CN1108984C - Regeneration method of working solution - Google Patents
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- CN1108984C CN1108984C CN97110726A CN97110726A CN1108984C CN 1108984 C CN1108984 C CN 1108984C CN 97110726 A CN97110726 A CN 97110726A CN 97110726 A CN97110726 A CN 97110726A CN 1108984 C CN1108984 C CN 1108984C
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
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- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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Abstract
A regeneration method of a working solution is herein disclosed in which various by-products which do not participate in the production of hydrogen peroxide and which are present in the working solution in a hydrogen peroxide production process utilizing an anthraquinone method can efficiently be converted into anthraquinones effective as reaction media for the production of hydrogen peroxide. The present invention is concerned with (1) a regeneration method of a working solution wherein at least a part of the unreduced working solution is brought into contact with a catalyst mainly comprising a gamma -alumina at a temperature of 40 to 150 DEG C., and (2) another regeneration method of a working solution.
Description
The present invention relates to a kind of in the hydrogen peroxide manufacture process renovation process of working solution.More particularly, the present invention relates to a kind of like this renovation process of working solution, do not participate in hydrogen peroxide manufacture and be present in and to change into effectively the effective anthraquinone analog compound of reaction medium by this method as the production hydrogen peroxide with the various by products in the working solution of anthraquinone hydrogen peroxide manufacture process.
The present main production method of implementing in technical scale of hydrogen peroxide is called anthraquinone, and anthraquinone is as reaction medium in this method.Usually, anthraquinone is dissolved in the suitable organic solvent uses.This organic solvent can be single organic solvent or blended organic solvent, but is generally the mixture of two kinds of organic solvents.Anthraquinone is dissolved in the solution that makes in the organic solvent is called " working solution ".
According to anthraquinone, the anthraquinone in the working solution in the presence of catalyzer, with hydrogen reduction (hereinafter referred to as " hydrogenation "), generates corresponding anthrahydroquinone in reduction step.Subsequently, in oxidation step, anthrahydroquinone changes into anthraquinone with air or oxygen containing gas cyaniding again with anthrahydroquinone, and generates hydrogen peroxide simultaneously.The hydrogen peroxide that generates in working solution water extraction in extraction step is usually separated it from working solution.The working solution of telling behind the hydrogen peroxide returns reduction step again, thereby constitutes a working cycle.This working cycle can mainly be produced hydrogen peroxide by hydrogen and air, so it is a kind of extremely effectively process.This working cycle has been used for the industrial production hydrogen peroxide.
In using anthraquinone hydrogen peroxide manufacture process, be contained in that the anthraquinone as reaction medium is reduced into anthrahydroquinone in the working solution, their further oxidations generate anthraquinone and hydrogen peroxide then.When repeating this step, generate alkoxyl group anthrone, alkyl tetrahydro anthraquinone ring oxide compound etc. by side reaction.These alkoxyl group anthrones, alkyl tetrahydro anthraquinone ring oxide compound etc. can not generate hydrogen peroxide, even when they reduce with oxidation repeatedly.In reduction and oxidation cycle each time, the growing amount of the compound that these are useless is seldom, but when repeating this circulation time, above-claimed cpd will accumulate in working solution, causes various troubles.
If the ring of alkyl-anthraquinone is hydrogenated, so just generate the alkyl tetrahydro anthraquinone, and these alkyl tetrahydro anthraquinones there be the ability of producing hydrogen peroxide by repeating to reduce with oxidation as alkyl-anthraquinone.Yet the alkyl tetrahydro anthraquinone can be easy to also obtain originally by alkyl-anthraquinone, but the alkyl tetrahydro anthraquinone that reduction obtains has such shortcoming: its rate of oxidation is low.So, show as German Patent 2003268, under the situation of alkyl tetrahydro anthraquinone as reduction and oxidation reaction medium, in oxidation step, need very lot of energy, therefore required half total energy or total power consumption over half are at oxidation step in working cycle, and this just causes a series of problems of relevant devices and economy.As a method that addresses these problems, as in US 5399333, can be in a suitable scope, to obtain favourable economically process with the reduction and the ratio control of oxidation between alkyl-anthraquinone and the alkyl tetrahydro anthraquinone.But when the alkyl tetrahydro anthraquinone increases and the ratio of reduction and oxidation when improving gradually, the problem of above-mentioned relevant devices and economy can occur again.
Because above-mentioned these problems, in using anthraquinone hydrogen peroxide manufacture process, need such step, alkyl tetrahydro anthraquinone and alkyl-anthraquinone are by compound such as alkyl tetrahydro anthraquinone ring oxide compound and the regeneration of alkoxyl group anthrone in this step, and it can not generate hydrogen peroxide; And needing such step, alkyl-anthraquinone is regenerated by the alkyl tetrahydro anthraquinone in this step.Therefore, many reference schemes have been proposed so far.
