CN101553427A - Process for producing monopersulfuric acid and monopersulfuric acid continuous production apparatus - Google Patents
Process for producing monopersulfuric acid and monopersulfuric acid continuous production apparatus Download PDFInfo
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- CN101553427A CN101553427A CNA2007800390744A CN200780039074A CN101553427A CN 101553427 A CN101553427 A CN 101553427A CN A2007800390744 A CNA2007800390744 A CN A2007800390744A CN 200780039074 A CN200780039074 A CN 200780039074A CN 101553427 A CN101553427 A CN 101553427A
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Abstract
A process for producing a highly stable solution of monopersulfuric acid, characterized by including mixing hydrogen peroxide of 35 wt.% or higher with sulfuric acid of 70 wt.% or higher, reacting them, cooling the reaction solution to 80 DEG C or below within 5 min from the initiation of the mixing and thereafter diluting the reaction solution with water amounting to at least 4 times the weight thereof. Further, there is provided a monopersulfuric acid continuous production apparatus characterized by having a first static mixer for mixing and reaction of hydrogen peroxide and sulfuric acid; a second static mixer for mixing the reaction solution obtained by the first static mixer with the diluent water; and a reaction solution transfer pipe from the first static mixer to the second static mixer, the first static mixer and reaction solution transfer pipe disposed in the water within a vessel. In this process for producing a solution of monopersulfuric acid, there can be attained minimization of any decomposition of monopersulfuric acid solution at the production thereof and stable, safe continuous production of monopersulfuric acid solution which can be stored for a prolonged period of time after production thereof.
Description
Technical field
The present invention relates to the preparation method of single persulfuric acid of yield height and excellent in stability.The invention still further relates to the device that is used for preparing continuously single persulfuric acid in addition.Prepared single persulfuric acid is used for the bleaching processing that draining is handled, system paper is used dissolving pulp etc.
Background technology
Single persulfuric acid is with chemical formula H
2SO
5Expression is called and is " Caro's acid ", and known all the time its has excellent bleaching effect, sterilization effect.Single persulfuric acid is because its strong oxidation capacity, and expectation is as the etching reagent of the surface working of the copper of metal finishing or copper alloy, as the purposes of pickling agent, or as the purposes of sterilant, waste water conditioner.
Known single persulfuric acid is generated by the reaction of the hydrogen peroxide and the vitriol oil.But, be attended by a large amount of heat releases and the single persulfate solution instability that is generated during owing to generation, can not preserve for a long time, therefore under laboratory level, use, and on industrial level, use hardly.
Method as the shortcoming of the poor stability of eliminating single persulfate solution has proposed several preparation methods.Because therefore the poor stability of the single persulfuric acid that is generated uses in the short period of time as far as possible, owing to decompose the method for the loss that is caused, proposed (near the field of employment, to prepare) at the scene the method for preparation as doing one's utmost to suppress after preparation.
Owing to exist because of hydrogen peroxide and the decomposition of emitting a large amount of single persulfuric acid that heat caused after the vitriol oil mixes, to disclose and made the reaction times be several seconds, be cooled to and afterwards, further use the water-reducible method of refrigerative below the normal temperature then.In this method, essential lot of energy of cooling or device can be implemented in limited production, but as the method existing problems (with reference to patent documentation 1) of producing a large amount of single persulfuric acid.
Someone has proposed to make hydrogen peroxide and strong sulfuric acid response in having the container of stirrer, that is, and and the method for in the waste water that contains cyanogen, adding continuously.In this method, in single persulfate solution of high temperature heat release, add new hydrogen peroxide, the vitriol oil, thereby exist hydrogen peroxide decomposition to make single persulfuric acid generate the problem (with reference to patent documentation 2) that yield significantly reduces.
It is big that the single persulfuric acid that has proposed at present prepares facility, and the refrigerating plant volume is also big, and as field device, cost might greatly as improveing the method that reactor makes its miniaturization, propose the method that is prepared in airtight ring-type reaction chamber.This method is the method with the part miniaturization of hydrogen peroxide and strong sulfuric acid response, for the unresolved any problem of decomposition (with reference to patent documentation 3) owing to the resultant list persulfuric acid that reaction heat caused.
Method as the reaction yield that improves single persulfuric acid discloses the method that branch adds hydrogen peroxide several times in the vitriol oil.This method exists device to maximize and complicated problems owing to cold water (water coolant) control reaction temperature, divide several stages to add chemical reagent.In addition, the stabilization for the single persulfuric acid that generates does not propose any countermeasure (with reference to patent documentation 4).
As the stabilization method of the single persulfate solution that generates, proposed pH is controlled at 0.5～2.0 method.Might stabilization if be controlled in this pH scope then, but industrial scene carries out pH to single persulfate solution of a large amount of generations and adjusts, owing to be attended by big heat release, is necessary to cool off, and therefore exists device to become big problem.In addition, the alkali of essential a large amount of adjustment pH, not preferred (with reference to patent documentation 5) economically.
As the preparation facilities of single persulfuric acid, the method for the hydroperoxidation of known sulfuric acid that makes high density and high density.But, if the temperature that heat release was caused when desiring to prepare single persulfuric acid in a large number and then be difficult to control because of reaction with intermittent mode rises, so the problem that exists the synthesis yield of single persulfuric acid to reduce.Further, also there is the prepared common deficient in stability of single persulfuric acid, is difficult to the problem of prolonged preservation.
As the technical scheme of avoiding the problems referred to above, the device that (so-called on-the-spot) prepares single persulfuric acid has continuously been proposed near the field of employment.
In the patent documentation 2, disclose 2 reaction reagent transfer limes, made the reaction unit that have chuck of product from certain water level overflow with balanced configuration.But when utilizing this device, when particularly being amplified to technical scale, because cooling performance is insufficient, existence can not be avoided the problem that reaction yield reduces or installation cost increases.
Further, disclose in the patent documentation 3 shape of reaction chamber has been studied the method for preparing single persulfuric acid effectively, but concrete record has not been arranged about cooling scheme to heat release.In addition, it is not on the books by the technical scheme of direct contacts such as operator on every side to spill Shi Buhui for the dope contingency at single persulfuric acid.
