CN103303871A - Working solution for producing hydrogen peroxide through stationary bed palladium catalyst process, and preparation method of working solution - Google Patents
Working solution for producing hydrogen peroxide through stationary bed palladium catalyst process, and preparation method of working solution Download PDFInfo
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- CN103303871A CN103303871A CN2013102841168A CN201310284116A CN103303871A CN 103303871 A CN103303871 A CN 103303871A CN 2013102841168 A CN2013102841168 A CN 2013102841168A CN 201310284116 A CN201310284116 A CN 201310284116A CN 103303871 A CN103303871 A CN 103303871A
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Abstract
The invention relates to a working solution for producing hydrogen peroxide through a stationary bed palladium catalyst process, and a preparation method of the working solution. The preparation method is characterized by comprising the steps of: with a mixture of amylanthraquinon and 2-ethylanthraquinone, or amylanthraquinon as a hydrogenated carrier, and a mixture of a C9-C10 benzene organic compound and one or more of esters, tetrabutyl urea TBU or diisobutylmethanol DIBC as a solvent, carrying out interaction on the hydrogenated carrier and the solvent to obtain a working solution system, mixing the working solution system with H2 to flow into a stationary bed reactor filled with a catalyst, carrying out a hydrogenation reaction under the conditions of temperature of 40-80 DEG C and pressure of 0.2-0.5atm to generate hydrogenated anthraquinone, then feeding the oxanthranol into an oxidation reactor for oxygen oxidization to obtain hydrogen peroxide, and oxidizing hydrogenated anthraquinone. The capability of producing the H2O2 through the unit working solution can be improved to 13-18g/l from 7-11g/l.
Description
Technical field
The present invention relates to a kind of production method of hydrogen peroxide, particularly disclose working fluid that adopts in a kind of Pd-catalyst In Fixed Bed legal system hydrogen peroxide manufacture process and preparation method thereof.
Background technology
Because hydrogen peroxide is as the extensive application of industrial chemicals in the oxidation building-up reactions, especially the application in propylene to prepare epoxy propane, make single covering device ability of hydrogen peroxide that higher requirement arranged, build 300,000 tons of propylene oxide of a cover, need supporting 230,000 tons of 100%H
2O
2, building 500,000 tons of propylene oxide of a maximum cover at present, must supporting 380,000 tons of 100%H
2O
2Device, and present only 110,000 tons of the hydrogen peroxide unit of single cover throughput maximum in the world.So no matter to mate the demand of producing propylene oxide, can only build 2 ~ 3 covering devices, be investment or management, and cost all can significantly improve; Perhaps simply amplify by existing apparatus equipment, even technical feasible, also can make equipment that very large amplification is arranged.
Therefore only be improved the throughput (being hydrogenation efficiency) of production of units hydrogen peroxide working liquid, could amplify the throughput that few situation is issued to be needed at equipment, can save in a large number the investment of chemical raw material and the energy consumption in the production simultaneously.
Summary of the invention
The objective of the invention is to overcome the lower defective of throughput that prior art exists, propose working fluid that a kind of Pd-catalyst In Fixed Bed legal system hydrogen peroxide uses and preparation method thereof, make working unit liquid produce H
2O
2Ability is increased to 13 ~ 18g/l from 7 present ~ 11g/l, and the working fluid internal circulating load that is equivalent to 230,000 tons of hydrogen peroxide manufacture devices of a cover reduces more than 40% than prior art.
