CN102659523A - Dehydrogenation method for synthesizing diphenylphenol or o-phenylphenol by condensing and dehydrogenating cyclohexanone - Google Patents
Dehydrogenation method for synthesizing diphenylphenol or o-phenylphenol by condensing and dehydrogenating cyclohexanone Download PDFInfo
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- CN102659523A CN102659523A CN2012101401819A CN201210140181A CN102659523A CN 102659523 A CN102659523 A CN 102659523A CN 2012101401819 A CN2012101401819 A CN 2012101401819A CN 201210140181 A CN201210140181 A CN 201210140181A CN 102659523 A CN102659523 A CN 102659523A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of synthesis of phenylphenol compounds, and particularly relates to a dehydrogenation method for synthesizing diphenylphenol or o-phenylphenol by condensing and dehydrogenating cyclohexanone, which comprises the following steps: proportionally adding an intermediate ketone polymer and a dehydrogenation catalyst into a dehydrogenation reactor; introducing nitrogen into the dehydrogenation reactor to remove oxygen in the dehydrogenation reactor; and finally, heating, and controlling the temperature at 400-500 DEG C for dehydrogenation, wherein the nitrogen is continuously introduced into the dehydrogenation reactor all along in the dehydrogenation process. The method solves the problems of low conversion rate and low selectivity in the existing technique, and enhances the yield of the target product.
Description
Technical field
The invention belongs to phenylphenol compounds synthetic technical field, the method for dehydrogenating in phenylbenzene phenol or the orthoxenol is synthesized in concrete a kind of pimelinketone condensation dehydrogenation that relates to.
Background technology
Along with the development of society, phenylbenzene phenol and orthoxenol applied more and more have been widely applied to industries such as dyestuffs industries, agricultural chemicals, food medicine, engineering plastics, insulating material.The synthetic relatively difficulty of phenylbenzene phenol and orthoxenol is seriously polluted now, is difficult to realize suitability for industrialized production, thereby has restricted the more wide application prospect of this compounds.Seeking the synthetic route of high-efficiency environment friendly, is phenylbenzene phenol and orthoxenol compound industry development key.In the prior art the pimelinketone condensation dehydriding that extensively adopts be to be raw material with the pimelinketone; Obtain trimerization or double focusing midbody through the condensation dehydration; Produce phenylbenzene phenol or orthoxenol through dehydrogenation again; And the ketal dehydrogenation in the building-up process is the key in the whole synthetic route, and present dehydrogenating technology is because catalyzer problem and processing condition and operational issue ubiquity transformation efficiency and the low shortcoming of selectivity.
Summary of the invention
The objective of the invention is to be directed against the defective of above-mentioned existence and provide a kind of pimelinketone condensation dehydrogenation to synthesize the method for dehydrogenating in phenylbenzene phenol or the orthoxenol; This method solves existing technology transformation efficiency and the low problem of selectivity, has improved the yield of title product.
Technical scheme of the present invention is: the method for dehydrogenating in synthetic phenylbenzene phenol of a kind of pimelinketone condensation dehydrogenation or the orthoxenol, and midbody polymerization ketone and the dehydrogenation catalyst that at first will synthesize phenylbenzene phenol or orthoxenol joins in the dehydrogenation reactor by the part by weight of 7:1; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 400 ℃～500 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor; Wherein dehydrogenation catalyst is Pt-Al
2O
3Or the Pd-C catalyst system, this dehydrogenation catalyst is with Pt-Al
2O
3Or Pd-C is that carrier is immersed in earlier through pickling process in the solution that contains potassium ion or sodium ion, cures through 400 ℃～500 ℃ then, at last at 300 ℃～450 ℃ reduction preparation gained.
The massfraction of the effective catalyst component content of dehydrogenation catalyst that the method for dehydrogenating in synthetic phenylbenzene phenol of described pimelinketone condensation dehydrogenation or the orthoxenol adopts is 0.1%～1.2%.
The method of dehydrogenating in phenylbenzene phenol or the orthoxenol is synthesized in described pimelinketone condensation dehydrogenation, at first will synthesize the midbody polymerization triketone and the dehydrogenation catalyst Pt-Al of phenylbenzene phenol
2O
3Catalyst system joins in the dehydrogenation reactor by the part by weight of 7:1; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 450 ℃～500 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor, polishing gets phenylbenzene phenol.
