CN105621369A - Method for improving oxidation yield in production of hydrogen peroxide by anthraquinone method - Google Patents
Method for improving oxidation yield in production of hydrogen peroxide by anthraquinone method Download PDFInfo
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Abstract
The invention discloses a method for improving the oxidation yield in production of hydrogen peroxide by an anthraquinone method. The method comprises the following steps: partitioning each of an upper section tower and a lower section tower of an oxidation tower into a primary reaction zone, a secondary reaction zone and a tertiary reaction zone from bottom to top; introducing a hydrogenation solution containing anthraquinone into the primary reaction zone of the upper section tower of the oxidation tower, an oxygen-containing gas I into the primary reaction zone of the lower section tower of the oxidation tower, a low-temperature oxygen-containing gas II into the secondary reaction zones of the upper section tower and the lower section tower in two strands, and a low-temperature oxygen-containing gas III into the tertiary reaction zones of the upper section tower and the lower section tower in two strands; and sequentially performing an oxidation reaction on the hydrogenation solution and the oxygen-containing gases in the primary reaction zone, the secondary reaction zone and the tertiary reaction zone of the upper section tower from bottom to top, performing gas-liquid separation on reaction products, treating a gas phase in an expansion refrigeration system to obtain a low-temperature tail gas, introducing a liquid phase into the primary reaction zone of the lower section tower, sequentially performing an oxidation reaction on the liquid phase and the oxygen-containing gases in the primary reaction zone, the secondary reaction zone and the tertiary reaction zone of the lower section tower from bottom to top, performing gas-liquid separation on the oxidized products, allowing a liquid phase to enter the next process, and introducing a gas phase into the primary reaction zone of the upper section tower for a continuous reaction. The method can reduce the oxidation time and improve the oxidation yield while ensuring complete oxidation, and contributes to improving the safety of an oxidation process.
Description
Technical field
The present invention relates to a kind of method improving hydrogen dioxide solution production by anthraquinone process oxidization-hydrogenation ratio.
Background technology
Hydrogen dioxide solution production by anthraquinone process is with 2-ethyl-anthraquinone (EAQ) for working material, it is made into working solution for working solvent with heavy aromatics (Ar), trioctyl phosphate (TOP) or other component, through operations such as anthraquinone hydrogenation, the oxidation of hydrogen anthraquinone, pure water extraction and working solution post processings, obtain hydrogen peroxide product.
In hydrogen anthraquinone oxidizing process, the Auto-oxidation reaction that working solution and substantial amounts of oxygen-containing gas (being generally adopted air) occur in oxidizing tower, in order to ensure the oxygen that oxidation is complete and makes full use of in oxygen-containing gas, oxidizing tower in existing Hydrogen Peroxide Production technology is generally divided into upper and lower two joint towers or tower is saved in upper, middle and lower three, be apparent serial flow between each joint tower, every Jie Tanei is hydride to move upward from entrance stream at the bottom of tower with air and the process of oxidation reaction occurs gradually. Hydrogen anthraquinone oxidizing process ubiquity Railway Project in prior art: (1) oxidation reaction is exothermic reaction, in course of reaction, temperature constantly raises, the rising of temperature causes gas-liquid mass transfer efficiency to reduce on the one hand, can cause the decomposition of hydrogen peroxide on the other hand, cause oxidization-hydrogenation ratio on the low side; (2) reaction carried out for large quantity of air and a large amount of hydrides containing aromatic hydrocarbons in oxidizing process, temperature raises or controls bad meeting and reaches the flash-point of hydride, causes sudden strain of a muscle quick-fried, also can cause the decomposition of hydrogen peroxide simultaneously, causes explosion accident. (3) air capacity in oxidizing process is very big, and the oxygen content in air is limited, and therefore oxidization time is longer, also can cause the decomposition of hydrogen peroxide while causing side reaction. Therefore, oxidation reaction process controls stable and suitable temperature, reduces oxidization time and ensure that oxidation is completely significant for oxidization-hydrogenation ratio and oxidizing process safety.
