CN1724524A - Method of preparing 1,2-epoxycyclohexane using cyclohexane - Google Patents
Method of preparing 1,2-epoxycyclohexane using cyclohexane Download PDFInfo
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- CN1724524A CN1724524A CN 200510031872 CN200510031872A CN1724524A CN 1724524 A CN1724524 A CN 1724524A CN 200510031872 CN200510031872 CN 200510031872 CN 200510031872 A CN200510031872 A CN 200510031872A CN 1724524 A CN1724524 A CN 1724524A
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- Prior art keywords
- tetrahydrobenzene
- reaction
- hexanaphthene
- cyclohexane
- hexalin
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 45
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 64
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 29
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 239000006227 byproduct Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011964 heteropoly acid Chemical class 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229930194542 Keto Natural products 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 125000000468 ketone group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- 150000003657 tungsten Chemical class 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- -1 salt compound Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 150000003681 vanadium Chemical class 0.000 claims description 2
- 229910052720 vanadium Chemical class 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 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 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 241001292396 Cirrhitidae Species 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000013070 direct material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000009466 transformation Effects 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
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for preparing 1,2-epoxycyclohexane by using cyclohexane as the main raw material and air as the oxygen source, which comprises oxidizing cyclohexane into cyclo-hexyl hydrogen peroxide, then charging cyclo-hexene for epoxidation reaction, thus obtaining 1,2-epoxycyclohexane and cyclo-hexanol, wherein the cyclo-hexanol can be dehydrated to produce cyclo-hexene to be put into circulated use as raw material for epoxidation reaction. The invention can solve the problem of large displacement of waste water.
Description
Technical field
The present invention relates to a kind of is feedstock production 1 with hexanaphthene, the method for 2-epoxy cyclohexane.
Background technology
1, the preparation method of 2-epoxy cyclohexane is a lot.Classify with the preparation raw material, hexalin method, ortho chloro phenol method, tetrahydrobenzene method, hexanaphthene method, pimelinketone method etc. are arranged.Existing industrialized many be raw material with the tetrahydrobenzene, its method can be divided into hypochlorous acid (salt) method, Ha Kang (Halcon) method, hydrogen peroxide oxidation method, molecular oxygen oxidation method, electrochemical preparation method etc. again.
In the production method of epoxide, the throughput of hypochlorous acid (salt) method, Halcon method and hydrogen peroxide oxidation method accounts for more than 99% of the world.But up to now, these three kinds of methods all have significant deficiency.The former produces a large amount of refuses such as brine waste---and one ton 1 of every production, 2-epoxy cyclohexane will produce about 20 tons of waste water, and energy consumption is big, and equipment corrosion is serious.Halcon method is because of the compound of hydroxyls such as the by-product phenylethyl alcohol or the trimethyl carbinol, it produces the restriction that seriously is subjected to the by product market capacity---if all epoxide are all produced with Halcon method, because of the market requirement consumption of by product less than 5% of theoretical generation, the by product of generation has 95% can't handle approximately! And be oxygen source with hydrogen peroxide in the hydrogen peroxide oxidation method, be that oxygen source produces 1 relatively directly with air, 2-epoxy cyclohexane, cost want high, and it is many that waste water is wanted.
With hexanaphthene preparation 1, original main technique of 2-epoxy cyclohexane: a, be hexalin by cyclohexane oxidation, after being dehydrated into tetrahydrobenzene, reoxidizing is 1, the 2-epoxy cyclohexane; B, being pimelinketone by cyclohexane oxidation, is the chlorination pimelinketone through chlorination, and hydrogenation is the chlorination hexalin, and cyclisation is 1 in the presence of alkali again, the 2-epoxy cyclohexane; C, be tetrahydrobenzene by cyclohexane dehydrogenation, epoxy turns to 1 again, the 2-epoxy cyclohexane.But problems such as these preparation technologies exist that route is long, side reaction many or yield is low.And can be from finding out, " hexanaphthene is a raw material " only is initial feed here, still is summed up as the problem of making direct material with tetrahydrobenzene etc. at last.
