CN106629617A - Solvent system in working liquid for hydrogen peroxide production with anthraquinone method, and applications thereof - Google Patents
Solvent system in working liquid for hydrogen peroxide production with anthraquinone method, and applications thereof Download PDFInfo
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- CN106629617A CN106629617A CN201510729678.8A CN201510729678A CN106629617A CN 106629617 A CN106629617 A CN 106629617A CN 201510729678 A CN201510729678 A CN 201510729678A CN 106629617 A CN106629617 A CN 106629617A
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- anthraquinone
- hydrogen peroxide
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Abstract
The invention relates to a solvent system in a working liquid for hydrogen peroxide production with an anthraquinone method, wherein the solvent system comprises, by volume, 40-70% of heavy aromatic hydrocarbon, 5-30% of trioctyl phosphate, 10-20% of 2-phenylethanol, 10-20% of diethanol dimethyl ether, and 0.5-5% of acetic acid. According to the present invention, the raw material components of the solvent system are easy to obtain; with the application of the solvent system to prepare the working liquid, compared to the working liquid prepared from the heavy aromatic hydrocarbon and trioctyl phosphate two-component solvent system in the prior art, the working liquid prepared from the solvent system of the present invention has the good hydrogen efficiency under the production condition.
Description
Technical field
The present invention relates to the dicyandiamide solution and its application in 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.Many valuable chemical products, such as inorganic peroxy acid and its salt, epoxides, organic peroxide and significant chemical reaction intermediate product can be prepared from hydrogen peroxide.Hydrogen peroxide has the selectivity more much higher than other oxidants as a kind of weaker oxidant, in organic synthesis.Hydrogen peroxide is used as bleaching agent in textile industry and paper-making industry, it is used as oxidant in chemical industry synthesis, it is used as disinfectant and bactericide in food and medicine industry, can be used to process toxic wastewater in terms of environmental protection, wherein processes at most and it is most useful that sulfide, cyanide and phenolic compound.Hydrogen peroxide can also be used to process poisonous fume, such as SO2, NO and H2S etc..Also it is used for the organic pollution oxidative degradation in water body.Hydrogen peroxide final reacting product itself is water, does not produce secondary pollution, is a kind of excellent green industry raw material and disinfectant.In recent years, as hydrogen peroxide is in environmental protection and the exploitation of other side new opplication, the demand of hydrogen peroxide increasingly increases.
Hydrogen peroxide preparation method mainly has：With carbon monoxide production peroxide passivation etc. in electrolysis, air cathode method, anthraquinone, hydrogen-oxygen direct synthesis technique, methyl-benzyl alcohol oxidizing process, isopropanol oxidation method, fuel cell method and the aqueous solution.Wherein, it is anthraquinone due to the advantages of its technology is advanced, production scale big, high degree of automation, cost and energy consumption are low, the three wastes are easy to improvement, there is greater advantage with respect to other methods.
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 property of solvent not only direct determination device, and to the efficiency of hydrogenation, oxidation and extracting operation process, the degraded of effective anthraquinone has considerable influence.Therefore, for the selection of solvent, typically require that it has strong to working material solvability, chemical stability is good, and the solubility in water and hydrogen peroxide is little, and, viscosity is little, low toxin with water stratification substantially.Under normal conditions, solvent is typically all and is formed by two kinds of organic solvent mixed preparings, a kind of solvent mainly as anthraquinone, another kind of solvent mainly as hydrogen anthraquinone.Anthraquinone solvent mainly uses C in domestic hydrogen peroxide unit9Heavy aromatics, wherein isomers containing trimethylbenzene, the first and second benzene, propyl benzene and indenes etc.；Using the esters of higher aliphatic, organic acid or inorganic acid more than hydrogen anthraquinone solvent, industrial applications has trioctyl phosphate, diisobutyl carbinol (DIBC), methyl cyclohexanol acetate etc..At present relatively common dicyandiamide solution is heavy aromatics and trioctyl phosphate.