In currently available technology, oxidizing tower reaction temperature control and oxidizing tower heat-obtaining almost all adopt embedded cooler to carry out. In CN201809195U and CN201817279U, the reaction temperature of oxidizing tower controls all to adopt embedded water cooler to carry out heat-obtaining, the heat-obtaining effect that the shortcoming of this structure is employing circulating water is undesirable, and owing to the flow pattern that the gas-liquid fluid in tower flows and mass transfer effect can be had adverse effect by embedded water cooler, thus affecting oxidization-hydrogenation ratio.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of method improving hydrogen dioxide solution production by anthraquinone process oxidization-hydrogenation ratio, and the method can ensure that oxidation reduces oxidization time completely simultaneously, improves oxidization-hydrogenation ratio, and is favorably improved oxidizing process safety.
The method improving hydrogen dioxide solution production by anthraquinone process oxidization-hydrogenation ratio of the present invention, including following content: save tower by upper and lower for oxidizing tower two and be respectively divided into first order reaction district, secondary response district and third-order reaction district from the bottom to top;
Hydride containing anthraquinone introduces the first order reaction district saving tower on oxidizing tower, oxygen-containing gas I introduces the first order reaction district saving tower under oxidizing tower, low temperature oxygen-containing gas II is divided into two bursts of secondary response districts introducing upper joint tower and lower joint tower, and low temperature oxygen-containing gas III is divided into two bursts of third-order reaction districts introducing upper joint tower and lower joint tower;
Hydride carries out oxidation reaction with the oxygen-containing gas in one, two, three reaction zone of upper joint tower from bottom to top successively, product is through gas-liquid separation, the expanded refrigeration system of gas phase obtains low temperature exhaust gas, liquid phase introduces Xia Jieta first order reaction district, oxidation reaction is carried out successively from bottom to top with the oxygen-containing gas in one, two, three reaction zone of lower joint tower, oxidation product is through gas-liquid separation, and liquid phase enters subsequent processing, and gas phase introduces the upper first order reaction district saving tower and continues reaction;
Wherein low temperature oxygen-containing gas II, III are respectively through oxygen-containing gas II |, III and swell refrigeration low temperature exhaust gas heat exchange obtain.
In the inventive method, described oxygen-containing gas is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and noble gas.
In the inventive method, described hydride be anthraquinone producing hydrogen peroxide hydrogenation process in obtain, hydride (m3/ h) with the volume flow (Nm of total oxygen-containing gas3/ h) than be 1:20��1:35.
In the inventive method, in oxidizing tower, overall reaction district height is benchmark, and first order reaction district height accounts for the 2/5��3/5 of overall reaction district, and secondary response district height accounts for the 1/5��3/10 of overall reaction district, and third-order reaction district height accounts for the 1/5��3/10 of overall reaction district.
In the inventive method, the upper and lower tower structure of oxidizing tower of routine can be adopted, preferably employing the oxidizing tower of following structure: oxidizing tower tower diameter successively decreases step by step according to reaction zone order from bottom to top, the tower diameter of oxidizing tower corresponding to first order reaction district, secondary response district and third-order reaction district is than for 1:0.7 ~ 0.8:0.6��0.7.
In the inventive method, described expansion refrigeration system is made up of cooler, gas-liquid separator and swell refrigeration unit, wherein swell refrigeration unit is to utilize oxidized tail gas pressure itself to carry out constant entropy expansion, and the external work done of gas in expansion process causes the pressure of gas, temperature to reduce.
In the inventive method, the temperature of oxygen-containing gas I is 40��45 DEG C, and the volume ratio of total oxygen-containing gas of oxygen-containing gas I and introducing oxidizing tower is 1:1��1:2.
In the inventive method, the temperature of low temperature oxygen-containing gas II is 20��25 DEG C, and in oxygen-containing gas II, the volume fraction of oxygen is 25%��40%, and the volume ratio of total oxygen-containing gas of oxygen-containing gas II and introducing oxidizing tower is 1:5��1:30; Wherein oxygen-containing gas II by with low temperature oxygen-containing gasHeat exchange obtains low temperature oxygen-containing gas II.
