CN100371309C - Hydrogenation process of hydrogen peroxide fluidized bed by anthraquinone - Google Patents
Hydrogenation process of hydrogen peroxide fluidized bed by anthraquinone Download PDFInfo
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- CN100371309C CN100371309C CNB2006100548346A CN200610054834A CN100371309C CN 100371309 C CN100371309 C CN 100371309C CN B2006100548346 A CNB2006100548346 A CN B2006100548346A CN 200610054834 A CN200610054834 A CN 200610054834A CN 100371309 C CN100371309 C CN 100371309C
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- anthraquinone
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Abstract
The present invention provides a stredford hydrogenation process of producing a hydrogen peroxide fluidized-bed, which is characterized in that an empty tower hydrogenization reactor with an amplification section on the top is adopted; working liquid and hydrogen move upward at specific speed, so that a powdered catalyst is suspended in a tower body to complete hydrogenization reaction by free contact; hydrogenated liquid is separated by a gas-liquid separating system, filtered by a filtering system and oxidized. Compared with other hydrogenization modes, the process has the advantages of more uniform distribution of a catalyst in the bed, higher utilization efficiency of the catalyst, higher reactor productivity, higher hydrogenization speed and shorter idle time.
Description
Technical field
The present invention relates to process for prepairng hydrogen peroxide by anthraquinone (H
2O
2) technology, particularly hydrogenation process.
Background technology
At present, producing the hydrogen peroxide majority both at home and abroad adopts anthraquinone.This method production process is: in the presence of catalyzer, under certain temperature and pressure, alkyl-anthraquinone (hereinafter to be referred as anthraquinone) and hydrogen reaction in the working fluid (organic solution that alkyl-anthraquinone and mixed organic solvents are made into by a certain percentage), generate corresponding hydrogen anthraquinone, this moment, working fluid was called hydride, hydrogen anthraquinone in the hydride and oxygen reaction, generate primary anthraquinone and hydrogen peroxide, hydride becomes oxidation liquid simultaneously, oxidation liquid obtains aqueous hydrogen peroxide solution through the pure water extraction, and raffinate circulates after treatment and returns hydrogenation process.
The main chemical reactions that exists in the hydrogen peroxide obtained by anthraquinone process production process is hydrogenation and oxidizing reaction, and reaction principle is that (R is C in the reaction formula
2～C
5Alkane):
Hydrogenation:
Oxidizing reaction:
The main chemical reactions and the principle of process for prepairng hydrogen peroxide by anthraquinone are basic identical both at home and abroad, but concrete technical scheme difference, the key distinction is the difference of working fluid composition, hydrogenation catalyst and hydrogenation mode.What the hydrogenation mode was commonly used is fixed-bed process and fluidized-bed process.
Compare with fixed-bed process, in fluidized-bed process, because working fluid and hydrogen is suspended in catalyzer wherein, catalyzer utilising efficiency height, consumption is few, consumption is low, and reactor volume is little, and hydrogenation efficiency is higher.
In Patent data GB 718,307, the hydrogenation of anthraquinone is to carry out in the bubble column fluidized-bed, and the tubulose inner member wherein is housed, and hydrogen is introduced from the bottom of each root, mixes with the mobile working fluid that makes progress in pipe then, enters reactor by a sparger.The shortcoming of this technology is that device structure is complicated, and mass flow between each inner member pipe and pressure equilibrium are difficult to control.
Propose the hydrogenation process carry out in the special bubble column fluidized-bed of wire packing is housed among the Patent data CN 1,298,369, hydrogen, is discharged from reactor from bottom introducing reactor then with after the working fluid that contains suspended catalyst mixes in mixing nozzle.Owing to wire packing is housed in the fluidized-bed of this technology, influenced the fluidization of catalyzer greatly, make catalyzer skewness in bed, influenced the utilising efficiency of catalyzer.