The present invention is achieved in that the working fluid preparation method that a kind of Pd-catalyst In Fixed Bed legal system hydrogen peroxide is used, and it is characterized in that: employing add mixture or the amyl anthraquinone that hydrogen carrier is amyl anthraquinone and 2-ethyl-anthraquinone, the solvent of employing is C
9~ C
10The benzene series organism and one or more the mixture among ester class or tetrabutyl urea TBU or the diisobutyl carbinol(DIBC) DIBC, with described working fluid system and the H that obtains after hydrogen carrier and the described solvent phase mutual effect that add
2Enter after the mixing in the fixed-bed reactor that catalyzer is housed, be that 40 ~ 80 ℃, pressure are to carry out hydrogenation under 0.2 ~ 0.5atm condition to generate the hydrogen anthraquinone in temperature, then enter in the oxidation reactor and obtain hydrogen peroxide by dioxygen oxidation, the hydrogen anthraquinone is oxidized simultaneously; Described ester class is selected a kind of in trioctyl phosphate TOP or 2-methyl cyclohexane acetic ester 2-MCHA; Described hydrogenation temperature is 40 ~ 80 ℃, and catalyst loading is 10 ~ 40hr
-1Described catalyzer is Pd-M/Al
2O
3Or Pd-M/SiO
2System, wherein Pd content is that 0.05 ~ 3%, M is aided metal salt, comprises Na, K, Ni, Mg, Mn, Ca, Fe salt, content is 0.05 ~ 5%.
The working fluid that described Pd-catalyst In Fixed Bed legal system hydrogen peroxide is used is characterized in that:
The described parts by weight that add hydrogen carrier are:
Or the mixture 1 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Described solvent is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 1~70，
2-MCHA and TOP 1 ~ 70,
2-MCHA and TBU 1 ~ 70,
2-MCHA and DIBC 1 ~ 70,
Or C
9~ C
10The benzene series organism: 100,
TBU and 2-MCHA 1 ~ 70,
TBU and TOP 1 ~ 70,
TBU and DIBC 1 ~ 70,
Or C
9~ C
10Benzene series organism 100,
DIBC and 2-MCHA 1 ~ 70,
DIBC and TBU 1 ~ 70,
DIBC and TOP 1 ~ 70.
Preferred version is:
The described parts by weight that add hydrogen carrier are:
Amyl anthraquinone 100 ~ 300g/l,
Or the mixture 100 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Described solvent is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 10~60，
2-MCHA and TOP 10 ~ 60,
2-MCHA and TBU 10 ~ 60,
2-MCHA and DIBC 10 ~ 60,
Or C
9~ C
10The benzene series organism: 100,
TBU 10~60，
TBU and 2-MCHA 10 ~ 60,
TBU and TOP 10 ~ 60,
TBU and DIBC 10 ~ 60,
Or C
9~ C
10Benzene series organism 100,
DIBC 10~60，
DIBC and 2-MCHA 10 ~ 60,
DIBC and TBU 10 ~ 60,
DIBC and TOP 10 ~ 60.
Preferred scheme is as follows:
The described parts by weight that add hydrogen carrier are:
Amyl anthraquinone 200 ~ 300g/l,
Or the mixture 2 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Described solvent is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 30~55，
2-MCHA and TOP 30 ~ 55,
2-MCHA and TBU 30 ~ 55,
2-MCHA and DIBC 30 ~ 55,
Or C
9~ C
10The benzene series organism: 100,
TBU 30~55，
TBU and 2-MCHA 30 ~ 55,
TBU and TOP 30 ~ 55,
TBU and DIBC 30 ~ 55,
Or C
9~ C
10Benzene series organism 100,
DIBC 30~55，
DIBC and 2-MCHA 30 ~ 55,
DIBC and TBU 30 ~ 55,
DIBC and TOP 30 ~ 55.
Adopt working fluid that preparation method of the present invention makes at Pd-catalyst In Fixed Bed legal system H
20
2Production process in, have following advantages:
1, effective anthraquinone is high, under 40 ℃ to amyl group solubilized 400g/l more than, also can reach more than the 300g/l mixing the anthraquinone dissolving, can also under low hydrogenation degree, improve the hydrogen effect, reduce side reaction;
2, high to hydrogen anthraquinone solubleness, can reach more than the 90g/l at least, reach as high as more than the 125g/l;
3, in high hydrogen effect situation, oxidization time does not obviously increase;
4, at high density H
2O
2In the situation (﹥ 40%), the working fluid partition ratio is also very high, easily extraction.