In Japanese patent laid-open publication gazette 8806/1964, proposed by making inert component change into the alkyl tetrahydro anthraquinone with alkali and alkali aqueous solution work of treatment solution.In addition, in Japanese patent laid-open publication gazette 11658/1968, be reported under 120 ℃ and handled the reductive working solution, generated alkyl tetrahydro anthraquinone ring oxide compound with caustic soda or water glass.But when the working solution that the anthrahydroquinone that obtains as its reduction when some anthraquinone in the working solution exists contacted with alkali aqueous solution, anthrahydroquinone was extracted by alkali aqueous solution, can produce economy problems, promptly caused expensive anthraquinone loss.
Japanese patent laid-open publication gazette 19164/1970 has reported that the available following steps of the regeneration of working solution are carried out: use the ozonize working solution, handle with the caustic soda aqueous solution, make it pass through activated alumina under 70～75 ℃ then.But this renovation process comprises 3 steps, and it is complicated; And because use expensive ozone, the problem relevant with economy and equipment still exists.
Japanese patent laid-open publication gazette 41040/1974 proposes a kind of under 130 ℃, in the presence of the palladium catalyst of load, makes alkoxyl group anthrone regenerated method with the olefin treated working solution; But in this method, use a large amount of alkene footpath and expensive platinum metals.Owing to these reasons, this method also is considered to disadvantageous economically process.
In addition, as a kind of method that the alkyl tetrahydro anthraquinone is changed into alkyl-anthraquinone, Japanese patent laid-open publication gazette 4474/1964 proposes, with working solution and have the compound of unsaturated link(age) such as alkene to contact, make the alkyl tetrahydro anthraquinone change into alkyl-anthraquinone by aluminum oxide, magnesium oxide, magnesium oxide-alumina spinel, carbon or metal (as palladium, platinum or nickel) that the hydrogenation ability arranged.But, in this case,, also use a large amount of alkene, and also need to use expensive platinum metals in order to improve speed of reaction.Therefore, the method that is proposed also is considered to disadvantageous economically process.
As by above-mentioned understanding, there are some problems relevant with equipment and economy with the regeneration of working solution method of conventional art.For example, need many steps, therefore operation is complicated, perhaps needs to add the compound except that catalyzer, perhaps may cause a certain proportion of anthraquinone loss.
In addition, in conventional art, can not solve, make the alkyl tetrahydro anthraquinone change into alkyl-anthraquinone again simultaneously by alkoxyl group anthrone and alkyl tetrahydro anthraquinone ring oxide compound regeneration alkyl-anthraquinone and alkyl tetrahydro anthraquinone.
On the other hand, the inventor finds that under the situation of the working solution that contains the alkyl tetrahydro anthraquinone at least, because anthraquinone repeats reduction and hydrogen peroxide is produced in oxidation, alkyl tetrahydroxy anthrone can accumulate in working solution.Alkyl tetrahydroxy anthrone can not generate hydrogen peroxide, even when repeating reduction and oxidation; So by circulation repeatedly, alkyl tetrahydroxy anthrone can accumulate in working solution, causes variety of issue uncomfortablely.In addition, this fact can cause producing the loss of the effective anthraquinone of hydrogen peroxide, and this is disadvantageous economically.The inventor finds that when using catalyzer such as alumina treatment reductive working solution, when purpose was particularly to make the reduction of alkyl tetrahydro anthraquinone ring oxide compound, the concentration of alkyl tetrahydroxy anthrone increased.In order to address this problem, in the process of using process for prepairng hydrogen peroxide by anthraquinone, the alkyl tetrahydro anthraquinone should be necessary by the regeneration of alkyl tetrahydroxy anthrone.
As the conventional art relevant with the regeneration of working solution method, except above-mentioned technology, a kind of method of being produced required compound by alkyl tetrahydro anthraquinone ring oxide compound is proposed in Japanese patent laid-open publication gazette 30801/1982, and, a kind of method by alkyl tetrahydro anthraquinone regeneration alkyl-anthraquinone is proposed in the 635th page (1994) at " research of Surface Science and katalysis " the 88th volume.
But, in these traditional technology, be not described in the working solution regeneration by alkyl tetrahydroxy anthrone at all.
Because these situations, now developed the present invention, first purpose of the present invention provide a kind of in using the process of process for prepairng hydrogen peroxide by anthraquinone the renovation process of working solution, this method comprises the step that the alkoxyl group anthrone in the working solution and alkyl tetrahydro anthraquinone is changed into alkyl-anthraquinone, and the step that the alkyl tetrahydro anthraquinone ring oxygenate conversion in the working solution is become the alkyl tetrahydro anthraquinone.
Second purpose of the present invention provide a kind of in using the process of process for prepairng hydrogen peroxide by anthraquinone the renovation process of working solution, this method comprises the step that the alkyl tetrahydroxy anthrone in the working solution is changed into the alkyl tetrahydro anthrahydroquinone.
