coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid.
2, the conversion per pass 2%-20% of hexahydrotoluene, the selective 30%-60% of cyclohexanemethanol, hexahydrobenzaldehyde
Selective 20%-30%, the selective 10%-50% of hexahydrobenzoid acid；
3, by optimization technique and heat integration, it can save energy 40% or more, circulation water consumption reduces 50% or more.
4, hexahydrotoluene utilization rate >=99.99%, prepare cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid purity >=
99.99%, yield is more than or equal to 99%.
Detailed description of the invention
A kind of Fig. 1: method and device signal of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid
Figure；
R1101: reactor, A1101: E1101: directional decomposition device divides cooler, E1102: air heat exchanger；
T2101: one effect rectifying column, T2201: two effect rectifying columns, T2301: three-effect rectification tower, T2401: quadruple effect rectifying column,
E2101:T2101 heat exchanger, E2102:T2101 reboiler, E2201:T2201 heat exchanger, E2301:T2301 heat exchanger,
E2302:T2301 overhead condenser, E2401:T2401 overhead condenser；
T3101: lightness-removing column, T3201: cyclohexanecarboxaldehyde tower, T3301: cyclohexanemethanol tower, E3101:T3101 overhead condenser,
E3102:T3101 reboiler, E3201:T3201 overhead condenser, E3202:T3201 heat exchanger, E3301:T3301 overhead condensation
Device, E3302:T3301 reboiler.
Specific embodiment
The invention proposes a kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid and
Device, with air (oxygen) for oxidant, prepares hexamethylene first by liquid-phase catalytic oxidation using hexahydrotoluene as raw material
Aldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid.The wherein conversion per pass 2%-20% of hexahydrotoluene, the selectivity of cyclohexanemethanol
30%-60%, the selective 20%-30% of hexahydrobenzaldehyde, the selective 10%-50% of hexahydrobenzoid acid, then by more
It imitates rectification process and recycles unreacted hexahydrotoluene, to greatly save the energy consumption in hexahydrotoluene removal process, finally
Cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid are refined by way of coupling rectification, and the hexamethylene first of purity >=99.99% can be obtained
Aldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid product, and make full use of in purification process the heats of different tastes, by process optimization,
Energy consumption needed for distillation process is greatly reduced, which can reduce energy consumption >=40%, and condensation water consumption reduces >=50%.It should
Process flow is simply easily achieved, it can be achieved that continuously preparing cyclohexanecarboxaldehyde, cyclohexanemethanol and hexamethylene as raw material using hexahydrotoluene
Formic acid substantially increases the economic benefit and social benefit of enterprise.
As shown in Figure 1, the device of a kind of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, packet
Include reaction unit, hexahydrotoluene recyclable device and refining plant:
Reaction unit of the invention mainly includes reactor R1101, directional decomposition device A1101；It is characterized in that reactor
R1101 is equipped with material inlet, air intlet, air outlet slit and material outlet；Wherein material inlet and air outlet slit are all connected with point
Cooler E1101, air intlet and material outlet are all connected with air heat exchanger E1102, the connection of air heat exchanger E1102 material outlet
Directional decomposition device A1101；A1101 is equipped with material inlet, top gas phase outlet and material outlet, and wherein material inlet connects
E1102, top gas phase outlet connect subsequent VOC processing unit, and material outlet connects hexahydrotoluene recovery system.
Hexahydrotoluene recyclable device mainly includes an effect rectifying column T2101, two effect rectifying column T2201, three-effect rectification tower
T2301 and quadruple effect rectifying column T2401；It is characterized in that an effect rectifying column T2101 is equipped with material inlet, top gaseous phase outlet, reflux
Material inlet, tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connects A1101 material outlet, top gaseous phase outlet
T2101 heat exchanger E2101 thermal material import is connected, reflux material inlet connects E2101 material outlet, and reboiler returns tower mouth company
Reboiler E2102 material outlet is connect, tower reactor produces mouth connection E2102 material inlet and two effect rectifying column T2102.
