CN101177246A - Method for producing oxydol by dihydrodiketoanthracene method - Google Patents
Method for producing oxydol by dihydrodiketoanthracene method Download PDFInfo
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- CN101177246A CN101177246A CNA2007101130820A CN200710113082A CN101177246A CN 101177246 A CN101177246 A CN 101177246A CN A2007101130820 A CNA2007101130820 A CN A2007101130820A CN 200710113082 A CN200710113082 A CN 200710113082A CN 101177246 A CN101177246 A CN 101177246A
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- hydrogen
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- anthraquinone
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- dioxide solution
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Abstract
The invention discloses an anthraquinone preparation method for producing hydrogen peroxide, which is characterized in that the catalyst palladium is put into the hydrogenation tower to activate hydrogen; the hydrogen replacement with nitrogen is performed and then the prepared operating fluid is sent to the hydrogenation tower. Under the catalysis of the palladium, the hydrogenation takes place with hydrogen and the corresponding hydrogenated fluid is obtained. Then the hydrogenated fluid is sent to the oxidation tower, and oxidation takes place; the oxidized fluid is counter-flow extracted with pure water and the hydrogen peroxide is obtained. After the purification, the finished product is obtained and the disposed extraction raffinate can be calculatedly as operating fluid with a characteristic of quenching and softening the catalyst palladium. The invention has the advantages that the degradation of anthraquinone caused by the high activity of the catalyst palladium at the beginning of the process effectively is reduced; the activity of the catalyst is made full use, and the stability for the system is increased.
Description
Technical field:
The present invention relates to produce the method for hydrogen peroxide, relate in particular to a kind of method of hydrogen dioxide solution production by anthraquinone process.
Background technology:
Hydrogen dioxide solution production by anthraquinone process is one of the most sophisticated production method of the sector in the world at present, and the hydrogenation catalyst that hydrogen dioxide solution production by anthraquinone process adopts is a palladium series catalyst at present substantially, comprises fixed bed catalyst and suspension bed catalyzer.This catalyzer is after feeding working fluid (with the diethyl anthraquinone is carrier, is solvent with aromatic hydrocarbons and trioctyl phosphate, is mixed with working fluid), working fluid is immersed in catalyzer inside, the dissolved anthraquinone also enters catalyzer inside thereupon in the working fluid, and in catalyzer inside, the inside diffusional resistance of anthraquinone is very big, and catalyzer has just been finished by the hydrogen activation this moment, activity is very high, very easily causes the anthraquinone excessive hydrogenation, thereby produces a large amount of degradation products, make system's fluctuation of service, also strengthened the consumption of anthraquinone.
Summary of the invention:
The object of the invention is to overcome the deficiency of above-mentioned prior art and provides a kind of technology simple, gives full play to catalyst activity, and system drives to operate steadily, and anthraquinone consumes the method for low a kind of hydrogen dioxide solution production by anthraquinone process.
Purpose of the present invention can reach by following measure: a kind of method of hydrogen dioxide solution production by anthraquinone process, its processing step activates for put into the logical hydrogen of palladium catalyst in the hydrogenation tower, after carry out nitrogen replacement, the working fluid of being prepared is fed in the hydrogenation tower, under via palladium-catalyzed dose the katalysis, carry out hydrogenation with hydrogen, obtain corresponding hydride, after hydride is fed oxidizing tower, the oxidation liquid of gained carries out counter-current extraction through extraction tower and pure water after the hydride oxidation, obtains hydrogen peroxide, again after purifying treatment, make finished product, raffinate recycles as working fluid after treatment, it is characterized in that the disappear softening of quenching of described palladium catalyst is handled.
In order further to realize purpose of the present invention, palladium catalyst disappeared, and to quench that softening handles be palladium catalyst to be immersed soak 2～15 hours in the solvent.
In order further to realize purpose of the present invention, described solvent is anthraquinone solvent or anthrahydroquinone solvent.
In order to realize that further purpose of the present invention, described anthraquinone solvent are the hot fat of heavy aromatics, tricresyl phosphate, C
9-C
11The mixture of one or more in high point petroleum aromatic hydrocarbons, methylnaphthalene, dimethylnaphthalene, the tert.-butylbenzene.
In order further to realize that purpose of the present invention, described anthrahydroquinone solvent are one or more the mixture in diisobutyl carbinol(DIBC), trialkylphosphate, acetic acid methyl cyclohexane ester, tetrabutyl urea, the hydrogenation terpene pine camphor.
