CN102391085A - Process for producing cyclohexanone by performing incomplete hydrogenation - Google Patents
Process for producing cyclohexanone by performing incomplete hydrogenation Download PDFInfo
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- CN102391085A CN102391085A CN2011102286673A CN201110228667A CN102391085A CN 102391085 A CN102391085 A CN 102391085A CN 2011102286673 A CN2011102286673 A CN 2011102286673A CN 201110228667 A CN201110228667 A CN 201110228667A CN 102391085 A CN102391085 A CN 102391085A
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Abstract
The invention discloses a process for producing cyclohexanone by performing incomplete hydrogenation. The production process comprises the following steps of: feeding benzene and hydrogen serving as raw materials into a reactor 1 in the volume ratio 1.17:1-1.19:1 in sequence, and reacting at the temperature 100-180 DEG C and under the pressure 3-10 MPa under the action of a ruthenium catalyst; when the residual hydrogen is less than 3-5 percent, making reaction intermediate materials naturally flow from the bottom outlet of the reactor 1 to the bottom inlet of a reactor 2, and continually reacting at the hydrogen feeding amount 3,600-3,800 m<3>/h at the temperature 100-180 DEG C and under the pressure 3-10 MPa; and when the reaction benzene transformation ratio is up to 50-60 percent, lowering the temperature to the normal temperature, lowering the pressure to the normal pressure, introducing reaction materials into a membrane separator of which the separating accuracy is 0.1-5 mum for separating to obtain a cyclohexanone intermediate product, hydrating and catalyzing cyclohexanone to generate a cyclohexanol intermediate product, and dehydrogenating cyclohexanol to generate cyclohexanone. According to the production process, a catalyst precipitating process is eliminated, and the use of a precipitating block and a precipitating groove is avoided; compared with a precipitating groove process, the process has the advantages: millions of equipment investment can be reduced, and a large quantity of technology introduction expenses can be saved; and the production process has wide development and application prospects.
Description
Technical field
The present invention relates to a kind of cyclohexanone production process, relate in particular to the incomplete hydrogenation catalyst separating technology of a kind of benzene.
Background technology
Pimelinketone is a colourless transparent liquid, is used to produce hexanolactam and hexanodioic acid, is used for industry such as rubber, coating, leather, printing ink and agricultural chemicals on a small quantity as industrial solvent.
The forties, the industrial production of pimelinketone adopts with phenol and is raw material hydrogenation generation hexalin, and dehydrogenation makes pimelinketone again.Along with the development of petrochemical complex, to method that cyclohexane oxidation is produced pimelinketone sixties dominate progressively in industry.1967, the method that one step of phenol hydrogenation of Dutch States Mines (DSM) exploitation is produced pimelinketone realized industriallization.This method Production Flow Chart weak point, good product quality, productive rate height, but raw material phenol and catalyzer price are higher, and also the shortcoming of this method is that cyclohexane oxidation process can produce the by product about 20%.Japan company of Asahi Chemical Industry has developed benzene partial hydrogenation technology to the eighties, makes raw material availability reach about 99%.This technological process is: with benzene raw material, and at 100～180 ℃, 3～10MPa; Carry out incomplete hydrogenation reaction under the condition of ruthenium catalyst and prepare tetrahydrobenzene, the transformation efficiency of benzene is 50～60%, and the selectivity of tetrahydrobenzene is 80%; 20% by product is a hexanaphthene, and under supersiliceous zeolite ZSM-5 catalyst action, cyclohexene hydration is produced hexalin; The per pass conversion of tetrahydrobenzene is 10～15%, and the selectivity of hexalin can reach 99.3%, and pimelinketone is produced in cyclohexanol dehydrogenation.This processes expend is low, and has effectively avoided the waste lye that produces in the cyclohexane oxidation technological process, has reduced environmental protection pressure, has tangible prospect.And at present, produce in the pimelinketone technological process in the incomplete hydrogenation reaction of benzene, the incomplete catalyst for hydrogenation separating technology of benzene is for introducing the high subsider sedimentation process of closing cost of Japan.
In sum, be to reduce the Cyclohexanone Production cost, the incomplete catalyst for hydrogenation separating and producing of benzene in the Cyclohexanone Production process is improved have very significant meaning.
Summary of the invention
It is higher to the present invention is directed to existing explained hereafter cost, a kind of incomplete catalyst for hydrogenation separating technology of brand-new benzene is provided, so that the catalyst separating work simplification reduces production costs.
