CN101693673A - Method for preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate - Google Patents
Method for preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate Download PDFInfo
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- CN101693673A CN101693673A CN200910308501A CN200910308501A CN101693673A CN 101693673 A CN101693673 A CN 101693673A CN 200910308501 A CN200910308501 A CN 200910308501A CN 200910308501 A CN200910308501 A CN 200910308501A CN 101693673 A CN101693673 A CN 101693673A
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- cyclohexanone
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- oxime
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Abstract
The invention discloses a method for preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate. The method is characterized by comprising the following steps: taking organic and inorganic compound heteropoly acid as catalyst, enabling cyclohexanone oxime, hydrogen peroxide solution and ammonia to react, separating cyclohexanone oxime after finishing reaction, processing residual phase through removing ammonia, and directly reclaiming separated catalyst. Compared with the prior art, the method can solve the problem of separating and reclaiming catalyst more simply while guaranteeing high cyclohexanone conversion rate and high selectivity of cyclohexanone oxime simultaneously.
Description
Technical field
The present invention relates to a kind of method of preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate, further saying so about a kind of compound heteropolyacid salt of organic-inorganic that adopts is the method for the preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate of catalyzer.
Background technology
Cyclohexanone-oxime is an intermediate of producing nylon-6 monomer ε-Ji Neixianan, traditional technology adopts pimelinketone-hydroxylamine assay mostly, main drawback is that technical process is long, process is complicated, condition is harsh, facility investment is high, and a large amount of inorganic salts (vitriol etc.) of by-product, discharge contaminative waste gas (NOx and/or SOx), cause equipment corrosion and environmental pollution.
1967, the Toa Gosei company of Germany at first proposed pimelinketone and NH
3/ H
2O
2Directly oximate generates the method (GB1092899) of cyclohexanone-oxime.This method employing phospho-wolframic acid, silicotungstic acid, iodine wolframic acid, tungstovanadophosphoric acid, phosphotungstomolybdic acid or these sour inorganic salt such as sylvite, sodium salt or organic salt such as pyridinium salt, cyclohexyl amine salt are made catalyzer, have catalytic activity preferably.But catalyst dissolution is in reaction system, do not realize the recovery and reuse of catalyzer, cause the waste of resource and the raising of cost, thereby exist catalyzer problem such as can not recycle, those skilled in the art does not expect that an effective means removes head it off yet.
In the follow-up study of amidoximeization, the technician has turned to research emphasis the reaction system of making catalyzer with HTS again, arrived the mid-80, people such as the Italy Montedipe Paolo Roffia of company have invented pimelinketone under titanium-silicon molecular sieve TS-1 catalysis, with the tertiary butanol and water is solvent, the novel process of liquid phase ammonia oximate synthesizing cyclohexane 1 ketoxime, the transformation efficiency of pimelinketone are greater than 90%, and the yield of cyclohexanone-oxime is greater than 99% (US4794198 and US5227525).But activity of such catalysts reduces in time gradually, causes the transformation efficiency of pimelinketone not high enough, and has the aftertreatment complexity, as shortcomings such as product cyclohexanone-oxime separation.
CN02100227 and CN02100228 disclose amidoxime product and the isolating method of catalyzer continuous sedimentation, catalyst recirculation is used, improved the hydrogen peroxide utilization ratio, on the other hand, because catalyzer dissolves loss in the basic solution of Ammoximation reaction, the time of continous-stable operation and separating of catalyzer will be had influence on.
The disclosed cyclohexanone oxamidinating process of EP0267362 is HTS to be mixed the back extruded moulding be used for oximation reaction with tackiness agent, and uses porous plate directly to tackle catalyzer.But this method catalyst deactivation is very fast, and the transformation efficiency of pimelinketone has only 72.9% behind the 30h, and the selectivity of cyclohexanone-oxime is 93.2%.
Yet, more than be the cyclohexanone oxamidinating reaction of catalyzer with the former powder of titanium silicon, the catalyzer diameter mostly is 0.1-0.3 μ m, adopt spinning liquid to be difficult to thorough the separation with subsidence style, cause catalyst loss, and when adopting means such as membrane sepn, because the too small segregational load that causes of particle is overweight, and catalyzer is easy swelling under alkaline condition, causes fenestra to stop up.
Though and the HTS moulding can improve particle diameter, but still the tackiness agent of using when existing moulding stops up molecular sieve part aperture, pore volume and specific surface area descend to some extent, and auxiliary agent and molecular sieve generation bonding, have reduced the problems such as activity of molecular sieve catalyst.