Patent documentation 1: No. 2789954 specification sheets of United States Patent (USP)
Patent documentation 2: Japanese kokai publication sho 57-132591 communique
Patent documentation 3: the flat 6-501672 communique of Japanese Unexamined Patent Application Publication
Patent documentation 4: No. 5141731 specification sheets of United States Patent (USP)
Patent documentation 5: Japanese kokai publication hei 10-95602 communique
Summary of the invention
First purpose of the present invention is, in the preparation of single persulfate solution, the decomposition of the single persulfate solution when preparation can be with preparation be suppressed at after inferior limit and the preparation can prolonged preservation single persulfate solution.
The inventor studies intensively for the method for preparing single persulfate solution with hydrogen peroxide and sulfuric acid, found that, with hydrogen peroxide with after sulfuric acid mixes, be cooled to specified temperature immediately at the appointed time, water with specified amount dilutes then, can obtain stable single persulfate solution thus, thereby finish the present invention.
That is, the present application relates to following formula (1)～(6).
(1) preparation method of single persulfate solution that stability is high, it is characterized in that, hydrogen peroxide more than the 35 weight % and the sulfuric acid more than the 70 weight % are mixed, they are reacted under the temperature more than 90 ℃, reaction soln is cooled to below 80 ℃ with interior mixing back 5 minutes of beginning, then reaction soln is diluted with the water more than 4 times of weight.
(2) as the method for above-mentioned (1), it is characterized in that, reaction soln is cooled to 40 ℃～80 ℃.
(3) as the method for above-mentioned (1), it is characterized in that, the water dilution of reaction soln with 4 times of weight～10 times of weight.
(4) as the method for above-mentioned (1), wherein, use iron level to be the sulfuric acid below the 20ppm.
(5) as the method for above-mentioned (1), wherein, after reaction soln being cooled to below 80 ℃, add alkali aqueous solution.
(6) preparation method of single persulfate solution, it is characterized in that, hydrogen peroxide more than the 35 weight % and the sulfuric acid more than the 70 weight % are mixed, they are being reacted above under 80 ℃ the temperature, reaction soln is cooled to below 80 ℃ with interior mixing back 5 minutes of beginning, then reaction soln is diluted with the water more than 4 times of weight.
Second purpose of the present invention is, is provided for device stable and the single persulfuric acid of continuous safely preparation.
The inventor studies intensively single persulfuric acid continuous preparation device, found that, by using static mixer and mixing tank being arranged in the water, can be with high yield and stably synthetic single persulfuric acid, and can not make the dope of single persulfuric acid directly leak into the outside, thereby finish the present invention.Promptly, the present invention relates to single persulfuric acid continuous preparation device, this device is characterised in that, have hydrogen peroxide and sulfuric acid mixed so that the 1st static mixer of their reactions, with reaction soln and dilution water blended the 2nd static mixer, reaction soln is transferred to the reaction soln transfer pipeline of the 2nd static mixer from the 1st static mixer, and the 1st static mixer and reaction soln transfer pipeline be arranged in the water in the container.
The 1st of preparation method of the present invention is characterised in that, the single persulfuric acid that causes being generated for a large amount of heat releases that produced when preparing single persulfate solution decomposes or problem that can not single persulfate solution that prolonged preservation generated, special cooling apparatus such as not necessarily essential refrigerator, be diluted to below the normality by will be cooled to the single persulfate solution below the specified temperature at the appointed time with common water such as process water, can be with high yield preparation single persulfate solution steady in a long-term.
The 2nd of preparation method of the present invention is characterised in that, with respect to the pH adjustment of carrying out single persulfate solution in order to make single persulfate solution stabilization, the method in the past of adding stablizer, owing to there is no need to add special chemical reagent, single persulfate solution of using high purity of hydrogen peroxide, high purity sulfuric acid to obtain can also be used for avoiding the purposes such as semi-conductor of impurity.
The 3rd of preparation method of the present invention is characterised in that, when preparing single persulfuric acid in the past since the impurity in the sulfuric acid (for example, iron cpd) cause single persulfate solution of hydrogen peroxide and generation to decompose increase, the reduction of single persulfuric acid yield, or because the problem that the heat release of the impurity in the sulfuric acid when causing reacting increases, single persulfuric acid yield reduces can be used the sulfuric acid that contains iron to a certain degree.
The 4th of preparation method of the present invention is characterised in that, when using iron level sulfuric acid how, because the decomposition reaction of single persulfate solution of hydrogen peroxide and generation, produce rapid heat release and oxygen, danger such as breaking of pipe might induce reaction, but cool off at short notice and dilute by single persulfate solution that will generate, the decomposition reaction of single persulfate solution of hydrogen peroxide and generation is inhibited, and can stably prepare single persulfuric acid.
The 5th of preparation method of the present invention is characterised in that, not necessarily must be used to cool off the refrigerator of the single persulfate solution that is generated, can prepare single persulfate solution as the packaged unit of equipment with single persulfate solution diluted mixture device of the mixing tank with chemical liquids pump, mixed chemical liquid, reaction vessel, generation etc.
The 6th of preparation method of the present invention is characterised in that, by diluting the single persulfuric acid that is generated, as the pipe arrangement of the single persulfate solution after the conveying dilution or the material of preserving the container of the single persulfate solution after diluting, can use cheap materials such as SUS304, SUS316, thereby make the cost of equipment cheapness.
According to the present invention, realized device stable and the single persulfuric acid of continuous safely preparation with lower cost.In addition, utilize preparation facilities of the present invention, can obtain stable single persulfuric acid with high yield.
Description of drawings
[Fig. 1] is the figure of an example of expression single persulfuric acid continuous preparation device of the present invention.
[Fig. 2] is the figure of an example of expression single persulfuric acid continuous preparation device of the present invention.
[Fig. 3] is the figure of an example of expression single persulfuric acid continuous preparation device of the present invention.
Nomenclature
1: the hydrogen peroxide supply-pipe
2: the sulfuric acid supply-pipe
3: the 1 static mixers
4: the reaction soln transfer pipeline
5: the dilution water supply-pipe
6: the 2 static mixers
7: tank
8: the supply-pipe of the water in the container
9: the vent pipe of the water in the container
Embodiment
Single persulfuric acid obtains by sulfuric acid is mixed with hydrogen peroxide.At this moment, the mol ratio of sulfuric acid/hydrogen peroxide is preferably 1～5.Mol ratio increases less than the concentration of hydrogen peroxide in single persulfate solution of generation in 1 o'clock, according to the purposes bad effect of this hydrogen peroxide generation sometimes.In addition, not preferred economically yet.Mol ratio is that the concentration of the 5 single persulfuric acid that generate when above reduces, and sulfuric acid concentration raises.According to purposes, not preferred this sulfuric acid concentration is necessary with the neutralization of alkali such as caustic soda, and is not preferred economically.