Two effect rectifying column T2201 are equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and again
Boiling device returns tower mouth, and wherein material inlet connection T2101 tower reactor produces mouth, top gaseous phase outlet connection heat exchanger E2201 thermal material
Import, reflux material inlet connect E2201 material outlet, and reboiler returns the outlet of tower mouth connection heat exchanger E2101 cold material, tower
Kettle produces mouth connection E2101 cold material import and three-effect rectification tower T2301.
Three-effect rectification tower T2301 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and again
Boiling device returns tower mouth, and wherein material inlet connection T2201 tower reactor produces mouth, top gaseous phase outlet connection heat exchanger E2301 thermal material
Import, E2301 material outlet connect condenser E2302 material inlet, and reflux material inlet connects E2302 material outlet, then
Boiling device returns the outlet of tower mouth connection heat exchanger E2201 cold material, and tower reactor produces mouth connection E2201 cold material import and quadruple effect rectifying column
T2401。
Quadruple effect rectifying column T2401 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and again
Boiling device returns tower mouth, and wherein material inlet connection T2301 tower reactor produces mouth, top gaseous phase outlet connection T2401 overhead condenser
E2401 material inlet, reflux material inlet connect E2401 material outlet, and reboiler returns tower mouth connection heat exchanger E2301 cold material
Outlet, tower reactor produce mouth connection E2301 cold material import and refining system.
Cyclohexanemethanol refining plant mainly includes lightness-removing column T3101, cyclohexanecarboxaldehyde tower T3201 and cyclohexanemethanol tower T3301；
It is characterized in that lightness-removing column T3101 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and reboiler
Tower mouth is returned, wherein material inlet connection T2401 tower reactor produces mouth, top gaseous phase outlet connection T3101 overhead condenser E3101 object
Expect import, reflux material inlet connects E3101 material outlet, and reboiler returns the outlet tower mouth connection reboiler E3102, tower reactor extraction
Mouth connection E3102 material inlet and cyclohexanecarboxaldehyde tower T3201.
Cyclohexanecarboxaldehyde tower T3201 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and again
Boiling device returns tower mouth, and wherein material inlet connection T3101 tower reactor produces mouth, top gaseous phase outlet connection T3201 overhead condenser
E3201 material inlet, reflux material inlet connect E3201 material outlet, and reboiler returns tower mouth connection heat exchanger E3202 cold material
Outlet, tower reactor produce mouth connection E3102 cold material import and cyclohexanecarboxaldehyde tower T3102.
Cyclohexanol tower T3301 is equipped with material inlet, top gaseous phase exports, reflux material inlet, side take-off mouth tower reactor are adopted
Outlet and reboiler return tower mouth, and wherein material inlet connection T3201 tower reactor produces mouth, top gaseous phase outlet connection heat exchanger
E3202 thermal material import, E3202 material outlet connect T3301 overhead condenser E3301 material inlet, and flow back material inlet
E3301 material outlet, side take-off mouth connecting side line cooler E3302 material inlet are connected, reboiler returns the connection of tower mouth and boils again
Device E3303 material outlet, tower reactor produce mouth and connect E3303 material inlet.
A kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid of the invention, it is special
Sign is that steps are as follows:
(1) reaction process: reactor R1101 is added after hexahydrotoluene and catalyst mixing, air is filled with instead from bottom
Device is answered, unreacted gas enters after reactor head discharge and divides cooler E1101, condensed liquid returning reactor, no
Solidifying gas emptying；Material after the reaction was completed enters directional decomposition device A1101 after air heat exchanger E1102 and air heat-exchange,
The peroxide directional decomposition that A1101 generates reaction, material enters an effect rectifying column T2101 after decomposition；
(2) hexahydrotoluene removal process: the material from directional decomposition device A1101 enters an effect rectifying column T2101,
T2101 top gaseous phase enters T2101 heat exchanger E2101 and exchanges heat, and material a part flows back after heat exchange, and a part is used as product
Extraction, kettle material enter two effect rectifying column T2201；T2201 top gaseous phase enters T2201 heat exchanger E2201 and exchanges heat, and changes
Material a part flows back after heat, and a part is produced as product, and kettle material enters three-effect rectification tower T2301；T2301 tower overhead gas
Mutually enter T2301 heat exchanger E2301 exchange heat, after heat exchange material enter T2301 overhead condenser carry out condensation cooling it is latter
Partial reflux, a part are produced as product, and kettle material enters quadruple effect rectifying column T2401；T2401 top gaseous phase enters
T2401 overhead condenser E2401 carry out condensation it is cooling after partial reflux, partially produced as product, kettle material enters de- light
Tower T3101；
(3) cyclohexanemethanol subtractive process: the kettle material from T2401 enters lightness-removing column T3101, lightness-removing column T3101 tower
Top gas mutually enters T3101 overhead condenser E3101 and carries out after condensing cooling, and partial reflux is partially produced as light impurity, tower reactor
Material enter cyclohexanecarboxaldehyde tower T3201, T3201 top gaseous phase enter T3201 overhead condenser E3201 carry out condensation it is cooling after,
Partial reflux, partially produces as cyclohexanecarboxaldehyde product, and kettle material enters cyclohexanemethanol tower T3301, T3301 top gaseous phase portion
Divide after being exchanged heat into T3201 heat exchanger E3202, returns to T3301 as reflux, partially enter T3301 overhead condenser
After E3301 carries out condensation cooling, partial reflux part is produced as cyclohexanemethanol product, and tower reactor produces heavy seeds.
Reactor of the invention is tank reactor, and quantity is 1 or more series connection.
Reaction process operating pressure of the present invention is 0.5-2MPa, and operation temperature is 150-300 DEG C.
The molar ratio of hexahydrotoluene and oxygen is 1:1-1:2 in reaction process of the present invention.
Reaction process used catalyst of the present invention be cobalt molybdenum, cobalt molybdenum manganese, the related salts of cobalt molybdenum zirconium or metalloporphyrin cobalt,
Manganese, Zr catalyst, total metal content is 50ug/g-200ug/g in reaction process.
Hexahydrotoluene removal process of the present invention is quadruple effect distillation process, process conditions are as follows:
One effect rectifying column T2101 operating pressure 0.3-1MPa, two effect rectifying column T2201 operating pressure 0.15-0.8MPa, two
Imitate rectifying column T2301 operating pressure 0.1-0.5MPa, two effect rectifying column T2401 operating pressure 0.01-0.1MPa.
Cyclohexanemethanol subtractive process of the present invention is coupling rectification process, process conditions are as follows:
Lightness-removing column T3101 operating pressure 0.01-0.1MPa, cyclohexanecarboxaldehyde tower T3201 operating pressure 0.01-0.1MPa, ring
Hexanol tower T3301 operating pressure 0.1-1MPa.
Embodiment 1
The method and device of a kind of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, including ring
Own methanol reaction system, hexahydrotoluene recovery system and refining system.Reaction is added after hexahydrotoluene and catalyst mixing
Device R1101, catalyst are that molybdenum, cobalt molybdenum manganese, the related salts of cobalt molybdenum zirconium or metalloporphyrin cobalt, manganese, zirconium, total metal content are
50ug/g, 150 DEG C of temperature of reactor, pressure 0.5MPa, air is filled with reactor, hexahydrotoluene and oxygen molar ratio from bottom
Enter after reactor head discharge for the unreacted gas of 1:1 and divides cooler E1101, condensed liquid returning reactor, no
Solidifying gas emptying.Material after the reaction was completed enters directional decomposition device A1101 after air heat exchanger E1102 and air heat-exchange,
The peroxide directional decomposition that A1101 generates reaction, material enters hexahydrotoluene recovery system after decomposition.From A1101
Material enter an effect rectifying column T2101, T2101 operating pressure 0.3MPa, T2101 top gaseous phase enters T2101 heat exchanger
E2101 exchanges heat, and material a part flows back after heat exchange, and a part is produced as product, and kettle material enters two effect rectifying columns
T2201；T2201 operating pressure 0.15MPa, T2201 top gaseous phase enters T2201 heat exchanger E2201 and exchanges heat, object after heat exchange
Material a part reflux, a part are produced as product, and kettle material enters three-effect rectification tower T2301, T2301 operating pressure
0.1MPa；T2301 top gaseous phase part enters T2301 heat exchanger E2301 and exchanges heat, and partially enters T2301 overhead condenser
Condensation cooling is carried out, after material and condensation are cooling after heat exchange after material mixing, a part reflux, a part is produced as product,
Kettle material enters quadruple effect rectifying column T2401, T2401 operating pressure 0.01MPa；It is cold that T2401 top gaseous phase enters T2401 tower top
Condenser E2401 carries out partial reflux after condensation cooling, partially produces as product, and kettle material enters refining system.