Summary of the invention
The technical problem to be solved in the present invention provides the novel hydrogenated technology of a kind of process for prepairng hydrogen peroxide by anthraquinone.This technology is a kind of efficient gas one liquid one solid phase reaction technology.Technical scheme of the present invention is, hydrogenation carries out in fluidized-bed, it is characterized in that adopting top to have the void tower hydrogenation reactor that amplifies section, working fluid and hydrogen move upward with certain speed, powdered catalyst is suspended in the tower body finishes hydrogenation by freely contacting, hydride enters oxidation section after Separate System of Water-jet separation and filtration system filters.The reactor of this technology is a void tower, and the bottom is the main body conversion zone, and top is for amplifying settling section, and catalyzer is more evenly distributed in bed, and the utilising efficiency of catalyzer is higher, so hydrogenation rate is fast, efficient is high.Accompanying drawing is this hydrogenation process schematic flow sheet.Operation after the hydrogenation, other processes of mixing the method preparing hydrogen peroxide with anthracene are identical.
The present invention realizes in the following manner: working fluid and hydrogen enter hydrogenation reactor 1 bottom through liquid distributor 3 and gas distributor 2 respectively, under certain temperature and pressure, anthraquinone in the working fluid and hydrogen, in the presence of the powdered catalyst that freely suspends, reaction generates the hydrogen anthraquinone.After hydrogenation was finished, hydride was through the amplification section on hydrogenation reactor 1 top, and most of catalyst sedimentation wherein, small part not sedimentation catalyzer, the unreacted hydrogen of residue and hydride enter gas-liquid separator 4 in the lump and carry out solution-air and separate.Separated hydrogen, small part emptying, all the other enter hydrogenation reactor 1 bottom with fresh hydrogen through gas distributor 2; Enter filtering system from the gas-liquid separator 4 isolated hydrides that contain little amount of catalyst, filter through filter 5 or 6, the catalyzer detention is filtered the back hydride and is entered hydride storage tank 9 in filtering system.
The strainer cleaning way is a scavenging solution recoil mode, and scavenging solution can be working fluid or hydride.Scavenging solution enters the strainer that is in the cleaning state from scavenging solution storage tank 7 through cleaning liquid pump 8, rinses out the catalyzer that is attached on the filtration medium, and the scavenging solution that contains catalyzer returns hydrogenation reactor 1 bottom.The scavenging solution flow is 0.1/1～0.9/1 with the ratio of working fluid flow, preferred 0.2/1～0.7/1.
For making the production serialization, filtering system preferably is made up of two groups or more strainer, and wherein at least one group (as accompanying drawing middle filtrator 5) is in the filtration state, separates the catalyzer of carrying secretly in the hydride; Other groups (as accompanying drawing middle filtrator 6) are in the backwash state, and the catalyst wash of detention is returned hydrogenation reactor 1, continue to use, and this two condition can be realized regularly automaticallying switch by valve.
The hydrogenation reactor of technology of the present invention is a heat-insulating, and the reactor interior reaction temperature is mediated by preheating of advancing a working fluid or precooling.This hydrogenation reactor divides two sections: hypomere main body conversion zone and epimere amplify settling section, and main body conversion zone aspect ratio is 10/1～100/1, and be preferred 15/1～30/1, and amplifying settling section is 2/1～5/1 with conversion zone diameter ratio, and preferred 4/1～5/1.
The hydrogenation reactor bottom is provided with gas-liquid distributor, this sparger is industrial common type such as orifice-plate type, gas-liquid distributor makes solid (powder palladium catalyst) the three-phase thorough mixing of gas (hydrogen) liquid (working fluid), realizes powder palladium catalyst fluidization operation according to this, finishes hydrogenation.
In order to implement the present invention, contain one or more anthraquinones and corresponding tetrahydro-anthraquinone thereof and be dissolved in the suitable solvent and form working solution.The alkyl-anthraquinone (RAQ) and the corresponding tetrahydro-anthraquinone (H thereof that can be used for the inventive method
4RAQ) have: 2-ethyl-anthraquinone, 2-sec.-propyl anthraquinone, 2-normal-butyl anthraquinone, 2-sec-butyl anthraquinone, 2-tertiary butyl anthraquinone, 2-amyl anthraquinone, 2-sec.-amyl sec-pentyl secondary amyl anthraquinone, 2-tert-pentyl anthraquinone or its mixture, and and their corresponding tetrahydro-anthraquinone and mixtures.For improving the solubleness of hydrogen anthraquinone in working fluid, the anthraquinone (RAQ) and the tetrahydro-anthraquinone (H of the used working fluid of this technology
4RAQ) the quality proportioning is 4: 1～1: 4, and preferable range is 3: 2～2: 3.
