CN102910589A - Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process - Google Patents
Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process Download PDFInfo
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Abstract
The invention discloses a method for improving the oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by an anthraquinone process. In an oxidation process, acid solution entering an oxidation tower is prepared by partially or totally substituting organic acid for phosphoric acid. Composite acid solution comprises, by mass, 2%-30% of the organic acid, 0-40% of phosphoric acid and the balance water, and the volume ration of the composite acid solution to the hydrogenation liquid is 1:(2-10)x10<4>. By the method, the oxidation yield of the hydrogenation liquid can be increased by more than 4%, oxidation residual liquid discharge amount is decreased by more than 40%, and H2O2 stability degree of oxidation residual liquid is increased from 43% to be more than 82%. Safety of oxidation equipment is improved by the aid of increase of the oxidation residual liquid stability degree and decrease of the oxidation residual liquid discharge amount.
Description
Technical field
The present invention relates to the method for process for prepairng hydrogen peroxide by anthraquinone, be specifically related to improve the method for hydride oxidization-hydrogenation ratio.
Background technology
The method of domestic production hydrogen peroxide is anthraquinone substantially at present, produces hydrogen peroxide by circulation hydrogenation, oxidation, extraction and the aftertreatment of working fluid.The hydride oxidization-hydrogenation ratio is an important indicator of anthraquinone preparing hydrogen peroxide technique, and its numerical value directly affects discharge of oxidization raffinate and hydrogen peroxide product yield.
At oxidation operation, generally be phosphate aqueous solution (phosphoric acid quality concentration 25%～45%) first with hydride (being organic phase) by volume 1: (5～10 * 10
4) after the mixing, entering oxidizing tower and air reaction, the hydroperoxide dissolution of generation is in oxidation solution.Because phosphoric acid is mineral acid, be dissolved in hardly hydride, and low to the hydrogen peroxide stabilizing power, cause hydride when oxidizing tower is oxidized, the hydrogen peroxide decomposition amount of generation is large, and it increases with oxidation efficiency.This is so that the interior hydride oxidization-hydrogenation ratio of oxidizing tower is low, and discharge of oxidization raffinate is large at the bottom of the tower, and hydrogen peroxide product yield is low.Content of hydrogen peroxide is high in the oxidized residual liquid, stability is low, very easily decomposes.This has also increased the danger of oxidizing tower equipment.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method that improves anthraquinone preparing hydrogen peroxide hydride oxidization-hydrogenation ratio, thereby reduces discharge of oxidization raffinate, increases hydrogen peroxide product yield, the security that improves oxidizing tower equipment.
For solving the problems of the technologies described above, technical scheme of the present invention is: at oxidation operation, the acid solution that enters oxidizing tower is partly or entirely to replace phosphoric acid formulated with organic acid.
The inventive method may further comprise the steps:
(1) organic acid, phosphoric acid, water are made into Compound-acid solution, massfraction is: organic acid is 2%～30%, and phosphoric acid is 0～40%, and all the other are water;
(2) with Compound-acid solution and hydride by volume 1: (2～10) * 10
4After fully mixing, enter oxidizing tower and oxygen-containing gas reacts, Hydrogen Peroxide.
In the described technical scheme, that organic acid is citric acid, organic phosphine acids anti-incrustation corrosion inhibitor, polycarboxylic acid dirt dispersion agent etc. is large to the hydrogen peroxide stabilizing power, a kind of or any two or more the mixture with the strong organic acid of hydride intermiscibility.
Described organic phosphine acids anti-incrustation corrosion inhibitor is hydroxy ethylidene-diphosphate (HEDP) or its sodium salt; diethylenetriamine pentamethylene phosphonic acids (DTPMPA) or its sodium salt; ethylenediamine tetramethylene phosphonic acid (EDTMPA) or its sodium salt; Amino Trimethylene Phosphonic Acid (ATMP) or its sodium salt; polyamino polyether methylene phosphonic acids (ATMP) or its sodium salt; the mixture of a kind of or any two kinds and the two or more materials such as 2-HPAA (HPAA) or its sodium salt.