Soaking step carries out before the activation of palladium catalyst hydrogen in the described palladium catalyst immersion solvent.
Soaking step carries out behind the activation of palladium catalyst hydrogen, nitrogen replacement in the described palladium catalyst immersion solvent.
Described palladium catalyst is sphere, bar shaped, special-shaped palladium catalyst.
The present invention can produce following positively effect compared with the prior art: palladium catalyst its absorption behind solvent soaking is approaching saturated, especially its absorption behind solvent soaking of catalyst activated elder generation has reached saturated, no longer adsorb working fluid after feeding working fluid again, anthraquinone in the working fluid will slow down greatly toward catalyzer internal divergence speed, anthraquinone excessive hydrogenation probability reduces, thereby suppress degraded, system is operated steadily, the anthraquinone consumption reduces.
Be below to palladium catalyst without solvent soaking with through the effect analysis of solvent soaking:
Reaction unit adopts small fixed hydrogenation unit, palladium catalyst 50g, working fluid (2-ethyl-anthraquinone content 60g/L) 500ml, use the plunger type metering pump cycle working fluid, ultra thermostat assurance device constant temperature, logical H-H reaction 24 hours, condition is: hydrogen pressure 0.3Mp, 70 ℃ of temperature of reaction.In 4 hours, 7 hours, sampling in 24 hours was measured anthraquinone and tetrahydro-anthraquinone content with the JP-303 polarographic analyze.
Example 1: get the palladium catalyst 50g that is untreated and pack in the reactive system, logical H-H reaction 24 hours and sampling analysis behind the nitrogen replacement.
Example 2: get 50g and example 1 same palladium catalyst and soaked 8 hours with heavy aromatics, in the reactive system of packing into afterwards, logical H-H reaction 24 hours and sampling analysis behind the nitrogen replacement.
Example 3: get 50g and example 1 same palladium catalyst and soaked 8 hours with the hot fat of tricresyl phosphate, in the reactive system of packing into afterwards, logical H-H reaction 24 hours and sampling analysis behind the nitrogen replacement.
Example 4: (heavy aromatics: the hot fat of tricresyl phosphate=3: 1) immersion is 8 hours, in the reactive system of packing into afterwards, leads to H-H reaction 24 hours and sampling analysis behind the nitrogen replacement with mixed solvent to get 50g palladium catalyst similarly to Example 1.
Analytical results sees Table 1:
Table 1
| Project | Example 1 | Example 2 | Example 3 | Example 4 | ||||
| Anthraquinone g/L | Tetrahydro-anthraquinone g/L | Anthraquinone g/L | Tetrahydro-anthraquinone g/L | Anthraquinone g/L | Tetrahydro-anthraquinone g/L | Anthraquinone g/L | Tetrahydro-anthraquinone g/L | |
| 4h | 43.2 | 12.9 | 52.8 | 5.3 | 50.4 | 6.7 | 51.3 | 6.4 |
| 7h | 29.3 | 22.8 | 47.6 | 7.8 | 38.6 | 14.3 | 41.5 | 12.3 |
| 24h | 0 | 44.6 | 10.5 | 39.2 | 5.3 | 41.4 | 6.8 | 40.3 |
By table 1 as seen, through the solvent soaking especially palladium catalyst after heavy aromatics soaks, its anthraquinone is converted into tetrahydro-anthraquinone speed obviously to be reduced, and its effective anthraquinone content also obviously improves than the palladium catalyst effective anthraquinone content that does not soak.
Embodiment:
Below the specific embodiment of the present invention is elaborated:
The method of hydrogen dioxide solution production by anthraquinone process of the present invention, be on the basis of prior art, carry out improved, the difference of itself and prior art is that the disappear softening of quenching is handled to palladium catalyst, is about to palladium catalyst and immerses in anthraquinone solvent or the anthrahydroquinone solvent and soaked 2～15 hours.
Embodiment 1: a kind of method of hydrogen dioxide solution production by anthraquinone process, putting into the logical hydrogen of palladium catalyst by prior art in the hydrogenation tower activates, after carry out nitrogen replacement, with immersing the heavy aromatics submergence in the palladium catalyst, soaked 8 hours, with the diethyl anthraquinone carrier by prior art, with aromatic hydrocarbons and trioctyl phosphate is solvent, be mixed with working fluid, working fluid fed in the hydrogenation tower, under via palladium-catalyzed dose the katalysis, carry out hydrogenation with hydrogen, obtain corresponding hydrogen anthraquinone solution, i.e. hydride, after hydride is fed oxidizing tower, hydrogen anthraquinone and oxygen in the hydride carry out oxidizing reaction, the hydrogen anthraquinone reverts to diethyl anthraquinone, i.e. oxidation liquid, and oxidation liquid carries out counter-current extraction through extraction tower and pure water, obtain hydrogen peroxide, after purifying treatment, make finished product again, raffinate recycles as working fluid after treatment.