Kettle material from T2401 enters lightness-removing column T3101, T3101 operating pressure 0.01MPa, T3101 top gaseous phase
Into T3101 overhead condenser E3101 carry out condensation it is cooling after, partial reflux is partially produced as light impurity, kettle material into
Enter cyclohexanecarboxaldehyde tower T3201, T3201 operating pressure 0.01MPa, T3201 top gaseous phase and enters T3201 overhead condenser E3201
After carrying out condensation cooling, partial reflux is partially produced as cyclohexanecarboxaldehyde product, and kettle material enters cyclohexanemethanol tower T3301,
T3301 operating pressure 0.1MPa, T3301 top gaseous phase part enters after T3201 heat exchanger E3202 exchanged heat, as reflux
T3301 is returned, partially enters T3301 overhead condenser E3301 and carries out after condensing cooling, partial reflux part is as cyclohexanemethanol
Product extraction, tower reactor produce heavy seeds.
The conversion per pass 2% of the hexahydrotoluene of this method, the selectivity 30% of cyclohexanemethanol, the choosing of hexahydrobenzaldehyde
Selecting property 20%, the selectivity 50% of hexahydrobenzoid acid；
Cyclohexanecarboxaldehyde, cyclohexanemethanol and the cyclohexanecarboxylic acid that this method is refining to obtain are 99.99%, yield 99%.
This method can save energy 40%, circulation water consumption reduces 50% by optimization technique and heat integration.
Embodiment 2
A kind of method and device method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, packet
Include cyclohexanemethanol reaction system, hexahydrotoluene recovery system and refining system.It is added after hexahydrotoluene and catalyst mixing
Reactor R1101, catalyst are that molybdenum, cobalt molybdenum manganese, the related salts of cobalt molybdenum zirconium or metalloporphyrin cobalt, manganese, zirconium, total metal content are
100ug/g, 200 DEG C of temperature of reactor, pressure 1MPa, air is filled with reactor, hexahydrotoluene and oxygen molar ratio from bottom
Enter after reactor head discharge for the unreacted gas of 1:1.5 and divides cooler E1101, condensed liquid returning reactor,
Fixed gas emptying.Material after the reaction was completed enters directional decomposition device after air heat exchanger E1102 and air heat-exchange
The peroxide directional decomposition that A1101, A1101 generate reaction, material enters hexahydrotoluene recovery system after decomposition.It comes from
The material of A1101 enters an effect rectifying column T2101, and T2101 operating pressure 0.6MPa, T2101 top gaseous phase enters T2101 heat exchange
Device E2101 exchanges heat, and material a part flows back after heat exchange, and a part is produced as product, and kettle material enters two effect rectifying
Tower T2201；T2201 operating pressure 0.3MPa, T2201 top gaseous phase enters T2201 heat exchanger E2201 and exchanges heat, after heat exchange
The reflux of material a part, a part are produced as product, and kettle material enters three-effect rectification tower T2301, T2301 operating pressure
0.2MPa；T2301 top gaseous phase part enters T2301 heat exchanger E2301 and exchanges heat, and partially enters T2301 overhead condenser
Condensation cooling is carried out, after material and condensation are cooling after heat exchange after material mixing, a part reflux, a part is produced as product,
Kettle material enters quadruple effect rectifying column T2401, T2401 operating pressure 0.05MPa；It is cold that T2401 top gaseous phase enters T2401 tower top
Condenser E2401 carries out partial reflux after condensation cooling, partially produces as product, and kettle material enters refining system.