The mixture of described polycarboxylic acid dirt dispersion agent a kind of or any two kinds and two or more materials for hydrolysis maleic anhydride (HPMA), maleic acid-acrylic acid copolymer (MA-AA), polyacrylic acid (PAA) or its sodium salt (molecular weight 2000-5000), poly-epoxy succinic acid (PESA) or its sodium salt, poly aspartic acid (PASP) or its sodium salt etc.
In the described technical scheme, preferred Compound-acid solution quality group becomes: organic acid is 2%～13%, and phosphoric acid is 20%～40%, and all the other are water.
Preferred Compound-acid solution quality group becomes: organic acid is 2%～7%, and phosphoric acid is 30%～40%, and all the other are water.
The invention has the beneficial effects as follows: significantly improved the stability of Hydrogen Peroxide in the oxidizing tower, reduced the hydrogen peroxide decomposition amount, thereby improved hydride oxidization-hydrogenation ratio, reduction discharge of oxidization raffinate, increased hydrogen peroxide product yield.After adopting present method, oxidization-hydrogenation ratio is increased to more than 95% by about 91% before using in the actual production operational process, can improve the oxidization-hydrogenation ratio of hydride more than 4%; Discharge of oxidization raffinate reduces more than 40%; H in the oxidized residual liquid
2O
2Stability is increased to more than 82% by about 45% before using.The raising of hydride oxidization-hydrogenation ratio can improve the yield of hydrogen peroxide product, increases the product income; The raising of oxidized residual liquid stability, the minimizing of quantity discharged have increased the security of oxidation furnaces.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
On the process for prepairng hydrogen peroxide by anthraquinone device, in the phosphoric acid solution Preparation tank ethylenediamine tetramethylene phosphonic acid, water being made into Compound-acid solution by massfraction ethylenediamine tetramethylene phosphonic acid 25%, water 75%, is the hydride by volume 1: (3 * 10 of 7.6g/L through hydrogenation liquid pump and hydrogenation efficiency
4) entering oxidizing tower and air reaction after the mixing, oxidized residual liquid is got rid of at the bottom of tower, and oxidizing reaction temperature is 50 ℃, and oxidized tail gas pressure is 0.22MPa.Experimental result sees Table 1.
Embodiment 2
On same hydrogen peroxide manufacture device, in the phosphoric acid solution Preparation tank, citric acid, phosphoric acid, water are made into Compound-acid solution by massfraction citric acid 10%, phosphoric acid 30%, water 60%, through the hydrogenation liquid pump with have and the hydride of embodiment 1 identical hydrogenation efficiency by volume 1: (5 * 10
4) enter oxidizing tower and air reaction after the mixing.Other are with embodiment 1.Experimental result sees Table 1.
Embodiment 3
On same hydrogen peroxide manufacture device, in the phosphoric acid solution Preparation tank, polyacrylic acid, phosphoric acid, water are made into Compound-acid solution by massfraction polyacrylic acid (number-average molecular weight 3000) 2%, phosphatase 24 0%, water 58%, through the hydrogenation liquid pump with have and the hydride of embodiment 1 identical hydrogenation efficiency by volume 1: (10 * 10
4) enter oxidizing tower and air reaction after the mixing.Other are with embodiment 1.Experimental result sees Table 1.
Claims (8)
1. method that improves anthraquinone preparing hydrogen peroxide hydride oxidization-hydrogenation ratio, at oxidation operation, the acid solution that enters oxidizing tower is partly or entirely to replace phosphoric acid formulated with organic acid.
2. method according to claim 1 may further comprise the steps:
(1) organic acid, phosphoric acid, water are made into Compound-acid solution, massfraction is: organic acid 2%～30%, and phosphoric acid 0～40%, all the other are water;
(2) with Compound-acid solution and hydride by volume 1: (2～10) * 10
4After fully mixing, enter oxidizing tower and oxygen-containing gas reacts, Hydrogen Peroxide.
3. method according to claim 2, described organic acid are a kind of in citric acid, organic phosphine acids anti-incrustation corrosion inhibitor or the polycarboxylic acid dirt dispersion agent or any two or more mixture.