As sulfuric acid, can use general industry sulfuric acid.As its concentration, can use the sulfuric acid of 70～98 weight %, be preferably 90～98 weight %, more preferably the vitriol oil of 95～98 weight %.As the sulfuric acid quality, the content of iron is very important.When having a large amount of iron,,, be preferably below the 10ppm, more preferably below the 5ppm so preferably iron level is below the 20ppm because the yield of single persulfuric acid that the decomposition of hydrogen peroxide, single persulfuric acid and cause because of this decompositions heat release is generated reduces.
As hydrogen peroxide, can use industrial chemical, as its concentration, can use the hydrogen peroxide of 35～90 weight %, be preferably 45～90 weight %, more preferably the hydrogen peroxide of 60～90 weight %.
The reaction of sulfuric acid and hydrogen peroxide can be carried out with intermittent type or continous way, but is preferably continous way on technical scale.Mixing machine during as continuous reaction can use static mixer.Because the heat release in the static mixer is big, as its material, is preferably Ha ス テ ロ イ (registered trademark) C or テ Off ロ Application (registered trademark).
Hydrogen peroxide and sulfuric acid, in order to finish most of reaction in the short period of time about 1 minute, the temperature that is up to of reaction soln was the temperature above 80 ℃ when preferable reaction temperature was promptly reacted.Below will be up to temperature sometimes and be called temperature of reaction.If the low then speed of response of temperature of reaction slows down, the yield of single persulfuric acid reduces.Therefore otherwise carry out very strong cooling because hydrogen peroxide is attended by very a large amount of heat releases when mixing with sulfuric acid,, then temperature of reaction is common above 80 ℃.Be preferably more than 90 ℃.The upper limit to temperature of reaction does not limit especially, but is preferably below 120 ℃.The Ruo Taigao then decomposition amount of hydrogen peroxide and single persulfuric acid increases.By when mixing beginning or the cooled reaction solution rapidly of beginning back, the single persulfate solution that makes generation mix back 5 minutes of beginning with interior be below 80 ℃.So can obtain single persulfuric acid.Be limited on the preferred cooling temperature below 70 ℃, more preferably below 60 ℃, further be preferably especially below 50 ℃, more preferably the following of cooling temperature is limited to more than 25 ℃, more preferably more than 30 ℃.Further preferably 5 minutes internal cooling to 40 ℃～80 ℃.In addition, be preferably more than 10 seconds from the time that begins to be mixed into dilution, more preferably more than 30 seconds, more preferably more than 1 minute.If this time, short then reaction was not fully carried out, thereby single persulfuric acid yield is reduced.Among the preparation method of the present invention, can before reacting, begin to cool down hydrogen peroxide and sulfuric acid, with both cool off and meanwhile they are reacted.At this moment, also beginning to make the temperature of reaction soln in back 5 minutes in mixing is below 80 ℃.This is because when diluting the single persulfuric acid that is generated under surpassing 80 ℃ temperature, because the decomposition of single persulfuric acid causes yield to reduce.If being cooled to the temperature that is lower than 40 ℃ then exists and is used to carry out that the refrigerative water cooler increases, cooling water inflow is necessary for a large amount of problems.
As method of cooling, can enumerate from outside water, cooling agent, the air of reaction vessel and cool off, be preferably water.This water coolant can use with refrigerator refrigerative water coolant, also can use common process water at normal temperatures.The size of reaction vessel is according to the overall heat transfer coefficient decision of the material of reaction vessel.The shape of reaction vessel and material are preferably can be with single persulfate solution of generating in the shape and the material of mixing below back 5 minutes internal cooling to 80 of beginning ℃.As the material that is used for this, be preferably Ha ス テ ロ イ (registered trademark) C or テ Off ロ Application (registered trademark).
In 5 minutes, be cooled to the single persulfate solution below 80 ℃, unstable and be difficult to prolonged preservation under this state.Therefore, among the preparation method of the present invention, with the above water dilution of 4 times of weight.Preferably be diluted to 4 times of weight～20 times of weight.When using less than the dilution of the water of 4 times of weight, thus the problem that exists the bad stability yield of single persulfuric acid to reduce.When diluting, use the concentration of point to reduce, have the shortcoming of reacting slack-off with the water that surpasses 20 times of weight.As dilution water, can dilute the water that uses in the cooling of the reaction vessel when still preferably utilizing single persulfuric acid to generate with new water.When being used for purposes such as semi-conductor, preferably use ultrapure water.As the temperature of dilution water, be preferably the water below 40 ℃.As dilution process, preferably in static mixer, mix.
So single persulfate solution of preparation can be delivered directly to field of employment or interim storage and be transported to the field of employment after in jar.
And single persulfate solution of preparation is strongly-acid under this state, is unsuitable for sometimes using according to purposes.At this moment, be necessary to add the pH that alkali such as caustic soda improve single persulfate solution.The interpolation of alkali is preferably carried out after the reaction soln with single persulfuric acid is cooled to below 80 ℃.For example have and adding the method that alkali dilutes then, the method for in dilution, adding alkali after the cooling, adding the method for alkali after the dilution, in dilution water, adding the method for alkali in advance.The addition of alkali can be in order to make single persulfate solution reach required pH value and required any amount, but be preferably for the stability of not damaging single persulfuric acid the sulfuric acid amount that is used for reacting and below the equivalent.
As mentioned above, preparation method of the present invention can use static mixer to carry out with continous way.Therefore, the present invention further provides the preparation facilities that can use above-mentioned preparation method.Below preparation facilities of the present invention is described.
As the static mixer that uses among the present invention, can use the conventional mixer that is provided with element (element) in the mixing tank.Shape to mixing tank does not limit especially, for example can use the piped mixing tank.The shape of element, number are not limited especially, for example can use utilization that rectangular plate is reversed the twisted blade linear element that obtains about 180 ° with the central shaft of length direction as the center, be provided with the mixing tank of 2 different above elements of torsional direction.
In the 1st static mixer of the present invention,, hydrogen peroxide generates single persulfuric acid by being mixed with sulfuric acid to react.Here operable hydrogen peroxide and sulfuric acid are as mentioned above.Hydrogen peroxide directly is connected with the 1st static mixer respectively with the vitriolic supply-pipe, hydrogen peroxide and sulfuric acid are collaborated in the 1st static mixer.In addition, thereby hydrogen peroxide is connected make hydrogen peroxide and sulfuric acid interflow with the vitriolic supply-pipe, but preferred junction of two streams is as far as possible near the position of mixing tank.
