CN1295143C - Operation process for hydrogenation reaction of anthraquinone work liquid during hydrogen perioxide production - Google Patents
Operation process for hydrogenation reaction of anthraquinone work liquid during hydrogen perioxide production Download PDFInfo
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- CN1295143C CN1295143C CNB2005100162859A CN200510016285A CN1295143C CN 1295143 C CN1295143 C CN 1295143C CN B2005100162859 A CNB2005100162859 A CN B2005100162859A CN 200510016285 A CN200510016285 A CN 200510016285A CN 1295143 C CN1295143 C CN 1295143C
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- anthraquinone
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- working solution
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- hydrogen peroxide
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Abstract
The present invention relates to an operating method of hydrogenization reaction of anthraquinone working solution in hydrogen peroxide production, which belongs to a technology for producing hydrogen peroxide by an anthraquinone method. The method adopts a fixed bed reactor, the inner part of which is provided with a Pd/Al2O3 catalyst, and anthraquinone working solution and hydrogen gas are added from the top of the reactor. The operation method is characterized in that the hydrogen gas is continuously added, the anthraquinone working solution is periodically added, the period is from 10 to 400s, the circular fission degree is from 0.1 to 0.9, the operation temperature of the reactor is from 40 to 70 DEG C, and the operation pressure is from 101.3 to 400.0kPa. The present invention has the advantages of easy control of operating condition, reactor efficiency increase, and obvious improvement of reaction conversion rate and reaction selectivity. Compared with a continuous feeding operating method, the conversion rate of the anthraquinone working solution can be improved by more than 5% and can reach 67.5%, and the effective anthraquinone degradation rate can be reduced by more than 9.5% and can reach more than 3%.
Description
Technical field
The present invention relates to the working method of anthraquinone working solution hydrogenation in a kind of hydrogen peroxide manufacture.Belong to the process for prepairng hydrogen peroxide by anthraquinone technology.
Background technology
The production technology of hydrogen peroxide mainly is anthraquinone derivative autoxidation method (being called for short anthraquinone).Anthraquinone typical chemical equation is seen (1) and (2).
R is an alkyl in the formula
Reaction process be in the presence of catalyzer with hydrogen with the alkyl-anthraquinone hydrogenation in the working fluid (described working fluid is the solution that alkyl-anthraquinone is dissolved in suitable organic solvent), generate corresponding alkyl hydrogen anthraquinone (seeing reaction formula 1).Hydrogen anthraquinone in the solvent and catalyst separating are after oxidation generates hydrogen peroxide, and the hydrogen anthraquinone restores and is anthraquinone (seeing reaction formula 2) simultaneously.Hydrogen peroxide in the last water extraction organic solvent obtains aqueous hydrogen peroxide solution.
Wherein the anthraquinone working solution hydrogenation carries out in fixed-bed reactor, is filled with beaded catalyst in the reactor, and the working pressure of reactor is 0.2～0.3MPa, and service temperature is 50～70 ℃.Existing fixed bed bioreactor working method all is that hydrogen and working fluid are continuously from the fixed-bed reactor its top feed.The problem that this working method exists is to exist the part of granules of catalyst wetting in fixed-bed reactor, the axial and radial distribution uneven phenomenon of liquid phase.For the part wetting phenomena of granules of catalyst, must overcome gas-liquid and liquid-solid resistance to mass transfer in the wetted portions gas phase; In wetted portions not, the easier generation of gas phase is effectively transmitted, and therefore speed of reaction improves, and the selectivity that also causes simultaneously reacting reduces.Liquid phase axle, radial distribution uneven phenomenon then cause the local utilising efficiency of reactor low.The long and is the local nonwetting of the wetting or reactor because of the granules of catalyst part, and reaction conversion ratio and selectivity are all low, and the effective anthraquinone degraded is serious, thereby has restricted the raising of throughput.
Summary of the invention
The object of the present invention is to provide the working method of anthraquinone working solution hydrogenation in a kind of hydrogen peroxide manufacture, this method operational condition is easily controlled, and has improved reactor efficiency, can significantly improve the transformation efficiency and the selectivity of reaction simultaneously.
The present invention is realized by following technical proposals, the working method of anthraquinone working solution hydrogenation in a kind of hydrogen peroxide manufacture, and this method adopts fixed-bed reactor, filling Pd/Al in the reactor
2O
3Catalyzer, anthraquinone working solution and hydrogen add from reactor head, and the operating characteristics of this method is that hydrogen adds continuously, and the anthraquinone working solution cycle adds, and the cycle is 10～400s, circulating fissionability (feed time with operational cycle ratio) is 0.1～0.9; The service temperature of reactor is 40～70 ℃, and working pressure is 101.3～400.0kPa.
The above-mentioned joining day in anthraquinone working solution cycle is 60s, circulating fissionability 0.5～0.75,50～65 ℃ of the service temperatures of reactor, the working pressure 250～300kPa of reactor.