US4 discloses a kind of method of producing hexalin in 814,511, and wherein process comprises: cyclohexane oxidation becomes cyclohexyl hydroperoxide, adds 1 ~ 5 mole of tetrahydrobenzene doubly again and carries out epoxidation reaction, generates to contain 1, the reaction mixture of 2-epoxy cyclohexane and hexalin.Carry out hydrogenation under palladium catalysis, 130 ℃ ~ 150 ℃ and 0.3MPa ~ 3.0MPa condition, make 1, the 2-epoxy cyclohexane is reduced to hexalin.By distillation reaction liquid, obtain product hexalin and pimelinketone at last.It has emphasized the utilization ratio of active oxygen in the cyclohexyl hydroperoxide, has improved the purpose of hexalin content in the head product to reach.Can increase the aftertreatment cost but tetrahydrobenzene is excessive, if tetrahydrobenzene is reduced into the means that hexanaphthene is a kind of minus economic growth, so satisfying under the processing condition, the tetrahydrobenzene proportioning should be controlled at the position of suitable economy in addition.
US 5,175, and 316 can think US4, the method improvement of " a kind of production hexalin " in 814,511.The one, it is more suitable that the mol ratio of tetrahydrobenzene and cyclohexyl hydroperoxide is transferred to: 0.7 ~ 1: 1.The 2nd, clearly the suitable production hexalin circulation technology that is major product.Its problem is: before reacting with tetrahydrobenzene, the reaction mixture that contains cyclohexyl hydroperoxide has been carried out rectifying concentrated, separated to walk hexanaphthene; And when adding the tetrahydrobenzene reaction, add hexanaphthene again, it is complicated that this process that makes becomes.And cyclohexyl hydroperoxide belongs to the easy decomposed substance of temperature-sensitive, and a many step rectifying and times, more cyclohexyl hydroperoxides make utilization ratio reduce self-decomposition, and side reaction increases.
Summary of the invention
The purpose of this invention is to provide a kind of with hexanaphthene preparation 1, the method for 2-epoxy cyclohexane.
The object of the present invention is achieved like this: at first, carry out cyclohexane oxidation.Gas reaction with hexanaphthene and molecule-containing keto, wherein can adopt no catalysis or cobalt salt catalyzed oxidation to prepare cyclohexyl hydroperoxide, the technology controlling and process index that oxidizing reaction adopts is: 120 ℃ ~ 180 ℃ of temperature, pressure 0.8MPa ~ 2.5MPa, molecule-containing keto 5vol% ~ 100vol% in the gas of molecular oxygen, oxygen content 0.5vol% ~ 5vol% in the control tail gas, hexanaphthene per pass conversion 2% ~ 20%.
The gas of hexanaphthene and molecule-containing keto reaction, be typically air, the typical control condition is: 130 ℃ ~ 150 ℃ of temperature, pressure 0.9MPa ~ 1.5MPa, oxygen content 0.5vol% ~ 5vol% in the control tail gas, corresponding typical hexanaphthene per pass conversion 3% ~ 7%.Its reaction solution component comprises (mass percent): 93% ~ 97% unconverted hexanaphthene, 1.0% ~ 6.5% cyclohexyl hydroperoxide, 0.3% ~ 1.6% hexalin, 0.1% ~ 0.9% pimelinketone, 0.05% ~ 0.5% is other by product, as hexanodioic acid, pentanedioic acid, the cyclohexyl of Succinic Acid and their correspondences thereof.