Description of drawings
Fig. 1 is the work liquid hydrogen effect testing apparatus workflow diagram that the inventive method makes.
Among the figure: 1, working fluid storage tank; 2, the first volume pump; 3, the second volume pump; 4, gas liquid mixer; 5, hydrogenation tower; 6, hydrogen pressure table; 7, temperature controller; 8, hydride storage tank; 9, Liquid level adjusting valve; 10, oxidizing tower; 11, the first blow-off valve; 12, the second blow-off valve; 13, extraction tower; 14, carclazyte bed.
Embodiment
Working fluid that a kind of Pd-catalyst In Fixed Bed legal system of the present invention hydrogen peroxide is used and preparation method thereof, employing add mixture or the amyl anthraquinone that hydrogen carrier is amyl anthraquinone and 2-ethyl-anthraquinone, the solvent of employing is C
9~ C
10The benzene series organism and one or more the mixture among ester class or tetrabutyl urea TBU or the diisobutyl carbinol(DIBC) DIBC.To add the working fluid system and the H that obtain after hydrogen carrier and the solvent phase mutual effect
2Enter after the mixing in the fixed-bed reactor that catalyzer is housed, be that 40 ~ 80 ℃, pressure are to carry out hydrogenation under 0.2 ~ 0.5atm condition to generate the hydrogen anthraquinone in temperature, then enter in the oxidation reactor and obtain hydrogen peroxide by dioxygen oxidation, the hydrogen anthraquinone is oxidized simultaneously.Used ester class is selected a kind of in trioctyl phosphate TOP or 2-methyl cyclohexane acetic ester 2-MCHA.The hydrogenation temperature is 40 ~ 80 ℃, and catalyst loading is 10 ~ 40hr
-1Catalyzer is Pd-M/Al
2O
3Or Pd-M/SiO
2System, wherein Pd content is that 0.05 ~ 3%, M is aided metal salt, comprises Na, K, Ni, Mg, Mn, Ca, Fe salt, content is 0.05 ~ 5%.
The used parts by weight that add hydrogen carrier are:
Or the mixture 1 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Solvent for use is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 1~70，
2-MCHA and TOP 1 ~ 70,
2-MCHA and TBU 1 ~ 70,
2-MCHA and DIBC 1 ~ 70,
Or C
9~ C
10The benzene series organism: 100,
TBU and 2-MCHA 1 ~ 70,
TBU and TOP 1 ~ 70,
TBU and DIBC 1 ~ 70,
Or C
9~ C
10Benzene series organism 100,
DIBC and 2-MCHA 1 ~ 70,
DIBC and TBU 1 ~ 70,
DIBC and TOP 1 ~ 70.
Embodiment 1:
Get 65 liters of heavy aromaticss, 35 liters of 2-MCHA, 30kg 2-amyl anthraquinone is dissolved in the above-mentioned solvent, use Fig. 1 testing apparatus, hydrogenation tower diameter is 40mm, highly is 1425mm, and loaded catalyst is 400ml.By beds, flow is 10 liters with above-mentioned working fluid, and being equivalent to air speed is 25hr
-1, temperature of reaction is 45 ℃, hydrogen effect 17.75g, 0.963(25 ℃ of working fluid proportion), oxidization time is 3 minutes, working fluid is at 35%H
2O
2Lower partition ratio is 76, at 45%H
2O
2Under be 78.
Embodiment 2:
Get 65 liters of heavy aromaticss, 20 liters of 2-MCHA, 15 liters of DIBC, 25kg 2-amyl anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 same method, obtain hydrogen effect 16.8g, oxidization time is 2 minutes and 30 seconds, 0.934(25 ℃ of working fluid proportion), 35%H
2O
2The time partition ratio be 71,45%H
2O
2Be 73.