In order to improve the solubility of anthraquinone, also there is the working solution using 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- methylcyclohexyls acetate be working solution system, improve anthraquinone solubility, improve hydrogenation efficiency.CN101798065A discloses a kind of Working solution prescription for process for prepairng hydrogen peroxide by anthraquinone, and wherein solvent is consisted of：Heavy aromatics 65%～80%, trioctyl phosphate 5%～25%, N- phenyl N- ethyl benzamides 4.5%～17.8%, the solubility of working material is big, working solution medium density, and live load is big, reduces anthraquinone degradation rate.Although the anthraquinone solubility that three compositions system is improved, hydrogenation efficiency is improve, the building-up process of third component N- phenyl N- ethyl benzamides is complicated, and is difficult purification, while increased the production cost of hydrogen peroxide.
The content of the invention
For hydrogen dioxide solution production by anthraquinone process in prior art hydrogenation efficiency and oxidation efficiency be not ideal enough, some components are difficult to obtain and the problems such as high cost, the invention provides a kind of five component solvents system.The dicyandiamide solution component raw material of the present invention is easy to get, and dicyandiamide solution is applied in working solution, improves the solubility of anthraquinone, improves hydrogenation efficiency, has broad application prospects in hydrogen peroxide production process.
The technical purpose of the present invention is achieved through the following technical solutions：
A kind of dicyandiamide solution in hydrogen dioxide solution production by anthraquinone process working solution, by percent by volume, the dicyandiamide solution includes following components：
Heavy aromatics
40%~70%
Trioctyl phosphate
5%~30%
2 phenylethyl alcohol
10%~20%
Diethyl diethylene glycol dimethyl ether
10%~20%
Acetic acid
0.5%~5%。
Further, the dicyandiamide solution includes the component of volumes below percentage：
Heavy aromatics
55%~65%
Trioctyl phosphate
10%~20%
2 phenylethyl alcohol
10%~15%
Diethyl diethylene glycol dimethyl ether
10%~15%
Acetic acid
1%~2%。
Further, the heavy aromatics is C9~C10Heavy aromatics, be in hydrogen dioxide solution production by anthraquinone process commonly use solvent.
The dicyandiamide solution of the present invention can be applicable in process for prepairng hydrogen peroxide by anthraquinone as alkyl-anthraquinone solvent, be configured to working solution, and alkyl-anthraquinone is known as working solution carrier, work liquid making method for those skilled in the art, wherein effective anthraquinone（2- EAQs and 2- ethyl tetrahydro-anthraquinones）Solubility in working solution is 120～180 g/l, and the hydrogen effect of working solution is 8～11 g/l.
Using above-mentioned working solution, in the presence of a catalyst, with hydrogen by the anthraquinone alkyl derivative hydro-reduction in working solution, hydrogen anthraquinone is generated, then hydrogen peroxide is obtained Jing after air oxidation in oxidation reactor, while hydrogen anthraquinone reduction is anthraquinone derivative.
Working solution of the present invention is applied to during process for prepairng hydrogen peroxide by anthraquinone, 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 1：1～30：1；Oxidizing process process conditions are：Oxidizing temperature is 30～70 DEG C, and oxidative pressure is 0.05～0.5MPa.
Compared with prior art, the invention has the advantages that：
Working solution is configured to the dicyandiamide solution of the present invention, during production hydrogen peroxide, in oxidation stage, 2 phenylethyl alcohol its own can be oxidized to 2- acetophenones, and hydrogen peroxide is produced in the process, and 2- acetophenones are reduced to 2 phenylethyl alcohol in hydrogenation process, recycle.2 phenylethyl alcohol is added in working solution, suitable constituent content is selected so as to be optimal with the common solubility of alkyl-anthraquinone, so as to obtain highest hydrogen effect, production capacity is improved；The addition of diethyl diethylene glycol dimethyl ether can improve oxidation rate, shorten oxidization time, while the selectivity of hydrogen peroxide can also be improved.Heavy aromatics is compared with two component solvent systems of trioctyl phosphate in prior art, under the working condition of the present invention, with more preferable hydrogen effect.
Specific embodiment
Effect and the effect of the present invention are further illustrated with reference to embodiment, but is not limited to following examples.