At above variety of issue in the prior art, provide a kind of promptly practical simply again, promptly help guaranteeing catalyzer efficient in reaction process, the technology that helps the recovery of catalyzer again is an important topic of the required solution of those skilled in the art.
Summary of the invention
The object of the present invention is to provide a kind of pimelinketone transformation efficiency height, cyclohexanone-oxime selectivity height, and catalyzer is easily separated and the method for the preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate of recovery.
For achieving the above object, the method of preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate provided by the invention, be as catalyzer with the compound heteropolyacid salt of organic-inorganic, with pimelinketone, hydrogen peroxide and ammonia is that raw material carries out Ammoximation reaction, after reaction finishes, isolate cyclohexanone-oxime, residue through removing ammonia treatment, directly reclaims the catalyzer of separating out mutually; The compound heteropolyacid salt catalyst of described organic-inorganic, it consists of Q
mH
nPM
12O
40Q is a cationic moiety, structural formula be in following three kinds any:
Glyoxaline cation pyridylium quaternary ammonium salt cationic
Wherein R, R
1, R
2, R
3Or R
4Be selected from carbon chain lengths and be 4～16 straight or branched alkane; M is W or W and V combination; 1＜=m＜=3; 0＜=n＜=2.
Reaction system of the present invention can be reacted under solvent-free or water are done the condition of solvent.
Of the present inventionly remove ammonia treatment and be distillation.PH value when wherein removing the ammonia treatment end is controlled at 7～10 and is advisable, and is preferably 7～8 especially.
Can being undertaken of the catalyzer that described recovery is separated out by the mode of filtration or centrifugal or sedimentation or spinning liquid.
Ammoximation reaction can go out cyclohexanone-oxime by extracting and separating after finishing.The solvent of extraction cyclohexanone-oxime is that carbonatoms is 4～10 alkane or naphthenic hydrocarbon, or their mixture.
The amidoxime temperature is 10～30 ℃.
The compound heteropolyacid salt of organic-inorganic that the present invention is used, heteropolyanion has very strong wetting ability, positively charged ion is alkyl substituent or other quaternary ammonium cation of pyridine or imidazolyl heterocycle, therefore have profit amphiphilic and regulatable characteristics, can between the reaction raw materials two-phase, shuttle back and forth, play the function of phase transition, and then effectively improve the selectivity of the transformation efficiency and the cyclohexanone-oxime of pimelinketone.
In addition, the present inventor determines the carbochain that alkyl on the positively charged ion in the compound heteropolyacid salt of organic-inorganic replaces 4～16, makes that catalyzer is that favourable successful reaction is carried out efficiently, helps the recovery of follow-up catalyzer again.Catalyzer of the present invention has and is dissolved in strong polar reaction system, water-fast characteristics, therefore, the catalyzer that the present invention selects for use in reaction process can be dissolved in the polar reaction system that has ammonia to exist well, as a kind of homogeneous catalyst catalysis oximation reaction, has preserved advantages such as homogeneous catalyst high reactivity, highly selective, after reaction finishes, by removing ammonia treatment, just recyclable catalyzer is reused.
Relatively more existing Ammoximation process, the advantage that the present invention had is: by the compound heteropolyacid salt catalyst of the organic-inorganic that the present invention selected for use especially, guaranteeing higher pimelinketone transformation efficiency and cyclohexanone-oxime optionally simultaneously, technology of the present invention is also by the follow-up simple high efficiente callback that the ammonia mode has realized catalyzer that removes.The rate of recovery by the resulting catalyzer of technology of the present invention is all more than 70%; The catalyzer that reclaims is used further to Ammoximation reaction, and reaction effect does not obviously reduce.
In sum, method of the present invention, not only reaction effect is good, can be simpler, solved relevant process catalyst separation in the prior art effectively, reclaim difficult problem.Whole features simple and practical process, but efficent use of resources the time, saved cost, help industrial applications.
Concrete implementation step of the present invention is:
Do at solvent-free or water under the condition of solvent, successively with pimelinketone, stir in ammonia and the catalyzer adding reactor, pimelinketone: the preferred mol ratio of catalyzer is 1: (0.001～0.01), when the temperature of reaction system is controlled at 10～30 ℃, by pimelinketone: ammonia: the mol ratio of hydrogen peroxide is 1: (1～10): (1～10) begins to drip hydrogen peroxide, the dropping time is 2～4 hours, reacted again after dripping 1～3 hour, after reaction finished, with solvent extraction cyclohexanone-oxime and pimelinketone, extracting phase removed deammoniation by distillation, filter at last, or centrifugal, or sedimentation, or spinning liquid reclaims the catalyzer of separating out.