Method of dehydrogenating in synthetic phenylbenzene phenol of described pimelinketone condensation dehydrogenation or the orthoxenol at first joins the midbody polymerization diketone of synthesizing o-phenylphenol and the dehydrogenation catalyst Pd-C catalyst system part by weight by 7:1 in the dehydrogenation reactor; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 400 ℃～450 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor, polishing gets orthoxenol.
Beneficial effect of the present invention is: the method for dehydrogenating in synthetic phenylbenzene phenol of pimelinketone condensation dehydrogenation of the present invention or the orthoxenol, the dehydrogenation catalyst that is adopted is with Pt-Al for the catalyzer after improveing
2O
3Or Pd-C is that carrier is immersed in the solution that contains potassium ion or sodium ion through pickling process; Through curing, reduce the preparation gained; The massfraction of effective catalyst component content of this kind dehydrogenation catalyst is 0.1%～1.2%, has improved the transformation efficiency and the selection rate of dehydrogenation reaction greatly.Because the existence of oxygen not only can influence the selectivity of dehydrogenation reaction in reaction process; And be co-located in the encloses container with hydrogen again; Thereby blast easily, increased security risk, the present invention feeds inert nitrogen gas earlier the oxygen in the dehydrogenation reactor is got rid of before dehydrogenation reaction; Both effectively improve the selectivity of dehydrogenation reaction, removed potential safety hazard again.The temperature of reaction of this kind method of dehydrogenating is controlled under 400 ℃～500 ℃, and neither can cause side reaction to increase in this TR because of temperature is too high influences transformation efficiency and selectivity, can not make speed of response slow excessively because of temperature is too low again.In the process of dehydrogenation reaction, feed nitrogen continuously, under 400 ℃～500 ℃ of temperature, high temperature nitrogen can in time be taken away the hydrogen G&W that reaction generates always, guarantees to react and carries out to the positive reaction direction.
Pass through foregoing description; The method of dehydrogenating that the present invention adopted makes the transformation efficiency of dehydrogenation reaction and selection rate reach 90%～96%; Efficiently solve existing technology transformation efficiency and the low problem of selectivity; Improve the yield of title product, made the synthesizing efficient environmental protection of phenylbenzene phenol or orthoxenol.
Embodiment
Through following specific embodiment the present invention is carried out detailed explanation below.
Embodiment one
Midbody polymerization triketone 50 grams and dehydrogenation catalyst Pt-Al that at first will synthesize phenylbenzene phenol
2O
3Catalyst system 7 grams join in the dehydrogenation reactor; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 450 ℃～500 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor, high temperature nitrogen in time will react the hydrogen G&W of generation and taken dehydrogenation reactor out of; Dehydrogenation catalyst Pt-Al wherein
2O
3Catalyst system is with Pt-Al
2O
3For carrier is immersed in earlier through pickling process in the solution that contains potassium ion or sodium ion, cure through 400 ℃～500 ℃ then, at 300 ℃～450 ℃ reduction preparation gained, the massfraction of effective catalyst component content of this dehydrogenation catalyst is 0.5% at last.Phenylbenzene phenol through the refining gained of this method is 42.2 grams, and then transformation efficiency is 94.6%, and selection rate is 89.2%, and under the condition of polymerization triketone same amount, by existing conventional dehydrogenating technology transformation efficiency only about 70%, and selection rate only about 50%.
Embodiment two
At first midbody polymerization diketone 50 grams with synthesizing o-phenylphenol join in the dehydrogenation reactor with dehydrogenation catalyst Pd-C catalyst system 7 grams; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 400 ℃～450 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor, high temperature nitrogen in time will react the hydrogen G&W of generation and taken dehydrogenation reactor out of; Wherein dehydrogenation catalyst Pd-C catalyst system is that carrier is immersed in the solution that contains potassium ion or sodium ion earlier through pickling process with Pd-C; Cure through 400 ℃～500 ℃ then; At 300 ℃～450 ℃ reduction preparation gained, the massfraction of effective catalyst component content of this dehydrogenation catalyst is 0.7% at last.Orthoxenol through the refining gained of this method is 42.9 grams, and then transformation efficiency is 95.2%, and selection rate is 90.4%, and under the condition of polymerization diketone same amount, by existing conventional dehydrogenating technology transformation efficiency only about 80%, and selection rate only about 70%.