For realizing the object of the invention, the incomplete catalyst for hydrogenation separating technology of this benzene is characterized in that may further comprise the steps:
A. after benzene feedstock, hydrogen get into reactor drum 1 successively with 1.17: 1～1.19: 1 volume ratio, under 100～180 ℃ of temperature, 3～10Mpa, ruthenium catalyst condition, react;
B. above-mentioned reactive hydrogen is residual less than 3～5% o'clock, and the reaction intermediates material is from the bottom inlet of reactor drum 1 outlet at bottom nature inflow reactor 2, then with 3600～3800m
3The hydrogen feed amount of/h, 100～180 ℃, 3～10MPa continuation reaction down;
C. when b step reaction benzene transformation efficiency reaches 50～60%, cooling decompression is to normal temperature, normal pressure, and then reaction mass being fed separation accuracy is that the membrane separation apparatus of 0.1～5 μ m separates and obtains the tetrahydrobenzene intermediates;
D. tetrahydrobenzene generates the hexalin intermediates after hydration catalysis, and hexalin generates the finished product pimelinketone again after dehydrogenation.
Said membrane separation apparatus adopts ceramic membrane separator or metallic membrane separator.
Said reactor drum 1 is arranged to be higher than reactor drum 2 height falls 1～3m.
The technical progress that the present invention obtained:
1, owing to adopts technology of the present invention; Make that the incomplete catalyst for hydrogenation separating and producing of benzene has saved catalyst sedimentation technology in the Cyclohexanone Production process, avoided using special sedimentation piece and subsider, significantly reduced facility investment; Compare with subsider technology; It is millions of to reduce facility investment, can save a large amount of technology introduction expenses simultaneously, has exploitation prospect widely.
2, owing to adopted ceramic membrane separator or metallic membrane separator, also can realize the separation of catalyzer, replace the patented technology of introducing Japan, reduce the production cost of enterprise.
3, owing to the height fall of two reactor drums being arranged to 1～3m, can spill into naturally second reactor drum from first reactor drum by the realization response material.
4, owing to adopted ceramic membrane separator or metallic membrane separator, also can realize the separation of catalyzer, replace special subsider catalyst separating technology, significantly reduce the technology introduction expense of facility investment and great number.
Description of drawings
Below in conjunction with accompanying drawing the present invention is described further.
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Embodiment 1: as shown in Figure 1, technological process of the present invention is following:
At first reactor drum 1 is arranged to be higher than reactor drum 2 height falls 1～3m, incites somebody to action then:
A. benzene feedstock, hydrogen, are reacted under 100 ℃ of temperature, 3MPa, ruthenium catalyst condition respectively after bottom inlet gets into reactor drum 1 successively with 1.17: 1 volume ratio.
B. above-mentioned reactive hydrogen is residual less than 3～5% o'clock, and the reaction intermediates material is from the bottom inlet of reactor drum 1 outlet at bottom nature inflow reactor 2, then with 3600～3800m
3The hydrogen feed amount of/h, 100 ℃, 3 MPa continuation reaction down;
C. when b step reaction benzene transformation efficiency reaches 50～60%; Arrive normal temperature, normal pressure through cooling decompression; Then reaction mass being fed separation accuracy is that the ceramic membrane separator of 0.1～5 μ m separates; Ooze out the tetrahydrobenzene intermediate product that obtains and after follow-up exquisite technology, make the pimelinketone finished product, carried Returning reactor 1 through HPP by the catalyzer that ceramic membrane is held back;
D. tetrahydrobenzene generates the hexalin intermediates after hydration catalysis, and hexalin generates the finished product pimelinketone again after dehydrogenation.
Embodiment 2: this enforcement with embodiment 1 difference is:
A. benzene feedstock, hydrogen, are reacted under 180 ℃ of temperature, 10MPa, ruthenium catalyst condition respectively after bottom inlet gets into reactor drum 1 successively with 1.19: 1 volume ratio;
B. above-mentioned reactive hydrogen is residual less than 3～5% o'clock, and the reaction intermediates material is from the bottom inlet of reactor drum 1 outlet at bottom nature inflow reactor 2, then with 3600～3800m
3The hydrogen feed amount of/h, 180 ℃, 10MPa continuation reaction down;
C. when b step reaction benzene transformation efficiency reaches 50～60%; Arrive normal temperature, normal pressure through cooling decompression; Then reaction mass being fed separation accuracy is that the metallic membrane separator of 0.1～3 μ m separates; Ooze out the tetrahydrobenzene intermediate product that obtains and after follow-up exquisite technology, make the pimelinketone finished product, carried Returning reactor 1 through HPP by the catalyzer that ceramic membrane is held back;
D. tetrahydrobenzene generates the hexalin intermediates after hydration catalysis, and hexalin generates the finished product pimelinketone again after dehydrogenation.