Kettle material from T2401 enters lightness-removing column T3101, T3101 operating pressure 0.05MPa, T3101 top gaseous phase
Into T3101 overhead condenser E3101 carry out condensation it is cooling after, partial reflux is partially produced as light impurity, kettle material into
Enter cyclohexanecarboxaldehyde tower T3201, T3201 operating pressure 0.05MPa, T3201 top gaseous phase and enters T3201 overhead condenser E3201
After carrying out condensation cooling, partial reflux is partially produced as cyclohexanecarboxaldehyde product, and kettle material enters cyclohexanemethanol tower T3301,
T3301 operating pressure 0.5MPa, T3301 top gaseous phase part enters after T3201 heat exchanger E3202 exchanged heat, as reflux
T3301 is returned, partially enters T3301 overhead condenser E3301 and carries out after condensing cooling, partial reflux part is as cyclohexanemethanol
Product extraction, tower reactor produce heavy seeds.
The conversion per pass 15% of this method hexahydrotoluene, the selectivity 55% of cyclohexanemethanol, the choosing of hexahydrobenzaldehyde
Selecting property 30%, the selectivity 25% of hexahydrobenzoid acid,
Cyclohexanecarboxaldehyde, cyclohexanemethanol and the cyclohexanecarboxylic acid that this method is refining to obtain are 99.99%, yield 99%.
This method can save energy 45%, circulation water consumption reduces 55% by optimization technique and heat integration.
Embodiment 3
A kind of method and device method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, packet
Include cyclohexanemethanol reaction system, hexahydrotoluene recovery system and refining system.It is added after hexahydrotoluene and catalyst mixing
Reactor R1101, catalyst are that molybdenum, cobalt molybdenum manganese, the related salts of cobalt molybdenum zirconium or metalloporphyrin cobalt, manganese, zirconium, total metal content are
100ug/g, 300 DEG C of temperature of reactor, pressure 2MPa, air is filled with reactor, hexahydrotoluene and oxygen molar ratio from bottom
Enter after reactor head discharge for the unreacted gas of 1:2 and divides cooler E1101, condensed liquid returning reactor, no
Solidifying gas emptying.Material after the reaction was completed enters directional decomposition device A1101 after air heat exchanger E1102 and air heat-exchange,
The peroxide directional decomposition that A1101 generates reaction, material enters hexahydrotoluene recovery system after decomposition.From A1101
Material enter an effect rectifying column T2101, T2101 operating pressure 1MPa, T2101 top gaseous phase enters T2101 heat exchanger E2101
It exchanges heat, material a part flows back after heat exchange, and a part is produced as product, and kettle material enters two effect rectifying column T2201；
T2201 operating pressure 0.8MPa, T2201 top gaseous phase enters T2201 heat exchanger E2201 and exchanges heat, material one after heat exchange
Divide reflux, a part is produced as product, and kettle material enters three-effect rectification tower T2301, T2301 operating pressure 0.5MPa；
T2301 top gaseous phase part enters T2301 heat exchanger E2301 and exchanges heat, and partially enters T2301 overhead condenser and is condensed
Cooling, after material and condensation are cooling after heat exchange after material mixing, a part reflux, a part is produced as product, kettle material
Into quadruple effect rectifying column T2401, T2401 operating pressure 0.1MPa；T2401 top gaseous phase enters T2401 overhead condenser E2401
Partial reflux after condensation cools down is carried out, is partially produced as product, kettle material enters refining system.