In order to improve the mixing efficiency in the static mixer, preferably with pump hydrogen peroxide is pressurizeed by hydrogen peroxide, and by sulfuric acid with pump to after the sulfuric acid pressurization, the sulfuric acid after hydrogen peroxide after the pressurization and the pressurization is supplied in the 1st static mixer.On the hydrogen peroxide supply-pipe and sulfuric acid supply-pipe of the 1st static mixer upstream, flow in the supply-pipe of another kind of raw material or prevent the refluence of reaction soln in order to prevent a kind of raw material, back pressure valve preferably is installed respectively.The optimum seeking site of back pressure valve is as far as possible near the position of junction of two streams.
Hydrogen peroxide and sulfuric acid are reacted, set both flow and the capacity of the 1st static mixer and the capacity of reaction soln transfer pipeline, make in the 1st static mixer, contact with sulfuric acid from hydrogen peroxide, to enter into the 2nd static mixer through the reaction soln transfer pipeline till, reaction can be finished.For example with the sulfuric acid of 45% hydrogen peroxide and 98% as reaction soln, with 1m
3The flow of/h imports in the 1st static mixer, when reacting thus, can use and be provided with a plurality of mixing of rectangular plate being turned round the turnback shape is that 15～30mm, length are that piped the 1st static mixer and internal diameter about 0.1～1m is that 15～30mm, length are the reaction soln transfer pipeline about 20～200m with the internal diameter of element.Reaction mol ratio and temperature of reaction are preferably in above-mentioned scope.
To in reaction soln transfer pipeline internal cooling, be transported in the 2nd static mixer from the reaction soln of the 1st static mixer derivation, in the 2nd static mixer, mix with dilution water.The length of decision reaction soln transfer pipeline makes that the temperature of reaction soln is preferably below 80 ℃ before soon collaborating with dilution water.If the temperature height of the reaction soln before the dilution easily generates hydrogen peroxide and sulfuric acid by single persulfuric acid and water when then diluting, the loss of the single persulfuric acid that generates in the 1st static mixer increases.
Reaction soln transfer pipeline and dilution water supply-pipe can directly be connected with the 2nd static mixer respectively, and reaction soln and dilution water are collaborated in the 2nd static mixer.In addition, the reaction soln transfer pipeline is connected with the upstream of dilution water supply-pipe at the 2nd static mixer, makes reaction soln and hydration stream, but junction of two streams is preferably as far as possible near the position of mixing tank.At this moment, the length of the flow of conditioned reaction solution and reaction soln transfer pipeline makes that to play at the 2nd static mixer be in 5 minutes with time till dilution water contacts to reaction soln from entering into the 1st static mixer.The amount of the dilution water that uses in the 2nd static mixer as mentioned above.On the reaction soln transfer pipeline and dilution water supply-pipe of the 2nd static mixer upstream, flow in the supply-pipe of another kind of liquid or prevent the refluence of diluting soln in order to prevent a kind of liquid, back pressure valve preferably is installed respectively.The optimum seeking site of back pressure valve is as far as possible near the position of junction of two streams.
Decision is installed in the pressure of the back pressure valve on reaction soln transfer pipeline and the dilution water supply-pipe and sets, and makes that the pressure of the diluting soln that pressure and the 2nd static mixer of the pressure of the reaction soln in the 1st static mixer and the reaction soln transfer pipeline and dilution water is interior is identical or higher.In addition, decision hydrogen peroxide and sulfuric acid pump size when the pressure of the back pressure valve that determines hydrogen peroxide supply-pipe and sulfuric acid supply-pipe is set make that the pressure of the reaction soln that hydrogen peroxide and vitriolic pressure and the 1st static mixer are interior is identical or higher.Usually, in blended reaction soln in the 2nd static mixer and dilution water, the liquid measure of dilution water is big overwhelmingly, and the pressure of the diluting soln in the 2nd static mixer and the supply pressure of dilution water are roughly the same.Therefore, preferably the supply pressure with dilution water is identical or higher with the vitriolic supply pressure for hydrogen peroxide.
From the single over cure acid solution of dilution that the 2nd static mixer is derived, use the field of employment that for example is delivered directly to single persulfuric acid such as drainage treatment equipment or association with pulp bleaching equipment.In addition, also can be housed in the jar until use.
Among the present invention, the 1st static mixer and reaction soln transfer pipeline are arranged in the interior water of container.That is, the outer surface of the 1st static mixer and reaction soln transfer pipeline contacts with water.Specifically, for example the reaction soln transfer pipeline of the 1st static mixer and coiled type is arranged in the water in the tank.In addition, make the housing department of static mixer and transfer pipeline form dual pipe, make that to have water between the pipe in the inboard pipe and the outside also be one of preferred implementation of the present invention.The 1st static mixer can all not contact with water with reaction soln transfer pipeline outer surface separately.All or part of of the 1st static mixer can be arranged in the water.All or part of of reaction soln transfer pipeline can be arranged in the water.Water in the container can be the water of normal temperature or the water that cooled off with refrigerator.
Further, preferably be provided for the stirrer of the water in the stirred vessel or be used to make the pump of water cycle.For the water in the container being stirred or makes its circulation, or the amount or the temperature of regulating the water in container, append, the equipment that preferably has the temperature of the water in the detection receptacle.
The 1st purpose that the 1st static mixer and reaction soln transfer pipeline are arranged in the water in the container is, will the reaction soln cooling of liquid temperature rise owing to hydrogen peroxide and vitriolic mix the heat release that caused.Therefore, for example consider and to supply with process water etc. from the inlet of container that warm water discharge is discharged in the outlet in container.In addition, feed rate, output in order to reduce the water in the container are necessary to have in addition the heat exchanger of setting, are used for the device of the water in the cooling vessel.
The 2nd purpose that the 1st static mixer and reaction soln transfer pipeline are arranged in the water in the container is, even when pipe connection portion of the 1st static mixer and reaction soln transfer pipeline periphery etc. spills single persulfuric acid of high temperature, high density, thus also can directly diluted realization safe.Therefore, preferred the 1st static mixer contacts with water with reaction soln transfer pipeline whole outer surfaces separately.Based on identical reason, preferably the interflow portion of hydrogen peroxide supply-pipe and sulfuric acid supply-pipe or the 2nd static mixer are arranged in the water in the container.