4. method according to claim 3, described organic phosphine acids anti-incrustation corrosion inhibitor are the mixture of a kind of or any two kinds and two or more materials in hydroxy ethylidene-diphosphate or its sodium salt, diethylenetriamine pentamethylene phosphonic acids or its sodium salt, ethylenediamine tetramethylene phosphonic acid or its sodium salt, Amino Trimethylene Phosphonic Acid or its sodium salt, polyamino polyether methylene phosphonic acids or its sodium salt, 2-HPAA or its sodium salt.
5. method according to claim 3, described polycarboxylic acid dirt dispersion agent is the mixture of a kind of or any two kinds and two or more materials in hydrolysis maleic anhydride, maleic acid-acrylic acid copolymer, polyacrylic acid or its sodium salt, poly-epoxy succinic acid or its sodium salt, poly aspartic acid or its sodium salt.
6. according to method claimed in claim 5, the molecular weight of described polyacrylic acid or its sodium salt is 2000-5000.
7. described method one of according to claim 2-6, Compound-acid solution quality group becomes: organic acid 2%～13%, phosphoric acid 20%～40%, all the other are water.
8. method according to claim 7, Compound-acid solution quality group becomes: organic acid 2%～7%, phosphoric acid 30%～40%, all the other are water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210410584 CN102910589A (en) | 2012-10-17 | 2012-10-17 | Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process |
| CN201310122513.5A CN103193204B (en) | 2012-10-17 | 2013-03-29 | Method for improving oxidation yield of hydrogenated liquid of hydrogen peroxide prepared by utilizing anthraquinone process |
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| CN 201210410584 CN102910589A (en) | 2012-10-17 | 2012-10-17 | Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process |
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| CN 201210410584 Pending CN102910589A (en) | 2012-10-17 | 2012-10-17 | Method for improving oxidation yield of hydrogenation liquid in hydrogen peroxide preparation by anthraquinone process |
| CN201310122513.5A Active CN103193204B (en) | 2012-10-17 | 2013-03-29 | Method for improving oxidation yield of hydrogenated liquid of hydrogen peroxide prepared by utilizing anthraquinone process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629617A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Solvent system in working liquid for hydrogen peroxide production with anthraquinone method, and applications thereof |
| CN109490427A (en) * | 2018-09-25 | 2019-03-19 | 黎明化工研究设计院有限责任公司 | A kind of gas chromatography analysis method of three solvent working solutions of anthraquinone producing hydrogen peroxide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB669274A (en) * | 1950-03-09 | 1952-04-02 | Buffalo Electro Chem Co | Production of hydrogen peroxide by cyclic hydrogenation and oxidation of alkylated anthraquinones |
| FR2632625B1 (en) * | 1988-06-13 | 1990-09-07 | Atochem | STABILIZATION OF HYDROGEN PEROXIDE |
| DE60140939D1 (en) * | 2000-06-19 | 2010-02-11 | Akzo Nobel Nv | ND THE COMPOSITION USED THEREOF |
| BRPI0809672B1 (en) * | 2007-04-05 | 2019-01-29 | Solvay | process for the manufacture of propylene oxide or epichlorohydrin |
| WO2010109011A1 (en) * | 2009-03-27 | 2010-09-30 | Solvay Sa | Method for the production of hydrogen peroxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629617A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Solvent system in working liquid for hydrogen peroxide production with anthraquinone method, and applications thereof |
| CN106629617B (en) * | 2015-11-02 | 2019-01-25 | 中国石油化工股份有限公司 | Dicyandiamide solution and its application in hydrogen dioxide solution production by anthraquinone process working solution |
| CN109490427A (en) * | 2018-09-25 | 2019-03-19 | 黎明化工研究设计院有限责任公司 | A kind of gas chromatography analysis method of three solvent working solutions of anthraquinone producing hydrogen peroxide |
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| CN103193204B (en) | 2015-03-11 |
| CN103193204A (en) | 2013-07-10 |
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Application publication date: 20130206 |