The inventor has carried out research widely, so that achieve the above object.Therefore, find that first purpose of the present invention can reach by the unreduced working solution of at least a portion is contacted under specific temperature with the catalyzer that mainly contains gama-alumina.In addition, second purpose of the present invention can contact under specified temp by working solution that contains specific concentrations alkyl tetrahydro anthrahydroquinone and the catalyzer that mainly contains gama-alumina and reach.
The present invention finishes on the basis of above-mentioned discovery.
That is to say, first purpose of the present invention can reach by a kind of like this regeneration of working solution method, this method comprises making and contains alkyl-anthraquinone and the alkyl tetrahydro anthraquinone step that working fluid repeats to reduce and hydrogen peroxide is produced in oxidation as anthraquinone that wherein the unreduced working solution of at least a portion contacts (first invention) with the catalyzer that mainly contains gama-alumina under 40～150 ℃.
Second purpose of the present invention can reach by a kind of like this regeneration of working solution method, this method comprises making and contains the step that the alkyl tetrahydro anthraquinone repeats to reduce as the anthraquinone working solution and hydrogen peroxide is produced in oxidation at least, wherein make working solution under 20～150 ℃, satisfy before catalytic treatment at the concentration h (mol) of alkyl tetrahydro anthrahydroquinone in working solution under the condition of following formula and contact with the catalyzer that mainly contains gama-alumina
(0.0018 * t-0.0285) * h≤0.05 wherein t be treatment temp (℃), make the alkyl tetrahydroxy anthrone in the working solution change into alkyl tetrahydro anthrahydroquinone (second invention).
The working solution that can be used for a method of the present invention is a kind of solution that contains anthraquinone as working medium or anthrahydroquinone, and this solution can be used as circulate soln in the process of using process for prepairng hydrogen peroxide by anthraquinone.
In the process of using process for prepairng hydrogen peroxide by anthraquinone, contain anthraquinone and at first in reduction step, use hydrogen reduction as the working solution of reaction medium, make the anthraquinone hydrogenation in the working solution, thereby generate corresponding anthrahydroquinone.Subsequently, in oxidation step, with this reductive solution oxide, make anthrahydroquinone change into corresponding anthraquinone once more with oxygen containing gas, and produce hydrogen peroxide simultaneously.In extraction step, the common water extraction of the hydrogen peroxide in working solution is told it from working solution.The working solution of isolating hydrogen peroxide returns reduction step again.As from above-mentioned understanding,, can produce hydrogen peroxide from hydrogen and air continuously by repeating reduction and oxide treatment anthraquinone.
Solvent to the working solution that is used to prepare the process that can be used for producing hydrogen peroxide has no particular limits, but the example of preferred solvent comprises the combination of the carboxylicesters of combination, aromatic hydrocarbons and the hexalin of aromatic hydrocarbons and higher alcohols or alkyl cyclohexanol, and quaternary urea.The combination of Three methyl Benzene and diisobutyl carbinol(DIBC) is particularly preferred.
In addition, all can use as the anthraquinone of reaction medium and alkyl-anthraquinone and alkyl tetrahydro anthraquinone.Here, the example of alkyl tetrahydro anthraquinone comprises methyl tetrahydro-anthraquinone, ethyl tetrahydro-anthraquinone, tertiary butyl tetrahydro-anthraquinone and composition thereof.In addition, the example of alkyl-anthraquinone comprises amyl anthraquinone, EAQ, tertiary butyl anthraquinone and composition thereof.
At first, first invention is described.
In first invention, can use the working solution that contains alkyl-anthraquinone and alkyl tetrahydro anthraquinone.In this case, alkyl-anthraquinone can use separately or its two or more mixture uses.In addition, the alkyl tetrahydro anthraquinone also can use separately or its two or more mixture uses.
In first invention, use unreduced working solution.If use the reductive working solution, by the alkyl tetrahydro anthraquinone alkyl-anthraquinone regenerated speed is reduced irrelevantly, and worse be, easily generate a large amount of other by products.
The preferred example that does not reduce working solution comprises the solution that contains 0.05 mol or more alkyl tetrahydro anthraquinones, contains the solution of 0.15 mol or lower alkyl tetrahydro anthrahydroquinone and contains 0.05 mol or more alkyl tetrahydro anthraquinones and 0.15 mol or the solution of alkyl tetrahydro anthrahydroquinone still less.
In first invention, the unreduced working solution of at least a portion contacts with the catalyzer that mainly contains gama-alumina.The catalyzer that mainly contains gama-alumina has high active and be favourable economically.Granularity to catalyzer has no particular limits, and granularity is preferably 8～100 orders.If granularity is less than this scope, the pressure-losses in the reactor can uncomfortable increase so, and on the other hand, if granularity greater than above-mentioned scope, activity of such catalysts can be impaired uncomfortablely.
