CN104370276A - Preparation method of hydrogen peroxide - Google Patents
Preparation method of hydrogen peroxide Download PDFInfo
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- CN104370276A CN104370276A CN201310514702.7A CN201310514702A CN104370276A CN 104370276 A CN104370276 A CN 104370276A CN 201310514702 A CN201310514702 A CN 201310514702A CN 104370276 A CN104370276 A CN 104370276A
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- 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
A preparation method of hydrogen peroxide is as follows: a working liquid and a hydrogen-containing gas are introduced into a slurry bed reactor, in the presence of a catalyst, the working liquid reacts with hydrogen to obtain a hydrogenated liquid, the hydrogenated liquid reacts with oxygen in an oxidation reactor to obtain an oxidizing solution containing hydrogen peroxide; the oxidizing solution is extracted and separated to obtain a hydrogen peroxide solution and a working fluid, the slurry bed reactor comprises a reaction cylinder (1), a separator (2) and a filter (3), a top opening of the reaction cylinder (1) extends into the separator (2), the outer wall of the reaction cylinder (1) is connected with the bottom of the separator (2), the separator (2) is communicated with the filter (3) by a liquid phase outlet (14), and a slurry outlet of the filter (3) is communicated with the bottom of the reaction cylinder (1). The method provided by the invention is stable in operation and easy in industrialization amplification. In the process of preparing of hydrogen peroxide, no alkali is introduced, and the danger of explosion led by hydrogen peroxide decomposition caused by an alkali can be avoided.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogen peroxide.
Background technology
Hydrogen peroxide is a kind of green chemical products; it is produced and use procedure is not almost polluted; therefore be called as the Chemicals of " cleaning "; as oxygenant, SYNTHETIC OPTICAL WHITNER, sterilizing agent, reductor, polymerization initiator and linking agent, be widely used in the industries such as chemical industry, papermaking, environment protection, electronics, food, medicine, weaving, mining industry, agricultural waste processing.
At present, the production method of hydrogen peroxide mainly contains electrolytic process, isopropanol method, O_2 cathodic reduction method, direct synthesis from hydrogen and oxygen, vacuum concentration method and anthraquinone etc.Wherein, anthraquinone be industrial hydrogen peroxide produce main stream approach, global industry hydrogen peroxide with yield meter more than 99% by anthraquinone production.Anthraquinonely comprise the techniques such as hydrogenation, oxidation, extraction and cycle working fluid aftertreatment.Although fixed bed hydrogenation technique is simple to operate, catalyzer need not be separated, also there is open defect, such as each several part reaction is uneven, causes hot localised points, easily produces working fluid degraded, causes catalyzer easy in inactivation, must regenerate or change; And due to the use of salt of wormwood drying tower, need the basicity controlling working fluid; Hydrogen effect low (6 ~ 7g/l) etc.Fluidized-bed hydrogenation technique is adopted can greatly to improve device production efficiency, reduce catalyzer and cycle working fluid consumption, reduce production cost, improve hydrogen effect (>10g/l), and by introducing and extract out catalyzer continuously to offset the decline of catalyst activity.Meanwhile, because fluidized-bed process makes anthraquinone hydrogenation react evenly, reaction process hot localised points is avoided to be formed and cause working fluid to be degraded.
CN1298369A and GB718307A adopts suspension bed hydrogenation.Described suspension bed hydrogenation reactor needs to fill inner member, complex structure, and between each inner member pipe, mass flow and pressure equilibrium are difficult to control, and inner member can affect the fluidization of catalyzer, affects the utilising efficiency of catalyzer.CN1817838A and CN202705039U adopts fluidized-bed hydrogenation process, and without inner member in reactor, structure is simple, easily operates.But fluidized-bed hydrogenation process device, except comprising reactor and strainer, also comprises the header tank for gas-liquid separation.When unit capacity is large, described header tank will occupy very large space, difficult arrangement.Anthraquinone adopted catalyzer is palladium, platinum isoreactivity metal is catalyzer, expensive.Fluidized-bed adopts a large amount of gas to provide circulation impellent.If granules of catalyst is carried out reactive system by gas, great loss will be caused.Even if adopt compressor that lifting gas is looped back reactor, the granules of catalyst carried out, wearing and tearing can be caused on the one hand to compressor, shorten compressor work-ing life, granules of catalyst can be caused to be broken into less particle on the other hand, cannot be tackled by strainer and enter oxidation reactor, cause decomposing hydrogen dioxide solution, can blast time serious.
CN101314120A discloses a kind of slurry bed circulatory flow reactor comprising upcast and downtake.Wherein, the negative area that upcast is expanded by reaction zone and caliber forms.Have aperture between negative area with reaction zone to be communicated with.In negative area, gas is separated with slurries, simultaneously partially catalyzed agent particles settling, and return to reaction zone by the aperture between negative area and reaction zone, the slurries after the sedimentation of granules of catalyst part enter in downtake and carry out solid-liquor separation.Because negative area catalyst particles concentration becomes Gradient distribution, bottom negative area, granules of catalyst concentration is higher, causes over-reactive generation, especially when for thermopositive reaction, easily causes the adverse consequences such as coking, catalyst deactivation.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of prepared in slurry bed reactor that adopts for the method for hydrogen peroxide, can realize continuous and stable operation.