Be applicable to that organic solvent of the present invention is that routine is used for those solvents of process for prepairng hydrogen peroxide by anthraquinone and composition thereof, particularly two or more are suitable for different quinone dissolved solvent mixtures.Suitable nonpolar aromatic solvent comprises the aromatic hydrocarbons, particularly C that alkyl replaces
8And C
12Alkylbenzene or its mixture.Suitable polar solvent comprises higher alcohols (as diisobutyl carbinol(DIBC) or sec-n-octyl alcohol), alkyl or aryl urea, phosphoric acid ester (as trioctyl phosphate), 2-Pyrrolidone, acetic acid methyl cyclohexane ester or its mixture.The nonpolar aromatic solvent (quinone solvent) of the used working fluid of this technology and polar solvent (hydroquinone solvents) volume proportion scope 4: 1～1: 4.Preferred proportion is different different because of solvent types.As (volume ratio): aromatic hydrocarbons: trioctyl phosphate=3: 1; Aromatic hydrocarbons: tetrabutyl urea=3: 1; Aromatic hydrocarbons: acetic acid methyl cyclohexane ester=1: 1; Aromatic hydrocarbons: diisobutyl carbinol(DIBC)=1: 1 etc.
Technology catalyst system therefor of the present invention is carrier model or non-supported catalyst, catalyzer median size 0.0001mm～2mm.Preferential all catalyst systems of the known and suitable suspension method of use technology.The supported catalyst active metallic content is 0.3%～5%.
Supported catalyst is made by one or more transition group of carrier granule load VIII family metal, as Pd/ synthetic zeolite, Pd/Al
2O
3Or Pd/SiO
2Deng.Though can use any solid support material that becomes known for preparing catalyzer in principle, but preferentially use gac, silicon carbide, aluminum oxide, silicon oxide, silicon-dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, lime carbonate, barium sulfate or its mixture, more preferably silicate such as aluminum oxide, synthetic zeolite or silicon-dioxide or aluminate class are carrier; Reactive metal preferentially uses platinum, rhodium, palladium, cobalt, nickel, ruthenium or its mixture, and override uses palladium.
The non-supported catalyst that same magnesium-yttrium-transition metal is made also can be used among the present invention, as raney nickel catalyst, palladium black catalyzer.
Process conditions of the present invention: hydrogenation reactor top gaseous pressure scope 0.1MPa～0.5MPa is preferably 0.15MPa～0.4MPa; 20 ℃～70 ℃ of reactor temperature scopes, preferred 40 ℃～60 ℃; 0.2h～1.0h when working fluid passes through the reactor sky, preferred 0.4h～0.7h.
The invention has the beneficial effects as follows: 1. do not have filler in the reactor, working fluid fully freely contacts with hydrogen, hydrogenation efficiency height, the throughput of raising reactor; 2. reactor top, base pressure difference are little, and the bed resistance is low.3. short when empty, hydrogenation rate is fast.
Description of drawings
Accompanying drawing is a fluidized-bed hydrogenation process schematic flow sheet.