Realize above-mentioned anthraquinone working solution periodically the time controller in the feed control system adopt time counter, or electromagnetism time controller, or other times monitoring instrument, computer program; Controlled valve member is a magnetic valve, or pneumavalve, or motorized valve, or other controlled valves.
The invention has the advantages that: in the half period of not charging of liquid phase, gas phase directly contacts with catalyzer, the concentration of the gas-phase reaction substrate concentration of catalyst surface during more near vapor liquid equilibrium, thus gaseous component is accumulated in a large number at catalyst surface; In the half period of liquid phase feeding, high liquid phase flow can significantly improve the wetting efficiency of catalyzer, and the gaseous component of accumulation and liquid phase feeding are reacted rapidly, takes away and replace original static liquid holdup simultaneously.Consequently, speed of reaction, selectivity, catalyst utilization improve.Implement simply, operational condition is easily controlled, and the efficient height can significantly improve the transformation efficiency and the selectivity of reactor.Adopt fixed-bed reactor working method of the present invention to compare with the continuously feeding working method, continuously feeding working method anthraquinone working solution transformation efficiency is 61.5%, adopt reactor working method anthraquinone working solution transformation efficiency of the present invention to reach 67.5%, the effective anthraquinone degradation rate can be reduced to 3% from 12.3%.
Embodiment
Embodiment 1 reactor inside diameter is φ 21mm, high 650mm, Pd/Al
2O
3The catalyzer diameter is 1.9mm, and equal flow is 10mL/min during working fluid, and the flow of hydrogen is 45mL/min, and the reactor service temperature is 60 ℃, and pressure is 300kPa.The result of hydrogenation is as shown in table 1.
Table 1 continuously feeding and cycle charging reactor performance are relatively
| Working method | Operational cycle s | Feed time s | Transformation efficiency % | Anthraquinone degradation rate % |
| Continuously feeding | ---- | ---- | 61.5 | 12.3 |
| The cycle charging | 60 | 30 | 67.5 | 3 |
| The cycle charging | 60 | 45 | 63.0 | 8 |
Embodiment 2 adopts above-mentioned same reactor, and equal flow is 5mL/min during working fluid, and the flow of hydrogen is 45mL/min, and the reactor service temperature is 60 ℃, and pressure is 250kPa.Continuously feeding and cycle charging fixed-bed reactor performance are relatively, and be as shown in table 2.
Table 2 continuously feeding and cycle charging reactor performance are relatively
| Working method | Operational cycle s | Feed time s | Transformation efficiency % | Anthraquinone degradation rate % |
| Continuously feeding | ---- | ---- | 57.5 | 4.0 |
| The cycle charging | 60 | 30 | 65 | 2.0 |
Data adopt fixed-bed reactor working method of the present invention to carry out the anthraquinone hydrogenation reaction as can be seen from table, and the transformation efficiency and the selectivity of reactor all are significantly improved.
Claims (1)
1. the working method of anthraquinone working solution hydrogenation in the hydrogen peroxide manufacture, this method adopts fixed-bed reactor, filling Pd/Al in the reactor
2O
3Catalyzer, anthraquinone working solution and hydrogen add from reactor head, and the operating characteristics of this method is: hydrogen adds continuously, joining day in anthraquinone working solution cycle is 60s, circulating fissionability 0.5～0.75,50～65 ℃ of the service temperatures of reactor, the working pressure 250～300kPa of reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100162859A CN1295143C (en) | 2005-03-11 | 2005-03-11 | Operation process for hydrogenation reaction of anthraquinone work liquid during hydrogen perioxide production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100162859A CN1295143C (en) | 2005-03-11 | 2005-03-11 | Operation process for hydrogenation reaction of anthraquinone work liquid during hydrogen perioxide production |
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| Publication Number | Publication Date |
|---|---|
| CN1673069A CN1673069A (en) | 2005-09-28 |
| CN1295143C true CN1295143C (en) | 2007-01-17 |
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| CNB2005100162859A Expired - Fee Related CN1295143C (en) | 2005-03-11 | 2005-03-11 | Operation process for hydrogenation reaction of anthraquinone work liquid during hydrogen perioxide production |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106649A (en) * | 1986-10-03 | 1988-04-20 | 底古萨有限公司 | A kind of method for preparing hydrogen peroxide |
| US5169618A (en) * | 1992-01-13 | 1992-12-08 | Kerr-Mcgee Corporation | Process for producing hydrogen peroxide |
| US6447744B1 (en) * | 1999-11-05 | 2002-09-10 | Degussa-Huls Ag | Process for the preparation of hydrogen peroxide |
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2005
- 2005-03-11 CN CNB2005100162859A patent/CN1295143C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106649A (en) * | 1986-10-03 | 1988-04-20 | 底古萨有限公司 | A kind of method for preparing hydrogen peroxide |
| US5169618A (en) * | 1992-01-13 | 1992-12-08 | Kerr-Mcgee Corporation | Process for producing hydrogen peroxide |
| US6447744B1 (en) * | 1999-11-05 | 2002-09-10 | Degussa-Huls Ag | Process for the preparation of hydrogen peroxide |
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