A preparation method for hydrogen peroxide, comprising: introduce in paste state bed reactor by working fluid and hydrogen-containing gas, in the presence of a catalyst, working fluid and hydrogen reaction, after gas-liquid separation, gas from gas outlet is discharged, and the clear liquid that slurries obtain after filtering is again hydride; Hydride obtains the oxidation solution containing hydrogen peroxide in oxidation reactor with oxygen reaction; Oxidation solution extracting and separating in extraction tower obtains superoxol and working fluid; Described paste state bed reactor comprises reaction tube 1, is positioned at the separator 2 on reaction tube top and strainer 3, separator 2 inside is stretched in the open top of described reaction tube 1, the outer wall of reaction tube 1 is connected with bottom separator 2, described separator 2 is communicated with strainer 3 through liquid-phase outlet 14, described strainer 3 serum outlet is communicated with the bottom of reaction tube 1, described separator 2 top is provided with pneumatic outlet 13, and the bottom of described reaction tube 1 is provided with gas inlet 12, liquid phase entrance 11 and discharge opening 15.
In method provided by the invention, hydrogenation operational condition is pressure is 0.1 ~ 1.0MPa, preferably 0.1 ~ 0.5MPa; Temperature is 30 ~ 80 DEG C, preferably 40 ~ 70 DEG C.Oxidizing reaction operational condition is pressure is 0.1 ~ 0.5MPa, preferably 0.2 ~ 0.5MPa; Temperature of reaction is 30 ~ 60 DEG C, preferably 40 ~ 55 DEG C.
The beneficial effect of slurry reactor device provided by the invention and application method thereof is:
The preparation method of hydrogen peroxide provided by the invention, adopts paste state bed reactor to realize gas-liquid-solid three-phase successive reaction, the separation of anthraquinone hydrogenation unit.Reactant flow flow velocity in the separator on paste state bed reactor top reduces, and realizes gas and is fully separated with slurries; To be entered in strainer by separator bottom containing the slurries of solid catalyst particle and carry out solid-liquor separation, strainer can on-line automatic back flushing in turn, and easy to operate, installation and repairing is easy, can the maximization of implement device and long-period stable operation.Preparation method's apparatus structure of hydrogen peroxide provided by the invention is simple, save energy consumption, stable operation, be easy to industrialization amplifies.In addition in the process preparing hydrogen peroxide, whole system does not introduce alkali, avoids the danger that alkali causes peroxide decomposition to be blasted.The hydrogenation liquid hydrogen effect of hydrogen peroxide preparation method provided by the invention is higher, can reach more than 10g/l.
Accompanying drawing explanation
Accompanying drawing 1 is the model process figure of hydrogen peroxide preparation method provided by the invention;
Accompanying drawing 2,3 is hydrogen peroxide preparation method hydrogenation reactor schematic flow sheet provided by the invention.
Wherein:
1-reaction tube, 2-separator, 3-strainer, 4-interchanger, 5-washing section, 6-compressor, 7,8-pipeline, 11-liquid phase entrance, 12-gas inlet, 13-pneumatic outlet, 14-liquid-phase outlet, 15-discharge opening, 16-catalyst charging hole, 17-backwash liquid inlet, 18-washings entrance, 19-purified liquor outlet, 20-fluid level controller, 21-differential pressure controller, 22-serum outlet, I-hydrogenation reactor, II-oxidation reactor, III-extraction tower, IV-after-treatment device, 30-compressor, 31 ~ 41 – are pipeline.
Embodiment
Below describe the specific embodiment of the present invention in detail, wherein, " top " of the container mentioned in specification sheets refers to the position of the 0-30% of container from top to bottom, " bottom " of container refers to that the position of the 50%-100% of container from top to bottom, " bottom " of container refer to the position of the 90%-100% of container from top to bottom.
A preparation method for hydrogen peroxide, comprising: working fluid and hydrogen-containing gas are introduced hydrogenation reactor, in the presence of a catalyst, working fluid and hydrogen reaction, after gas-liquid separation, gas from gas outlet is discharged, and the clear liquid that slurries obtain after filtering is again hydride; Hydride obtains the oxidation solution containing hydrogen peroxide in oxidation reactor with oxygen reaction; Oxidation solution extracting and separating in extraction tower obtains superoxol and working fluid; Described hydrogenation reactor is paste state bed reactor.
Method provided by the invention comprises hydrogenation unit, oxidizing reaction unit and extraction cells.