Then, above-mentioned mixed solution and the tetrahydrobenzene that contains cyclohexyl hydroperoxide carried out epoxidation reaction.Adopting a kind of in molybdenum class, tungsten class or vanadium class complex compound or the compound in epoxidation reaction is Preparation of Catalyst 1, the 2-epoxy cyclohexane.Oxide compound, salt, heteropolyacid salt, heteropoly compound, organism complex compound that the complex compound of use therein catalyzer molybdenum class (or tungsten class or vanadium class) or compound can be them.For example: ammonium meta-vanadate NH
4VO
3, vanadium oxide V
2O
5, molybdenum (VI) closes methyl ethyl diketone MoO
2(acac)
2, tungsten (VI) closes (oxine), heteropolyacid phospho-molybdic acid H
7(PMo
2O
7)
6, molybdenum heteropolyacid compound [N (C
4H
9)
4]
3PO
4(MoO
3)
4, heteropoly tungstic acid compound (C
5H
5NC
16H
33)
3PO
4(WO
4)
4, heteropoly tungstic acid compound [N (C
18H
37)
4]
3PO
4(WO
5)
4
The processing condition that epoxidation reaction adopts are: charge ratio is in the 1mol cyclohexyl hydroperoxide, tetrahydrobenzene is 0.5mol ~ 1.6mol, and catalyzer is 0.2mmol ~ 2.0mmol, and temperature of reaction is 40 ℃ ~ 150 ℃, reaction times is 20min ~ 100min, is reflected in the liquid phase to carry out.The amount ranges of tetrahydrobenzene the best is 0.8mol ~ 1.1mol, and the amount ranges of catalyzer the best is 0.5mmol ~ 1.0mmol, and best temperature range is 75 ℃ ~ 135 ℃, and best reaction time range is 40min ~ 70min.The cyclohexyl hydroperoxide optimal conversion is more than 95% in this step reaction, and 1,2-epoxy cyclohexane best selective is more than 85%.
Then, the dehydration of cyclohexanol that produces in the epoxidation reaction is generated tetrahydrobenzene, recycle, isolate product 1 simultaneously as one of epoxidised raw material, 2-epoxy cyclohexane and byproduct pimelinketone and tetrahydrobenzene, specifically finish by following steps:
A, rectifying tower top are isolated the hexanaphthene of the tetrahydrobenzene that contains 0.1% ~ 0.9% weight, are recycled to the cyclohexane oxidation system.
Material at the bottom of b, the rectifying tower then carries out rectifying separation, and isolates the product 1 of purity more than 99.0%, 2-epoxy cyclohexane.
C, oneself is isolated 1, content and 98% above hexalin and cyclohexanone mixture are isolated in the tower bed material rectifying again of 2-epoxy cyclohexane.
Hexalin in this mixture is carried out the dehydration reaction cyclohexene.Wherein an acidic catalyst of 70 ℃ ~ 95 ℃ of dehydrations of Tuo Shui temperature can be mineral acid, acid salt, acidic resins.Obtain containing pimelinketone and tetrahydrobenzene mixed solution.
Get byproduct pimelinketone and tetrahydrobenzene by this mixed solution of rectifying separation.Wherein epoxidation reaction is returned in the circulation of 30% ~ 100% tetrahydrobenzene, reacts with cyclohexyl hydroperoxide.The preferable circulation of the tetrahydrobenzene amount of returning is 75% ~ 100%.
D, will isolate the still liquid that contains catalyzer behind hexalin and the pimelinketone and also circulate and return (2), and enter the epoxidation reaction step, and replenish an amount of raw catalyst.
Compare with prior art, positively effect of the present invention is:
1, raw material is cheap and easy to get, and product is single, has reduced cost significantly.Adopting cyclohexane give cheap and easy to get is main raw material, utilizes the present invention to set up a kind of preparation 1, the brand-new technology of 2-epoxy cyclohexane.After its technology runs well, only need a kind of organic raw material---hexanaphthene, also only produce a kind of target product in theory---1,2-epoxy cyclohexane (going back the participation of organic/inorganic substance air and the generation of water certainly).Having replaced is the various traditional technology modes of main raw material with the tetrahydrobenzene, makes cost reduce at double---present market price: about 1.1 ten thousand yuan/ton of hexanaphthene, about 1.9 ten thousand yuan/ton of tetrahydrobenzene; Market price before 2 years: about 0.5 ten thousand yuan/ton of hexanaphthene, about 0.9 ten thousand yuan/ton of tetrahydrobenzene.