In the inventive method, the temperature of low temperature oxygen-containing gas III is 10��20 DEG C, and in oxygen-containing gas III, the volume fraction of oxygen is 40%��80%, and oxygen-containing gas III is with to introduce the ratio of total oxygen-containing gas of oxidizing tower be 1:10��1:40; Wherein oxygen-containing gasBy obtaining low temperature oxygen-containing gas with swell refrigeration oxidized tail gas secondary heat exchange��
In the inventive method, the operating condition that oxidizing tower saves tower reaction zone at different levels is: first order reaction district operation pressure 0.20��0.22MPaG, and operation temperature is 52��54 DEG C; The operation pressure 0.22��0.24MPaG in secondary response district, operation temperature is 50��52 DEG C; The operation pressure 0.24��0.26MPaG in third-order reaction district, operation temperature is 48��50 DEG C.
In the inventive method, the operating condition saving tower reaction zone at different levels under oxidizing tower is: operation pressure 0.26��0.28MPaG, and operation temperature is 52��54 DEG C; The operation pressure 0.28��0.30MPaG in secondary response district, operation temperature is 50��52 DEG C; The operation pressure 0.30��0.32MPG in third-order reaction district, operation temperature is 48��50 DEG C.
In the inventive method, reactant is 8��20 minutes in the total residence time of oxidizing tower, wherein upper joint, lower joint tower the time of staying be respectively 4��10 minutes.
In the inventive method, owing to oxidation reaction is exothermic reaction, the Gas-Liquid Absorption mass transfer reaction speed of hydrogen anthraquinone oxidizing process and temperature have close relationship, namely along with the temperature that carries out of reaction constantly raises, it is unfavorable for absorption and the mass transfer of gas-liquid, the decomposition of the reduction of gas-liquid mass transfer efficiency, response time prolongation and hydrogen peroxide can be caused, cause oxidization-hydrogenation ratio on the low side, and reactive absorption mass transport process is promote by suitable low temperature; Additionally,
Oxidizing process is gas and liquid flowing course of reaction from bottom to top in oxidizing tower, and in course of reaction, oxygen gradually uses up, and causes that tolerance from bottom to top gradually decreases the low gas-liquid mass transfer motive force of gas prompt drop and reduces oxidization-hydrogenation ratio and reduce. In sum, couple controlling reaction temperature (Cryogenic air passing into different potential temperature according to extent of reaction diverse location in tower is come) with control gas-liquid flow velocity (tower diameter, gas flow, gas oxygen content), strengthen gas-liquid mass transfer further, target is the time reducing and reaching complete oxidation, improves oxidization-hydrogenation ratio.
Accompanying drawing explanation
Fig. 1 is the oxidation technology flow chart (for reducing oxidizing tower in figure) of the hydrogen dioxide solution production by anthraquinone process of oxidizing tower of the present invention.
Wherein 1 is the hydride containing hydrogen anthraquinone, and 2 is oxygen-containing gas I, and 3 is oxygen-containing gas II, and 4 is oxygen-containing gas5 for saving tower in oxidation, 6 for saving tower under oxidation, 7 is oxidized tail gas, 8 is water cooler, 9,10,11 is gas-liquid separator, and 12 is first-class heat exchanger, and 13 is secondary heat exchanger, 14 is three grades of heat exchangers, 15 is the upper reacted hydride of joint tower, and 16 is the oxygen-containing gas that lower joint tower is reacted, and 17 is swell refrigeration unit, 18 is oxidized tail gas, 19 is the low temperature oxygen-containing gas II in Shang Jieta secondary response district, and 20 is the low temperature oxygen-containing gas II in Xia Jieta secondary response district, and 21 is the low temperature oxygen-containing gas in Shang Jieta third-order reaction district, 22 is the low temperature oxygen-containing gas in Xia Jieta third-order reaction district, 23 is the oxidation solution that lower joint tower enters subsequent processing.
Detailed description of the invention
Illustrate with embodiment, this technological invention scheme to be described in detail below in conjunction with accompanying drawing, but the present invention is not by the restriction of following embodiment.