Kettle material from T2401 enters lightness-removing column T3101, T3101 operating pressure 0.1MPa, T3101 top gaseous phase
Into T3101 overhead condenser E3101 carry out condensation it is cooling after, partial reflux is partially produced as light impurity, kettle material into
Enter cyclohexanecarboxaldehyde tower T3201, T3201 operating pressure 0.1MPa, T3201 top gaseous phase enter T3201 overhead condenser E3201 into
After row condensation is cooling, partial reflux is partially produced as cyclohexanecarboxaldehyde product, and kettle material enters cyclohexanemethanol tower T3301,
T3301 operating pressure 1MPa, T3301 top gaseous phase part enters after T3201 heat exchanger E3202 exchanged heat, and returns as reflux
T3301 is returned, partially enters T3301 overhead condenser E3301 and carries out after condensing cooling, partial reflux part is produced as cyclohexanemethanol
Product extraction, tower reactor produce heavy seeds.
The conversion per pass 20% of this method hexahydrotoluene, the selectivity 55% of cyclohexanemethanol, the choosing of hexahydrobenzaldehyde
Selecting property 30%, the selectivity 25% of hexahydrobenzoid acid,
Cyclohexanecarboxaldehyde, cyclohexanemethanol and the cyclohexanecarboxylic acid that this method is refining to obtain are 99.99%, yield 99%.
This method can save energy 42%, circulation water consumption reduces 53% by optimization technique and heat integration.
The invention proposes a kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid and
Device, with air (oxygen) for oxidant, prepares hexamethylene first by liquid-phase catalytic oxidation using hexahydrotoluene as raw material
Aldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid.Wherein conversion per pass >=2-20% of hexahydrotoluene, the selectivity of cyclohexanemethanol
30%-60%, the selective 20%-30% of hexahydrobenzaldehyde, the selective 10%-50% of hexahydrobenzoid acid, then by more
It imitates rectification process and recycles unreacted hexahydrotoluene, to greatly save the energy consumption in hexahydrotoluene removal process, finally
Cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid are refined by way of coupling rectification, and the hexamethylene first of purity >=99.99% can be obtained
Aldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid product, and make full use of in purification process the heats of different tastes, by process optimization,
Energy consumption needed for distillation process is greatly reduced, which can reduce energy consumption >=40%, and condensation water consumption reduces >=50%.It should
Process flow is simply easily achieved, it can be achieved that continuously preparing cyclohexanecarboxaldehyde, cyclohexanemethanol and hexamethylene as raw material using hexahydrotoluene
Formic acid substantially increases the economic benefit and social benefit of enterprise.
The technical solution that the present invention is disclosed and proposed, those skilled in the art can be appropriate to change by using for reference present disclosure
The links such as condition route are realized, although method and technology of preparing of the invention is described by preferred embodiment, phase
Can obviously the content of present invention not departed from, carried out in spirit and scope to methods and techniques described herein route by closing technical staff
It changes or reconfigures, to realize final technology of preparing.In particular, it should be pointed out that all similar replacements and change pair
It is it will be apparent that they are considered as being included in spirit of that invention, range and content for those skilled in the art.
Claims (9)
1. a kind of method of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, is with hexahydrotoluene
Raw material prepares cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid by liquid-phase catalytic oxidation using air as oxidant；It is special
Sign is to include the following steps
(1) reaction process: being added reactor R1101 after hexahydrotoluene and catalyst mixing, and air is filled with reactor from bottom,
Unreacted gas enters after reactor head discharge and divides cooler E1101, condensed liquid returning reactor, fixed gas row
It is empty；Material after the reaction was completed enters directional decomposition device A1101 after air heat exchanger E1102 and air heat-exchange, and A1101 will
The peroxide directional decomposition generated is reacted, material enters an effect rectifying column T2101 after decomposition；
(2) hexahydrotoluene removal process: the material from directional decomposition device A1101 enters an effect rectifying column T2101,
T2101 top gaseous phase enters T2101 heat exchanger E2101 and exchanges heat, and material a part flows back after heat exchange, and a part is used as product
Extraction, kettle material enter two effect rectifying column T2201；T2201 top gaseous phase enters T2201 heat exchanger E2201 and exchanges heat, and changes
Material a part flows back after heat, and a part is produced as product, and kettle material enters three-effect rectification tower T2301；T2301 tower overhead gas
Mutually enter T2301 heat exchanger E2301 exchange heat, after heat exchange material enter T2301 overhead condenser carry out condensation cooling it is latter
Partial reflux, a part are produced as product, and kettle material enters quadruple effect rectifying column T2401；T2401 top gaseous phase enters
T2401 overhead condenser E2401 carry out condensation it is cooling after partial reflux, partially produced as product, kettle material enters de- light
Tower T3101；
(3) cyclohexanemethanol subtractive process: the kettle material from T2401 enters lightness-removing column T3101, lightness-removing column T3101 tower overhead gas
Mutually enter T3101 overhead condenser E3101 to carry out after condensing cooling, partial reflux is partially produced as light impurity, kettle material
Enter T3201 overhead condenser E3201 into cyclohexanecarboxaldehyde tower T3201, T3201 top gaseous phase to carry out after condensing cooling, part
Reflux, partially as cyclohexanecarboxaldehyde product produce, kettle material enter cyclohexanemethanol tower T3301, T3301 top gaseous phase part into
Enter after T3201 heat exchanger E3202 exchanged heat, return to T3301 as reflux, partially enter T3301 overhead condenser E3301 into
After row condensation is cooling, partial reflux part is produced as cyclohexanemethanol product, and tower reactor produces heavy seeds.
