CN105600755A - Working solution for producing hydrogen peroxide by anthraquinone process - Google Patents
Working solution for producing hydrogen peroxide by anthraquinone process Download PDFInfo
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- CN105600755A CN105600755A CN201610154173.8A CN201610154173A CN105600755A CN 105600755 A CN105600755 A CN 105600755A CN 201610154173 A CN201610154173 A CN 201610154173A CN 105600755 A CN105600755 A CN 105600755A
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- hydrogen peroxide
- anthraquinone
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- producing hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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Abstract
The invention provides a working solution for producing hydrogen peroxide by an anthraquinone process. The working solution comprises a mixed solvent and a working carrier, wherein the mixed solvent is prepared from the following components in percentage by volume: 50%-80% of heavy aromatics and 20%-50% of phthalic acid; and the working carrier is a mixture of alkylanthraquinone and corresponding tetralin alkylanthraquinone. The working solution for producing hydrogen peroxide by the anthraquinone process has a relatively large distribution coefficient (100-400); the amount of an extracting agent in the extraction process can be reduced; the content of hydrogen peroxide in extraction raffinate can be reduced; the yield of hydrogen peroxide can be improved; meanwhile, the height of an extraction tower can be reduced; the equipment investment cost can be reduced; and meanwhile, the working solution has relatively high anthraquinone solubility.
Description
Technical field
The invention belongs to hydrogen peroxide preparing technical field, especially relate to a kind of anthraquinone production peroxidatingHydrogen working solution.
Background technology
Hydrogen peroxide is the aqueous solution of hydrogen peroxide, due to its free of contamination feature in use, therefore quiltBe called the most clean oxidant. At present hydrogen peroxide be mainly used to prepare bleaching agent, disinfectant, deoxidier,The product such as polymerization initiator and crosslinking agent, is widely used in papermaking, weaving, medicine, chemical industry, environmental protectionEtc. industry. In recent years, the hydrogen peroxide cause of China is rapidly developed, and its production capacity is with annual 15% speedIncrease, current national production capacity has exceeded 5,000,000 tons/year (calculating with concentration 27.5%). In addition, withThe rapid popularization of hydrogen peroxide in the synthetic field of various green chemical industries, especially at hydrogen peroxide propyleneApplication in the technology such as preparing epoxypropane by epoxidation (HPPO) and green caprolactam are synthetic, makesChina's hydrogen peroxide industry has welcome new development opportunity.
At present, the industrial main stream approach of hydrogen peroxide is anthraquinone, and anthraquinone production principle can be generalDraw together as follows: be mixed with working solution with organic solvent dissolution working material (alkyl-anthraquinone), at catalyst andUnder the effect of hydrogen, anthraquinone hydrogenation reduction generates hydrogen anthraquinone, then passes through air or oxygen hydrogen oxide anthraquinoneBecome anthraquinone again, obtain hydrogen peroxide simultaneously. Utilize pure water to extract the working solution that contains hydrogen peroxideObtain hydrogen peroxide, simultaneously raffinate is working solution through filtering, returns to hydrogenation process after regeneration and proceedHydrogenation reaction.
Anthraquinone middle working solution is mainly made up of working material and mixed solvent, and working material is mainly ethylAnthraquinone, propyl group anthraquinone, amyl anthraquinone, tertiary butyl anthraquinone etc. and corresponding tetrahydrochysene derivative; Mixed solvent is logicalNormal by two kinds of dissimilar solvent compositions, wherein a kind of solvent is used for dissolving alkyl-anthraquinone, another kind of moltenAgent is used for dissolving alkyl hydrogen anthraquinone. Aromatic series, aliphatic hydro carbons or cycloalkyl hydro carbons and their mixingThing, is often used as alkyl-anthraquinone solvent, trioctyl phosphate, methyl cyclohexanol acetate, tetrabutyl urea etc.Polar solvent is often used as the solvent of alkyl hydrogen anthraquinone.
The working solution solvent that current domestic hydrogen peroxide producer is used is mainly heavy aromatics and trioctyl phosphateMixture, this dicyandiamide solution has the advantages such as anthraquinone solubility is large, viscosity-density is moderate, toxicity is little,But also showing in actual use some shortcomings part, is exactly wherein that this dicyandiamide solution is to mistakeThe distribution coefficient of hydrogen oxide is less. The different proportion work being formed by heavy aromatics and trioctyl phosphate (TOP)The distribution coefficient of making liquid is as follows:
The distribution coefficient of the different composition of table 1. working solution to hydrogen peroxide
Project | 20%top | 25%top | 30%top | 35%top | 40%top |
Distribution coefficient | 82 | 66.6 | 59 | 40.5 | 34.2 |
As can be seen from the above table, the distribution coefficient of working solution raises with the reduction of TOP content, when moltenWhen agent reaches 80:20 than (volume ratio of heavy aromatics and trioctyl phosphate), the distribution coefficient of systemReach more than 80. Because working solution distribution coefficient is low at present, cause extraction column of hydrogen peroxide extraction efficiency low,Hydrogen peroxide yield is low, and product hydrogen peroxide concentration is low. If can develop a kind of novel working solution system,Make this system there is larger distribution coefficient, can reduce Solvent quantity in extraction process, reduce raffinateMiddle content of hydrogen peroxide, improves hydrogen peroxide yield, can also reduce extraction tower height simultaneously, and minimizing is establishedStandby investment cost.