In the inventive method, oxidizing tower is divided in oxidation saving under tower (5) and oxidation saving tower (6), and often joint tower divides and is divided into first order reaction district, secondary response district and third-order reaction district from the bottom to top. the first order reaction district saving tower (5) in hydride (1) autoxidation containing anthraquinone introduces, and flows out successively after upper and lower tower reacts. by oxygen-containing gas I(2) introduce the first order reaction district saving tower under oxidizing tower, oxygen-containing gas (3) becomes the low temperature oxygen-containing gas of 20��25 DEG C after carrying out heat exchange with swell refrigeration tail gas, then two strands (19) and (20) it are divided into introduce the upper joint tower of oxidizing tower and the secondary response district of lower joint tower respectively, oxygen-containing gas (4) becomes the low temperature oxygen-containing gas of 10��20 DEG C after carrying out heat exchange with swell refrigeration tail gas, is then divided into two strands (21) and (22) to introduce the upper joint tower of oxidizing tower and the third-order reaction district of lower joint tower respectively. the reacted material in oxidized Shang Ta third-order reaction district carries out gas-liquid separation, liquid phase (15) after separation enters the first order reaction district of the lower tower of oxidation, after separation oxidized tail gas (7) initially enter one-level cooler (8), gas-liquid separation is completed subsequently into gas-liquid separator (9), low temperature exhaust gas heat exchanger (12) after isolated gas phase and swell refrigeration carries out heat exchange, enter two grades of gas-liquid separators (10), isolated gas phase enters swell refrigeration unit (17), the cold tail gas brought out of expanded refrigeration unit enters three grades of gas-liquid separators (11), isolated gas enters back into tail gas heat exchanger (13, 12) hot junction of expansion refrigerator group is entered after carrying out heat exchange, tail gas (18) after compression discharges system. the one-level of oxidized lower joint tower, two grades and the reacted product in third-order reaction district carry out gas-liquid separation, and isolated gas phase (16) entrance saves the first order reaction district of tower, and isolated liquid phase (23) enters subsequent processing.
Comparative example 1
One common oxidizing tower, is divided into upper and lower two joints, embedded two the U-tube coolers of upper tower. Hydride enters from upper joint tower, flows out successively after upper and lower tower reacts, and all under air then autoxidation tower, tower enters, and draws successively after upper and lower tower reacts. Oxidizing tower tower diameter 800mm, height 6900mm, oxidizing tower cumulative volume is 3.53m3. Hydride flow 4.97m3/ h, total air addition 222.3Nm3/ h. In course of reaction China, recording oxidation upper tower reaction temperature 50��56 DEG C, pressure 0.2��0.22MPaG, when the reaction mass time of staying in tower is 22��26 minutes, oxidized reacted oxidization-hydrogenation ratio is 86%��92%, and tail oxygen content is 5%��10%.
Embodiment 1
Oxidizing tower is divided into upper and lower two joints, often joint tower is divided into one-level, two grades and third-order reaction district from the bottom to top, tower diameter respectively 1000mm, 700mm, the 600mm in each three districts saving tower, the height in three districts respectively 3500mm, 1700mm and 1700mm, the total height of single tower joint is 6900mm, and oxidizing tower cumulative volume is 3.88m3. First by��45 DEG C of oxygen-containing gas I155.6Nm3/ h is introduced directly under oxidizing tower tower, introduce in the centre position aoxidizing upper and lower tower temperature be 22 DEG C, concentration be 35% oxygen-containing gas II24Nm3/ h, aoxidize upper and lower tower upper position introduce temperature be 15 DEG C, concentration be 60% oxygen-containing gas II9.34Nm3/ h. Hydride flow 4.97m3/ h, in course of reaction, record on the upper tower of oxidation, in, the reaction temperature of bottom respectively 52��54 DEG C, 50��52 DEG C, 48��50 DEG C, pressure is 0.2��0.22MPaG respectively, 0.22��0.24MPaG, 0.24��0.26MPaG, record on the lower tower of oxidation, in, the reaction temperature of bottom respectively 52��54 DEG C, 50��52 DEG C, 48��50 DEG C, pressure is 0.26��0.28MPaG respectively, 0.28��0.30MPaG, 0.30��0.32MPaG, reaction mass total residence time in tower is 12��14 minutes, oxidized reacted oxidization-hydrogenation ratio is 97.5%��99.0%, tail oxygen content is 4.5%��5.2%.