2. the method as described in claim 1, it is characterized in that reactor is tank reactor, quantity is 1 or more series connection.
3. the method as described in claim 1, it is characterized in that reaction process operating pressure is 0.5-2MPa, operation temperature 150-
300℃。
4. the method as described in claim 1, it is characterized in that the molar ratio of hexahydrotoluene and oxygen is 1:1-1:2 catalysis used
Agent is cobalt molybdenum, cobalt molybdenum manganese, the related salts of cobalt molybdenum zirconium or metalloporphyrin cobalt, manganese, Zr catalyst, total metal content in reaction process
For 50ug/g-200ug/g.
5. the method as described in claim 1, it is characterized in that an effect rectifying column T2101 operating pressure 0.3-1MPa；Two effect rectifying
Tower T2201 operating pressure 0.15-0.8MPa；Two effect rectifying column T2301 operating pressure 0.1-0.5MPa；Two effect rectifying column T2401
Operating pressure 0.01-0.1MPa；Lightness-removing column T3101 operating pressure 0.01-0.1MPa；Cyclohexanecarboxaldehyde tower T3201 operating pressure
0.01-0.1MPa；Cyclohexanol tower T3301 operating pressure 0.1-1MPa.
6. the device of methyl cyclohexane alkoxide coproduction cyclohexanecarboxaldehyde, cyclohexanemethanol and cyclohexanecarboxylic acid, it is characterized in that including reaction dress
It sets, hexahydrotoluene recyclable device and refining plant；It is characterized in that reaction unit includes reactor R1101, directional decomposition device
A1101；Hexahydrotoluene recyclable device include one effect rectifying column T2101, two effect rectifying column T2201, three-effect rectification tower T2301 and
Quadruple effect rectifying column T2401；Refining plant includes lightness-removing column T3101, cyclohexanecarboxaldehyde tower T3201 and cyclohexanemethanol tower T3301.
7. device as claimed in claim 6, it is characterized in that the reactor R1101 of reaction unit be equipped with material inlet, air into
Mouth, air outlet slit and material outlet；Wherein material inlet and air outlet slit are all connected with point cooler E1101, air intlet and a material
Outlet is all connected with air heat exchanger E1102, and air heat exchanger E1102 material outlet connects directional decomposition device A1101；A1101
Equipped with material inlet, top gas phase outlet and material outlet, wherein material inlet connects E1102, after top gas phase outlet connection
Continuous VOC processing unit, material outlet connect hexahydrotoluene recovery system.