Summary of the invention
In view of this, the present invention is intended to propose a kind of hydrogen dioxide solution production by anthraquinone process working solution, this working solutionHydrogen peroxide is had to high distribution coefficient, have larger anthraquinone solubility simultaneously.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of hydrogen dioxide solution production by anthraquinone process working solution, comprises mixed solvent and working material, described mixingSolvent comprises the component of following percent by volume: heavy aromatics 50%-80%, phthalic acid 20%-50%;Described working material is the mixture of alkyl-anthraquinone and corresponding tetrahydrochysene alkyl-anthraquinone.
Further, the structural formula of described phthalic acid ester is:
Wherein, n is 1,2,3,4,5,6,7,8 or 9.
Preferably, in described mixed solvent, the percent by volume of each component is: heavy aromatics 65%-75%, neighbourPhthalic acid 25%-35%.
Further, the mixture of described alkyl-anthraquinone and corresponding tetrahydrochysene alkyl-anthraquinone is in working solutionSolubility is 120-150g/L.
Further, described heavy aromatics is C9-C10Heavy aromatics.
With respect to prior art, hydrogen dioxide solution production by anthraquinone process of the present invention has following excellent with working solutionGesture:
Producing hydrogen peroxide by using anthraquinone method working solution of the present invention has larger distribution coefficient(100-400), can reduce Solvent quantity in extraction process, reduce content of hydrogen peroxide in raffinate,Improve hydrogen peroxide yield, can also reduce extraction tower height, reduce equipment investment expense, simultaneously simultaneouslyThis working solution has larger anthraquinone solubility.
Detailed description of the invention
Unless otherwise indicated, term used herein all has conventional containing of understanding of those skilled in the artJustice, for the ease of understanding the present invention, has carried out following definitions by terms more used herein.
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
Working solution compound method is as follows: mixed solvent: heavy aromatics 50% (v/v), phthalic acid fourthEster 50% (v/v); Working material: total anthraquinones content 120g/L, wherein 2-EAQ 110g/L,2-ethyl tetrahydro-anthraquinone 10g/L.
Embodiment 2
Working solution compound method is as follows: mixed solvent: heavy aromatics 60% (v/v), phthalic acid pentaEster 40% (v/v); Working material: total anthraquinones content 130g/L, wherein 2-EAQ 100g/L,2-ethyl tetrahydro-anthraquinone 30g/L.
Embodiment 3
Working solution proportioning is as follows: mixed solvent: heavy aromatics 65% (v/v), the own ester 35% of phthalic acid(v/v); Working material: total anthraquinones content 150g/L, wherein 2-EAQ 90g/L, 2-ethyl fourHydrogen anthraquinone 60g/L.
Embodiment 4
Working solution proportioning is as follows: mixed solvent: heavy aromatics 70% (v/v), O-phthalic heptyl heptylate 30%(v/v); Working material: total anthraquinones content 150g/L, wherein 2-EAQ 80g/L, 2-ethyl fourHydrogen anthraquinone 70g/L.
Embodiment 5
Working solution proportioning is as follows: mixed solvent: heavy aromatics 75% (v/v), O-phthalic heptyl heptylate 25%(v/v); Working material: total anthraquinones content 140g/L, wherein 2-EAQ 50g/L, 2-ethyl fourHydrogen anthraquinone 90g/L.
Embodiment 6
Working solution proportioning is as follows: mixed solvent: heavy aromatics 80% (v/v), O-phthalic heptyl heptylate 20%(v/v); Working material: total anthraquinones content 140g/L, wherein 2-EAQ 20g/L, 2-ethyl fourHydrogen anthraquinone 120g/L.
Embodiment 7
Working solution proportioning is as follows: mixed solvent: heavy aromatics 80% (v/v), octyl phthalate 20%(v/v); Working material: total anthraquinones content 150g/L, wherein 2-EAQ 30g/L, 2-ethyl fourHydrogen anthraquinone 120g/L.
Embodiment 8
Working solution proportioning is as follows: mixed solvent: heavy aromatics 75% (v/v), phthalic acid ester in the ninth of the ten Heavenly Stems 25%(v/v); Working material: total anthraquinones content 150g/L, wherein 2-EAQ 140g/L, 2-ethylTetrahydro-anthraquinone 10g/L.