Among the present invention, preferably has the pump that is used for the water in the container is supplied to as dilution water the 2nd static mixer.By water in the dual-purpose container and dilution water, have can conserve water consumption maybe can save the effect of the device of the water in the cooling vessel.In addition, even when in container, spilling single persulfuric acid from the 1st static mixer and reaction soln transfer pipeline, because the single persulfuric acid that spills is transported in the field of employment or jar of single persulfuric acid with dilution water, has single persulfuric acid that can not make high density and flows out to outside effect.In order to detect the leakage of single persulfuric acid, preferably have superoxide or sour device in the water in the detection receptacle.
When water in the dual-purpose container and dilution water, preferably have the equipment of the water yield in the detection receptacle, and have the equipment that supplies to the amount of the water in the container based on the water yield control that is detected.By making the water yield in the container keep certain, the feed rate of regulating dilution water can be regulated the flow that flows into the water in the container.
Among the present invention, when changing the turnout of single persulfuric acid, change hydrogen peroxide, sulfuric acid and dilution water feed rate separately usually pro rata.At this moment, when not utilizing water in the container,, be necessary to control the cooling efficiency of the water in the container for the temperature of the single over cure acid solution of dilution that will be generated keeps certain as dilution water.On the other hand, when utilizing the interior water of container,, just the temperature of the single over cure acid solution after the dilution can be kept roughly certain only by changing the flow of each liquid pro rata as dilution water.
In the interflow portion of hydrogen peroxide supply-pipe and sulfuric acid supply-pipe, the 1st static mixer with the reaction soln transfer pipeline in reaction raw materials or the material of the part that contacts of reaction soln, be preferably fluoro-resin, Ha ス テ ロ イ (registered trademark) C or tantalum.
In the device of the present invention, preferably have the equipment of detection, have the equipment that stops hydrogen peroxide and/or vitriolic supply based on the temperature of the reaction soln of deriving from the 1st static mixer from the temperature of the reaction soln of the 1st static mixer derivation.Thus, thus the temperature can detect hydrogen peroxide and decompose unusually the time rises or the temperature when the 1st static mixer periphery spills reaction soln reduces the supply of directly blocking raw material.
Further, in the device of the present invention, preferably have the equipment of detection, have the equipment that stops hydrogen peroxide and/or vitriolic supply based on the temperature of the reaction soln of deriving from the 2nd static mixer from the temperature of the reaction soln of the 2nd static mixer derivation.Thus, thus the temperature can detect dilution water and stop the time rising or the temperature when the 2nd static mixer periphery spills reaction soln reduces the supply of directly blocking raw material.
Concrete example by Fig. 1～3 pair single persulfuric acid continuous preparation device of the present invention describes respectively.
Among Fig. 1, has the 1st static mixer 3 in downstream near the interflow portion of hydrogen peroxide supply-pipe 1 and sulfuric acid supply-pipe 2, have the 2nd static mixer 6, the 1 static mixers 3 in the downstream near reaction soln transfer pipeline 4 and the interflow portion of dilution water supply-pipe 5 in the 1st static mixer 3 downstreams and reaction soln transfer pipeline 4 is arranged in the tank 7.The vent pipe 9 of the water in the supply-pipe 8 of the water in tank 7 and the container and the container is connected.The vent pipe 9 of the water in the container is arranged on the position higher than the 1st static mixer 3 and reaction soln transfer pipeline 4, thereby the water in the tank 7 are overflowed.
Among Fig. 2, has the 1st static mixer 3 in downstream near the interflow portion of hydrogen peroxide supply-pipe 1 and sulfuric acid supply-pipe 2, the downstream near reaction soln transfer pipeline 4 and the interflow portion of dilution water supply-pipe 5 in the 1st static mixer 3 downstreams has the 2nd static mixer 6, the shell of the 1st static mixer 3 and reaction soln transfer pipeline 4 forms dual pipe, and the supply-pipe 8 that can be by the water in the container and the vent pipe 9 of the water in the container are present between the pipe in the pipe of inboard of dual pipe and the outside water in the container.
Among Fig. 3, has the 1st static mixer 3 in downstream near the interflow portion of hydrogen peroxide supply-pipe 1 and sulfuric acid supply-pipe 2, having the 2nd static mixer 6, the 1 static mixers 3, reaction soln supply-pipe 4 and the 2nd static mixer 6 in the downstream near reaction soln transfer pipeline 4 and the interflow portion of dilution water supply-pipe 5 in the 1st static mixer 3 downstreams is arranged in the tank 7.
The vent pipe 9 of the water in the supply-pipe 8 of the water in tank 7 and the container and the container is connected, and the other end of the vent pipe 9 of the water in the container is connected with suction port one side of diluting water pump 10.Discharge opening one side of dilution water pump 10 is connected with tank 7 by the circulation tube 11 of the water in the container respectively, is connected with the 2nd static mixer 6 upstream portions by dilution water supply-pipe 5.
The flow that flow indication accommodometer 12 control dilution waters are set midway at dilution water supply-pipe 5.In addition, by the water level of the water in the container in the water level gauge 13 detection tanks 7, signal is outputed to the valve midway 15 of the supply-pipe 8 of the water in the control container in the controller 14.Remain in certain scope by water level, make the feed rate of the interior water of dilution water feed rate and container identical in essence the water in the container in the tank 7.
The temperature of the 16 detection reaction solution of thermometer midway by being arranged on reaction soln transfer pipeline 4 outputs to signal in the controller 17, can stop hydrogen peroxide plenum system 18 and sulfuric acid plenum system 19 during reaction soln temperature anomaly.In addition, thermometer midway 21 by the single over cure acid solution of the dilution that is arranged on the 2nd static mixer 6 downstreams transfer pipeline 20, detect the temperature of the single over cure acid solution of dilution, signal is outputed in the controller 17, dilute single persulfuric acid liquid temp when unusual, stop hydrogen peroxide plenum system 18 and sulfuric acid plenum system 19.
In the device of the present invention, as required, can further have the equipment that is used for the mixed base aqueous solution.Specifically, the further equipment of the mixed base aqueous solution in the 2nd static mixer for example, in the downstream that is positioned at the 1st static mixer and the downstream that is positioned at the position of upstream of the 2nd static mixer or the 2nd static mixer the equipment of the 3rd static mixer mixed base aqueous solution is set.The 3rd static mixer preferably is arranged in the interior water of container.The equipment that is preferred for the mixed base aqueous solution is the alkali aqueous solution supply-pipe, and this supply-pipe has back pressure valve.In addition, when using the interior water of container, can have the equipment that adds alkali aqueous solution in the water in container as dilution water.