Wherein: the 1st, hydrogenation reactor
The 2nd, gas distributor
The 3rd, liquid distributor
The 4th, gas-liquid separator
The 5th, strainer I
The 6th, strainer II
The 7th, the scavenging solution storage tank
The 8th, scavenging pump
The 9th, the hydride storage tank
Embodiment
Embodiment 1
Prepare hydrogen peroxide on whole process (comprising hydrogenation, oxidation, extraction, postprocessing working procedures) hydrogen peroxide unit, hydrogenation process adopts technology of the present invention (seeing accompanying drawing).Working fluid system: heavy aromatics+acetic acid methyl cyclohexane ester+2-ethyl-anthraquinone+tetrahydrochysene 2-ethyl-anthraquinone.Wherein: heavy aromatics: acetic acid methyl cyclohexane ester (V: V)=1: 1; 2-ethyl-anthraquinone: the tetrahydrochysene 2-ethyl-anthraquinone (m: m)=2: 1.It is the catalyzer of carrier loaded palladium that catalyzer adopts with aluminate, mean diameter 0.18mm, palladium content 1.86%.Hydrogenation reactor conversion zone Ф 40 * 3500mm amplifies settling section Ф 100 * 7000mm.The hydrogenation process process conditions: hydrogenation reactor top gaseous pressure is 0.2MPa, and temperature is 45 ℃ in the hydrogenation reactor, and working fluid is 0.52h by hydrogenation reactor when empty, and the scavenging solution flow is 0.3 with the ratio of working fluid flow.Related data is listed in table 1.
Embodiment 2
Prepare hydrogen peroxide on whole process (comprising hydrogenation, oxidation, extraction, postprocessing working procedures) hydrogen peroxide unit, hydrogenation process adopts technology of the present invention (seeing accompanying drawing).Working fluid system: heavy aromatics+trioctyl phosphate+2-ethyl-anthraquinone+tetrahydrochysene 2-ethyl-anthraquinone.Wherein: heavy aromatics: trioctyl phosphate (V: V)=3: 1; 2-ethyl-anthraquinone: the tetrahydrochysene 2-ethyl-anthraquinone (m: m)=2: 1.It is the catalyzer of carrier loaded palladium that catalyzer adopts with silicate, mean diameter 0.14mm, palladium content 2%.Hydrogenation reactor conversion zone Ф 500 * 15000mm amplifies settling section Ф 100mm * 3000mm.The hydrogenation process process conditions: hydrogenation reactor top gaseous pressure is 0.3MPa, and temperature is 50 ℃ in the hydrogenation reactor, and working fluid is 0.67h by hydrogenation reactor when empty, and the scavenging solution flow is 0.4 with the ratio of working fluid flow.Related data is listed in table 1.
Table 1 embodiment data
| Embodiment | Catalyst reactor density, g/L | Hydrogenation efficiency, gL -1 | Total anthraquinones content in the working fluid, gL -1 | The anthraquinone transformation efficiency, % | Hydrogenation reactor throughput, kgm -3·h -1 | During the work liquid air, h | The bed roof pressure, MPa | The bed base pressure, MPa |
| Embodiment 1 | 12 | 8.9 | 125 | 50 | 364 | 0.53 | 0.15 | 0.1 |
| Embodiment 2 | 15 | 9.9 | 125 | 55.5 | 369.6 | 0.67 | 0.2 | 0.15 |
Annotate: working fluid equals reactor volume divided by the working fluid flow by the empty duration of hydrogenation reactor.
Claims (10)
1. hydrogenation process of hydrogen peroxide fluidized bed by anthraquinone, it is characterized in that: adopt top to have the void tower hydrogenation reactor that amplifies section, working fluid and hydrogen move upward with certain speed, powdered catalyst is suspended in the tower body finishes hydrogenation by freely contacting, hydride enters oxidation operation after Separate System of Water-jet separation and filtration system filters.
2. according to the described technology of claim 1, it is characterized in that hydrogenation reactor main body conversion zone aspect ratio is 10/1～100/1, amplifying settling section is 2/1～5/1 with main body conversion zone diameter ratio, and the catalyzer median size is 0.0001mm～2mm.
3. according to claim 1 or 2 described technologies, it is characterized in that hydrogenation reactor main body conversion zone aspect ratio is 15/1～30/1, amplifying settling section is 4/1～5/1 with main body conversion zone diameter ratio.
4. according to the described technology of claim 1, it is characterized in that catalyzer is meant that with gac, silicon carbide, aluminum oxide, silicon oxide, silicon-dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, lime carbonate, barium sulfate or its mixture be carrier, is the carried catalyst of reactive metal with platinum, rhodium, palladium, cobalt, nickel, ruthenium or its mixture.