2, the advantage that had both kept Halcon method has solved the critical defect of common Halcon method again.Epoxidation reaction belongs to Halcon method among the present invention, has the advantage of Halcon method highly selective, high conversion and high product quality: usually, selectivity can reach about 90%, and transformation efficiency can reach about 97%, product 1, and 2-epoxy cyclohexane content reaches more than 99.0%.But cyclohexane oxidation preparation 1, the 2-epoxy cyclohexane generates the by product of equimolar this hydroxyl of hexalin simultaneously, through dehydration for recycling as one of epoxidation raw material behind the tetrahydrobenzene, thereby overcome the fatal disadvantage of the hydroxy-containing compounds of common Halcon method by-product.
3, environmental friendliness.Compare with other technology, particularly compare environmental friendliness with chlorohydrination, every production is one ton 1 in epoxidation reaction, the 2-epoxy cyclohexane, and the water of generation is less than 0.2 ton.And one ton 1 of the every production of chlorohydrination, the 2-epoxy cyclohexane will produce about 20 tons of brine wastes.
4, the present invention compares its common ground with the prior art of using " it is anti-that cyclohexyl hydroperoxide and tetrahydrobenzene carry out epoxidation ": all be based upon cyclohexane oxidation and tetrahydrobenzene and organic hydroperoxide carry out epoxidation (common name Halcon method) these very on the basis of maturation process.And relatively their innovation of the present invention is:
Though 1. the basis of invention is most of similar, the present invention seeks to main production 1,2-epoxy cyclohexane product, and above-mentioned purpose is the main hexalin product of producing, so in the technological operation He in the quality control essential distinction is being arranged.
2. the present invention has set up: dehydration of cyclohexanol generates the technology that tetrahydrobenzene recycles as one of epoxidised raw material.This is unprecedented in the cyclohexane oxidation technology, also is that the hydroxy-containing compounds of by-product can recycle common Halcon method when preparing epoxide is unprecedented!
3. the improvement of cyclohexane oxidation partitioning cycle: omitted the rectifying enrichment step.Because general hexanaphthene per pass conversion 3%-7%, 95% hexanaphthene will recycle approximately in addition.With tetrahydrobenzene reaction before, the reaction mixture that contains cyclohexyl hydroperoxide is not concentrated, can make that oxygen source obtains maximized effective utilization in the cyclohexyl hydroperoxide.Make that so not only operation is simpler, and process is more economical rationally.
4. the simplification of cyclohexane oxidation partitioning cycle: omitted step of hydrogenation.Before in the prior art smart distilled hexanaphthene being entered the oxidizing reaction system, need carry out hydrogenation.And the present invention is under preferable epoxidation proportioning and condition, can control tetrahydrobenzene mass content in the smart distilled hexanaphthene less than 0.5% even lower, facts have proved whole system and quality product are not exerted an influence under this concentration.
Embodiment
Embodiment 1: get in the reactor of stirring of 100mol hexanaphthene input band and thermometer, be warming up to 140 ℃ ~ 150 ℃ of temperature, blast pressurized air, remain on pressure 1.4MPa ~ 1.5MPa, oxygen content 1vol% ~ 3vol% in the control tail gas, reaction 20min ~ 30min extracts reaction solution and analyzes, and its component comprises (mass percent): 94% ~ 97% hexanaphthene, 2.5% ~ 4.5% cyclohexyl hydroperoxide, 0.5% ~ 1.0% hexalin, 0.2% ~ 0.6% pimelinketone, 0.1% ~ 0.3% is other by product, as 1, the 2-epoxy cyclohexane, Pentyl alcohol, tetrahydrobenzene, cyclopentanol, hexanodioic acid, pentanedioic acid, the various esters that Succinic Acid and they are formed etc.