Kind to gama-alumina has no particular limits, and can be extensive use of commercially available gama-alumina usually.In addition, in the present invention, also can use the catalyzer that contains the following calcium oxide of gama-alumina and about 10% (weight) or 10% (weight), magnesium oxide, cupric oxide, or mainly contain the material of these oxide compounds, as CaOA1
2O
3Or MgOAl
2O
3
In the present invention, unreduced working solution contacts with the catalyzer that mainly contains gama-alumina, but in this case, the temperature of catalytic treatment is chosen in 40～150 ℃.If this temperature is lower than 40 ℃, speed of reaction is too low so, so that impracticable, and on the other hand, if temperature is higher than 150 ℃, is prone to other the useless reactions except that desirable regenerative response.In addition, the catalytic treatment time is relevant with the kind and the catalytic treatment temperature of catalyzer, and it can not determination, but it is in about 10 to 120 minutes scopes usually.And, without particular limitation to the type of the reactor that can be used for this catalytic treatment, any band stir tremble type, the fixed bed type all can use with reactor fluid bed type.
As mentioned above, when unreduced working solution passes through to use the catalyst regeneration of simple equipment and cheapness, alkoxyl group anthrone and alkyl tetrahydro anthraquinone contained in working solution can change into alkyl-anthraquinone effectively, and contained alkyl tetrahydro anthraquinone ring oxide compound can change into the alkyl tetrahydro anthraquinone effectively in working solution, and effectively anthraquinone does not lose.
Secondly, second invention will be described.
In second invention, use and contain the working solution of alkyl tetrahydro anthraquinone at least, and especially preferably contain the working solution of alkyl tetrahydro anthraquinone and alkyl-anthraquinone mixture.In this case, the alkyl tetrahydro anthraquinone can use separately or two or more are used in combination.And alkyl-anthraquinone also can use separately or two or more are used in combination.
In second invention, unreduced working solution or reductive working solution all can use.Catalyzer as contacting with this working solution can use the catalyzer that mainly contains gama-alumina, and this catalyzer can with in first invention, describe identical.
In second invention, working solution is under 20～150 ℃, and the concentration h (mol) of alkyl tetrahydro anthrahydroquinone in working solution satisfies following formula before catalytic treatment
(contact with the catalyzer that mainly contains gama-alumina under the condition of 0.0018 * t-0.0285) * h≤0.05.Make the alkyl tetrahydroxy anthrone in the working solution change into the alkyl tetrahydro anthrahydroquinone.In the formula, t be treatment temp (℃).In this case, because the concentration of alkyl tetrahydro anthrahydroquinone is low in working solution, the concentration of alkyl tetraalkyl anthrone may reduce in the regenerated working solution.In addition, because temperature is low, the concentration of alkyl tetraalkyl anthrone may descend.But if temperature is lower than 20 ℃, speed of reaction is too low so, so that is unpractical.Preferably treatment condition are, treatment temp is 20～150 ℃, and the concentration h (mol) of alkyl tetrahydro anthrahydroquinone in working solution is 0.15 mol or lower before catalytic treatment, and satisfies following formula
(in 0.0018 * t-0.0285) * h≤0.02 formula, t be treatment temp (℃).
The concentration of alkyl tetrahydro anthrahydroquinone in working solution can suitably be regulated by making the working solution oxidation.And, the type of reactor that is used for this catalytic treatment is had no particular limits, any band stirs and type, the fixed bed type all can use with reactor fluid bed type.
When working solution was regenerated under such condition, the alkyl tetraalkyl anthrone in the working solution can change into the alkyl tetrahydro anthrahydroquinone effectively.
Below, will describe the present invention in more detail, but scope of the present invention is not limited to these embodiment.
Embodiment 1
The amyl group tetrahydro-anthraquinone is dissolved in 60% (volume) 1,2, in the mixed solvent of 4-trimethylbenzene and 40% (volume) diisobutyl carbinol(DIBC), the concentration that makes the amyl group tetrahydro-anthraquinone is the working solution of 0.225 mol, with the abundant oxidation of working solution, make the concentration of reductive agent anthrahydroquinone adjust to 0.000 mol then.In this embodiment, the AA400G (14～18 order) that Alcan chemical company produces is as gama-alumina.Subsequently, 100 milliliters of above-mentioned working solutions are put into 200 ml flasks, and begin logical nitrogen, then under agitation with working solution hydrogenation to 120 ℃.When the temperature of working solution reaches 120 ℃, add 10.0 gram gama-aluminas, reacted 1 hour.Temperature of reaction controls to 120 ℃.
In order to the working solution that following methods analyst draws off from reactor, obviously the concentration of amyl group tetrahydro-anthraquinone is 0.194 mol, and the concentration of amyl group anthrone is 0.021 mol.The concentration of regenerated alkyl tetrahydro anthraquinone is 0.021 mol.