(1) hydrogenation unit:
In method provided by the invention, the hydrogenation reactor that hydrogenation unit adopts is paste state bed reactor, comprise reaction tube 1, be positioned at separator 2 and the strainer 3 on reaction tube top, separator 2 inside is stretched in the open top of described reaction tube 1, the outer wall of reaction tube 1 is connected with bottom separator 2, described separator 2 is communicated with strainer 3 through liquid-phase outlet 14, described strainer 3 serum outlet is communicated with the bottom of reaction tube 1, described separator 2 top is provided with pneumatic outlet 13, the bottom of described reaction tube 1 is provided with gas inlet 12, liquid phase entrance 11 and discharge opening 15.
Working fluid is by liquid phase entrance, hydrogen-containing gas is entered in the reaction tube of paste state bed reactor by gas inlet, and the working fluid slurries containing granules of catalyst in reaction tube mix, and contact and hydrogenation occurs with granules of catalyst, anthraquinone hydrogenation is hydrofenating anthraquinone, upwards flows simultaneously; Reactant flow flows into separator from reaction tube open top, and after carrying out gas-liquid separation, slurries enter strainer from liquid-phase outlet, and hydrogenated tail gas is from the pneumatic outlet discharger at separator top; After slurries filter in the filter, clear liquid by purified liquor outlet caterpillar as hydride product; The slurries flowed out by the serum outlet of strainer return in reaction tube and continue to participate in reaction.
In described paste state bed reactor, described reaction tube 1 is 1:1.1 ~ 10 with the internal diameter ratio of separator 2.
In paste state bed reactor, the described reaction tube 1 open top height stretched in separator 2 is 10% ~ 90% of separator 2 total height.
In paste state bed reactor, described reaction tube 1 is also provided with catalyst charging hole 16.Described catalyst charging hole 16 is arranged on the sidewall of reaction tube, can be one or morely to be symmetrically distributed in sidewall circumferentially.
In paste state bed reactor, described reaction tube bottom is provided with gas inlet 12, liquid phase entrance 11 and discharge opening 15.Wherein, described liquid phase entrance 11 and gas inlet are preferably placed at reaction tube lower sides, can be one or morely to be symmetrically distributed in sidewall circumferentially, and liquid phase entrance 11 can be positioned at above or below gas inlet 12.Described discharge opening 15 is preferably placed at bottom or the bottom surface of reaction tube.In paste state bed reactor, described gas inlet place preferably arranges gas distributor, and described liquid phase ingress preferably arranges liquid distributor, is uniformly distributed and enters paste state bed reactor gas and liquid starting material.
In paste state bed reactor, described liquid-phase outlet 14 is preferably placed at the bottom of separator 2, is more preferably positioned at the bottommost of separator 2.
In paste state bed reactor, preferably interchanger 4 is set in described reaction tube 1.Described interchanger 4 can be any known interchanger form, preferred fixed tube sheet heat exchanger, double-pipe exchanger, plate-type heat exchanger, coil heat exchanger, more preferably fixed tube sheet heat exchanger.In separator 2, also interchanger 4 can be set.Also single or multiple lift interchanger can be set in hydrogenation reactor as required.
In paste state bed reactor, before described pneumatic outlet 13, be provided with washing section 5.Washing section 5 can be arranged on inside or the outside of described separator, can install inner member, as filler in washing section.In washing section, remove the solid catalyst particle carried in gas with washings.Described washings can be working fluid or reaction product hydrogenation liquid or other are containing the liquid phase medium of solid particulate.Preferred reaction product hydride.
In paste state bed reactor, described separator 2 is provided with fluid level controller 20, by regulating the leaching of purified liquor outlet 19, controls liquid level equilibrium in separator 2.
In paste state bed reactor, described strainer 3 is made up of at least one road, all right multiple strainer of arranged in parallel, the multiple strainer of preferred arranged in parallel.Arranging multichannel strainer makes easy to operate, and installation and repairing is easy, and slurry reactor device long-term stability is run.Each strainer is provided with independently filtration pressure difference and detects and automatic backflushing switching valve, utilizes the on-line automatic in turn back flushing that filter differential pressure realizes between multichannel strainer.Filtration medium in strainer 3 can be by any known filtering material as pottery, porous metal as sintering stainless steel or other make.Filtration media pore diameters should meet and not allow granules of catalyst to pass through, after comprising abrasion of particles.Therefore, its size depends on average particle size and size-grade distribution.Filtration media pore diameters scope is 0.1 ~ 100 micron, preferably 0.1 ~ 50 micron, more preferably 0.1 ~ 20 micron.Strainer 3 backwash liquid used can be liquid or gas, preferred liquid.Liquid can be the rear hydride clear liquid of fresh working fluid or filter, preferably hydride clear liquid after filter.
In method provided by the invention, described hydrogenation condition is: working pressure is 0.1 ~ 1.0MPa, preferably 0.1 ~ 0.5MPa; Temperature is 30 ~ 80 DEG C, preferably 40 ~ 70 DEG C.
