CN106629617B - Dicyandiamide solution and its application in hydrogen dioxide solution production by anthraquinone process working solution - Google Patents
Dicyandiamide solution and its application in hydrogen dioxide solution production by anthraquinone process working solution Download PDFInfo
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- CN106629617B CN106629617B CN201510729678.8A CN201510729678A CN106629617B CN 106629617 B CN106629617 B CN 106629617B CN 201510729678 A CN201510729678 A CN 201510729678A CN 106629617 B CN106629617 B CN 106629617B
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- anthraquinone
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- dicyandiamide
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Abstract
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%.Dicyandiamide solution component raw material of the invention is easy to get, and is configured to working solution with dicyandiamide solution of the invention, compared with two component solvent systems of heavy aromatics in the prior art and trioctyl phosphate, under working condition of the invention, has better hydrogen effect.
Description
Technical field
The present invention relates in a kind of hydrogen dioxide solution production by anthraquinone process working solution dicyandiamide solution and its application.
Background technique
Hydrogen peroxide is a kind of important chemical products, is widely used in fields such as papermaking, chemical industry, food, environmental protection.From dioxygen
Water, which sets out, can prepare many valuable chemical products, as inorganic peroxy acid and its salt, epoxides, organic peroxide with
And significant chemical reaction intermediate product.Hydrogen peroxide has in organic synthesis than other as a kind of weaker oxidant
The much higher selectivity of oxidant.Hydrogen peroxide is used as bleaching agent in textile industry and paper-making industry, and oxidation is used as in chemical industry synthesis
Agent is used as disinfectant and fungicide in food and medicine industry, can be used for handling toxic wastewater in environmental protection, wherein handling
At most and it is most useful that sulfide, cyanide and phenolic compound.Hydrogen peroxide can also be used to handle poisonous fume, such as SO2、
NO and H2S etc..Also it is used for the organic pollutant oxidative degradation in water body.Hydrogen peroxide final reacting product itself is water,
Secondary pollution is not generated, is a kind of excellent green industry raw material and disinfectant.In recent years, as hydrogen peroxide is environmentally friendly and other
The demand of the exploitation of aspect new opplication, hydrogen peroxide increasingly increases.
Hydrogen peroxide preparation method mainly has: electrolysis method, air cathode method, anthraquinone, hydrogen-oxygen direct synthesis technique, methylbenzyl
With carbon monoxide production peroxide passivation etc. in alcohol oxidizing process, isopropanol oxidation method, fuel cell method and aqueous solution.Wherein, anthracene
Quinone method is since its technology is advanced, production scale is big, high degree of automation, cost and that low energy consumption, the three wastes are easy to administer etc. is excellent
Point, relatively other methods have greater advantage.
In hydrogen dioxide solution production by anthraquinone process technique, working solution is mainly by the solvent group of working material and dissolution working material
At.The production capacity of the property of solvent not only direct determination device, but also to the efficiency of hydrogenation, oxidation and extracting operation process,
The degradation of effective anthraquinone has larger impact.Therefore, it for the selection of solvent, generally requires it to have and energy is dissolved to working material
Power is strong, and chemical stability is good, and the solubility in water and hydrogen peroxide is small, and obvious with water stratification, viscosity is small, and it is excellent that toxicity is low etc.
Point.In general, solvent is typically all and is formed by two kinds of organic solvent mixed preparings, a kind of mainly as the molten of anthraquinone
Agent, another solvent mainly as hydrogen anthraquinone.Anthraquinone solvent mainly uses C in domestic hydrogen peroxide unit9Heavy aromatics,
Wherein containing trimethylbenzene, the first and second benzene, propyl benzene and isomers of indenes etc.；Hydrogen anthraquinone solvent mostly uses higher aliphatic, organic acid or nothing
The esters of machine acid, industrial applications has trioctyl phosphate, diisobutyl carbinol (DIBC), methyl cyclohexanol acetate etc..At present relatively
Common solvents system 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 one kind
Organic solvent system in hydrogen peroxide production process, uses C9~C10Aromatic hydrocarbons, trioctyl phosphate and 2- methylcyclohexyl acetic acid
Ester is working solution system, improves anthraquinone solubility, improves hydrogenation efficiency.CN101798065A discloses a kind of for anthraquinone
Method produces the Working solution prescription of hydrogen peroxide, and wherein solvent group becomes: heavy aromatics 65%~80%, trioctyl phosphate 5%~25%, N-
Phenyl N- ethyl benzamide 4.5%~17.8%, the solubility of working material is big, working solution medium density, and workload is big, drop
Low aq degradation rate.Although the anthraquinone solubility that three compositions system improves, improves hydrogenation efficiency, third component N- phenyl N- second
The synthesis process of yl-benzamide is complicated, and is difficult to purify, while increasing the production cost of hydrogen peroxide.