[analysis of the back working solution that reacts completely]
With the working solution that the cooling tube cooling draws off from reactor, fully oxidation washes with water, and hydration is filtered, and uses liquid chromatography analysis then, measures each component concentrations.
Absorb on the basis of quantity of oxygen the concentration of anthrahydroquinone in the evaluation work solution at the per unit volume working solution.In addition, by reacting the quantity that deducts regenerated alkyl-anthraquinone from the alkoxyl group anthrone in the alkyl-anthraquinone quantity that increases in the working solution of back, calculate the quantity that the alkyl tetrahydro anthraquinone changes into alkyl-anthraquinone.This numerical value that calculates will be considered as the regeneration amount of alkyl tetrahydro anthraquinone simply.
Embodiment 2
Reaction is undertaken by step identical among the embodiment 1, different be to use so a kind of working solution, wherein the amyl group tetrahydro-anthraquinone is by partial reduction, so that the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.080 mol, and the concentration of alkyl tetrahydro anthraquinone is 0.145 mol.
Analyze the working solution that from reactor, draws off with the mode identical with embodiment 1, its result, the concentration of amyl group tetrahydro-anthraquinone is 0.196 mol, and the concentration of amyl anthraquinone is 0.010 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.010 mol.
Embodiment 3
The working solution that makes is used for such experimental installation, wherein contains amyl anthraquinone and amyl group tetrahydro-anthraquinone and is alternately reduced and oxidation as the working solution of reaction medium, to produce hydrogen peroxide.In this working solution, the concentration of amyl group tetrahydro-anthraquinone is 0.150 mol, the concentration of amyl group tetrahydrochysene anthrahydroquinone be 0.05 rub rise/liter, the concentration of amyl anthraquinone is 0.580 mol, the concentration of pentyloxy anthrone is 0.012 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.010 mol.In this working solution, the content of solid ingredient except above-mentioned points is about 10% (weight) of total solids component, but because they are almost constant in this embodiment, hereinafter they are not particularly related to.Reactor is equipped with the AA400G (14～48 order) of 300 milliliters of Alcan chemical companies productions as gama-alumina.After the abundant purge of nitrogen, the working solution of above-mentioned preparation is sent into 220 milliliters/hour speed, carry out regenerative response.Temperature of reaction controls to 120 ℃.
Send into the regenerative response that working solution carries out working solution by bottom to the top from fixed bed type of reactor that gama-alumina is housed.These fixed-bed reactor are made by stainless steel, are about 20 microns fixing upper-lower position of adorning catalyst member of filter screen with sieve mesh.Reactor itself is also from indirect heating, and working solution is heated to predetermined temperature in advance, sends into the dress catalyst member then, so that make the temperature of dress catalyst member even as much as possible.In addition, the working solution of sending into was wanted sufficient nitrogen envelope before sending into reactor.
Analyze the working solution that from reactor, draws off (beginning through after 24 hours) with mode identical among the embodiment 1 from reaction.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.188 mol, and the concentration of amyl anthraquinone is 0.607 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.015 mol.
Embodiment 4
Reaction is undertaken by step identical among the embodiment 3, different be to use a kind of like this working solution, wherein the concentration of amyl group tetrahydro-anthraquinone is 0.08 mol, the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.12 mol, the concentration of amyl anthraquinone is 0.580 mol, the concentration of pentyloxy anthrone is 0.012 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.010 mol.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.190 mol, and the concentration of amyl anthraquinone is 0.597 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.005 mol.
Embodiment 5
Reaction is undertaken by step identical among the embodiment 3, and different is that the Sunbead AN gama-alumina that Shokubai chemical company produces is as catalyzer.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.188 mol, and the concentration of amyl anthraquinone is 0.607 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.015 mol.
Embodiment 6
Reaction is undertaken by step identical among the embodiment 3, and different is that the KHD-24 gama-alumina that Sumitomo chemical company produces is used as catalyzer.
Fully oxidation of the working solution that will draw off from reactor (reaction begin through 24 hours after) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.190 mol, and the concentration of amyl anthraquinone is 0.605 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.013 mol.
Embodiment 7
Reaction is undertaken by embodiment 1 identical step, and different is that the GB-13 gama-alumina that Mizusawa chemical company produces is as catalyzer.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.190 mol, and the concentration of amyl anthraquinone is 0.605 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.013 mol.
Comparative Examples 1
Reaction is undertaken by step identical among the embodiment 3, different is, use a kind of like this reductive working solution, wherein the concentration of amyl group tetrahydro-anthraquinone is 0.35 mol, the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.165 mol, the concentration of amyl anthraquinone is 0.580 mol, and the concentration of pentyloxy anthrone is 0.012 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.010 mol.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.185 mol.The concentration of amyl anthraquinone is 0.593 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.001 mol.