Embodiment 3:
Get 60 liters of heavy aromaticss, 40 liters of 2-MCHA, 10kg 2-ethyl-anthraquinone, 15kg 2-amyl anthraquinone are dissolved in the above-mentioned solvent, with embodiment 1 same method, obtain the hydrogen effect and be 13g, oxidization time is 2 minutes, working fluid proportion 0.96,35%H
2O
2The time partition ratio be 50,45% to be 93.
Embodiment 4:
Get 65 liters of heavy aromaticss, 20 liters of 2-MCHA, 15 liters of TOP, 12kg 2-ethyl-anthraquinone, 20kg2-amyl anthraquinone are dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 13.2g, oxidization time is 3 minutes and 40 seconds, working fluid proportion 0.97, partition ratio is that 48,45%H2O2 partition ratio is 68 during 35%H2O2.
Embodiment 5:
Get 60 liters of heavy aromaticss, 40 liters of DIBC, 30kg 2-amyl anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 18.7g, oxidization time is 4 minutes, and proportion 0.93,35%H2O2 partition ratio are 48, and the 45%H2O2 partition ratio is 52.
Embodiment 6:
Get 65 liters of heavy aromaticss, 15 liters of DIBC, 20 liters of 2-MCHA, the 25kg amyl anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 16.8g, oxidization time is 2 minutes and 10 seconds, working fluid proportion 0.934, partition ratio is that 71.5,45%H2O2 partition ratio is 73.3 during 35%H2O2.
Embodiment 7:
Get 70 liters of heavy aromaticss, 30 liters of DIBC, 12kg 2-ethyl-anthraquinone, 20kg 2-amyl anthraquinone are dissolved in the above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 13.2g, oxidization time is 3 minutes and 30 seconds, working fluid proportion 0.9376,35%H
2O
2The time partition ratio be that 73.5,45%H2O2 partition ratio is 70.
Embodiment 8:
Get 65 liters of heavy aromaticss, 15 liters of DIBC, 20 liters of TOP, 12kg 2-ethyl-anthraquinone, 20kg 2-amyl anthraquinone are dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 13.5g, oxidization time is 4 minutes and 30 seconds, working fluid proportion 0.9554, partition ratio is that 46.75,45%H2O2 partition ratio is 40.9 during 35%H2O2.
Embodiment 9:
Get 65 liters of heavy aromaticss, 35 liters of TBU, 25kg 2-amyl anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 16.1g, working fluid proportion 0.929, oxidization time are 5 minutes and 30 seconds, partition ratio is that 42.4,45%H2O2 partition ratio is 40.5 during 35%H2O2.
Embodiment 10:
Get 65 liters of heavy aromaticss, 20 liters of TBU, 15 liters of DIBC, 30kg 2-amyl anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 15.3g, oxidization time is 4 minutes and 40 seconds, working fluid proportion 0.946,35%H
2O
2The time partition ratio be 58.6,45%H
2O
2Partition ratio is 48.2.
Embodiment 11:
Get 65 liters of heavy aromaticss, 35 liters of TBU, 10kg 2-ethyl-anthraquinone, 15kg 2-amyl anthraquinone are dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 16.6g, oxidization time is 7 minutes and 50 seconds, working fluid proportion 0.9384, partition ratio is that 53.4,45%H2O2 partition ratio is 52 during 35%H2O2.
Embodiment 12:
Get 65 liters of heavy aromaticss, 15 liters of TBU, 20 liters of 2-MCHA, 12kg 2-ethyl-anthraquinone, 20kg 2-amyl anthraquinone are dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 15.5g, oxidization time is 4 minutes and 05 second, working fluid proportion 0.942, partition ratio is that 61.4,45%H2O2 partition ratio is 61.6 during 35%H2O2.
Comparative example 1:
Get 75 liters of heavy aromaticss, 25 liters of TOP, the 15kg 2-ethyl-anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 8.5g, oxidization time is 9 minutes and 22 seconds, working fluid proportion 0.925, partition ratio is that 55,45%H2O2 partition ratio is 46 during 35%H2O2.