In method provided by the invention, described hydrogen-containing gas is the mixed gas of pure hydrogen or pure hydrogen and rare gas element.Wherein, rare gas element preferred nitrogen.After system stability, according to the amounts of hydrogen that reaction consumes, fill into pure hydrogen to hydrogenation reactor continuously; Along with the loss of rare gas element, gap fills into rare gas element to hydrogenation reactor.
In method provided by the invention, it is formulated that described working fluid is that alkyl-anthraquinone is dissolved in organic solvent.Alkyl-anthraquinone is preferably from 2-alkyl-9, 10-anthraquinone, alkyl substituent is wherein containing 1 to 5 carbon atoms, such as methyl, ethyl, sec-butyl, the tertiary butyl, tert-pentyl and isopentyl, and 5 of correspondence, 6, 7, 8,-four hydroperoxide derivatives, or also can be selected from 9, 10-dialkyl group anthraquinone, alkyl substituent wherein can be identical or different, containing 1 to 5 carbon atoms, as methyl, ethyl and the tertiary butyl, such as 1, 3-dimethyl, 1, 4-dimethyl, 2, 7-dimethyl, 1, 3-diethyl, 2, 7-bis-(tertiary butyl), 2-ethyl-6-(the tertiary butyl) and corresponding 5, 6, 7, 8,-four hydroperoxide derivatives.The mixture of organic solvent preferably non-polar compound and polar compound.Non-polar compound preferably from the petroleum fractions of boiling point higher than 140 DEG C, wherein mainly containing the aromatic hydrocarbon of at least 9 carbon atoms, as the isomer of the isomer of Three methyl Benzene, tetramethyl-benzene, tert.-butylbenzene, the isomer of methylnaphthalene and the isomer of dimethylnaphthalene.The preferred self-saturation alcohol of non-polar compound, preferably containing the saturated alcohol of 7 to 11 carbon atoms, as diisobutyl carbinol(DIBC), 3,5,5-trimethyl hexanols, iso-heptanol; Carboxylicesters, as methylcyclohexyl acetate, heptyl acetate, butyl benzoate and oil of cognac; Phosphoric acid ester, as trioctyl phosphate, tricresyl phosphate-2-ethyl butyl ester, tricresyl phosphate-2-ethylhexyl and tricresyl phosphate-n-octyl; Quaternary urea, as four-normal-butyl urea.
In method provided by the invention, described catalyzer can use prior art known and all catalyst systems of applicable suspension method, can be supported catalyst or non-carrier type catalyzer, preferred vector type catalyzer.Supported catalyst is coated with metal by carrier granule, and wherein metal is metal in periodictable transition group VIII, preferred platinum, rhodium, palladium, cobalt, nickel or ruthenium or its two or more mixture; Equally in principle all can metal, preferably copper and/or the rhenium of life cycle table transition group I and VII.Carrier can use any known material that can be used for Kaolinite Preparation of Catalyst carrier, preferred gac, silicon carbide, aluminum oxide, silicon oxide, silicon-dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, calcium carbonate, barium sulfate or its mixture, more preferably aluminum oxide and zirconium dioxide.In carried catalyst, active metallic content is generally between about 0.01 ~ 30wt%, preferably 0.01 ~ 5wt%, especially preferably 0.1 ~ 5wt%.
Described catalyst particle diameter is 0.1 ~ 5000 micron, preferably 0.1 ~ 500 micron, more preferably 1 ~ 100 micron.Along with the reduction of catalyst activity, live catalyst can be filled into from hydrogenation reactor catalyst charging hole interval.
In method provided by the invention, the hydride that described filtration obtains before entering oxidizing reaction unit preferably again through at least one-level accurate filter, further interception small catalyst particles, especially wear and tear the granules of catalyst formed, to ensure that the hydride amount entering oxidizing reaction unit is no more than 10mg/l.
The hydride that described filtration obtains is preferably all or part of through carclazyte bed before entering oxidizing reaction unit, to regenerate the degradation product that hydrogenation produces.Wherein, the main active component of carclazyte bed is gama-alumina.
The hydrogenated tail gas of discharging after described paste state bed reactor hydrogenation preferably compresses Posterior circle to hydrogenation reactor through compressor.
In method provided by the invention, the superficial gas velocity of gas in reaction tube 1 is 0.01 ~ 1.0m/s, preferably 0.1 ~ 0.3m/s.
In method provided by the invention, the beneficial effect of hydrogenation unit preferred implementation is:
At hydrogenation unit, method provided by the invention arranged gas scrubbing section preferred embodiment before paste state bed reactor gaseous phase outlet, can effectively prevent solid catalyst particle from being taken out of by the gas of outer row.Preferably heat taking and exchanging device is set in reaction tube, according to the size of reaction heat, can be used for taking out reaction heat, control temperature of reaction, to ensure reaction efficiency.Preferred embodiment middle liquid-phase outlet is positioned at separator bottommost, makes the whole inflow filter of slurries containing solid catalyst particle, sedimentation does not occur at inside reactor, avoids that local catalyst granule density is too high causes over-reactive situation.