Comparative Examples 2
Reaction is undertaken by step identical among the embodiment 3, different is, use so a kind of reductive working solution, wherein the concentration of amyl group tetrahydro-anthraquinone is 0.000 mol, the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.20 mol, and the concentration of amyl anthraquinone is 0.44 mol, concentration 0.14 mol of amyl group anthrahydroquinone, the concentration of pentyloxy anthrone is 0.012 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.010 mol.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.176 mol, and the concentration of amyl anthraquinone is 0.557 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is that the concentration of 0.000 mol and pentyloxy anthrone is 0.035 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.000 mol.
Embodiment 8
Reaction is undertaken by step identical among the embodiment 3, and different is that the temperature of reaction of working solution is 100 ℃.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.205 mol, and the concentration of amyl anthraquinone is 0.597 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide and pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.005 mol.
Embodiment 9
Reaction is undertaken by step identical among the embodiment 3, and different is that the temperature of reaction of working solution is 80 ℃.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.206 mol, and the concentration of amyl anthraquinone is 0.594 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.005 mol, and the concentration of pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.002 mol.
Comparative Examples 3
Reaction is undertaken by step identical among the embodiment 3, and different is that the temperature of reaction of working solution is 30 ℃.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.200 mol, and the concentration of amyl anthraquinone is 0.587 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.010 mol, and the concentration of pentyloxy anthrone is 0.005 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.000 mol.
Embodiment 10
Reaction is undertaken by step identical among the embodiment 3, and different is that the temperature of reaction of working solution is 60 ℃.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.195 mol, and the concentration of amyl anthraquinone is 0.594 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.009 mol, and the concentration of pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.002 mol.
Embodiment 11
Reaction is undertaken by step identical among the embodiment 3, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydro-anthraquinone is 0.15 mol, the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.05 mol, the concentration of amyl anthraquinone is 0.532 mol, and the concentration of pentyloxy anthrone is 0.06 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.010 mol.
Fully oxidation of the working solution that will draw off from reactor (beginning through after 24 hours from reaction) is analyzed by embodiment 1 identical mode then.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.191 mol, and the concentration of amyl anthraquinone is 0.594 mol, and the concentration of amyl group tetrahydro-anthraquinone epoxide is 0.006 mol, and the concentration of pentyloxy anthrone is 0.000 mol.The regeneration amount of alkyl tetrahydro anthraquinone is 0.002 mol.
Embodiment 12
Prepare a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.377 mol, and the concentration of amyl group tetrahydro-anthraquinone is 0.000 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.063 mol.In this embodiment, the AA400G (14-18 order) that uses the production of Alcan chemical company is as gama-alumina.Subsequently, 100 milliliters of above-mentioned working solutions are packed in 200 ml flasks, begin to send into nitrogen, under agitation working solution is heated to 60 ℃ then.When the temperature of working solution reaches 60 ℃, add 10.0 gram gama-aluminas, reaction was carried out 2 hours.After this, with the abundant oxidation of working solution, wash with water, dehydration is filtered, and uses liquid chromatography analysis then, to measure each component concentrations.As a result, the concentration of amyl group tetrahydro-anthraquinone is 0.371 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.029 mol.
In this respect,, used 60% (volume) 1,2, the mixed solvent of 4-trimethylbenzene and 40% (volume) diisobutyl carbinol(DIBC) for preparation work solution.In addition, with the working solution of liquid chromatography analysis oxidation when the reaction beginning in the working solution all alkyl tetrahydro anthraquinones be reduced into the alkyl tetrahydro anthrahydroquinone and carry out later on.The concentration of the anthrahydroquinone on the basis of per unit volume working solution oxygen absorbed in the evaluation work solution (hereinafter identical).
Embodiment 13
Reaction is undertaken by step identical among the embodiment 12, different is, uses a kind of like this working solution, and wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.000 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.337 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.063 mol.After reacting completely, measure various component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.390 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.005 mol, and the concentration of amyl anthraquinone is 0.003 mol.
Embodiment 14
Reaction is undertaken by the same steps as among the embodiment 12, different is, uses a kind of like this working solution, and wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.169 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.168 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.063 mol.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone is 0.382 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.017 mol.
Embodiment 15
Reaction is undertaken by embodiment 12 identical steps, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.000 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.337 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 80 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.386 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.007 mol, and the concentration of amyl anthraquinone is 0.002 mol.
Embodiment 16
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.051 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.286 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 80 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.383 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.013 mol, and the concentration of amyl anthraquinone is 0.002 mol.
Embodiment 17
Reaction is undertaken by step identical among the embodiment 12, different is, use so a kind of working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.337 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.000 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 80 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.362 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.041 mol, and the concentration of amyl anthraquinone is 0.000 mol.
Embodiment 18
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.000 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.337 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 100 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.373 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.011 mol, and the concentration of amyl anthraquinone is 0.014 mol.
