CN106629614A - Solvent system in process of producing hydrogen peroxide with anthraquinone method and application of solvent system - Google Patents
Solvent system in process of producing hydrogen peroxide with anthraquinone method and application of solvent system Download PDFInfo
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- CN106629614A CN106629614A CN201510729313.5A CN201510729313A CN106629614A CN 106629614 A CN106629614 A CN 106629614A CN 201510729313 A CN201510729313 A CN 201510729313A CN 106629614 A CN106629614 A CN 106629614A
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Abstract
The invention provides a solvent system in a process of producing hydrogen peroxide with an anthraquinone method. The solvent system is prepared from the following components in percentage by volume: 65 percent to 80 percent of heavy aromatic hydrocarbon, 5 percent to 15 percent of trioctyl phosphate, 5 percent to 15 percent of diisobutylcarbinol and 5 percent to 15 percent of 2-phenylethanol. According to the solvent system provided by the invention, the raw materials are convenient to obtain; the solvent system is prepared into a working solution; compared with a three-component solvent system containing the heavy aromatic hydrocarbon, the trioctyl phosphate and the diisobutylcarbinol in the prior art, the solvent system has the advantages that the solubility of anthraquinone in the working solution is improved; meanwhile, the solubility of oxanthranol can be improved; based on the advantages, the solvent system has a better hydrogen effect under a 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.
CN103303871A discloses a kind of working solution of Pd-catalyst In Fixed Bed legal system hydrogen peroxide and preparation method thereof, and, for amyl anthraquinone and the mixture or amyl anthraquinone of 2- EAQs, the solvent for adopting is for C for adopt plus hydrogen carrier9-C10Benzene series organic matter and esters or tetrabutyl urea or one or more the mixture in diisobutyl carbinol (DIBC).Addition mainly emphasize in anthraquinone solubility and hydrogenation efficiency, but patent or carrier amyl anthraquinone is improve, the solubility of anthraquinone is improve.But the production cost of amyl anthraquinone is of a relatively high, the production cost of hydrogen peroxide is improve.
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 dicyandiamide solution, its component raw material is easy to get, dicyandiamide solution is applied in working solution, improve the solubility of anthraquinone, hydrogenation efficiency is improve, is had 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
65%～80%
Trioctyl phosphate 5% ~ 15%
Diisobutyl carbinol (DIBC) 5% ~ 15%
2 phenylethyl alcohol 5% ~ 15%.
Further, the dicyandiamide solution includes the component of volumes below percentage：
Heavy aromatics
70%～75%
Trioctyl phosphate 8% ~ 12%
Diisobutyl carbinol (DIBC) 8% ~ 12%
2 phenylethyl alcohol 8% ~ 12%.
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 150～180 g/l, and the hydrogen effect of working solution is more than 10 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；Heavy aromatics, trioctyl phosphate are compared with three component solvent systems of diisobutyl carbinol (DIBC) in prior art, the dicyandiamide solution of the present invention improves solubility of the anthraquinone in working solution, the solubility of hydrogen anthraquinone can be improved simultaneously, based on more than some, 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：Diisobutyl carbinol (DIBC)：2 phenylethyl alcohol=70：10：12：8（Volume ratio）For the liquid medium that works, effective anthraquinone（2- EAQs and 2- ethyl tetrahydro-anthraquinones）Solubility is 170 g/l.Hydrogenation temperature is 50 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 10h-1, hydrogen liquor ratio is 6：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa.Hydrogen effect is 10.64 g/l
Embodiment 2
With heavy aromatics：Trioctyl phosphate：Diisobutyl carbinol (DIBC)：2 phenylethyl alcohol=70：12：8：10（Volume ratio）For the liquid medium that works, effective anthraquinone（2- EAQs and 2- ethyl tetrahydro-anthraquinones）Solubility is 160 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.30MPa, and air speed is 15h-1, hydrogen liquor ratio is 6：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa.Hydrogen effect is 10.26 g/l.
Comparative example 1
With heavy aromatics：Trioctyl phosphate=75：25（Volume ratio）For the liquid medium that works, effective anthraquinone（2- EAQs and 2- ethyl tetrahydro-anthraquinones）Solubility is 129 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25
MPa, 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 6.43 g/l.
Comparative example 2
With heavy aromatics：Trioctyl phosphate=50：50（Volume ratio）For the liquid medium that works, effective anthraquinone（2- EAQs and 2- ethyl tetrahydro-anthraquinones）Solubility is 105 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25
MPa, air speed is 10h-1, hydrogen liquor ratio is 6：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.15 MPa.Hydrogen effect is 5.39 g/l.
Comparative example 3
With heavy aromatics：Trioctyl phosphate：Diisobutyl carbinol (DIBC)=70：20：10（Volume ratio）For the liquid medium that works, effective anthraquinone（2- EAQs and 2- ethyl tetrahydro-anthraquinones）Solubility is 165 g/l.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25MPa, and air speed is 10h-1, hydrogen liquor ratio is 6：1.Oxidizing temperature is 50 DEG C, and oxidative pressure is 0.20MPa.Hydrogen effect is 9.16 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 65%～80%
Trioctyl phosphate 5% ~ 15%
Diisobutyl carbinol (DIBC) 5% ~ 15%
2 phenylethyl alcohol 5% ~ 15%.
2. dicyandiamide solution according to claim 1, it is characterised in that：The dicyandiamide solution includes the component of volumes below percentage：
Heavy aromatics 70%～75%
Trioctyl phosphate 8% ~ 12%
Diisobutyl carbinol (DIBC) 8% ~ 12%
2 phenylethyl alcohol 8% ~ 12%.
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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2975033A (en) * | 1956-11-24 | 1961-03-14 | Fmc Corp | Process for preparation of hydrogen peroxide |
| CN101032699A (en) * | 2006-03-10 | 2007-09-12 | 中国石油化工股份有限公司 | Catalyst support added with hydrogen, peroxide catalyst produced by anthraquinone method and the producing process |
| CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
-
2015
- 2015-11-02 CN CN201510729313.5A patent/CN106629614A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2975033A (en) * | 1956-11-24 | 1961-03-14 | Fmc Corp | Process for preparation of hydrogen peroxide |
| CN101032699A (en) * | 2006-03-10 | 2007-09-12 | 中国石油化工股份有限公司 | Catalyst support added with hydrogen, peroxide catalyst produced by anthraquinone method and the producing process |
| CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
Non-Patent Citations (1)
| Title |
|---|
| 辽宁省石油化学工业厅编: "2-乙基蒽醌", 《辽宁化工产品大全》 * |
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