(2) oxidizing reaction unit
In method provided by the invention, in oxidizing reaction unit, oxygen-containing gas enters oxidation reactor, from the hydrofenating anthraquinone in the hydride of hydrogenation unit and oxygen contact reacts, Hydrogen Peroxide, obtain the oxidation solution containing hydrogen peroxide, unreacted gas discharges oxidation reactor as oxidized tail gas.
In method provided by the invention, described oxidation pressure is 0.1 ~ 0.5MPa, preferably 0.2 ~ 0.5MPa; Temperature of reaction is 30 ~ 60 DEG C, preferably 40 ~ 55 DEG C.
Described oxygen-containing gas can be the mixture of pure oxygen, air, pure oxygen and rare gas element.
Described hydride can first mix with pH value regulator, pH value is adjusted to subacidity, then enters oxidation reactor, the decomposition of the hydrogen peroxide generated to avoid oxidizing reaction.Described pH value regulator can be any known organic acid or inorganic acid solution, preferably phosphoric acid.
Described oxidation reactor can be the reactor of any form known, as stirring tank, packing tower, tray column.In oxidation reactor, the gas-liquid distribution apparatus such as filler, sieve plate, gas distributor, liquid distributor can be installed.In oxidation reactor, gas-to-liquid contact mode can be following current, also can be adverse current or cross-flow.Oxidation reactor can internal or external interchanger, takes the reaction heat that oxidizing reaction produces away, to avoid overtemperature in oxidation reactor.Oxidation reactor can within establish or peripheral hardware gas-liquid separator, for oxidation solution and oxidized tail gas being separated, caused working fluid to lose to avoid oxidation solution by the gas system of taking out of.
Described oxidized tail gas can discharge system after recycling, or compressed Returning oxidation reactor continues to participate in reaction.
In order to meet oxidizing reaction desired reaction temperature, described hydride can enter oxidation reactor again after interchanger heating or cooling.
(3) extraction cells
In method provided by the invention, aqueous extractant injects extraction tower, and the oxidation solution from oxidation reactor enters extraction tower, and after contacting with extraction agent, oxidation solution hydrogen peroxide is extracted to aqueous phase by aqueous extractant, and the raffinate of formation discharges extraction tower.Aqueous phase containing hydrogen peroxide, as object product superoxol, discharges extraction tower.
Described extraction tower pressure is normal pressure, and temperature is 40 ~ 50 DEG C.
Described aqueous extractant can be the mixture of pure water or pure water and pH value regulator.Described pH value regulator can be any known organic acid or inorganic acid solution, preferably phosphoric acid.
Described raffinate can loop back hydrogenation unit as working fluid and again participate in reaction.Raffinate preferably returns hydrogenation unit through dehydration Posterior circle.Raffinate can separate contained a small amount of moisture through coalescer, or removes moisture through other after-treatment devices, and preferred raffinate enters vacuum drying tower, and after vacuum dehydration, hydrogenation unit is returned in recirculation.Described vacuum-drying pressure is 0.1 ~ 20kPa, preferably 1 ~ 10kPa.
Described extraction tower can be the tower of any form known, as packing tower, sieve-tray tower, spray tower, pulsed packed tower etc.Liquid distributor can be installed in extraction tower.Two-phase is counter current contact in extraction tower.
Described vacuum drying tower can be tower or the separating tank of any form known, as packing tower, sieve-tray tower etc.
The concentration of described the finished product superoxol can be any known in which hydrogen peroxide solution product concentration, as 27.5%, 35%, 50% etc.
In order to satisfied extraction is temperature required, described oxidation solution can enter extraction tower again before entering extraction tower after interchanger heating or cooling.Described aqueous extractant also can enter extraction tower again after interchanger heating or cooling.
Described raffinate or the working fluid after vacuum drying tower dehydration are before looping back hydrogenation unit, preferably all or part of through carclazyte bed, to regenerate the degradation product that hydrogenation produces.Wherein, the main active component of carclazyte bed is gama-alumina.
In method provided by the invention, described " hydrogen effect " means the amount of hydrogen peroxide, with gram to represent, if namely in oxidation reactor the yield of oxidation step be 100%, the hydrogen peroxide that 1 liter of working fluid can provide when oxidation step completes.
Hydrogen peroxide preparation method provided by the invention is described with reference to the accompanying drawings, but the present invention is not therefore subject to any restriction.