Summary of the invention
Hydrogenation efficiency and oxidation efficiency for hydrogen dioxide solution production by anthraquinone process in the prior art are not ideal enough, some components are difficult
The problems such as to obtain and is at high cost, the present invention provides a kind of five component solvent systems.Dicyandiamide solution component raw material of the invention
It is easy to get, dicyandiamide solution is applied in working solution, the solubility of anthraquinone is improved, improves hydrogenation efficiency, in Hydrogen Peroxide Production
It has broad application prospects in the process.
Technical purpose of the 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 following volumes 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 common solvent in hydrogen dioxide solution production by anthraquinone process.
Dicyandiamide solution of the invention can be applied in process for prepairng hydrogen peroxide by anthraquinone be configured to work as alkyl-anthraquinone solvent
Make liquid, alkyl-anthraquinone is as working solution carrier, and the liquid making method that works is known to those skilled in the art, wherein effective anthraquinone
The solubility of (2- ethyl hydrazine and 2- ethyl tetrahydro-anthraquinone) in working solution is 120~180 grams per liters, and the hydrogen effect of working solution is 8
~11 grams per liters.
Using above-mentioned working solution, in the presence of a catalyst, with hydrogen by the anthraquinone alkyl derivative hydrogen in working solution
Change reduction, generates hydrogen anthraquinone and obtain hydrogen peroxide, while hydrogen anthraquinone reduction then in oxidation reactor after air oxidation
For anthraquinone derivative.
Working solution of the present invention is applied to during process for prepairng hydrogen peroxide by anthraquinone, hydrogenation process process conditions are as follows: hydrogenation temperature
Degree 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；Oxidation process work
Skill condition are as follows: oxidizing temperature is 30~70 DEG C, and oxidative pressure is 0.05~0.5MPa.
Compared with prior art, the present invention has the following advantages:
It is configured to working solution with dicyandiamide solution of the invention, during producing hydrogen peroxide, in oxidation stage, 2- benzene second
Its own can be oxidized to 2- acetophenone with alcohol, and generate hydrogen peroxide in the process, and 2- acetophenone restores in hydrogenation process
For 2 phenylethyl alcohol, recycle.2 phenylethyl alcohol is added in working solution, selects suitable constituent content, makes itself and alkyl-anthraquinone
Common solubility be optimal, so as to obtain highest hydrogen effect, improve production capacity；The addition of diethyl diethylene glycol dimethyl ether can be with
Oxidation rate is improved, shortens oxidization time, while the selectivity of hydrogen peroxide can also be improved.With heavy aromatics in the prior art and phosphorus
Two component solvent systems of sour three monooctyl esters are compared, and under working condition of the invention, have better hydrogen effect.
Specific embodiment
The function and effect of the present invention is further illustrated below with reference to embodiment, but is not limited to following embodiment.
It is that hydrogenation is carried out using 10mL fixed-bed micro-reactor in evaluation experimental of the invention, it will after hydrogenation
Gained sample carries out oxidation 1 hour using 50 DEG C of air, then is extracted four times with separatory funnel, detects the content of wherein hydrogen peroxide.
Hydrogen peroxide content detection uses permanganimetric method.Catalyst is using the Pd/Al routinely prepared2O3Catalyst.Catalyst particle size
0.4mm-0.5mm, hole hold 0.6cm3/g-0.7cm3/ g, specific surface area 150m2/g-180m2/ g, Pd content are 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) be
Work liquid medium, and 2- ethyl hydrazine solubility is 120 grams per liters.Hydrogenation temperature is 50 DEG C, hydrogenation pressure 0.25MPa, and air speed is
5h-1, hydrogen liquor ratio is 12:1.Oxidizing temperature is 50 DEG C, oxidative pressure 0.20MPa.Hydrogen effect is 8.87 grams per liters.