Embodiment
Then the present invention is carried out specific description by embodiment.The concentration of the chemical reagent that uses is represented with weight %.And embodiment shown below is used for example that the present invention is specifically described, and the present invention is not carried out any qualification.
The analytical procedure of single persulfuric acid is undertaken by following method.
1) single persulfate solution 1g that weighing generates in the volumetric flask of 50ml uses the pure water constant volume.
2) in adding has the conical beaker of pure water, 4N-sulfuric acid 10ml, ice, add 1) 5ml.
3) add several o-phenanthroline iron indicator.
4) carry out titration with the 1/40N-cesium sulfate solution.Become blue titer=aml by redness
5) in adding has the conical beaker of pure water, 4N-sulfuric acid 10ml, ice, add 1) 5ml.
6) add an amount of potassiumiodide.
7) add several ammonium molybdate saturated solutions.
8) carry out titration with 1/10N-thiosulfuric acid solution.Near terminal point the time, add Starch Indicator.
Become colourless titer=bml by purple
9) chemical agent concentration is calculated
Single persulfuric acid concentration (%)=5.7309 * (b-a/4) * (50/5/ sample size) * 0.1
Concentration of hydrogen peroxide (%)=1.701 * (a/4) * (50/5/ sample size) * 0.1
Embodiment 1
Getting 98% sulfuric acid 150g (1.5 moles) sample is immersed in beaker in the cold water in the conical beaker of 500ml.In sulfuric acid, added 45% hydrogen peroxide 37.78g (0.5 mole) when stirring and both are mixed synthetic single persulfate solution (being up to temperature is 92 ℃) with 15 seconds with agitator.Be low to moderate at the liquid temperature drop after 25 ℃ time point (mix beginning 5 minutes after) dilutes with 20 ℃ water 1126.7g (6 times of weight amount), the single persulfuric acid concentration in the diluent is 2.97%.And single persulfuric acid concentration of adding in the solution (undiluted) of beginning after 1 minute is 21.1%, is benchmark with this value, and the residual rate that calculates the single persulfuric acid after the dilution is 98.7%.
Except the temperature in single persulfate solution is respectively the time point dilute with water of 40 ℃ (mixing beginning after 3 minutes), 60 ℃ (mixing beginning after 2 minutes), 80 ℃ (mixing beginning after 1 minute 30 seconds), carry out similarly to Example 1.
Except beaker being immersed in (being up to temperature is 82 ℃) in the frozen water, being the time point dilute with water of 80 ℃ (mixing beginning after 30 seconds) in the temperature of single persulfate solution, carry out similarly to Example 1.
Comparative example 1
Except the temperature in single persulfate solution is the time point dilute with water of 90 ℃ (mixing beginning after 1 minute), carry out similarly to Example 1.
Comparative example 2～3
Except after adding hydrogen peroxide, beaker being immersed in (being up to temperature is 136 ℃) in the cold water, being respectively the time point dilute with water of 110 ℃ (mixing beginning after 2 minutes), 130 ℃ (mixing beginning after 1 minutes), carry out similarly to Example 1 in the temperature of single persulfate solution.
Comparative example 4
In beaker being immersed in-10 ℃ cooling agent (being up to temperature is 68 ℃), be respectively the time point dilute with water of 65 ℃ (mixing beginning after 30 seconds) in the temperature of single persulfate solution, carry out similarly to Example 1.
[table 1]
| Temperature of reaction (℃) | Single persulfuric acid temperature before the dilution (℃) | H 2SO 5 (％) | H 2O 2 (％) | H 2SO 5Residual rate (%) | |
| Embodiment 1 | 92 | 25 | 2.97 | 0.368 | 98.7 |
| 2 | 92 | 40 | 2.98 | 0.365 | 99.0 |
| 3 | 92 | 60 | 2.91 | 0.386 | 96.8 |
| 4 | 92 | 80 | 2.79 | 0.422 | 92.8 |
| 5 | 82 | 80 | 2.78 | 0.425 | 92.4 |
| Comparative example 1 | 92 | 90 | 2.45 | 0.523 | 81.3 |
| 2 | 136 | 110 | 1.92 | 0.681 | 63.8 |
| 3 | 136 | 130 | 1.24 | 0.884 | 41.1 |
| 4 | 68 | 65 | 2.63 | 0.470 | 87.4 |
When preparing single persulfuric acid, because the vitriolic hydration heat causes being attended by in the preparation a large amount of heat releases.Therefore, carrying out refrigerative reacts simultaneously.Temperature before single persulfuric acid dilution is as shown in table 1 to the influence of single persulfuric acid residual rate.By this result as can be known, the temperature of single persulfuric acid before the dilution is more than 90 ℃ the time, and single persulfuric acid residual rate reduces and concentration of hydrogen peroxide increases, and the temperature of the single persulfate solution that is generated when dilution is preferably below 80 ℃.
Except the temperature that changes single persulfate solution by the temperature of adjusting water coolant underspeeds, the time that is reduced to 80 ℃ is respectively outside 1 minute, 2.5 minutes, 5 minutes, other carries out similarly to Example 1.
Comparative example 5～7
Except the temperature that changes single persulfate solution by the temperature of adjusting water coolant underspeeds, the time that is reduced to 80 ℃ is respectively outside 7 minutes, 10 minutes, 15 minutes, other carries out similarly to Example 1.
[table 2]
| Time before the dilution (minute) | H 2SO 5 (％) | H 2SO 5Residual rate (%) | |
| |
1 | 2.80 | 93.0 |
| 7 | 2.5 | 2.78 | 92.4 |
| 8 | 5 | 2.72 | 90.4 |
| Comparative example 5 | 7.5 | 2.49 | 83.8 |
| 6 | 10 | 2.07 | 69.7 |
| 7 | 15 | 1.68 | 56.6 |
As shown in table 2 from the influence of time that is prepared into dilution of single persulfate solution.By this result as can be known, this time is more than 7.5 minutes the time, and the residual rate variation of single persulfuric acid is so be preferably below 5 minutes.
Get 98% sulfuric acid 150g (1.5 moles) sample in the conical beaker of 500ml, in sulfuric acid, add 45% hydrogen peroxide 37.78g (0.5 mole) when stirring, immediately beaker is immersed in the frozen water after the interpolation with agitator.The temperature of single persulfate solution is the highest to rise to 95 ℃, and the time point (mixing beginning after 3 minutes) being reduced to 40 ℃ dilutes with 20 ℃ water 751.1g (4 times of weight amount).With this liquid in 40 ℃ thermostatic bath, place 0.5h, 12h, 24h, 3 days, observe its stability.