Comparative example 2:
Get 70 liters of heavy aromaticss, 30 liters of 2-MCHA, the 20kg 2-ethyl-anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 11.2g, working fluid proportion 0.945, oxidization time are 4 minutes and 20 seconds, partition ratio is that 65,45%H2O2 partition ratio is 78 during 35%H2O2.
Comparative example 3:
Get 70 liters of heavy aromaticss, 30 liters of TBU, the 17kg 2-ethyl-anthraquinone is dissolved in above-mentioned solvent, with embodiment 1 method, obtain the hydrogen effect and be 9.6g, working fluid proportion 0.92, oxidization time are 5 minutes and 15 seconds, and partition ratio is 55 during 35%H2O2, and the 45%H2O2 partition ratio is 58.
The oxidization time measuring method:
Get the 5ml hydride, add 1-2ml phosphoric acid, after room temperature, pass into the O2 of purity 90%, take the complete oxidized required time of hydride as oxidization time.
The mensuration of partition ratio:
Leaving standstill analysis after certain concentration H2O2 and the working fluid high-speed stirring, measure remaining H2O2 content in the working fluid, take this H2O2 concentration divided by the ratio of the remaining H2O2 concentration of working fluid as partition ratio.
The mensuration of hydrogenation efficiency:
Get the 5mL hydride from thief hole and place the 250mL pear shape separatory funnel, add 20mL water, 2mL phosphoric acid solution (2+13), logical industrial oxygen to solution is faint yellow (approximately needing 10min), take off separating funnel, jolting 1min, standing demix is collected in water in the 150mL Erlenmeyer flask, and organic phase partly with the extraction of 20mL water once, repeat again once, water still is collected in the Erlenmeyer flask, adds 20mL sulphuric acid soln (1+4), uses C(1/5KMnO4)=0.10mol/L potassium permanganate reference liquid decides the solution titration, be heated to 65 ℃ during nearly terminal point, continue to be titrated to the solution pinkiness and keep 30s.
With reference to the accompanying drawings, the work liquid hydrogen effect experiment process that makes of the inventive method is as follows:
The working fluid of preparing in embodiment or the comparative example is added working fluid storage tank 1, with the first volume pump 2 working fluid is entered gas liquid mixer 4 and H
2Mix, and then enter hydrogenation tower 5, and hydrogen pressure is controlled at 3kg(and can be read by hydrogen pressure table 6), the temperature of hydrogenation tower 5 is by temperature controller 7 controls, the working fluid that goes out hydrogenation tower 5 is hydride, and the part hydride turns back to gas liquid mixer 4 and hydrogenation tower 5 by the second volume pump 3; Another partly enters hydride storage tank 8, again by Liquid level adjusting valve 9, enter oxidizing tower 10, the first blow-off valve 11 is equipped with on oxidizing tower 10 tops, be oxidation solution from oxidizing tower 10 working fluid out, oxidation solution enters extraction tower 13, and the second blow-off valve 12 is equipped with on extraction tower 13 tops, and extraction tower 13 bottoms emit H
2O
2, return working fluid storage tank 1 after the working fluid on top is processed through carclazyte bed 14 and recycle.
Claims (4)
1. working fluid preparation method that Pd-catalyst In Fixed Bed legal system hydrogen peroxide is used is characterized in that: employing add mixture or the amyl anthraquinone that hydrogen carrier is amyl anthraquinone and 2-ethyl-anthraquinone, the solvent of employing is C
9~ C
10The benzene series organism and one or more the mixture among ester class or tetrabutyl urea TBU or the diisobutyl carbinol(DIBC) DIBC, with described working fluid system and the H that obtains after hydrogen carrier and the described solvent phase mutual effect that add
2Enter after the mixing in the fixed-bed reactor that catalyzer is housed, be that 40 ~ 80 ℃, pressure are to carry out hydrogenation under 0.2 ~ 0.5atm condition to generate the hydrogen anthraquinone in temperature, then enter in the oxidation reactor and obtain hydrogen peroxide by dioxygen oxidation, the hydrogen anthraquinone is oxidized simultaneously; Described ester class is selected a kind of in trioctyl phosphate TOP or 2-methyl cyclohexane acetic ester 2-MCHA; Described hydrogenation temperature is 40 ~ 80 ℃, and catalyst loading is 10 ~ 40hr
-1Described catalyzer is Pd-M/Al
2O
3Or Pd-M/SiO
2System, wherein Pd content is that 0.05 ~ 3%, M is aided metal salt, comprises Na, K, Ni, Mg, Mn, Ca, Fe salt, content is 0.05 ~ 5%.