Embodiment 3: this enforcement with embodiment 1 difference is
:
A. benzene feedstock, hydrogen, are reacted under 150 ℃ of temperature, 5MPa, ruthenium catalyst condition respectively after bottom inlet gets into reactor drum 1 successively with 1.18: 1 volume ratio;
B. above-mentioned reactive hydrogen is residual less than 3～5% o'clock, and the reaction intermediates material is from the bottom inlet of reactor drum 1 outlet at bottom nature inflow reactor 2, then with 3600～3800m
3The hydrogen feed amount of/h, 160 ℃, 6MPa continuation reaction down;
C. when b step reaction benzene transformation efficiency reaches 50～60%; Arrive normal temperature, normal pressure through cooling decompression; Then reaction mass being fed separation accuracy is that the ceramic membrane separator of 0.1～5 μ m separates; Ooze out the tetrahydrobenzene intermediate product that obtains and after follow-up exquisite technology, make the pimelinketone finished product, carried Returning reactor 1 through HPP by the catalyzer that ceramic membrane is held back;
D. tetrahydrobenzene generates the hexalin intermediates after hydration catalysis, and hexalin generates the finished product pimelinketone again after dehydrogenation.
Claims (3)
1. incomplete hydrogenation cyclohexanone production process is characterized in that may further comprise the steps:
A. after benzene feedstock, hydrogen get into reactor drum 1 successively with 1.17: 1～1.19: 1 volume ratio, under 100～180 ℃ of temperature, 3～10Mpa, ruthenium catalyst condition, react;
B. above-mentioned reactive hydrogen is residual less than 3～5% o'clock, and the reaction intermediates material is from the bottom inlet of reactor drum 1 outlet at bottom nature inflow reactor 2, then with 3600～3800m
3The hydrogen feed amount of/h, 100～180 ℃, 3～10MPa continuation reaction down;
C. when b step reaction benzene transformation efficiency reaches 50～60%, cooling decompression is to normal temperature, normal pressure, and then reaction mass being fed separation accuracy is that the membrane separation apparatus of 0.1～5 μ m separates and obtains the tetrahydrobenzene intermediates;
D. tetrahydrobenzene generates the hexalin intermediates after hydration catalysis, and hexalin generates the finished product pimelinketone again after dehydrogenation.
2. incomplete hydrogenation cyclohexanone production process according to claim 1 is characterized in that said membrane separation apparatus adopts ceramic membrane separator or metallic membrane separator.
3. incomplete hydrogenation cyclohexanone production process according to claim 1 and 2 is characterized in that said reactor drum 1 is arranged to be higher than reactor drum 2 height falls 1～3m.
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| CN2011102286673A CN102391085A (en) | 2011-08-11 | 2011-08-11 | Process for producing cyclohexanone by performing incomplete hydrogenation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898268A (en) * | 2012-09-29 | 2013-01-30 | 中国天辰工程有限公司 | Method for continuously producing cyclohexene |
| CN104672069A (en) * | 2015-01-21 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone or substituted cyclohexanone |
| CN105967984A (en) * | 2016-06-02 | 2016-09-28 | 中国化学赛鼎宁波工程有限公司 | Method and system for producing cyclohexanone with phenol |
| CN111217684A (en) * | 2019-10-29 | 2020-06-02 | 山西潞宝兴海新材料有限公司 | Production method for improving yield of cyclohexanone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270468A2 (en) * | 1986-12-05 | 1988-06-08 | Rhone-Poulenc Chimie | Process for preparing a mixture containing cyclohexanol and cyclohexanone from cyclohexane |
| CN1489574A (en) * | 2001-01-31 | 2004-04-14 | ������������ʽ���� | Process for producing cyclohexanone oxime |
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2011
- 2011-08-11 CN CN2011102286673A patent/CN102391085A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270468A2 (en) * | 1986-12-05 | 1988-06-08 | Rhone-Poulenc Chimie | Process for preparing a mixture containing cyclohexanol and cyclohexanone from cyclohexane |
| CN1489574A (en) * | 2001-01-31 | 2004-04-14 | ������������ʽ���� | Process for producing cyclohexanone oxime |
Non-Patent Citations (1)
| Title |
|---|
| 《当代化工》 20090228 马见波 环己烷选择性氧化合成环己醇和环己酮的研究进展 65-68 1-3 第38卷, 第1期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898268A (en) * | 2012-09-29 | 2013-01-30 | 中国天辰工程有限公司 | Method for continuously producing cyclohexene |
| CN102898268B (en) * | 2012-09-29 | 2014-12-24 | 中国天辰工程有限公司 | Method for continuously producing cyclohexene |
| CN104672069A (en) * | 2015-01-21 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone or substituted cyclohexanone |
| CN104672069B (en) * | 2015-01-21 | 2016-08-24 | 中国科学院兰州化学物理研究所 | A kind of Ketohexamethylene or the preparation method of substituted cyclohexanone |
| CN105967984A (en) * | 2016-06-02 | 2016-09-28 | 中国化学赛鼎宁波工程有限公司 | Method and system for producing cyclohexanone with phenol |
| CN105967984B (en) * | 2016-06-02 | 2018-04-17 | 中国化学赛鼎宁波工程有限公司 | The method and system of phenol production cyclohexanone |
| CN111217684A (en) * | 2019-10-29 | 2020-06-02 | 山西潞宝兴海新材料有限公司 | Production method for improving yield of cyclohexanone |
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Application publication date: 20120328 |