The compound heteropolyacid salt catalyst of organic-inorganic of the present invention is to adopt the mode of following method or the record of other document to prepare:
According to mol ratio is that a kind of and phospho-wolframic acid or the tungstovanadophosphoric acid that 3: 1 ratio takes by weighing in pyridine villaumite, imidazoles bromine salt or the bromination amine salt made the aqueous solution respectively, under constantly stirring, a kind of aqueous solution in pyridine villaumite, imidazoles bromine salt or the bromination amine salt slowly is added dropwise in the aqueous solution of phospho-wolframic acid or tungstovanadophosphoric acid, and insulation has precipitation to generate about 60 ℃ gradually, after dropwising, continue to stir 1h, ageing 1h is centrifugal then, washing is in 70 ℃ of oven dry.
Embodiment
Below by embodiment invention is further described, but does not therefore limit protection scope of the present invention.
Embodiment 1
0.02mol chlorinated butyl pyridine is dissolved in the 50ml water, is preheated to 60 ℃, again with phospho-wolframic acid: pyridine villaumite mol ratio is 1: 3 preparation phosphotungstic acid aqueous solution, slowly is added drop-wise in the there-necked flask, and 60 ℃ of following insulation reaction 1 hour, ageing 1 hour obtained white precipitate.Centrifugal repeatedly washing, splashing in the silver nitrate aqueous solution to water lotion does not have precipitation, in 70 ℃ of dry 24h down, makes white powder (C
5H
5NC
4H
9)
3PW
12O
40
The synthetic method of the compound heteropolyacid salt of other organic-inorganic is similar to above-mentioned steps.
Embodiment 2
In the glass reaction still of 250ml band magnetic agitation, add 4.1g catalyzer (C
5H
5NC
8H
17)
3PW
12O
40, 15g pimelinketone and 41.6g concentration are 27% ammoniacal liquor, and temperature control is at 20 ℃, and it is 30% hydrogen peroxide 27.7g that beginning at the uniform velocity drips concentration, and the dropping time is 4 hours, dropwises the back and prolongs reaction 1 hour.With hexanaphthene extraction product three times, the hexanaphthene consumption is 25g/ time, and extracting phase is separated out catalyzer gradually by vacuum distilling, stops distillation when solution ph=8.0, filter catalyzer 2.8g.Transformation efficiency is 93.02%, and selectivity is 88.77%.
The catalyzer that reclaims is carried out Ammoximation reaction again, tests as follows:
In the glass reaction still of 250ml band magnetic agitation, add the catalyzer (C that 2.0g reclaims
5H
5NC
8H
17)
3PW
12O
40, 7.5g pimelinketone and 20.7g concentration are 27% ammoniacal liquor, and temperature control is at 20 ℃, and it is 30% hydrogen peroxide 14.0g that beginning at the uniform velocity drips concentration, and the dropping time is 4 hours, dropwises the back and prolongs reaction 1 hour.Transformation efficiency is 90.96%, and selectivity is 100.00%.
Embodiment 3
In the glass reaction still of 250ml band magnetic agitation, add 3.9g catalyzer (C
5H
5NC
4H
9)
3PW
12O
40, 15g pimelinketone and 41.6g concentration are 27% ammoniacal liquor, and temperature control is at 20 ℃, and it is 30% hydrogen peroxide 27.7g that beginning at the uniform velocity drips concentration, and the dropping time is 4 hours, dropwises the back and prolongs reaction 1 hour.With hexanaphthene extraction product three times, the hexanaphthene consumption is 25g/ time, and extracting phase is separated out catalyzer gradually by vacuum distilling, stops distillation when solution ph=8.0, filter catalyzer 2.6g.Transformation efficiency is 90.12%, and selectivity is 97.79%.
Embodiment 4
In the glass reaction still of 250ml band magnetic agitation, add 4.3g catalyzer (C
12H
25(CH
3)
3N)
3PW
12O
40, 15g pimelinketone and 41.4g concentration are 27% ammoniacal liquor, and temperature control is at 20 ℃, and it is 30% hydrogen peroxide 28.2g that beginning at the uniform velocity drips concentration, and the dropping time is 4 hours, dropwises the back and prolongs reaction 1 hour.With hexanaphthene extraction product three times, the hexanaphthene consumption is 25g/ time, and extracting phase is separated out catalyzer gradually by vacuum distilling, stops distillation when solution ph=8.0, filter catalyzer 3.2g.Transformation efficiency is 88.16%, and selectivity is 91.87%.