Embodiment 19
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.182 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.155 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 100 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.363 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.033 mol, and the concentration of amyl anthraquinone is 0.004 mol.
Embodiment 20
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.000 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.337 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 120 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.339 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.023 mol, and the concentration of amyl anthraquinone is 0.039 mol.
Embodiment 21
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.167 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.170 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 120 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.339 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.043 mol, and the concentration of amyl anthraquinone is 0.020 mol.
Comparative Examples 4
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.337 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.000 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 120 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.327 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.063 mol.
Comparative Examples 5
Reaction is undertaken by step identical among the embodiment 4, and different is that temperature of reaction is 140 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.327 mol, and the concentration of amyl group tetra hydroxyanthraquinone is 0.074 mol.
Comparative Examples 6
Reaction is undertaken by step identical among the embodiment 12, different is, use a kind of like this working solution, wherein the concentration of amyl group tetrahydrochysene anthrahydroquinone is 0.237 mol, the concentration of amyl group tetrahydro-anthraquinone is 0.100 mol, the concentration of amyl group tetrahydroxy anthrone is 0.063 mol, and temperature of reaction is 150 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.320 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.064 mol, and the concentration of amyl anthraquinone is 0.014 mol.
Comparative Examples 7
Reaction is undertaken by step identical among the embodiment 4, and different is that temperature of reaction is 100 ℃.After reacting completely, measure each component concentrations.Its result, the concentration of amyl group tetrahydro-anthraquinone are 0.347 mol, and the concentration of amyl group tetrahydroxy anthrone is 0.053 mol.
Claims (5)
1. the renovation process of a working solution, this method comprise make contain that alkyl-anthraquinone and alkyl tetrahydro anthraquinone repeat to reduce as the working solution of anthraquinone and oxidation to produce the step of hydrogen peroxide, wherein the unreduced solution of at least a portion contacts under 40～150 ℃ with the catalyzer that mainly contains gama-alumina, and condition is that to contain concentration be 0.15 mol or lower alkyl tetrahydro anthrahydroquinone to untreated working fluid.
2. according to the regeneration of working solution method of claim 1, it is 0.05 mol or higher alkyl tetrahydro anthraquinone that wherein unreduced working solution contains concentration.
3. according to the regeneration of working solution method of claim 1, it is that 0.05 mol or higher alkyl tetrahydro anthraquinone and concentration are 0.15 mol or lower alkyl tetrahydro anthrahydroquinone that wherein unreduced working solution contains concentration.
4. the renovation process of a working solution, this method comprise make contain at least that the alkyl tetrahydro anthraquinone repeats to reduce as the working solution of anthraquinone and oxidation to produce the step of hydrogen peroxide, wherein working solution contacts with the catalyzer that mainly contains gama-alumina down at 20～150 ℃, the concentration h of alkyl tetrahydro anthrahydroquinone in working solution before the catalytic treatment, mol satisfies the condition of following formula
(in 0.0018 * t-0.0285) * h≤0.05 formula, t be treatment temp (℃) so that the alkyl tetra hydroxyanthraquinone in the working solution changes into the alkyl tetrahydro anthrahydroquinone.
5. according to the regeneration of working solution method of claim 4, wherein at the concentration h of alkyl tetrahydro anthrahydroquinone in working solution before the catalytic treatment, mol is 0.15 mol or lower, and satisfies following formula
(in 0.0018 * t-0.0285) * h≤0.02 formula, t be treatment temp (℃).
