CN106672912A - Solvent system for producing hydrogen peroxide working liquid by anthraquinone method and use thereof - Google Patents
Solvent system for producing hydrogen peroxide working liquid by anthraquinone method and use thereof Download PDFInfo
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- CN106672912A CN106672912A CN201510761509.2A CN201510761509A CN106672912A CN 106672912 A CN106672912 A CN 106672912A CN 201510761509 A CN201510761509 A CN 201510761509A CN 106672912 A CN106672912 A CN 106672912A
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Abstract
The invention discloses a solvent system for producing a hydrogen peroxide working liquid by an anthraquinone method and a use thereof. The solvent system comprises, by volume, 65% to 80% of a heavy aromatic hydrocarbon, 10% to 30% of trioctyl phosphate, 5% to 20% of 2-phenethyl alcohol and 0.5% to 5% of diethyl ether, and preferably comprises, by volume, 70% to 75% of a heavy aromatic hydrocarbon, 10% to 20% of trioctyl phosphate, 5% to 15% of 2-phenethyl alcohol and 1% to 2% of diethyl ether. The solvent system utilizes easily available components, is applied to the working fluid, improves the solubility of anthraquinone, improves the hydrogenation efficiency and has a wide application prospect in the process of hydrogen peroxide production.
Description
Technical field
The present invention relates to a kind of dicyandiamide solution of hydrogen dioxide solution production by anthraquinone process working solution and its application.
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, it is another kind of mainly as
The solvent of 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 the deficiencies in the prior art, the invention provides a kind of dicyandiamide solution of hydrogen dioxide solution production by anthraquinone process working solution and its application.The dicyandiamide solution component raw material 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 dicyandiamide solution of the hydrogen dioxide solution production by anthraquinone process working solution of the present invention, the percent by volume of each component is in dicyandiamide solution:Heavy aromatics 65%~80%, preferably 70%~75%, trioctyl phosphate 10% ~ 30%, preferably 10% ~ 20%, 2 phenylethyl alcohol 5%~20%, preferably 5%~15%, ether 0.5%-5%, preferred 1%-2%.
In working solution of the present invention, described heavy aromatics is the C commonly used in hydrogen dioxide solution production by anthraquinone process9~C10Heavy aromatic solvent, density is 0.860-0.885g/cm3。
In working solution of the present invention, described trioctyl phosphate is transparent oily liquid, and density is 0.921 ~ 0.927 g/cm3。
Present invention simultaneously provides a kind of working solution prepared by above-mentioned dicyandiamide solution, working solution carrier is alkyl-anthraquinone commonly used in the art, work liquid making method is known for those skilled in the art, wherein solubility of the 2- EAQs in working solution is 120~180 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 is prepared using work liquid and preparation method thereof well known to those skilled in the art.
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 hydrogen dioxide solution production by anthraquinone 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.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 present invention has following features:2 phenylethyl alcohol, with heavy aromatics and trioctyl phosphate mixed dissolution anthraquinone alkyl derivative, improves solubility of the anthraquinone in working solution as solvent, can be imitated with larger raising hydrogen, so as to improve production capacity.
Specific embodiment
Effect and the effect of the present invention are further illustrated with reference to embodiment, but is not limited to following examples.
The present invention is to carry out hydrogenation using 10mL fixed-bed micro-reactors, and gained sample is carried out into oxidation 1 hour 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:2 phenylethyl alcohol:Ether=70:20:9:1(Volume ratio)For the liquid medium that works, 2- EAQs solubility is 170 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 10.24 g/l
Embodiment 2
With heavy aromatics:Trioctyl phosphate:2 phenylethyl alcohol=75:19:5:1(Volume ratio)For the liquid medium that works, 2- EAQs solubility is 150 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 8.78 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 (9)
1. a kind of dicyandiamide solution of hydrogen dioxide solution production by anthraquinone process working solution, it is characterised in that:The percent by volume of each component is in dicyandiamide solution:Heavy aromatics 65%~80%, trioctyl phosphate 10% ~ 30%, 2 phenylethyl alcohol 5%~20%, ether 0.5%-5%.
2. according to the dicyandiamide solution described in claim 1, it is characterised in that:The percent by volume of each component is in dicyandiamide solution:Heavy aromatics 70%~75%, trioctyl phosphate 10% ~ 20%, 2 phenylethyl alcohol 5%~15%, ether 1%-2%.
3. according to the dicyandiamide solution described in claim 1 or 2, it is characterised in that:Described heavy aromatics is the C commonly used in hydrogen dioxide solution production by anthraquinone process9~C10Heavy aromatic solvent, density is 0.860-0.885g/cm3。
4. according to the dicyandiamide solution described in claim 1 or 2, it is characterised in that:Described trioctyl phosphate is transparent oily liquid, and density is 0.921 ~ 0.927 g/cm3。
5. the working solution that the dicyandiamide solution described in a kind of claim 1 or 2 is constituted, it is characterised in that:Solubility of the 2- EAQs in working solution is 120~180 g/l.
6. according to the working solution described in claim 5, it is characterised in that:The hydrogen effect of working solution is 8~11 g/l.
7. application of the working solution described in a kind of claim 5 during hydrogen dioxide solution production by anthraquinone process.
8. according to the application described in claim 7, it is characterised in that: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.
9. according to the application described in claim 7, it is characterised in that:Oxidizing process process conditions are:Oxidizing temperature is 30~70 DEG C, and oxidative pressure is 0.05~0.5MPa.
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Citations (4)
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---|---|---|---|---|
US2975033A (en) * | 1956-11-24 | 1961-03-14 | Fmc Corp | Process for preparation of hydrogen peroxide |
CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
CN101798065A (en) * | 2010-03-17 | 2010-08-11 | 江山市双氧水有限公司 | Formula of working liquid for hydrogen peroxide production based on anthraquinone process |
CN103588177A (en) * | 2013-11-27 | 2014-02-19 | 潍坊门捷化工有限公司 | Hydrogen peroxide working solution and its application in preparation of hydrogen peroxide |
-
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- 2015-11-11 CN CN201510761509.2A patent/CN106672912A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2975033A (en) * | 1956-11-24 | 1961-03-14 | Fmc Corp | Process for preparation of hydrogen peroxide |
CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
CN101798065A (en) * | 2010-03-17 | 2010-08-11 | 江山市双氧水有限公司 | Formula of working liquid for hydrogen peroxide production based on anthraquinone process |
CN103588177A (en) * | 2013-11-27 | 2014-02-19 | 潍坊门捷化工有限公司 | Hydrogen peroxide working solution and its application in preparation of hydrogen peroxide |
Non-Patent Citations (1)
Title |
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辽宁省石油化学工业厅编: "《辽宁化工产品大全》", 31 December 1994 * |
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