, carry out similarly to Example 9 with the dilution of the water of 10 times of weight, 20 times of weight except respectively.
Comparative example 8～9
, carry out similarly to Example 9 with the dilution of the water of 0 times of weight, 2 times of weight except respectively.
[table 3]
| The dilution water yield (times of weight) | 0h | 0.5 | 12h | 24h | 3 | ||
| Embodiment | |||||||
| 9 | 4 | 4.51％ (100) | 4.50％ (99.8) | 4.27％ (94.7) | 4.01％ (88.9) | 3.84％ (85.1) | |
| 10 | 10 | 2.20％ (100) | 2.20％ (100) | 2.18％ (99.1) | 2.14％ (97.3) | 2.07％ (94.1) | |
| 11 | 20 | 1.10％ (100) | 1.10％ (100) | 1.10％ (100) | 1.10％ (100) | 1.09％ (99.1) | |
| Comparative example 8 | 0 | 22.0％ (100) | 20.3％ (92.3) | 18.2％ (82.7) | 16.4％ (74.5) | 11.6％ (52.7) | |
| 9 | 2 | 7.02％ (100) | 6.20％ (88.3) | 4.42％ (62.9) | 2.75％ (39.2) | 1.83％ (26.1) |
In () is conservation rate %
The result of the stability of single persulfate solution is as shown in table 3.In the table 3, the concentration of single persulfuric acid that the value representation of epimere is calculated with aforesaid method.The value of hypomere is that the concentration with the single persulfuric acid by with 0 hour the time is that the residual rate that the concentration of single persulfuric acid of each time of 100 o'clock is tried to achieve is expressed as conservation rate.The stable non-constant of the single persulfate solution of the high density during preparation must use immediately after preparation, and by dilute with water, stability improves, can prolonged preservation.As the dilution water yield, be preferably more than 4 times of weight.
Except making the concentration of iron in the sulfuric acid that uses among the embodiment 1 be 5ppm, use further to be added with beyond the sulfuric acid of the iron that is respectively 5ppm, 10ppm, 15ppm, carry out similarly to Example 1.Measure the harsh single persulfuric acid concentration that becomes after back and 40 ℃, 24h place of single persulfuric acid.
And iron adds with the form of ferrous sulfate.
Comparative example 10～12
Except in embodiment 1, use beyond the sulfuric acid of the iron that further is added with 25ppm, 50ppm, 100ppm respectively, other carries out similarly to Example 1.Measure the harsh single persulfuric acid concentration that becomes after back and 40 ℃, 24h place of single persulfuric acid.And iron adds with the form of ferrous sulfate.
[table 4]
| Fe addition (ppm) | H 2SO 5(behind %, the harsh one-tenth) | H 2SO 5(behind %, the 24h) | |
| Embodiment 1 | 0 | 3.01 | 2.98 |
| |
5 | 3.01 | 2.94 |
| 13 | 10 | 3.00 | 2.91 |
| 14 | 15 | 2.97 | 2.83 |
| Comparative example 10 | 25 | 2.84 | 2.29 |
| 11 | 50 | 2.61 | 1.87 |
| 12 | 100 | 2.36 | 1.48 |
As the sulfuric acid quality, be the sulfuric acid below the 20ppm by using Fe content, can make concentration behind the harsh one-tenth of single persulfuric acid and the concentration behind the 24h maintain high density.
In the present embodiment, use the device of above explanation to prepare single persulfuric acid continuously by reference Fig. 3.
Thereby pump work is transported to 45% hydrogen peroxide 150kg/h and 98% sulfuric acid 600kg/h respectively in hydrogen peroxide supply-pipe 1 and the sulfuric acid supply-pipe 2.In the 1st static mixer 3 that is arranged near the downstream of interflow portion, hydrogen peroxide and sulfuric acid are mixed, make hydrogen peroxide and sulfuric acid reaction thus.Be reflected under 92 ℃ and carry out.As the 1st static mixer, use Noritake Co., the static mixer N60 type of Limited system (enclosure material: Hastelloy C-22, element material: PTFE), this mixing tank is arranged on all surfaces that makes this mixing tank in the water contacts with water.Making the reaction soln of deriving from the 1st static mixer is that 17mm, length are the reaction soln transfer pipeline 4 of 100m by the internal diameter that is connected with the 1st static mixer 3 downstreams, makes the temperature that is about to flow into the reaction soln in the 2nd static mixer be reduced to 40 ℃.The time of being derived till arriving the 2nd static mixer by the 1st static mixer from reaction soln is 3 minutes.Reaction soln transfer pipeline 4 is connected with the 2nd static mixer in its downstream side, and reaction soln transfer pipeline 4 and the 2nd static mixer are arranged in the water.Supply with the water of the amount of 10 times of amounts that are equivalent to reaction soln from dilution water supply-pipe 5 with the flow of 7580kg/h, in the 2nd static mixer, reaction soln is mixed with dilution water, prepare single persulfuric acid (yield that with the hydrogen peroxide is benchmark is 70%) thus.Single persulfuric acid of obtaining is placed under the condition identical with the condition described in 40 ℃ the embodiment 9, measured after its stability as can be known, obtain the conservation rate equal with embodiment 9.
Claims (26)
1. the preparation method of the high single persulfate solution of stability, it is characterized in that, hydrogen peroxide more than the 35 weight % and the sulfuric acid more than the 70 weight % are mixed, they are reacted under the temperature more than 90 ℃, reaction soln is cooled to below 80 ℃ with interior mixing back 5 minutes of beginning, then reaction soln is diluted with the water more than 4 times of weight.
2. the method for claim 1 is characterized in that, reaction soln is cooled to 40 ℃～80 ℃.
3. the method for claim 1 is characterized in that, with the water dilution of reaction soln with 4 times of weight～10 times of weight.
4. the method for claim 1, wherein use iron level to be the sulfuric acid below the 20ppm.
5. the method for claim 1, wherein after reaction soln being cooled to below 80 ℃, add alkali aqueous solution.
6. the preparation method of single persulfate solution, it is characterized in that, hydrogen peroxide more than the 35 weight % and the sulfuric acid more than the 70 weight % are mixed, they are being reacted above under 80 ℃ the temperature, reaction soln is cooled to below 80 ℃ with interior mixing back 5 minutes of beginning, then reaction soln is diluted with the water more than 4 times of weight.