(VI) closes methyl ethyl diketone MoO with the 0.5mmol molybdenum
2(acac)
2With the 1.5mol tetrahydrobenzene, drop in the reactor of being with stirring and thermometer, to open and stir, heat begins the continuous reaction solution that contains the 1mol cyclohexyl hydroperoxide that oneself makes that adds to about 80 ℃.React 55min ~ 65min after adding again.Reaction solution is carried out rectifying, collects 128 ℃ ~ 131 ℃ cut, promptly get 99.2% 1,2-epoxy cyclohexane product, in cyclohexyl hydroperoxide, the yield of product is 85.3%.
Then, collect 154 ℃ ~ 162 ℃ cut, wherein more than hexalin and the cyclohexanone content and 98%.The sulfuric acid that this cut is added 0.1% ~ 2% weight is made catalyzer (in hexalin), and reflux is dewatered and promptly got pimelinketone and tetrahydrobenzene mixed solution, gets byproduct pimelinketone and tetrahydrobenzene by this mixed solution of rectifying separation.In hexalin, tetrahydrobenzene yield 90% ~ 99%.Generally getting 75% ~ 100% tetrahydrobenzene recycles as one of raw material of epoxidation reaction.
Embodiment 2: close (oxine) and get embodiment 1 prepared 1.5mol tetrahydrobenzene and put in the reactor of band thermometer with 1mmol tungsten (VI), open to stir logical N
2, be incubated about 45 ℃, constantly add the 1.4mol cyclohexyl hydroperoxide that oneself makes.React 90 ~ 95min after adding again.Other operation is with embodiment 1.
Embodiment 3: with 2.0mmol ammonium meta-vanadate NH
4VO
3With get the embodiment 2 0.7mol tetrahydrobenzene in obtained and put in the reactor of band thermometer, open and stir, be heated to about 130 ℃, constantly the 1.3mol cyclohexyl hydroperoxide that made of adding.React 35 ~ 40min after adding again.Other operation is with embodiment 1.
Embodiment 4: with 2.5mmol vanadium oxide V
2O
5Stir with the tetrahydrobenzene input band of 1.2mol and the reactor of thermometer in, open and stir, hot to about 145 ℃, begin the 1.3mol cyclohexyl hydroperoxide that continuous adding has made.React 20 ~ 25min after adding again.Other operation is with embodiment 1.
Embodiment 5: with 2.1mmol heteropolyacid salt phospho-molybdic acid H
7(PMo
2O
7)
6Throw to the reactor of band stirring and thermometer with the 0.7mol tetrahydrobenzene, open and stir, heat begins the 1.4mol cyclohexyl hydroperoxide that continuous adding has made to about 95 ℃.React 50 ~ 60min after adding again.Other operation together
Embodiment 1.
Claims (7)
1, a kind of with hexanaphthene preparation 1, the method of 2-epoxy cyclohexane, it is characterized in that: be raw material with the hexanaphthene, earlier cyclohexane oxidation is become cyclohexyl hydroperoxide, add tetrahydrobenzene again and carry out epoxidation reaction, generate product 1,2-epoxy cyclohexane and byproduct hexalin, the byproduct hexalin generates tetrahydrobenzene through dehydration, recycles as one of epoxidised raw material, is specifically finished by following step:
(1) cyclohexane oxidation: the gas reaction of hexanaphthene and molecule-containing keto, wherein can adopt no catalysis or bore the salt catalyzed oxidation and prepare cyclohexyl hydroperoxide, the process control condition that oxidizing reaction adopts is: 120 ℃～180 ℃ of temperature, pressure 0.8MPa～2.5MPa, reaction times 10-60min, oxygen content 5vol%～100vol% in the gas of molecule-containing keto, oxygen content 0.5vol%～5vol% in the control tail gas
(2) epoxidation of cyclohexene reaction: cyclohexyl hydroperoxide and cyclohexene that above-mentioned reaction is generated carry out epoxidation reaction; In epoxidation reaction, adopt a kind of in molybdenum class, tungsten class or vanadium class complex compound or the compound to prepare 1 for catalyst; The 2-7-oxa-bicyclo[4.1.0; The process conditions that epoxidation reaction adopts are: charge ratio is in the 1mol cyclohexyl hydroperoxide; Cyclohexene is 0.5mol～1.6mol; Catalyst is 0.2mmol～2.0mmol; Reaction temperature is 40 ℃～150 ℃; Reaction time is 20min～100min