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9123996A JPH09278420A (en) | 1996-04-12 | 1996-04-12 | Regenerating method of actuating solution used for hydrogen peroxide production |
| JP091238/96 | 1996-04-12 | ||
| JP091239/1996 | 1996-04-12 | ||
| JP9123896A JPH09278419A (en) | 1996-04-12 | 1996-04-12 | Regenerating method of actuating solution used for hydrogen peroxide production |
| JP091239/96 | 1996-04-12 | ||
| JP091238/1996 | 1996-04-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1166450A CN1166450A (en) | 1997-12-03 |
| CN1108984C true CN1108984C (en) | 2003-05-21 |
Family
ID=26432701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97110726A Expired - Lifetime CN1108984C (en) | 1996-04-12 | 1997-04-11 | Regeneration method of working solution |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | USH1787H (en) |
| KR (1) | KR100474503B1 (en) |
| CN (1) | CN1108984C (en) |
| CA (1) | CA2202435C (en) |
| DE (1) | DE19715034A1 (en) |
| ID (1) | ID16589A (en) |
| TW (1) | TW432009B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022078427A1 (en) | 2020-10-14 | 2022-04-21 | 中国石油化工股份有限公司 | Method and system for preparing hydrogen peroxide |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1012267A3 (en) * | 1998-11-05 | 2000-08-01 | Solvay | Manufacturing method of hydrogen peroxide. |
| FI108432B (en) * | 2000-03-06 | 2002-01-31 | Kemira Chemicals Oy | Regeneration of the working solution in the hydrogen peroxide production process |
| TWI383951B (en) * | 2006-05-09 | 2013-02-01 | Mitsubishi Gas Chemical Co | Method for producing hydrogen peroxide containing a regeneration step of an action solution |
| TWI443063B (en) * | 2007-07-11 | 2014-07-01 | Mitsubishi Gas Chemical Co | Method for producing regenerative catalyst for producing hydrogen peroxide working solution |
| CN103803500B (en) * | 2012-11-07 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of working fluid reclaiming process of hydrogen dioxide solution production by anthraquinone process |
| CN106540685B (en) * | 2015-09-17 | 2021-01-08 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, regeneration method for producing hydrogen peroxide working solution by anthraquinone method and method for producing hydrogen peroxide |
| JP7327414B2 (en) * | 2018-11-20 | 2023-08-16 | 三菱瓦斯化学株式会社 | How to treat the working solution |
| CN109806875A (en) * | 2019-02-26 | 2019-05-28 | 浙江巴陵恒逸己内酰胺有限责任公司 | It is catalyzed the regeneration method of catalyst of regenerating anthraquinone degradation products and preparation method thereof and cycle working fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2739875A (en) * | 1951-12-06 | 1956-03-27 | Du Pont | Regeneration of degraded alkylanthraquinone solutions for the production of hydrogen peroxide |
| CN86107428A (en) * | 1985-12-13 | 1987-06-17 | Fmc公司 | A kind of purification process of working solution |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3432267A (en) * | 1967-05-26 | 1969-03-11 | Fmc Corp | Regeneration of anthraquinone working solution used in the production of hydrogen peroxide |
| DE2003268C3 (en) * | 1970-01-26 | 1974-01-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Device for carrying out the oxidation in the anthraquinone process for the production of hydrogen peroxide |
| US3965251A (en) * | 1970-08-18 | 1976-06-22 | Mitsubishi Gas Chemical Company, Inc. | Method of regenerating a degraded working solution for the production of hydrogen peroxide |
| US3880596A (en) * | 1971-09-24 | 1975-04-29 | Degussa | Apparatus for the production of hydrogen peroxide |
| US4061598A (en) * | 1976-06-25 | 1977-12-06 | E. I. Du Pont De Nemours And Company | Catalyst for hydrogenating anthraquinones |
| US4566998A (en) * | 1981-09-28 | 1986-01-28 | Foret S.A. | Production of hydrogen peroxide |
| US4800075A (en) * | 1987-12-14 | 1989-01-24 | E. I. Du Pont De Nemours And Company | Fixed-bed hydrogen peroxide catalyst |
| BE1006352A6 (en) * | 1991-12-12 | 1994-08-02 | Solvay Interox | Method for manufacturing hydrogen peroxide. |
| JP3617532B2 (en) * | 1992-12-25 | 2005-02-09 | 三菱瓦斯化学株式会社 | Method for producing hydrogen peroxide |
| KR0130851B1 (en) * | 1994-11-03 | 1998-04-21 | 강박광 | Method of removing anthraquinone and processing its restoration |
-
1997
- 1997-03-26 US US08/829,696 patent/USH1787H/en not_active Abandoned
- 1997-04-08 KR KR1019970012801A patent/KR100474503B1/en not_active IP Right Cessation
- 1997-04-08 TW TW086104444A patent/TW432009B/en not_active IP Right Cessation
- 1997-04-11 CN CN97110726A patent/CN1108984C/en not_active Expired - Lifetime
- 1997-04-11 DE DE19715034A patent/DE19715034A1/en not_active Withdrawn
- 1997-04-11 CA CA002202435A patent/CA2202435C/en not_active Expired - Lifetime
- 1997-04-14 ID IDP971222A patent/ID16589A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2739875A (en) * | 1951-12-06 | 1956-03-27 | Du Pont | Regeneration of degraded alkylanthraquinone solutions for the production of hydrogen peroxide |
| CN86107428A (en) * | 1985-12-13 | 1987-06-17 | Fmc公司 | A kind of purification process of working solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022078427A1 (en) | 2020-10-14 | 2022-04-21 | 中国石油化工股份有限公司 | Method and system for preparing hydrogen peroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2202435A1 (en) | 1997-10-12 |
| KR970069873A (en) | 1997-11-07 |
| TW432009B (en) | 2001-05-01 |
| CA2202435C (en) | 2008-07-22 |
| USH1787H (en) | 1999-02-02 |
| ID16589A (en) | 1997-10-16 |
| DE19715034A1 (en) | 1997-10-30 |
| KR100474503B1 (en) | 2005-07-18 |
| CN1166450A (en) | 1997-12-03 |
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