Embodiment 5
In the glass reaction still of 250ml band magnetic agitation, add 4.5g catalyzer (C
20H
39N
2)
3PW
12O
40, 15g pimelinketone and 41.0g concentration are 27% ammoniacal liquor, and temperature control is at 20 ℃, and it is 30% hydrogen peroxide 27.9g that beginning at the uniform velocity drips concentration, and the dropping time is 4 hours, dropwises the back and prolongs reaction 1 hour.With hexanaphthene extraction product three times, the hexanaphthene consumption is 25g/ time, and extracting phase is separated out catalyzer gradually by vacuum distilling, stops distillation when solution ph=8.0, filter catalyzer 3.2g.Transformation efficiency is 92.16%, and selectivity is 84.73%.
Embodiment 6
In the glass reaction still of 250ml band magnetic agitation, add 4.0g catalyzer (C
16H
33(CH
3)
3N)
3PW
11VO
40, the 15g pimelinketone, 31.2g concentration is 27% ammoniacal liquor and 10g water, and temperature control is at 30 ℃, and it is 30% hydrogen peroxide 28.2g that beginning at the uniform velocity drips concentration, and the dropping time is 3 hours, dropwises the back and prolongs reaction 2 hours.With hexanaphthene extraction product three times, the hexanaphthene consumption is 25g/ time, and extracting phase is separated out catalyzer gradually by vacuum distilling, stops distillation when solution ph=8.0, filter catalyzer 3.0g.Transformation efficiency is 80.16%, and selectivity is 70.54%.
Claims (9)
1. the method for a preparing cyclohexanone oxime through cyclohexanone liquid phase ammonia oximate, it is characterized in that: with the compound heteropolyacid salt of organic-inorganic as catalyzer, with pimelinketone, hydrogen peroxide and ammonia is that raw material carries out Ammoximation reaction, after reaction finishes, isolate cyclohexanone-oxime, residue through removing ammonia treatment, directly reclaims the catalyzer of separating out mutually; The compound heteropolyacid salt of described organic-inorganic, it consists of QmHnSM12O40; Q is a cationic moiety, structural formula be in following three kinds any:
Wherein to be selected from carbon chain lengths be 4～16 straight or branched alkane for R, R1, R2, R3 or R4; S is P; M is the combination of W or W and V; 1＜=m＜=3; 0＜=n＜=2.
2. method according to claim 1 is characterized in that: the described ammonia mode of removing is distillation.
3. method according to claim 1 and 2 is characterized in that: be controlled at 7～10 to removing the pH value of ammonia treatment when finishing.
4. method according to claim 1 is characterized in that: the mode of described recovery catalyzer is to filter or centrifugal or sedimentation or spinning liquid.
5. method according to claim 1 is characterized in that: the mode of described cyclohexanone oxime is extraction.
6. method according to claim 5 is characterized in that: the solvent of extraction cyclohexanone-oxime is that carbonatoms is 4～10 alkane or naphthenic hydrocarbon, or their mixture.
7. method according to claim 1 is characterized in that: pimelinketone: the mol ratio of catalyzer is 1: (0.001～0.01).
8. method according to claim 1 is characterized in that: the amidoxime temperature is 10～30 ℃.
9. method according to claim 1 is characterized in that: reaction system is done at solvent-free or water under the condition of solvent and is reacted.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710326A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Acetaldehyde oxime preparation method |
| CN104926689A (en) * | 2015-06-12 | 2015-09-23 | 华东师范大学 | Method for preparing cyclohexanone-oxime in solvent-free mode |
| CN111517984A (en) * | 2020-06-01 | 2020-08-11 | 河北工业大学 | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
-
2009
- 2009-10-20 CN CN200910308501A patent/CN101693673A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710326A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Acetaldehyde oxime preparation method |
| CN104926689A (en) * | 2015-06-12 | 2015-09-23 | 华东师范大学 | Method for preparing cyclohexanone-oxime in solvent-free mode |
| CN111517984A (en) * | 2020-06-01 | 2020-08-11 | 河北工业大学 | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
| CN111517984B (en) * | 2020-06-01 | 2023-02-28 | 河北工业大学 | Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate |
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Application publication date: 20100414 |