(3) mixed solution after the epoxidation reaction is set up circulating system by rectifying separation, particularly dehydration of cyclohexanol system hexamethylene cyclenes is set up the circulating system of epoxidation reaction, isolate product and byproduct simultaneously, all available normal pressure or negative pressure during rectifying, specifically finish by following steps:
A, rectifying tower top are isolated the hexanaphthene of the tetrahydrobenzene that contains 0.1%～0.9% weight, be recycled in (1) cyclohexane oxidation system,
B, the material at the bottom of the rectifying tower is then carried out rectifying separation, and isolate the product 1 of purity more than 99.0%, the 2-epoxy cyclohexane,
C, will isolate 1, the tower bed material rectifying again of 2-epoxy cyclohexane, isolate hexalin and cyclohexanone mixture, hexalin in this mixture is carried out dehydration reaction, get tetrahydrobenzene, again tetrahydrobenzene and pimelinketone mixed solution are got byproduct pimelinketone, tetrahydrobenzene by rectifying separation, wherein (2) are returned in the circulation of 30%～100% tetrahydrobenzene, carry out the epoxidation reaction step with cyclohexyl hydroperoxide
D, will isolate the still liquid that contains catalyzer behind hexalin and the pimelinketone and also circulate and return (2), enter the epoxidation reaction step.
2, according to claim 1 a kind of with hexanaphthene preparation 1, the method of 2-epoxy cyclohexane, it is characterized in that, the gas of hexanaphthene and molecule-containing keto reaction, be typically air, typical process control condition is: 130 ℃～150 ℃ of temperature, pressure 0.9MPa～1.5MPa, oxygen content 1vol%～3vol% in the control tail gas, hexanaphthene per pass conversion 3%-7%.
3, according to claim 1 a kind of with hexanaphthene preparation 1, the method of 2-epoxy cyclohexane, it is characterized in that the complex compound or the compound of the catalyzer molybdenum class of using in the epoxidation reaction (or tungsten class or vanadium class): oxide compound, salt, heteropolyacid, heteropolyacid salt compound, the organism complex compound that can be them.
4, according to claim 1 a kind of with hexanaphthene preparation 1, the method of 2-epoxy cyclohexane, it is characterized in that, the optimum process condition that epoxidation reaction adopts is: the tetrahydrobenzene amount ranges is 0.8mol～1.1mol, the catalyst levels scope is 0.5mmol～1.0mmol, temperature range is 75 ℃～135 ℃, and reaction time range is 40min～70min.
5, according to claim 1 a kind of with hexanaphthene preparation 1, the method of 2-epoxy cyclohexane, it is characterized in that, be back in the working cycle of epoxidation reaction at dehydration of cyclohexanol, isolate the mixture that contains hexalin and pimelinketone, hexalin wherein dewaters under an acidic catalyst and 70 ℃ of-95 ℃ of conditions, and an acidic catalyst can be mineral acid, acid salt, acidic resins.
6, according to claim 1,5 is described a kind of with hexanaphthene preparation 1, and the method for 2-epoxy cyclohexane is characterized in that, gets byproduct pimelinketone, tetrahydrobenzene by rectifying separation pimelinketone and tetrahydrobenzene mixed solution.
7, according to claim 1,6 is described a kind of with hexanaphthene preparation 1, the method of 2-epoxy cyclohexane, it is characterized in that, wherein 30%～100% of by-product cyclic hexene circulation turns back to (2), carry out epoxidation reaction with cyclohexyl hydroperoxide, the preferable circulation of the tetrahydrobenzene amount of returning is 75%～100%.
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