It is that hydrogenation is carried out using 10mL fixed-bed micro-reactors in the evaluation experimental of the present invention, gained sample is carried out into oxidation 1 hour for 50 DEG C using air after hydrogenation, then is extracted four times with separatory funnel, the content of detection wherein hydrogen peroxide.Hydrogen peroxide content detection adopts permanganimetric method.Catalyst is using the conventional Pd/Al for preparing2O3Catalyst.Catalyst particle size 0.4mm-0.5mm, pore volume 0.6cm3/g-0.7cm3/ g, specific surface area 150m2/g-180m2/ g, Pd content is 0.25%-0.35%.
Embodiment 1
With heavy aromatics：Trioctyl phosphate：Benzyl carbinol：Diethyl diethylene glycol dimethyl ether：Acetic acid=55：20：14：10：1（Volume ratio）For the liquid medium that works, 2- EAQs solubility is 120 g/l.Hydrogenation temperature is 50 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 5h-1, hydrogen liquor ratio is 12：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa.Hydrogen effect is 8.87 g/l.
Embodiment 2
With heavy aromatics：Trioctyl phosphate：Benzyl carbinol：Diethyl diethylene glycol dimethyl ether：Acetic acid=60：15：12：12：1（Volume ratio）For the liquid medium that works, 2- EAQs solubility is 170 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.30MPa, and air speed is 5h-1, hydrogen liquor ratio is 10：1.Oxidizing temperature is 55 DEG C, and oxidative pressure is 0.20MPa.Hydrogen effect is 10.69 g/l.
Comparative example 1
With heavy aromatics：Trioctyl phosphate=75：25（Volume ratio）For the liquid medium that works, 2- EAQs solubility is 129 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25 MPa, and air speed is 5h-1, hydrogen liquor ratio is 12：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa.Hydrogen effect is 7.20 g/l.
Comparative example 2
With heavy aromatics：Trioctyl phosphate=50：50（Volume ratio）For the liquid medium that works, 2- EAQs solubility is 98 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25 MPa, and air speed is 10h-1, hydrogen liquor ratio is 15：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.15 MPa.Hydrogen effect is 5.10 g/l.
Comparative example 3
Working solution is prepared according to embodiment in CN1552618A 3,2- EAQs solubility is 154 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25 MPa, and air speed is 5h-1, hydrogen liquor ratio is 12：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20 MPa.Hydrogen effect is 8.32 g/l.
Claims (4)
1. the dicyandiamide solution in a kind of hydrogen dioxide solution production by anthraquinone process working solution, it is characterised in that：By percent by volume, the dicyandiamide solution includes following components：
Heavy aromatics
40%~70%
Trioctyl phosphate
5%~30%
2 phenylethyl alcohol
10%~20%
Diethyl diethylene glycol dimethyl ether
10%~20%
Acetic acid
0.5%~5%。
2. dicyandiamide solution according to claim 1, it is characterised in that：The dicyandiamide solution includes the component of volumes below percentage：
Heavy aromatics
55%~65%
Trioctyl phosphate
10%~20%
2 phenylethyl alcohol
10%~15%
Diethyl diethylene glycol dimethyl ether
10%~15%
Acetic acid
1%~2%。
3. dicyandiamide solution according to claim 1, it is characterised in that：The heavy aromatics is C9~C10Heavy aromatics.
4. the dicyandiamide solution described in claim 1 ~ 3 any one in process for prepairng hydrogen peroxide by anthraquinone as the application of alkyl-anthraquinone solvent, it is characterised in that：During process for prepairng hydrogen peroxide by anthraquinone, 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 1：1～30：1；Oxidizing process process conditions are：Oxidizing temperature is 30～70 DEG C, and oxidative pressure is 0.05～0.5MPa.
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| CN109675453A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of gas-liquid mixed equipment and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109675453A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of gas-liquid mixed equipment and application |
| CN109675453B (en) * | 2017-10-19 | 2021-05-04 | 中国石油化工股份有限公司 | Gas-liquid mixing equipment and application |
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Effective date of registration: 20230817 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
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