Embodiment 9
Working solution proportioning is as follows: mixed solvent: heavy aromatics 75% (v/v), phthalic acid ester in the last of the ten Heavenly stems 25%(v/v); Working material: total anthraquinones content 150g/L, wherein 2-EAQ 80g/L, 2-ethyl fourHydrogen anthraquinone 70g/L.
The working solution that embodiment 1-9 is obtained carry out hydrogen peroxide distribution coefficient measure, concrete grammar asUnder:
(1) test condition:
Temperature 50 C, mixing time 30min, work liquid measure 50ml, working solution and hydrogen peroxide volumeThan 1:1, stratification time 90min.
(2) concrete determination step:
Get 50ml working solution to be measured in 250ml round-bottomed flask, add isopyknic hydrogenperoxide steam generator,By controlling water bath with thermostatic control temperature, in assurance device, temperature is always 50 DEG C. Start stirring, stir 30min,Then, the working solution in device and hydrogenperoxide steam generator are moved in 500ml separatory funnel, leave standstill 90min,Concentration of hydrogen peroxide in sample analysis work liquid phase and water respectively, calculates according to following distribution coefficient definitionDistribution coefficient:
Concentration of hydrogen peroxide in concentration of hydrogen peroxide/working solution in distribution coefficient=water
The test result obtaining is in table 2:
The distribution coefficient of the hydrogen peroxide of table 2 working solution
Sequence number | Distribution coefficient |
Embodiment 1 | 102 |
Embodiment 2 | 125 |
Embodiment 3 | 156 |
Embodiment 4 | 220 |
Embodiment 5 | 330 |
Embodiment 6 | 350 |
Embodiment 7 | 350 |
Embodiment 8 | 380 |
Embodiment 9 | 380 |
Data from upper table can find out, the working solutions of different compositions are carried the distribution coefficient of hydrogen peroxideHigh to 100-400, can reduce Solvent quantity in extraction process, reduce content of hydrogen peroxide in raffinate,Improve hydrogen peroxide yield, can also reduce extraction tower height, reduce equipment investment expense, have simultaneouslyMarket application foreground.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all at thisWithin the spirit and principle of invention, any amendment of doing, be equal to replacement, improvement etc., all should be included inWithin protection scope of the present invention.
Claims (5)
1. a producing hydrogen peroxide by using anthraquinone method working solution, is characterized in that: described working solution comprisesMixed solvent and working material, described mixed solvent comprises the component of following percent by volume: heavy aromatics50%-80%, phthalic acid 20%-50%; Described working material is alkyl-anthraquinone and corresponding tetrahydrochysene alkylThe mixture of anthraquinone.
2. producing hydrogen peroxide by using anthraquinone method working solution according to claim 1, is characterized in that:The structural formula of described phthalic acid ester is:
Wherein, n is 1,2,3,4,5,6,7,8 or 9.
3. producing hydrogen peroxide by using anthraquinone method working solution according to claim 1 and 2, its featureBe: in described mixed solvent, the percent by volume of each component is: heavy aromatics 65%-75%, O-phthalicAcid 25%-35%.
4. producing hydrogen peroxide by using anthraquinone method working solution according to claim 3, is characterized in that:The solubility of the mixture of described alkyl-anthraquinone and corresponding tetrahydrochysene alkyl-anthraquinone in working solution is120-150g/L。
5. producing hydrogen peroxide by using anthraquinone method working solution claimed in claim 3, is characterized in that: instituteStating heavy aromatics is C9-C10Heavy aromatics.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106044720A (en) * | 2016-05-30 | 2016-10-26 | 中国天辰工程有限公司 | Novel organic solvent system for hydrogen peroxide production |
CN107539956A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Dicyandiamide solution, working solution and the application of hydrogen dioxide solution production by anthraquinone process |
CN109534429A (en) * | 2018-11-20 | 2019-03-29 | 黎明化工研究设计院有限责任公司 | Sewerage pretreatment method in a kind of process for prepairng hydrogen peroxide by anthraquinone |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106044720A (en) * | 2016-05-30 | 2016-10-26 | 中国天辰工程有限公司 | Novel organic solvent system for hydrogen peroxide production |
CN107539956A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Dicyandiamide solution, working solution and the application of hydrogen dioxide solution production by anthraquinone process |
CN107539956B (en) * | 2016-06-23 | 2019-10-15 | 中国石油化工股份有限公司 | Dicyandiamide solution, working solution and the application of hydrogen dioxide solution production by anthraquinone process |
CN109534429A (en) * | 2018-11-20 | 2019-03-29 | 黎明化工研究设计院有限责任公司 | Sewerage pretreatment method in a kind of process for prepairng hydrogen peroxide by anthraquinone |
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