8. device as claimed in claim 6, it is characterized in that an effect rectifying column T2101 is equipped with material inlet, top gaseous phase exports,
Reflux material inlet, tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connects A1101 material outlet, top gaseous phase
Outlet connection T2101 heat exchanger E2101 thermal material import, reflux material inlet connect E2101 material outlet, and reboiler returns tower
Mouth connection reboiler E2102 material outlet, tower reactor produce mouth connection E2102 material inlet and two effect rectifying column T2102；Two effect essences
It evaporates tower T2201 and returns tower mouth equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and reboiler, wherein
Material inlet connect T2101 tower reactor produce mouth, top gaseous phase outlet connection heat exchanger E2201 thermal material import, reflux material into
Mouth connection E2201 material outlet, reboiler return the outlet of tower mouth connection heat exchanger E2101 cold material, and tower reactor produces mouth and connects
The import of E2101 cold material and three-effect rectification tower T2301；Three-effect rectification tower T2301 is equipped with material inlet, top gaseous phase outlet, returns
Stream material inlet, tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connection T2201 tower reactor produces mouth, top gaseous phase
Outlet connection heat exchanger E2301 thermal material import, E2301 material outlet connect condenser E2302 material inlet, and flow back material
Import connects E2302 material outlet, and reboiler returns the outlet of tower mouth connection heat exchanger E2201 cold material, and tower reactor produces mouth connection
The import of E2201 cold material and quadruple effect rectifying column T2401；Quadruple effect rectifying column T2401 is equipped with material inlet, top gaseous phase outlet, returns
Stream material inlet, tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connection T2301 tower reactor produces mouth, top gaseous phase
Outlet connection T2401 overhead condenser E2401 material inlet, reflux material inlet connect E2401 material outlet, and reboiler returns tower
The outlet of mouth connection heat exchanger E2301 cold material, tower reactor produce mouth connection E2301 cold material import and refining system.
9. device as claimed in claim 6, it is characterized in that refining plant includes lightness-removing column T3101, cyclohexanecarboxaldehyde tower T3201 and
Cyclohexanemethanol tower T3301；Lightness-removing column T3101 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth
And reboiler returns tower mouth, wherein material inlet connection T2401 tower reactor produces mouth, top gaseous phase outlet connection T3101 overhead condensation
Device E3101 material inlet, reflux material inlet connect E3101 material outlet, and reboiler returns tower mouth connection reboiler E3102 and goes out
Mouthful, tower reactor produces mouth connection E3102 material inlet and cyclohexanecarboxaldehyde tower T3201；Cyclohexanecarboxaldehyde tower T3201 be equipped with material inlet,
Top gaseous phase outlet, reflux material inlet, tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connects T3101 tower reactor
Mouth, top gaseous phase outlet connection T3201 overhead condenser E3201 material inlet are produced, reflux material inlet connects E3201 material
Outlet, reboiler return the outlet of tower mouth connection heat exchanger E3202 cold material, and tower reactor produces mouth connection E3102 cold material import and ring
Own formaldehyde tower T3102；Cyclohexanol tower T3301 is equipped with material inlet, top gaseous phase outlet, reflux material inlet, side take-off mouth
Tower reactor extraction mouth and reboiler return tower mouth, and wherein material inlet connection T3201 tower reactor produces mouth, top gaseous phase outlet connection heat exchange
Device E3202 thermal material import, E3202 material outlet connect T3301 overhead condenser E3301 material inlet, reflux material into
Mouth connection E3301 material outlet, side take-off mouth connecting side line cooler E3302 material inlet, reboiler return the connection of tower mouth again
Device E3303 material outlet is boiled, tower reactor produces mouth and connects E3303 material inlet.
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| CN115382233A (en) * | 2021-05-25 | 2022-11-25 | 山东洪达化工有限公司 | Cyclohexanone rectification device and method |
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| CN108863794A (en) * | 2018-06-11 | 2018-11-23 | 天津中科拓新科技有限公司 | A kind of preparation method and device of the secondary butyl ester of high-purity acetic acid |
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| CN107812393A (en) * | 2017-10-27 | 2018-03-20 | 烟台国邦化工机械科技有限公司 | A kind of methanol three-effect rectification system and technique |
| CN108863794A (en) * | 2018-06-11 | 2018-11-23 | 天津中科拓新科技有限公司 | A kind of preparation method and device of the secondary butyl ester of high-purity acetic acid |
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