Claims (4)
1. the method for dehydrogenating in synthetic phenylbenzene phenol of a pimelinketone condensation dehydrogenation or the orthoxenol, midbody polymerization ketone and the dehydrogenation catalyst that at first will synthesize phenylbenzene phenol or orthoxenol joins in the dehydrogenation reactor by the part by weight of 7:1; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 400 ℃～500 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor; Wherein dehydrogenation catalyst is Pt-Al
2O
3Or the Pd-C catalyst system, this dehydrogenation catalyst is with Pt-Al
2O
3Or Pd-C is that carrier is immersed in earlier through pickling process in the solution that contains potassium ion or sodium ion, cures through 400 ℃～500 ℃ then, at last at 300 ℃～450 ℃ reduction preparation gained.
2. the method for dehydrogenating in synthetic phenylbenzene phenol of pimelinketone condensation dehydrogenation according to claim 1 or the orthoxenol is characterized in that the massfraction of effective catalyst component content of described dehydrogenation catalyst is 0.1%～1.2%.
3. the method for dehydrogenating in phenylbenzene phenol or the orthoxenol is synthesized in pimelinketone condensation dehydrogenation according to claim 1, at first will synthesize the midbody polymerization triketone and the dehydrogenation catalyst Pt-Al of phenylbenzene phenol
2O
3Catalyst system joins in the dehydrogenation reactor by the part by weight of 7:1; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 450 ℃～500 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor, polishing gets phenylbenzene phenol.
4. the method for dehydrogenating in synthetic phenylbenzene phenol of pimelinketone condensation dehydrogenation according to claim 1 or the orthoxenol at first joins the midbody polymerization diketone of synthesizing o-phenylphenol and the dehydrogenation catalyst Pd-C catalyst system part by weight by 7:1 in the dehydrogenation reactor; In dehydrogenation reactor, feed nitrogen then, the oxygen in the dehydrogenation reactor is got rid of; Heating and controlled temperature carry out dehydrogenation under 400 ℃～450 ℃ condition at last, simultaneously in certain embodiments always successive nitrogen is passed in the dehydrogenation reactor, polishing gets orthoxenol.
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| CN2012101401819A CN102659523A (en) | 2012-05-09 | 2012-05-09 | Dehydrogenation method for synthesizing diphenylphenol or o-phenylphenol by condensing and dehydrogenating cyclohexanone |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088702A (en) * | 1975-05-14 | 1978-05-09 | Sugai Chemical Industry Company Limited | Process for preparing o-phenylphenol |
| CN101524643A (en) * | 2008-03-04 | 2009-09-09 | 中国石油化工集团公司 | Method for preparing catalyst for use in production of o-phenylphenol |
| CN101555196A (en) * | 2009-04-23 | 2009-10-14 | 浙江大学 | Synthetic method of o-phenylphenol |
| CN101903320A (en) * | 2007-12-17 | 2010-12-01 | 巴斯夫欧洲公司 | Method for the production of 4,4'-[1-(trifluoromethyl)alkylidene]-bis-(2,6-diphenylphenols) |
-
2012
- 2012-05-09 CN CN2012101401819A patent/CN102659523A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088702A (en) * | 1975-05-14 | 1978-05-09 | Sugai Chemical Industry Company Limited | Process for preparing o-phenylphenol |
| CN101903320A (en) * | 2007-12-17 | 2010-12-01 | 巴斯夫欧洲公司 | Method for the production of 4,4'-[1-(trifluoromethyl)alkylidene]-bis-(2,6-diphenylphenols) |
| CN101524643A (en) * | 2008-03-04 | 2009-09-09 | 中国石油化工集团公司 | Method for preparing catalyst for use in production of o-phenylphenol |
| CN101555196A (en) * | 2009-04-23 | 2009-10-14 | 浙江大学 | Synthetic method of o-phenylphenol |
Non-Patent Citations (1)
| Title |
|---|
| 陈欢等: "环己酮三聚物催化脱氢制备2，6-二苯基苯酚", 《现代化工》 * |
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Application publication date: 20120912 |