2. the working fluid used of the Pd-catalyst In Fixed Bed legal system hydrogen peroxide that obtains of the described preparation method of a claim 1 is characterized in that: used add mixture or the amyl anthraquinone that hydrogen carrier is amyl anthraquinone and 2-ethyl-anthraquinone, used solvent is C
9~ C
10The benzene series organism and one or more the mixture among ester class or tetrabutyl urea TBU or the diisobutyl carbinol(DIBC) DIBC, described ester class is selected a kind of in trioctyl phosphate TOP or 2-methyl cyclohexane acetic ester 2-MCHA;
The described parts by weight that add hydrogen carrier are:
Amyl anthraquinone 1 ~ 400g/l,
Or the mixture 1 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Described solvent is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 1~70，
2-MCHA and TOP 1 ~ 70,
2-MCHA and TBU 1 ~ 70,
2-MCHA and DIBC 1 ~ 70,
Or C
9~ C
10The benzene series organism: 100,
TBU 1~70，
TBU and 2-MCHA 1 ~ 70,
TBU and TOP 1 ~ 70,
TBU and DIBC 1 ~ 70,
Or C
9~ C
10Benzene series organism 100,
DIBC 1~70，
DIBC and 2-MCHA 1 ~ 70,
DIBC and TBU 1 ~ 70,
DIBC and TOP 1 ~ 70.
3. the working fluid used of described Pd-catalyst In Fixed Bed legal system hydrogen peroxide according to claim 2 is characterized in that:
The described parts by weight that add hydrogen carrier are:
Amyl anthraquinone 100 ~ 300g/l,
Or the mixture 100 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Described solvent is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 10~60，
2-MCHA and TOP 10 ~ 60,
2-MCHA and TBU 10 ~ 60,
2-MCHA and DIBC 10 ~ 60,
Or C
9~ C
10The benzene series organism: 100,
TBU 10~60，
TBU and 2-MCHA 10 ~ 60,
TBU and TOP 10 ~ 60,
TBU and DIBC 10 ~ 60,
Or C
9~ C
10Benzene series organism 100,
DIBC 10~60，
DIBC and 2-MCHA 10 ~ 60,
DIBC and TBU 10 ~ 60,
DIBC and TOP 10 ~ 60.
4. the working fluid used of described Pd-catalyst In Fixed Bed legal system hydrogen peroxide according to claim 2 is characterized in that:
The described parts by weight that add hydrogen carrier are:
Amyl anthraquinone 200 ~ 300g/l,
Or the mixture 200 ~ 300g/l of amyl anthraquinone and 2-ethyl-anthraquinone;
Described solvent is selected a kind of in following three groups, and each component volume ratio is:
C
9~ C
10Benzene series organism 100,
2-MCHA 30~55，
2-MCHA and TOP 30 ~ 55,
2-MCHA and TBU 30 ~ 55,
2-MCHA and DIBC 30 ~ 55,
Or C
9~ C
10The benzene series organism: 100,
TBU 30~55，
TBU and 2-MCHA 30 ~ 55,
TBU and TOP 30 ~ 55,
TBU and DIBC 30 ~ 55,
Or C
9~ C
10Benzene series organism 100,
DIBC 30~55，
DIBC and 2-MCHA 30 ~ 55,
DIBC and TBU 30 ~ 55,
DIBC and TOP 30 ~ 55.