Accompanying drawing 1 is the model process figure of hydrogen peroxide preparation method provided by the invention, as shown in Figure 1, mainly comprise hydrogenation unit, oxidizing reaction unit and extraction cells, working fluid enters in hydrogenation reactor I through pipeline 31, hydrogen-containing gas through pipeline 32, described hydrogenation reactor I adopts paste state bed reactor, adopt hydrogenation catalyst, granules of catalyst particle diameter is preferably 1 ~ 100 micron, the operational condition of hydrogenation reactor I is: pressure is preferably 0.1 ~ 0.5MPa, and temperature is preferably 40 ~ 70 DEG C.Reacted rear gas-liquid-solid three-phase to be separated, gas discharges hydrogenation reactor I through pipeline 36, and returns hydrogenation reactor I after compressor 30 pressurizes; Enter oxidation reactor II through pipeline 39 after isolated hydride adjust ph, in oxidation reactor II, oxygen-containing gas is introduced through pipeline 34, and the hydrofenating anthraquinone in hydride and oxygen are obtained by reacting the oxidation solution containing hydrogen peroxide under the conditions.After gas-liquid separation, oxidized tail gas is discharged through pipeline 37, oxidation solution enters extraction tower III through pipeline 40, extraction agent introduces extraction tower III through pipeline 35, described extraction agent is the pure water of phosphoric acid, go out superoxol through pipeline 38 discharger through extracting and separating, isolated working fluid is drawn by pipeline 41, returns hydrogenation reactor I recycle after subsequent processing device IV process.
Accompanying drawing 2 is hydrogen peroxide preparation method hydrogenation reactor schematic flow sheet provided by the invention, as shown in Figure 2, hydrogenation reactor adopts slurry reactor device, comprise reaction tube 1, the separator 2 on reaction tube 1 top and strainer 3, the internal diameter of described reaction tube 1 and separator 2 is than being 1:1.1 ~ 10.Separator 2 inside is stretched in the open top of described reaction tube 1, and the height that separator 2 is stretched in reaction tube 1 open top accounts for 1/10 ~ 9/10 of separator 2 total height.The outer wall of reaction tube 1 is connected with bottom separator 2, is communicated with bottom described separator 2 through liquid-phase outlet 14 with strainer 3, is communicated with bottom described strainer 3 with the bottom of reaction tube 1; Described separator 2 top is provided with pneumatic outlet 13, and the bottom of described reaction tube 1 is provided with gas inlet 12, liquid phase material entrance 11 and discharge opening 15.Interchanger 4(is set as shown in Figure 3) bottom preferred reaction cylinder.
Hydrogen-containing gas enters the bottom of the reaction tube 1 of paste state bed reactor through gas inlet 12, and sets up reactor pressure, and working pressure is 0.1 ~ 1.0MPa, preferably 0.1 ~ 0.5MPa, and temperature is 30 ~ 80 DEG C, preferably 40 ~ 70 DEG C.Working fluid enters paste state bed reactor from liquid phase entrance 11.Under the lifting of gas, working fluid flows from bottom to top in reaction tube 1, after degassed to separator 2, and the liquid-phase outlet 14 bottom self-separation device 2, and through pipeline 7 inflow filter 3, then return bottom reaction tube 1 through pipeline 8, form the self-circulation of working fluid.After working fluid circulation is set up, autocatalysis agent charging opening 16 adds the granules of catalyst of aequum to hydrogenation reactor.Along with adding of granules of catalyst, in reaction tube 1 working fluid in the presence of a catalyst with hydrogen reaction, form hydride slurries and filter through filter 3.After filtration, the hydride serum recycle being rich in granules of catalyst obtained returns reaction tube 1 to be continued to participate in reaction, and the hydride clear liquid obtained flows out from purified liquor outlet 19, enters oxidizing reaction unit.In separator 2, the isolated tail gas containing hydrogen discharging from pneumatic outlet 13 in washing section 5 after washings cleaning, also can return after compressor boosting bottom reaction tube 1 and continue to participate in reaction.
The liquid level of separator 2 is controlled by the load of adjusted cleaner liquid, backwash liquid can be injected from backwash liquid inlet 17 when strainer pressure at both sides is excessive and online backwashing is carried out to strainer 3, backwash liquid can use raw material liq, also can use the clear liquid after filter.
Be provided with interchanger 4 bottom reaction tube 1, the cold media such as recirculated water are passed into interchanger 4, take reaction heat away and regulate temperature of reaction.Live catalyst adds in reaction tube 1 by catalyst charging hole 16, and spent catalyst discharges reaction tube 1 by the discharge opening 15 bottom reaction tube, and catalyzer adds or takes out can periodical operation, also can on-line continuous carry out.
Further illustrate the present invention by the following examples, but the present invention is not therefore subject to any restriction.
Hydrogen effect measuring method in embodiment and comparative example: get 5mL hydride in separating funnel, then add the heavy aromatics of 10mL and the H of 20mL
2sO
4solution (H
2sO
4be 1:4 with the volume ratio of water); Logical O in above-mentioned mixing solutions
2, till bubbling is oxidizing to glassy yellow or safran (about 10 ~ 15min); With pure water extractive reaction liquid 4 ~ 5 times, about 20mL water at every turn; With the KMnO of concentration 0.1mol/L in extraction liquid
4standardized solution is titrated to blush, and 30s is colour-fast is terminal.Then hydrogen effect (gH
2o
2/ L)=concentration of standard solution (0.1mol/L) × standardized solution volume (mL) × 17.01/5.