Embodiment 2
Oxidizing tower is divided into upper and lower two joints, often joint tower is divided into one-level, two grades and third-order reaction district from the bottom to top, tower diameter respectively 1000mm, 800mm, the 700mm in three districts of two tower joints, the height in three districts respectively 3400mm, 1400mm and 1400mm, the total height of single tower joint is 6200mm, and oxidizing tower cumulative volume is 3.91m3. First by oxygen-containing gas I133.37Nm3/ h is introduced directly under oxidizing tower tower, introduce in the centre position aoxidizing upper and lower tower temperature be 20 DEG C, concentration be 35% oxygen-containing gas II21.34Nm3/ h, aoxidize upper and lower tower upper position introduce temperature be 12 DEG C, concentration be 60% oxygen-containing gas II18.67Nm3/ h. Hydride flow 4.97m3/ h, in course of reaction, record on the upper tower of oxidation, in, the reaction temperature of bottom respectively 52��54 DEG C, 50��52 DEG C, 48��50 DEG C, pressure is 0.2��0.22MPaG respectively, 0.22��0.24MPaG, 0.24��0.26MPaG, record on the lower tower of oxidation, in, the reaction temperature of bottom respectively 52��54 DEG C, 50��52 DEG C, 48��50 DEG C, pressure is 0.26��0.28MPaG respectively, 0.28��0.30MPaG, 0.30��0.32MPaG, when reaction mass total residence time in tower is 12��14 minutes, oxidized reacted oxidization-hydrogenation ratio is 98.4%��99.7%, tail oxygen content is 3.5%��4.5%.
Embodiment 3
Oxidizing tower is divided into upper and lower two joints, and often joint tower is divided into one-level, two grades and third-order reaction district from the bottom to top, and the tower diameter in two Ta Jiesange districts is 800mm, and the height of single tower joint is 6900mm, and oxidizing tower cumulative volume is 3.53m3. First by oxygen-containing gas I144.29Nm3/ h is introduced directly under oxidizing tower tower, introduce in the centre position aoxidizing upper and lower tower temperature be 20 DEG C, concentration be 30% oxygen-containing gas II27.83Nm3/ h, aoxidize upper and lower tower upper position introduce temperature be 12 DEG C, concentration be 70% oxygen-containing gas II11.9Nm3/ h. Hydride flow 4.97m3/ h, in course of reaction, record on the upper tower of oxidation, in, the reaction temperature of bottom respectively 52��54 DEG C, 50��52 DEG C, 48��50 DEG C, pressure is 0.2��0.22MPaG respectively, 0.22��0.24MPaG, 0.24��0.26MPaG, record on the lower tower of oxidation, in, the reaction temperature of bottom respectively 52��54 DEG C, 50��52 DEG C, 48��50 DEG C, pressure is 0.26��0.28MPaG respectively, 0.28��0.30MPaG, 0.30��0.32MPaG, when reaction mass total residence time in tower is 12��14 minutes, oxidized reacted oxidization-hydrogenation ratio is 92%��94%, tail oxygen content is 3%��6%.
Claims (12)
1. the method improving hydrogen dioxide solution production by anthraquinone process oxidization-hydrogenation ratio, it is characterised in that include following content: save tower by upper and lower for oxidizing tower two and be respectively divided into first order reaction district, secondary response district and third-order reaction district from the bottom to top; Hydride containing anthraquinone introduces the first order reaction district saving tower on oxidizing tower, oxygen-containing gas I introduces the first order reaction district saving tower under oxidizing tower, low temperature oxygen-containing gas II is divided into two bursts of secondary response districts introducing upper joint tower and lower joint tower, and low temperature oxygen-containing gas III is divided into two bursts of third-order reaction districts introducing upper joint tower and lower joint tower; Hydride carries out oxidation reaction with the oxygen-containing gas in one, two, three reaction zone of upper joint tower from bottom to top successively, product is through gas-liquid separation, the expanded refrigeration system of gas phase obtains low temperature exhaust gas, liquid phase introduces Xia Jieta first order reaction district, oxidation reaction is carried out successively from bottom to top with the oxygen-containing gas in one, two, three reaction zone of lower joint tower, oxidation product is through gas-liquid separation, and liquid phase enters subsequent processing, and gas phase introduces the upper first order reaction district saving tower and continues reaction; Wherein low temperature oxygen-containing gas II, III are respectively through oxygen-containing gas II |, III and swell refrigeration low temperature exhaust gas heat exchange obtain.
2. in accordance with the method for claim 1, it is characterised in that: described oxygen-containing gas is the one in the mixture of air, oxygen and nitrogen or the mixture of oxygen and noble gas.
