CN105621368A - Working fluid for production of hydrogen peroxide by anthraquinone process, and application thereof - Google Patents
Working fluid for production of hydrogen peroxide by anthraquinone process, and application thereof Download PDFInfo
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- CN105621368A CN105621368A CN201410603897.7A CN201410603897A CN105621368A CN 105621368 A CN105621368 A CN 105621368A CN 201410603897 A CN201410603897 A CN 201410603897A CN 105621368 A CN105621368 A CN 105621368A
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Abstract
The invention discloses a working fluid for production of hydrogen peroxide by an anthraquinone process, and application thereof. The working fluid comprises a solvent and a working fluid carrier, wherein the solvent comprises the following components by volume percentage: 50% to 80% of heavy aromatic, preferably 70% to 75%, and 20% to 50% of N-ethyl p-toluenesulfonamide, preferably 25% to 30%; and the working fluid carrier is alkyl anthraquinone. The working fluid provided by the invention adopts a two-component solvent system, so anthraquinone solubility and hydrogenation efficiency are improved; and compared with a three-component system, the two-component solvent system simplifies constitution and reduces production cost.
Description
Technical field
The present invention relates to the compound method of a kind of working solution, specifically, relate to the compound method of a kind of hydrogen dioxide solution production by anthraquinone process working solution.
Background technology
Hydrogen peroxide is a kind of important chemical products, is widely used in fields such as papermaking, chemical industry, food, environmental protection. A lot of valuable chemical products can be prepared, such as inorganic peroxy acid and salt, epoxide, organic peroxide and significant chemical reaction intermediate product from hydrogen peroxide. Hydrogen peroxide, as a kind of more weak oxidant, has the selectivity more much higher than other oxidants in organic synthesis. Hydrogen peroxide is used as bleach in textile industry and paper-making industry, it is used as oxidant in chemical industry synthesizes, food and medicine industry is used as disinfectant and antibacterial, can be used for processing toxic wastewater in environmental protection, wherein process at most and it is most useful that sulfide, cyanide and phenolic compound. Hydrogen peroxide can be additionally used in process poisonous fume, such as SO2, NO and H2S etc. Also it is used to the organic pollution oxidative degradation in water body. The final reacting product of hydrogen peroxide own is water, does not produce secondary pollution, is a kind of excellent green industry raw material and disinfectant. In recent years, along with hydrogen peroxide is in the exploitation of environmental protection and other side new opplication, the demand of hydrogen peroxide increases day by day.
Hydrogen peroxide preparation method mainly has: produce peroxide passivation etc. with carbon monoxide in electrolysis, air cathode method, anthraquinone, hydrogen-oxygen direct synthesis technique, methyl-benzyl alcohol oxidizing process, isopropanol oxidation method, fuel cell method and aqueous solution. Wherein, anthraquinone owing to its Technology is advanced, production scale is big, automaticity is high, cost and energy consumption is low, the three wastes are prone to the advantages such as improvement, other method has greater advantage relatively.
In hydrogen dioxide solution production by anthraquinone process technique, working solution is mainly made up of the solvent of working material and dissolving working material. The production capacity of the character of solvent not only direct determination device, and the efficiency to hydrogenation, oxidation and extracting operation process, the degraded of effective anthraquinone has considerable influence. Therefore, for the selection of solvent, generally requiring that it has working material solvability strong, chemical stability is good, and the dissolubility in water and hydrogen peroxide is little, and obvious with water stratification, viscosity is little, low toxin. Under normal conditions, solvent is typically all and is formed by two kinds of organic solvent mixed preparing, a kind of solvent mainly as anthraquinone, the another kind of solvent mainly as hydrogen anthraquinone. In domestic hydrogen peroxide unit, anthraquinone solvent mainly uses C9Heavy aromatics, wherein containing the isomer etc. of trimethylbenzene, the first and second benzene, propyl benzene and indenes; The esters of hydrogen anthraquinone solvent many employings high fatty alcohol, organic acid or mineral acid, industrial applications has trioctyl phosphate, diisobutyl carbinol (DIBC), methyl cyclohexanol acetate etc. Current relatively common dicyandiamide solution is heavy aromatics and trioctyl phosphate.