In embodiment and comparative example: method for preparing catalyst is, pseudo-boehmite, silicon sol, boric acid powder and deionized water are mixed to get slurries, then obtained support of the catalyst after dry, roasting.Support of the catalyst be distributed in the solution containing Palladous chloride, deionized water, dipping, dry, roasting, obtain oxidized catalyst.With pure hydrogen, this oxidized catalyst is reduced under 150 DEG C of conditions, i.e. obtained required catalyzer.
Working fluid is the mixture of EAQ, tetrahydrochysene EAQ, trioctyl phosphate and heavy aromatics.The concentration of general anthraquinone is 130 ~ 140g/l, and the volume ratio of heavy aromatics and trioctyl phosphate is 75:25.Wherein, general anthraquinone refers to the summation of EAQ and tetrahydrochysene EAQ.
Hydride is the mixture of EAQ, tetrahydrochysene EAQ, ethyl anthracene quinhydrones, tetrahydrochysene ethyl anthracene quinhydrones, trioctyl phosphate and heavy aromatics.The concentration of general anthraquinone is 130 ~ 140g/l, and the volume ratio of heavy aromatics and trioctyl phosphate is 75:25.Wherein, general anthraquinone refers to the summation of EAQ, tetrahydrochysene EAQ, ethyl anthracene quinhydrones and tetrahydrochysene ethyl anthracene quinhydrones, and ethyl anthracene quinhydrones and tetrahydrochysene ethyl anthracene quinhydrones account for 45 % by weight of general anthraquinone.
Comparative example 1
Hydrogenation unit adopts diameter 300mm, and the fixed-bed reactor of high 8000mm, in-built median size is the granules of catalyst of 3 ~ 5mm.Pure hydrogen 22Nm
3/ h and working fluid 4.8m
3/ h, under 40 ~ 60 DEG C of reaction conditionss with 0.3MPa, after reacting in reactor, after gas-liquid separation, hydrogenated tail gas emptying, a hydride part returns reactor through heat-obtaining Posterior circle, and a part is through being cooled to 45 DEG C, after acid content is adjusted to 5mg/l by 85% phosphoric acid solution that reinjects, enter oxidation reactor.In oxidation reactor, hydride and 100Nm
3/ h air reacts the oxidation solution obtained containing hydrogen peroxide.In extraction tower, oxidation solution carries out contacting with the phosphoric acid pure water of 89kg/h and extracts, and obtains the superoxol that the finished product are 27.5%.Raffinate, after coalescer dehydration, enters salt of wormwood drying tower and to dewater further hydrogenation reactor after Posterior circle.
The hydrogen effect of hydride clear liquid is 7g/l.
Embodiment 1
As shown in Figure 3, hydrogenation unit adopts paste state bed reactor.Reaction tube diameter is 300, and separator diameter is 800; Being provided with washing section diameter is 300, the BX500 filler of in-built high 300mm.Pure hydrogen 42Nm
3/ h enters paste state bed reactor through gas inlet, and heater via is preheated to the working fluid 4.8m of 60 DEG C
3/ h enters paste state bed reactor from liquid phase entrance, and the catalyzer autocatalysis agent charging opening of 72kg adds paste state bed reactor.Under 60 DEG C of reaction conditionss with 0.4MPa, in working fluid, anthraquinone generation hydrogenation reaction forms hydride.Form hydride slurries through filter, use the strainer of three groups of parallel connections, in-built metal filtering core, adopt hydride clear liquid as backwash liquid, every 1h recoil is once.The slurries being rich in granules of catalyst after filtration are cooled to 45 DEG C of Posterior circle through interchanger and return continuation participation reaction in reaction tube, and the hydride clear liquid obtained through filter flows out hydrogenation unit from purified liquor outlet.
Air 260Nm
3/ h is through air compressor machine force feed to oxidation reactor, and setting up reactor pressure is 0.3MPa.Hydride from hydrogenation unit is cooled to 45 DEG C through water cooler, injects 85% phosphoric acid solution and acid content is adjusted to 5mg/l, then after two-stage accurate filter, enter in oxidation reactor.Hydride and oxygen contact reacts, Hydrogen Peroxide, obtains the oxidation solution containing hydrogen peroxide.Oxidized tail gas is through cooling recovery operation liquid, and emptying after carbon fiber absorbs.
Pure water 62kg/h containing phosphoric acid injects extraction tower.Oxidation solution from oxidation reactor enters extraction tower, after contacting with water, oxidation solution hydrogen peroxide is extracted by water, and the raffinate of formation loops back hydrogenation unit as working fluid after coalescer and vacuum drying tower dehydration, and the pressure of vacuum drying tower is 5kPa.Water obtains the superoxol that the finished product are 45% after being extracted by hydrogen peroxide.