5. according to claim 1 or 4 described technologies, it is characterized in that catalyzer is meant that with aluminum oxide or silicon-dioxide be carrier, is the carried catalyst of reactive metal with the palladium.
6. according to the described technology of claim 1, it is characterized in that catalyzer is meant Raney Ni or palladium black unsupported catalysts.
7. according to the described technology of claim 1, it is characterized in that nonpolar aromatic solvent and polar solvent volume ratio are 4: 1～1: 4 in the working fluid, nonpolar aromatic solvent is meant aromatic hydrocarbons or its mixture that alkyl replaces, and polar solvent is higher alcohols, alkyl or aryl urea, phosphoric acid ester, 2-Pyrrolidone, acetic acid methyl cyclohexane ester or its mixture; Anthraquinone is meant 2-ethyl-anthraquinone, 2-sec.-propyl anthraquinone, 2-normal-butyl anthraquinone, 2-sec-butyl anthraquinone, 2-tertiary butyl anthraquinone, 2-amyl anthraquinone, 2-sec.-amyl sec-pentyl secondary amyl anthraquinone, 2-tert-pentyl anthraquinone or its mixture in the working fluid, with their corresponding tetrahydro-anthraquinones or its mixture, anthraquinone and tetrahydro-anthraquinone mass ratio are 4: 1～1: 4.
8. according to the described technology of claim 1, it is characterized in that filtering system comprises two set filters at least, one group is in the filtration state, and other groups are in the backwash state, and the strainer working order can realize regular automatic switchover; The strainer cleaning way is a scavenging solution recoil mode, and scavenging solution is working fluid or hydride; The scavenging solution flow is 0.1/1～0.9/1 with the ratio of working fluid flow.
9. according to the described technology of claim 1, it is characterized in that hydrogenation reactor top gaseous pressure is 0.1MPa～0.5MPa; 20 ℃～70 ℃ of reactor temperature scopes; 0.2h～1.0h when working fluid passes through the reactor sky.
10. according to the described technology of claim 1, it is characterized in that hydrogenation reactor is a heat-insulating, reactor temperature is mediated by preheating of advancing the reactor working fluid or precooling.
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|---|---|---|---|
| CNB2006100548346A CN100371309C (en) | 2006-02-17 | 2006-02-17 | Hydrogenation process of hydrogen peroxide fluidized bed by anthraquinone |
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| CN100371309C true CN100371309C (en) | 2008-02-27 |
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| CN107098317B (en) * | 2017-06-15 | 2023-06-27 | 扬州惠通科技股份有限公司 | System and method for producing hydrogen peroxide by anthraquinone process |
| CN107032305B (en) * | 2017-06-15 | 2023-07-14 | 扬州惠通科技股份有限公司 | Hydrogen peroxide production system and production method |
| CN109626336A (en) * | 2019-01-09 | 2019-04-16 | 中国科学院金属研究所 | The production method of hydrogen peroxide on a kind of structural catalyst |
| CN110040690A (en) * | 2019-01-31 | 2019-07-23 | 滨化集团股份有限公司 | Hydrogenation fluid catalyst separation extraction technique and its device in a kind of hydrogen peroxide manufacture |
| CN111732083A (en) * | 2020-05-26 | 2020-10-02 | 湖北三里枫香科技有限公司 | Fluidized bed hydrogen peroxide process |
| CN114702012A (en) * | 2022-04-06 | 2022-07-05 | 山东华鲁恒升化工股份有限公司 | Working solution, preparation method thereof and application of working solution in production of hydrogen peroxide by anthraquinone process |
| CN116281870B (en) * | 2023-02-14 | 2023-10-13 | 江苏中煦科技有限公司 | Process for producing hydrogen peroxide by anthraquinone method |
| CN117380183B (en) * | 2023-12-04 | 2024-02-20 | 黎明化工研究设计院有限责任公司 | Preparation method and application of supported palladium nanoparticle catalyst |
| CN117548043B (en) * | 2024-01-09 | 2024-04-02 | 黎明化工研究设计院有限责任公司 | Fluidized bed hydrogenation device for producing hydrogen peroxide by anthraquinone process and application method thereof |
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