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Cited By (8)
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| CN103708426A (en) * | 2014-01-08 | 2014-04-09 | 石祖嘉 | Device for producing hydrogen peroxide by adopting anthraquinone process |
| CN104495756A (en) * | 2014-12-02 | 2015-04-08 | 江苏三鼎石化科技有限公司 | Hydrogenation method for preparing hydrogen peroxide by adopting anthraquinone process |
| CN105565277A (en) * | 2014-11-03 | 2016-05-11 | 中国石油化工股份有限公司 | Working solution for producing hydrogen peroxide through anthraquinone process |
| CN105621368A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Working fluid for production of hydrogen peroxide by anthraquinone process, and application thereof |
| CN105797748A (en) * | 2016-03-21 | 2016-07-27 | 武汉理工大学 | Preparation method of Pd-Fe/SiO2 hydrogenation catalyst |
| CN107098318A (en) * | 2017-06-15 | 2017-08-29 | 扬州惠通化工科技股份有限公司 | Produce the fluid bed hydrogenation system and hydrogenation processes of hydrogen peroxide |
| CN109806861A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of nanometer sandwich structure noble metal catalyst and application in hydrogen peroxide is directly synthesized in hydrogen and oxygen |
| CN111071994A (en) * | 2019-12-25 | 2020-04-28 | 山东新龙集团有限公司 | Fluidized hydrogenation process for preparing hydrogen peroxide by anthraquinone method |
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| CN103708426A (en) * | 2014-01-08 | 2014-04-09 | 石祖嘉 | Device for producing hydrogen peroxide by adopting anthraquinone process |
| CN103708426B (en) * | 2014-01-08 | 2015-07-29 | 石祖嘉 | Anthraquinone oxydol production apparatus |
| CN105621368B (en) * | 2014-11-03 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of working solution of hydrogen dioxide solution production by anthraquinone process and application |
| CN105565277A (en) * | 2014-11-03 | 2016-05-11 | 中国石油化工股份有限公司 | Working solution for producing hydrogen peroxide through anthraquinone process |
| CN105621368A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Working fluid for production of hydrogen peroxide by anthraquinone process, and application thereof |
| CN104495756B (en) * | 2014-12-02 | 2016-11-30 | 江苏三鼎石化科技有限公司 | The anthraquinone method for hydrogenation preparing hydrogen peroxide |
| CN104495756A (en) * | 2014-12-02 | 2015-04-08 | 江苏三鼎石化科技有限公司 | Hydrogenation method for preparing hydrogen peroxide by adopting anthraquinone process |
| CN105797748A (en) * | 2016-03-21 | 2016-07-27 | 武汉理工大学 | Preparation method of Pd-Fe/SiO2 hydrogenation catalyst |
| CN107098318A (en) * | 2017-06-15 | 2017-08-29 | 扬州惠通化工科技股份有限公司 | Produce the fluid bed hydrogenation system and hydrogenation processes of hydrogen peroxide |
| CN107098318B (en) * | 2017-06-15 | 2023-07-14 | 扬州惠通科技股份有限公司 | Fluidized bed hydrogenation reaction system and hydrogenation reaction method for producing hydrogen peroxide |
| CN109806861A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of nanometer sandwich structure noble metal catalyst and application in hydrogen peroxide is directly synthesized in hydrogen and oxygen |
| CN109806861B (en) * | 2017-11-20 | 2020-06-23 | 中国科学院大连化学物理研究所 | Preparation of nano-sandwich structure noble metal catalyst and application of nano-sandwich structure noble metal catalyst in hydrogen and oxygen direct synthesis of hydrogen peroxide |
| CN111071994A (en) * | 2019-12-25 | 2020-04-28 | 山东新龙集团有限公司 | Fluidized hydrogenation process for preparing hydrogen peroxide by anthraquinone method |
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