7. single persulfuric acid continuous preparation device, it is characterized in that, in single persulfuric acid continuous preparation device, have hydrogen peroxide and sulfuric acid mixed so that the 1st static mixer of their reactions, with the reaction soln that obtains in the 1st static mixer and dilution water blended the 2nd static mixer, reaction soln is transferred to the reaction soln transfer pipeline of the 2nd static mixer from the 1st static mixer, and the 1st static mixer and reaction soln transfer pipeline be arranged in the water in the container.
8. single persulfuric acid continuous preparation device as claimed in claim 7 wherein, is equipped with hydrogen peroxide supply-pipe and sulfuric acid supply-pipe in the 1st static mixer provided upstream, and described hydrogen peroxide supply-pipe and described sulfuric acid supply-pipe have back pressure valve respectively.
9. single persulfuric acid continuous preparation device as claimed in claim 7 wherein, is equipped with reaction soln transfer pipeline and dilution water supply-pipe in the 2nd static mixer provided upstream, and described reaction soln transfer pipeline and described dilution water supply-pipe have back pressure valve respectively.
10. single persulfuric acid continuous preparation device as claimed in claim 7, wherein, the 2nd static mixer is arranged in the water.
11. single persulfuric acid continuous preparation device as claimed in claim 7 wherein, has the pump that is used for the water in the container is supplied to as dilution water the 2nd static mixer.
12. single persulfuric acid continuous preparation device as claimed in claim 7 wherein, has the equipment of the water yield in the detection receptacle, and has the equipment of controlling the water yield of supplying with based on the water yield that detects in container.
13. single persulfuric acid continuous preparation device as claimed in claim 7 wherein, has superoxide or sour device in the water in the detection receptacle.
14. single persulfuric acid continuous preparation device as claimed in claim 7, wherein, have the equipment of detection, and the temperature that has based on the reaction soln of deriving from the 1st static mixer stops supply, vitriolic supply or the hydrogen peroxide of hydrogen peroxide and the equipment that vitriolic is supplied with from the temperature of the reaction soln of the 1st static mixer derivation.
15. single persulfuric acid continuous preparation device as claimed in claim 7, wherein, have the equipment of detection, and the temperature that has based on the reaction soln of deriving from the 2nd static mixer stops supply, vitriolic supply or the hydrogen peroxide of hydrogen peroxide and the equipment that vitriolic is supplied with from the temperature of the reaction soln of the 2nd static mixer derivation.
16. single persulfuric acid continuous preparation device as claimed in claim 7, wherein, the further mixed base aqueous solution in the 2nd static mixer.
17. single persulfuric acid continuous preparation device as claimed in claim 7, wherein, in the downstream that is positioned at the 1st static mixer and the position that is positioned at the upstream of the 2nd static mixer have reaction soln and alkali aqueous solution blended the 3rd static mixer.
18. single persulfuric acid continuous preparation device as claimed in claim 7 wherein, has diluting reaction solution and alkali aqueous solution blended the 3rd static mixer in the downstream of the 2nd static mixer.
19. as any described single persulfuric acid continuous preparation device in the claim 16～18, wherein, the alkali aqueous solution supply-pipe has back pressure valve.
20., wherein, the 3rd static mixer is arranged in the water as claim 17 or 18 described single persulfuric acid continuous preparation device.
21. single persulfuric acid continuous preparation device as claimed in claim 11 wherein, has the equipment that adds alkali aqueous solution in the water in container.
22. the continuous preparation method of single persulfate solution, it is characterized in that, use the described single persulfuric acid continuous preparation device of claim 7, hydrogen peroxide more than the 35 weight % and the sulfuric acid more than the 70 weight % are mixed, they are being reacted above under 80 ℃ the temperature, reaction soln is cooled to below 80 ℃ with interior mixing back 5 minutes of beginning, then reaction soln is diluted with the water more than 4 times of weight.
23. preparation method as claimed in claim 22 is characterized in that, reaction soln is cooled to 40 ℃～80 ℃.
24. preparation method as claimed in claim 22 is characterized in that, with the water dilution of reaction soln with 4 times of weight～10 times of weight.
25. preparation method as claimed in claim 22 wherein, uses iron level to be the sulfuric acid below the 20ppm.
26. preparation method as claimed in claim 22 wherein, after reaction soln being cooled to below 80 ℃, adds alkali aqueous solution.
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| CN201410003315.1A CN103832980B (en) | 2006-10-18 | 2007-10-18 | The preparation method of single persulfuric acid and single persulfuric acid continuous preparation device |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104508024A (en) * | 2012-08-15 | 2015-04-08 | 布莱恩·波尔马斯特 | Polymeric surface oxidation using peracids |
| CN113526467A (en) * | 2021-08-20 | 2021-10-22 | 中国科学院生态环境研究中心 | Treatment device and method for recycling chlorine-containing waste acid |
| CN113845093A (en) * | 2021-10-23 | 2021-12-28 | 浙江金科日化原料有限公司 | Method for continuously preparing peroxysulfuric acid by using microchannel reactor |
| CN114375283A (en) * | 2019-09-13 | 2022-04-19 | 栗田工业株式会社 | Method for suppressing reduction in concentration of oxidizing agent in sulfuric acid solution containing persulfate |
-
2007
- 2007-10-18 CN CNA2007800390744A patent/CN101553427A/en active Pending
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2009
- 2009-04-08 ZA ZA200902444A patent/ZA200902444B/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104508024A (en) * | 2012-08-15 | 2015-04-08 | 布莱恩·波尔马斯特 | Polymeric surface oxidation using peracids |
| CN114375283A (en) * | 2019-09-13 | 2022-04-19 | 栗田工业株式会社 | Method for suppressing reduction in concentration of oxidizing agent in sulfuric acid solution containing persulfate |
| CN113526467A (en) * | 2021-08-20 | 2021-10-22 | 中国科学院生态环境研究中心 | Treatment device and method for recycling chlorine-containing waste acid |
| CN113845093A (en) * | 2021-10-23 | 2021-12-28 | 浙江金科日化原料有限公司 | Method for continuously preparing peroxysulfuric acid by using microchannel reactor |
| CN113845093B (en) * | 2021-10-23 | 2024-05-28 | 浙江金科日化新材料股份有限公司 | Method for continuously preparing peroxymonosulfuric acid by utilizing microchannel reactor |
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Application publication date: 20091007 |