The hydrogen effect of hydride clear liquid is 13.3g/l.
Embodiment 2
The device adopted and flow process are with embodiment 1, and it is 32Nm that hydrogenation unit enters pure hydrogen amount
3/ h, air capacity that oxidation reactor enters is 198Nm
3/ h, it is 73kg/h that extraction cells enters phosphoric acid pure water, and other conditions are with embodiment 1.The hydrogen effect of hydride clear liquid is 10.1g/l, and the finished product are the superoxol of 35%.
From embodiment 1,2 and comparative example 1, the hydrogen effect of hydrogen peroxide preparation method provided by the invention can be increased to more than 10g/l, and prepared superoxol concentration also correspondingly can be increased to more than 30%.There is good economic benefit, and contribute for the energy-saving and cost-reducing environmental protection of downstream industry.
Claims (18)
1. a preparation method for hydrogen peroxide, comprising: introduce in paste state bed reactor by working fluid and hydrogen-containing gas, in the presence of a catalyst, working fluid and hydrogen reaction, after gas-liquid separation, gas from gas outlet is discharged, and the clear liquid that slurries obtain after filtering is again hydride, hydride obtains the oxidation solution containing hydrogen peroxide in oxidation reactor with oxygen reaction, oxidation solution extracting and separating in extraction tower obtains superoxol and working fluid, it is characterized in that, described paste state bed reactor comprises reaction tube (1), be positioned at separator (2) and the strainer (3) on reaction tube top, separator (2) inside is stretched in the open top of described reaction tube (1), the outer wall of reaction tube (1) is connected with separator (2) bottom, described separator (2) is communicated with strainer (3) through liquid-phase outlet (14), described strainer (3) serum outlet is communicated with the bottom of reaction tube (1), described separator (2) top is provided with pneumatic outlet (13), the bottom of described reaction tube (1) is provided with gas inlet (12), liquid phase entrance (11) and discharge opening (15).
2. method according to claim 1, is characterized in that, described reaction tube (1) is 1:1.1 ~ 10 with the internal diameter ratio of separator (2).
3. method according to claim 1, is characterized in that, the height that separator (2) is stretched in described reaction tube (1) open top is 10% ~ 90% of separator (2) total height.
4. method according to claim 1, is characterized in that, arranges interchanger (4) in described reaction tube (1).
5. according to any one method in claim 1-4, it is characterized in that, described reaction tube (1) is also provided with catalyst charging hole (16).
6. according to any one method in claim 1-4, it is characterized in that, described liquid-phase outlet (14) is positioned at the bottom of separator (2).
7. according to any one method in claim 1-4, it is characterized in that, in described separator (2), interchanger (4) is set.
8. according to any one method in claim 1-4, it is characterized in that, before described pneumatic outlet (13), be provided with washing section (5), introduce the granules of catalyst carried in working fluid or hydride washing gas at washing section (5).
9. according to any one method in claim 1-4, it is characterized in that, the pneumatic outlet expellant gas of described paste state bed reactor loops back paste state bed reactor.
10. according to any one method in claim 1-4, it is characterized in that, the superficial gas velocity of gas in reaction tube is 0.01 ~ 1.0m/s.
11. methods according to claim 10, is characterized in that, the superficial gas velocity of gas in reaction tube 1 is 0.1 ~ 0.3m/s.
12., according to any one method in claim 1-4, is characterized in that, described strainer is metal film filter.
13., according to any one method in claim 1-4, is characterized in that, described catalyzer is the supported catalyst of load regulation group VIII metal on heat-resistant inorganic oxide.
14. methods according to claim 12, is characterized in that, described granules of catalyst particle diameter is 0.1 ~ 5000 micron.
15. methods according to claim 12, is characterized in that, described granules of catalyst particle diameter is 1 ~ 100 micron.
16., according to any one method in claim 1-4, is characterized in that, it is formulated that described working fluid is that alkyl-anthraquinone is dissolved in organic solvent.
17., according to any one method in claim 1-4, is characterized in that, the hydride from slurry bed system enters oxidation reactor again after at least one-level secondary filter.
18., according to any one method in claim 1-4, is characterized in that, the working fluid that described extraction tower obtains returns in paste state bed reactor after vacuum dehydration.
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| 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 |
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| CN114644321A (en) * | 2020-12-21 | 2022-06-21 | 大连理工江苏研究院有限公司 | Improved system and process for preparing hydrogen peroxide based on anthraquinone method |
| CN115784167A (en) * | 2022-12-20 | 2023-03-14 | 江苏嘉宏新材料有限公司 | Oxidation extraction process for preparing hydrogen peroxide by anthraquinone process |
| CN115784167B (en) * | 2022-12-20 | 2024-05-07 | 江苏嘉宏新材料有限公司 | Oxidation extraction process for preparing hydrogen peroxide by anthraquinone method |
| CN117548043A (en) * | 2024-01-09 | 2024-02-13 | 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 |
| 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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