In order to improve the dissolubility of anthraquinone, also there is the working solution adopting three dicyandiamide solutions. CN1552618A discloses the organic solvent system in a kind of hydrogen peroxide production process, and it adopts C9~C10Aromatic hydrocarbons, trioctyl phosphate and 2-methylcyclohexyl acetate be working solution system, improve anthraquinone dissolubility, improve hydrogenation efficiency. CN101798065A discloses a kind of Working solution prescription for process for prepairng hydrogen peroxide by anthraquinone, wherein group of solvents becomes: heavy aromatics 65%��80%, trioctyl phosphate 5%��25%, N-phenyl N-ethyl benzamide 4.5%��17.8%, the dissolubility of working material is big, working solution medium density, workload is big, reduces anthraquinone degradation rate. Although the anthraquinone dissolubility that three compositions system improves, improve hydrogenation efficiency, but the addition of the 3rd component, also make mixed solvent composition more complicated, add the production cost of hydrogen peroxide simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides the working solution of a kind of hydrogen dioxide solution production by anthraquinone process and application. This working solution adopts two component solvent systems, improves anthraquinone dissolubility, improves hydrogenation efficiency, compared with three compositions system, simplifies composition, reduces production cost.
The working solution of hydrogen dioxide solution production by anthraquinone process of the present invention, including solvent and working solution carrier, wherein in solvent, the percent by volume of each component is: heavy aromatics 50%��80%, it is preferable that 70%��75%, N-ethyl para toluene sulfonamide 20%��50%, it is preferable that 25%��30%; Working solution carrier is alkyl-anthraquinone.
In working solution of the present invention, described heavy aromatics is the heavy aromatic solvent that hydrogen peroxide industry is special, and density is 0.860-0.885g/cm3��
In working solution of the present invention, 2-ethyl-anthraquinone dissolubility in working solution is 130��190 g/l, and the hydrogen effect of working solution is 8��11 g/l.
The working solution of hydrogen dioxide solution production by anthraquinone process of the present invention adopts working solution preparation method well known to those skilled in the art preparation.
Adopting above-mentioned working solution, in the presence of a catalyst, with hydrogen by the anthraquinone alkyl derivative hydro-reduction in working solution, generate hydrogen anthraquinone, then in oxidation reactor after air oxidation, obtain hydrogen peroxide, hydrogen anthraquinone reduction is anthraquinone derivative simultaneously.
Working solution of the present invention is applied to hydrogen dioxide solution production by anthraquinone process process, and hydrogenation process process conditions are: hydrogenation temperature is 30��80 DEG C, and hydrogenation pressure is 0.2��0.5MPa, and air speed is 1��30h-1, hydrogen liquor ratio is 1:1��300:1. The process conditions of oxidizing process are: oxidizing temperature is 30��70 DEG C, and oxidative pressure is 0.05��0.5MPa.
Compared with prior art, the present invention has a characteristic that when being added without three components, improves anthraquinone dissolubility in working solution, it is possible to bigger raising hydrogen effect, thus improving production capacity, reduces production cost.
Detailed description of the invention
Further illustrate effect and the effect of the present invention below in conjunction with embodiment, but be not limited to following example.
The present invention adopts 10mL fixed-bed micro-reactor to carry out hydrogenation, gained sample adopts after hydrogenation air 50 DEG C carry out oxidation 1 hour, then extracts four times with separatory funnel, detect the content of wherein hydrogen peroxide. Hydrogen peroxide content detection adopts permanganimetric method. Catalyst adopts the Pd/Al of routine preparation2O3Catalyst. Catalyst particle size 0.4-0.5mm, pore volume 0.6-0.7cm3/ g, specific surface area 150-180m2/ g, Pd content is 0.25wt%-0.35wt%.
Embodiment 1
With heavy aromatics, N-ethyl para toluene sulfonamide=75:25(volume ratio) for working solution medium, 2-ethyl-anthraquinone dissolubility is 190 g/l. Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 10h-1, hydrogen liquor ratio is 12:1. Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa. Hydrogen effect is 10.02 g/l
Embodiment 2
With heavy aromatics, N-ethyl para toluene sulfonamide=60:40(volume ratio) for working solution medium, 2-ethyl-anthraquinone dissolubility is 165 g/l. Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.30MPa, and air speed is 10h-1, hydrogen liquor ratio is 15:1. Oxidizing temperature is 55 DEG C, and oxidative pressure is 0.20MPa. Hydrogen effect is 8.53 g/l.
Comparative example 1
With heavy aromatics, trioctyl phosphate=75:25(volume ratio) for working solution medium, 2-ethyl-anthraquinone dissolubility is 129 g/l. Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 10h-1, hydrogen liquor ratio is 12:1. Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa. Hydrogen effect is 6.82 g/l.
Comparative example 2
With heavy aromatics, trioctyl phosphate=60:40(volume ratio) for working solution medium, 2-ethyl-anthraquinone dissolubility is 106 g/l. Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 10h-1, hydrogen liquor ratio is 15:1. Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.15MPa. Hydrogen effect is 5.73 g/l.