3. in accordance with the method for claim 1, it is characterised in that: hydride (m3/ h) with the volume flow (Nm of total oxygen-containing gas3/ h) than be 1:20��1:35.
4. in accordance with the method for claim 1, it is characterized in that: in oxidizing tower, overall reaction district height is benchmark, first order reaction district height accounts for the 2/5��3/5 of overall reaction district, and secondary response district height accounts for the 1/5��3/10 of overall reaction district, and third-order reaction district height accounts for the 1/5��3/10 of overall reaction district.
5. in accordance with the method for claim 1, it is characterised in that: the tower diameter of oxidizing tower successively decreases step by step according to reaction zone order from bottom to top, and the tower diameter of oxidizing tower corresponding to first order reaction district, secondary response district and third-order reaction district is than for 1:0.7 ~ 0.8:0.6��0.7.
6. in accordance with the method for claim 1, it is characterised in that: described expansion refrigeration system is made up of cooler, gas-liquid separator and swell refrigeration unit.
7. in accordance with the method for claim 1, it is characterised in that: the temperature of oxygen-containing gas I is 40��45 DEG C, and the volume ratio of total oxygen-containing gas of oxygen-containing gas I and introducing oxidizing tower is 1:1��1:2.
8. in accordance with the method for claim 1, it is characterized in that: the temperature of low temperature oxygen-containing gas II is 20��25 DEG C, in oxygen-containing gas II, the volume fraction of oxygen is 25%��40%, and the volume ratio of total oxygen-containing gas of oxygen-containing gas II and introducing oxidizing tower is 1:5��1:30; Wherein oxygen-containing gas II by with low temperature oxygen-containing gasHeat exchange obtains low temperature oxygen-containing gas II.
9. in accordance with the method for claim 1, it is characterized in that: the temperature of low temperature oxygen-containing gas III is 10��20 DEG C, in oxygen-containing gas III, the volume fraction of oxygen is 40%��80%, and oxygen-containing gas III is with to introduce the ratio of total oxygen-containing gas of oxidizing tower be 1:10��1:40; Wherein oxygen-containing gasBy obtaining low temperature oxygen-containing gas with swell refrigeration oxidized tail gas secondary heat exchange��
10. in accordance with the method for claim 1, it is characterised in that: the operating condition saving tower reaction zone at different levels on oxidizing tower is: first order reaction district operation pressure 0.20��0.22MPaG, and operation temperature is 52��54 DEG C; The operation pressure 0.22��0.24MPaG in secondary response district, operation temperature is 50��52 DEG C; The operation pressure 0.24��0.26MPaG in third-order reaction district, operation temperature is 48��50 DEG C.
11. in accordance with the method for claim 1, it is characterised in that: the operating condition saving tower reaction zone at different levels under oxidizing tower is: operation pressure 0.26��0.28MPaG, and operation temperature is 52��54 DEG C; The operation pressure 0.28��0.30MPaG in secondary response district, operation temperature is 50��52 DEG C; The operation pressure 0.30��0.32MPG in third-order reaction district, operation temperature is 48��50 DEG C.
12. in accordance with the method for claim 1, it is characterised in that: reactant is 8 ~ 20 minutes in the total residence time of oxidizing tower, wherein upper joint, lower joint tower the time of staying be respectively 4��10 minutes.
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| CN1654315A (en) * | 2005-01-31 | 2005-08-17 | 黎明化工研究院 | Safe production technique for hydrogen dioxide |
| US7056485B2 (en) * | 2002-10-16 | 2006-06-06 | Degussa Ag | Continuous hydrogenation process |
| CN103663385A (en) * | 2012-09-21 | 2014-03-26 | 中国石油化工股份有限公司 | Method and device of producing hydrogen peroxide |
| CN103803501A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Oxidation method for producing hydrogen peroxide by anthraquinone method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7056485B2 (en) * | 2002-10-16 | 2006-06-06 | Degussa Ag | Continuous hydrogenation process |
| CN1654315A (en) * | 2005-01-31 | 2005-08-17 | 黎明化工研究院 | Safe production technique for hydrogen dioxide |
| CN103663385A (en) * | 2012-09-21 | 2014-03-26 | 中国石油化工股份有限公司 | Method and device of producing hydrogen peroxide |
| CN103803501A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Oxidation method for producing hydrogen peroxide by anthraquinone method |
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