Embodiment 2: a kind of method of hydrogen dioxide solution production by anthraquinone process, in the hydrogenation tower, put into palladium catalyst palladium catalyst is immersed the hot fat submergence of tricresyl phosphate, soaked 12 hours, by the logical hydrogen of prior art palladium catalyst is activated then, after carry out nitrogen replacement, by prior art is carrier with the diethyl anthraquinone, with aromatic hydrocarbons and trioctyl phosphate is solvent, be mixed with working fluid, working fluid fed in the hydrogenation tower, under via palladium-catalyzed dose the katalysis, carry out hydrogenation with hydrogen, obtain corresponding hydrogen anthraquinone solution, i.e. hydride, after hydride is fed oxidizing tower, hydrogen anthraquinone and oxygen in the hydride carry out oxidizing reaction, the hydrogen anthraquinone reverts to diethyl anthraquinone, i.e. oxidation liquid, and oxidation liquid carries out counter-current extraction through extraction tower and pure water, obtain hydrogen peroxide, after purifying treatment, make finished product again, raffinate recycles as working fluid after treatment.
Embodiment 3: a kind of method of hydrogen dioxide solution production by anthraquinone process, substantially with embodiment 1, its difference is and will immerses C in the palladium catalyst
9-C
11The mixture of high point petroleum aromatic hydrocarbons, methylnaphthalene, dimethylnaphthalene and tert.-butylbenzene soaked 2 hours.
Embodiment 4: a kind of method of hydrogen dioxide solution production by anthraquinone process, substantially with embodiment 2, its difference is to soak 15 hours immersing hydrogenation terpene pine camphor in the palladium catalyst.
Embodiment 5: a kind of method of hydrogen dioxide solution production by anthraquinone process, substantially with embodiment 1, its difference is to soak 5 hours immersing the mixture of diisobutyl carbinol(DIBC), trialkylphosphate, acetic acid methyl cyclohexane ester in the palladium catalyst.
Embodiment 6: a kind of method of hydrogen dioxide solution production by anthraquinone process, substantially with embodiment 2, its difference is to soak 10 hours immersing the mixture of tetrabutyl urea, hydrogenation terpene pine camphor in the palladium catalyst.
Embodiment 7: a kind of method of hydrogen dioxide solution production by anthraquinone process, substantially with embodiment 1, its difference is and will immerses the mixture of heavy aromatics, methylnaphthalene and tert.-butylbenzene in the palladium catalyst, soaked 9 hours.
Claims (8)
1. the method for a hydrogen dioxide solution production by anthraquinone process, its processing step activates for put into the logical hydrogen of palladium catalyst in the hydrogenation tower, after carry out nitrogen replacement, the working fluid of being prepared is fed in the hydrogenation tower, under via palladium-catalyzed dose the katalysis, carry out hydrogenation with hydrogen, obtain corresponding hydride, after hydride is fed oxidizing tower, the oxidation liquid of gained carries out counter-current extraction through extraction tower and pure water after the hydride oxidation, obtains hydrogen peroxide, again after purifying treatment, make finished product, raffinate recycles as working fluid after treatment, it is characterized in that the disappear softening of quenching of described palladium catalyst is handled.
2. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 1, it is characterized in that palladium catalyst disappeared, to quench that softening handles be palladium catalyst to be immersed soak 2～15 hours in the solvent.
3. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 2 is characterized in that described solvent is anthraquinone solvent or anthrahydroquinone solvent.
4. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 3 is characterized in that described anthraquinone solvent is the hot fat of heavy aromatics, tricresyl phosphate, C
9-C
11The mixture of one or more in high point petroleum aromatic hydrocarbons, methylnaphthalene, dimethylnaphthalene, the tert.-butylbenzene.
5. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 3 is characterized in that described anthrahydroquinone solvent is one or more the mixture in diisobutyl carbinol(DIBC), trialkylphosphate, acetic acid methyl cyclohexane ester, tetrabutyl urea, the hydrogenation terpene pine camphor.
6. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 2 is characterized in that soaking step carries out in the described palladium catalyst immersion solvent before the activation of palladium catalyst hydrogen.
7. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 2 is characterized in that soaking step carries out in the described palladium catalyst immersion solvent behind the activation of palladium catalyst hydrogen, nitrogen replacement.
8. the method for a kind of hydrogen dioxide solution production by anthraquinone process according to claim 1 and 2 is characterized in that described palladium catalyst is sphere, bar shaped, special-shaped palladium catalyst.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173391A (en) * | 2011-01-15 | 2011-09-07 | 王继华 | Method for producing H2O2 with Pa catalytic agent in working solution containing three solvents |
| CN103663385A (en) * | 2012-09-21 | 2014-03-26 | 中国石油化工股份有限公司 | Method and device of producing hydrogen peroxide |
| CN106829872A (en) * | 2017-02-10 | 2017-06-13 | 钦州学院 | The preparation method of hydrogen peroxide |
| CN110294460A (en) * | 2019-06-28 | 2019-10-01 | 平湖石化有限责任公司 | A kind of dicyandiamide solution of the complete acid hydrogen-peroxide working solution of anthraquinone production |
| CN110436418A (en) * | 2019-09-23 | 2019-11-12 | 扬州荣祥科技发展有限公司 | A kind of technique of hydrogen dioxide solution production by anthraquinone process |
| CN110441465A (en) * | 2019-07-22 | 2019-11-12 | 鲁西催化剂有限公司 | A kind of anthraquinone hydrogenation catalyst selective evaluation device and evaluation method |
| CN112456448A (en) * | 2020-11-23 | 2021-03-09 | 安徽国泰化工有限公司 | Novel process for producing hydrogen peroxide by anthraquinone method |
| WO2022078427A1 (en) * | 2020-10-14 | 2022-04-21 | 中国石油化工股份有限公司 | Method and system for preparing hydrogen peroxide |
| CN114906821A (en) * | 2022-06-17 | 2022-08-16 | 贵州赛邦科技发展有限公司 | Method for producing hydrogen peroxide by full acidity |
| CN116281870A (en) * | 2023-02-14 | 2023-06-23 | 扬州荣祥科技发展有限公司 | Process for producing hydrogen peroxide by anthraquinone method |
-
2007
- 2007-11-02 CN CNB2007101130820A patent/CN100540460C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173391A (en) * | 2011-01-15 | 2011-09-07 | 王继华 | Method for producing H2O2 with Pa catalytic agent in working solution containing three solvents |
| CN103663385A (en) * | 2012-09-21 | 2014-03-26 | 中国石油化工股份有限公司 | Method and device of producing hydrogen peroxide |
| CN106829872A (en) * | 2017-02-10 | 2017-06-13 | 钦州学院 | The preparation method of hydrogen peroxide |
| CN106829872B (en) * | 2017-02-10 | 2019-12-27 | 中国石油化工股份有限公司 | Process for preparing hydrogen peroxide |
| CN110294460A (en) * | 2019-06-28 | 2019-10-01 | 平湖石化有限责任公司 | A kind of dicyandiamide solution of the complete acid hydrogen-peroxide working solution of anthraquinone production |
| CN110441465A (en) * | 2019-07-22 | 2019-11-12 | 鲁西催化剂有限公司 | A kind of anthraquinone hydrogenation catalyst selective evaluation device and evaluation method |
| CN110436418A (en) * | 2019-09-23 | 2019-11-12 | 扬州荣祥科技发展有限公司 | A kind of technique of hydrogen dioxide solution production by anthraquinone process |
| WO2022078427A1 (en) * | 2020-10-14 | 2022-04-21 | 中国石油化工股份有限公司 | Method and system for preparing hydrogen peroxide |
| CN112456448A (en) * | 2020-11-23 | 2021-03-09 | 安徽国泰化工有限公司 | Novel process for producing hydrogen peroxide by anthraquinone method |
| CN114906821A (en) * | 2022-06-17 | 2022-08-16 | 贵州赛邦科技发展有限公司 | Method for producing hydrogen peroxide by full acidity |
| CN116281870A (en) * | 2023-02-14 | 2023-06-23 | 扬州荣祥科技发展有限公司 | Process for producing hydrogen peroxide by anthraquinone method |
| CN116281870B (en) * | 2023-02-14 | 2023-10-13 | 江苏中煦科技有限公司 | Process for producing hydrogen peroxide by anthraquinone method |
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