Comparative example 3
Preparing working solution according to embodiment in CN1552618A 3,2-ethyl-anthraquinone dissolubility is 154 g/l. Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 10h-1, hydrogen liquor ratio is 12:1. Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa. Hydrogen effect is 8.03 g/l.
Claims (8)
1. the working solution of a hydrogen dioxide solution production by anthraquinone process, including solvent and working solution carrier, it is characterised in that: in solvent, the percent by volume of each component is: heavy aromatics 50%��80%, it is preferable that 70%��75%, N-ethyl para toluene sulfonamide 20%��50%, it is preferable that 25%��30%; Working solution carrier is alkyl-anthraquinone.
2. the working solution described in claim 1, it is characterised in that: in solvent, the percent by volume of each component is: heavy aromatics 70%��75%, N-ethyl para toluene sulfonamide 25%��30%.
3. the working solution described in claim 1 or 2, it is characterised in that: described heavy aromatics is the heavy aromatic solvent that hydrogen peroxide industry is special, and density is 0.860-0.885g/cm3��
4. the working solution described in claim 1 or 2, it is characterised in that: 2-ethyl-anthraquinone dissolubility in working solution is 130��190 g/l.
5. the working solution described in claim 1 or 2, it is characterised in that: the hydrogen effect of working solution is 8��11 g/l.
6. the application in hydrogen dioxide solution production by anthraquinone process process of the working solution described in a claim 1 or 2.
7. the application described in claim 6, it is characterised in that: the process conditions of hydrogenation process are: hydrogenation temperature is 30��80 DEG C, and hydrogenation pressure is 0.2��0.5MPa, and air speed is 1��30h-1, hydrogen liquor ratio is 1:1��300:1.
8. the application described in claim 6, it is characterised in that: the process conditions of oxidizing process are: oxidizing temperature is 30��70 DEG C, and oxidative pressure is 0.05��0.5MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109896503A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of dicyandiamide solution and method of hydrogen dioxide solution production by anthraquinone process |
| CN111071993A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Working solution solvent system |
| TWI762710B (en) * | 2017-09-08 | 2022-05-01 | 日商三菱瓦斯化學股份有限公司 | Preparation method of working solution for hydrogen peroxide production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803063A (en) * | 1987-04-16 | 1989-02-07 | Atochem | Process for the cyclic production of hydrogen peroxide |
| CN1519193A (en) * | 2003-01-24 | 2004-08-11 | 中国石油化工股份有限公司巴陵分公司 | Application of tetra-n-butylurea in preparing hydrogen dioxide |
| CN1552618A (en) * | 2003-06-06 | 2004-12-08 | 上海苏鹏实业有限公司 | Organic flux system in hydrogen peroxide producing process |
| CN103303871A (en) * | 2013-07-08 | 2013-09-18 | 傅骐 | Working solution for producing hydrogen peroxide through stationary bed palladium catalyst process, and preparation method of working solution |
-
2014
- 2014-11-03 CN CN201410603897.7A patent/CN105621368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803063A (en) * | 1987-04-16 | 1989-02-07 | Atochem | Process for the cyclic production of hydrogen peroxide |
| CN1519193A (en) * | 2003-01-24 | 2004-08-11 | 中国石油化工股份有限公司巴陵分公司 | Application of tetra-n-butylurea in preparing hydrogen dioxide |
| CN1552618A (en) * | 2003-06-06 | 2004-12-08 | 上海苏鹏实业有限公司 | Organic flux system in hydrogen peroxide producing process |
| CN103303871A (en) * | 2013-07-08 | 2013-09-18 | 傅骐 | Working solution for producing hydrogen peroxide through stationary bed palladium catalyst process, and preparation method of working solution |
Non-Patent Citations (1)
| Title |
|---|
| 刘航等: "蒽醌法生产过氧化氢反应机理和工作液研究进展", 《工业催化》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI762710B (en) * | 2017-09-08 | 2022-05-01 | 日商三菱瓦斯化學股份有限公司 | Preparation method of working solution for hydrogen peroxide production |
| CN109896503A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of dicyandiamide solution and method of hydrogen dioxide solution production by anthraquinone process |
| CN109896503B (en) * | 2017-12-08 | 2021-10-08 | 中国石油化工股份有限公司 | Solvent system and method for producing hydrogen peroxide by anthraquinone process |
| CN111071993A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Working solution solvent system |
| CN111071993B (en) * | 2018-10-22 | 2021-06-04 | 中国石油化工股份有限公司 | Working solution solvent system |
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