Embodiment 2
With heavy aromatics: trioctyl phosphate: benzyl carbinol: diethyl diethylene glycol dimethyl ether: acetic acid=60:15:12:12:1(volume ratio) be
Work liquid medium, and 2- ethyl hydrazine solubility is 170 grams per liters.Hydrogenation temperature is 55 DEG C, hydrogenation pressure 0.30MPa, and air speed is
5h-1, hydrogen liquor ratio is 10:1.Oxidizing temperature is 55 DEG C, oxidative pressure 0.20MPa.Hydrogen effect is 10.69 grams per liters.
Comparative example 1
With heavy aromatics: trioctyl phosphate=75:25(volume ratio) it is work liquid medium, 2- ethyl hydrazine solubility is 129
Grams per liter.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25 MPa, air speed 5h-1, hydrogen liquor ratio is 12:1.Oxidizing temperature is 50
DEG C, oxidative pressure 0.20MPa.Hydrogen effect is 7.20 grams per liters.
Comparative example 2
With heavy aromatics: trioctyl phosphate=50:50(volume ratio) it is work liquid medium, 2- ethyl hydrazine solubility is 98
Grams per liter.Hydrogenation temperature is 55 DEG C, and hydrogenation pressure is 0.25 MPa, air speed 10h-1, hydrogen liquor ratio is 15:1.Oxidizing temperature is 50
DEG C, oxidative pressure is 0.15 MPa.Hydrogen effect is 5.10 grams per liters.
Comparative example 3
Working solution is prepared according to embodiment 3 in CN1552618A, 2- ethyl hydrazine solubility is 154 grams per liters.Hydrogenation temperature
It is 55 DEG C, hydrogenation pressure is 0.25 MPa, air speed 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 grams per liters.
Claims (4)
1. the dicyandiamide solution in a kind of hydrogen dioxide solution production by anthraquinone process working solution, it is characterised in that: press percent by volume, the solvent
System 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 following volumes percentage
Component:
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. dicyandiamide solution described in claim 1 ~ 3 any one is used as alkyl-anthraquinone solvent in process for prepairng hydrogen peroxide by anthraquinone
Application, it is characterised in that: during process for prepairng hydrogen peroxide by anthraquinone, hydrogenation process process conditions are as follows: hydrogenation temperature is
30~80 DEG C, hydrogenation pressure is 0.2~0.5MPa, and air speed is 1~30h-1, hydrogen liquor ratio is 1:1~30:1；Oxidation process technique item
Part are as follows: oxidizing temperature is 30~70 DEG C, and oxidative pressure is 0.05~0.5MPa.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
| CN102910589A (en) * | 2012-10-17 | 2013-02-06 | 黎明化工研究设计院有限责任公司 | Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process |
| CN103496674A (en) * | 2013-10-18 | 2014-01-08 | 湖南兴鹏化工科技有限公司 | Method of preparing hydrogen peroxide from all-acid working solution system by anthraquinone process |
| CN104401944A (en) * | 2014-10-29 | 2015-03-11 | 广西田东达盛化工科技有限公司 | Preparation process of high-purity hydrogen peroxide |
| CN104445080A (en) * | 2014-12-12 | 2015-03-25 | 湖南兴鹏化工科技有限公司 | Compound type solvent system for anthraquinone method hydrogen peroxide production process |
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2015
- 2015-11-02 CN CN201510729678.8A patent/CN106629617B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037190A (en) * | 2007-04-13 | 2007-09-19 | 福州大学 | Working solution prescription and technology for preparing hydrogen peroxide by anthraquinone process |
| CN102910589A (en) * | 2012-10-17 | 2013-02-06 | 黎明化工研究设计院有限责任公司 | Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process |
| CN103193204A (en) * | 2012-10-17 | 2013-07-10 | 黎明化工研究设计院有限责任公司 | Method for improving oxidation yield of hydrogenated liquid of hydrogen peroxide prepared by utilizing anthraquinone process |
| CN103496674A (en) * | 2013-10-18 | 2014-01-08 | 湖南兴鹏化工科技有限公司 | Method of preparing hydrogen peroxide from all-acid working solution system by anthraquinone process |
| CN104401944A (en) * | 2014-10-29 | 2015-03-11 | 广西田东达盛化工科技有限公司 | Preparation process of high-purity hydrogen peroxide |
| CN104445080A (en) * | 2014-12-12 | 2015-03-25 | 湖南兴鹏化工科技有限公司 | Compound type solvent system for anthraquinone method hydrogen peroxide production process |
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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. |