CN113454064A - Process for producing organic peroxide - Google Patents
Process for producing organic peroxide Download PDFInfo
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- CN113454064A CN113454064A CN202080015750.XA CN202080015750A CN113454064A CN 113454064 A CN113454064 A CN 113454064A CN 202080015750 A CN202080015750 A CN 202080015750A CN 113454064 A CN113454064 A CN 113454064A
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Abstract
The present invention relates to a process for the production of organic peroxides and the separation, purification and concentration of sulfuric acid from the aqueous effluent of said organic peroxide production process.
Description
The present invention relates to an acid-catalyzed process for the production of organic peroxides. Several organic peroxide production processes are acid catalyzed and require the use of large amounts of strong acids. The acid preferably used is sulfuric acid. The use of large amounts of sulfuric acid results in the formation of large sulfate-containing waste streams.
It is an object of the present invention to reduce these sulfate-containing waste streams.
From CN101857563 and CN 108658824 it is known to recycle streams in processes for the production of organic peroxides from alcohols or ketones. CN101857563 and CN 108658824 disclose a process for the preparation of tert-butyl hydroperoxide by reacting tert-butanol with hydrogen peroxide in the presence of sulfuric acid, wherein part of the mother liquor is recycled to be reused as solvent for the newly added reactants. To avoid infinite dilution of the process stream, only the mother liquor fraction is recycled. Since only part of the mother liquor is recycled to the process, only part of the sulfuric acid and unreacted hydrogen peroxide and tert-butanol are reused. In fact, a large portion of the sulfuric acid used will ultimately become a waste stream in the disclosed process.
The object of further reducing sulphate-containing waste streams has been achieved by the process of the present invention, comprising the steps of purifying, concentrating and reusing a sulphuric acid stream originating from an organic peroxide production process.
The sulfuric acid stream contains peroxide: hydrogen peroxide, residues of generated organic peroxides, or combinations thereof. The sulfuric acid stream also contains other organic species. For reuse, it is necessary to purify the sulfuric acid from the organic residue. It is also necessary to concentrate the sulfuric acid to the concentration required for its reuse. Furthermore, peroxide residues have to be removed from the stream, since not all process steps using this purified and recycled stream allow the presence of peroxide residues.
The process for producing an organic peroxide according to the present invention comprises the steps of:
a. reacting an alcohol or ketone with hydrogen peroxide, thereby forming a reaction mixture comprising:
an organic phase comprising an organic peroxide, and
-an aqueous phase comprising (i) at least 5% by weight of H2SO4And (ii) H2O2And/or organic peroxide residuesThe residue is left on the device to be treated,
b. the aqueous phase is separated from the organic phase,
c. optionally adding H to the aqueous phase2O2And/or removing any residual organic compounds from the aqueous phase,
d. obtaining a catalyst containing 5-60 wt% of H2SO4And 0.3-35 wt% of H2O2An aqueous phase of (A), and
e. heating the aqueous phase of step d at a temperature in the range of 20-300 ℃ and a pressure of 0.001 to 1 bar, thereby decomposing at least part of the H2O2Removing part of the water and subjecting the aqueous mixture to H2SO4The concentration is increased by at least 7 weight percent to a concentration in the range of 12-95 weight percent.
It was very surprising that the stream comprising sulphuric acid could be concentrated by a simple step, step e) above, wherein water is evaporated. As known to those skilled in the art, the formation of acetone peroxide cannot be prevented when reacting an alcohol or ketone with hydrogen peroxide in the presence of sulfuric acid. Acetone peroxide has a risk of solidification in water evaporation steps such as step e) above, and acetone peroxide crystals are known to be friction sensitive explosives. However, in the process of the present invention, the accumulation of acetone peroxide and the formation of colored products is unexpectedly inhibited by combining steps c), d) and e) of the process of the present invention, and the amount of acetone peroxide is kept below levels that would pose safety problems.
It should be noted that US 4,168,274 and GB1501356 disclose a process involving the recycling of a sulphuric acid waste stream, wherein there is a concentration step of the sulphuric acid solution. However, these documents relate to the preparation of peracids by reacting an organic acid with hydrogen peroxide in the presence of sulfuric acid. When peracid is prepared by reacting an acid with hydrogen peroxide, acetone peroxide is not formed, as opposed to reacting an alcohol or ketone with hydrogen peroxide, as is known to those skilled in the art.
The aqueous phase resulting from step e may be used for any suitable purpose, such as for example the production of phosphoric acid from phosphate rock, the production of ammonium sulphate from a coke-oven plant, the production of aluminium sulphate from bauxite, the production of dye solutions, the production of hydrogen via a sulphur-iodine cycle (Bunsen reaction), as an industrial cleaning solution or as an electrolyte in lead acid batteries.
In a preferred embodiment, at least part of the aqueous phase resulting from step e is reused in the organic peroxide production process. For the same organic peroxide, this may be the same process that produced it, but may also be a process for producing another organic peroxide.
The advantage of the process of the present invention is that no contaminating materials, such as metals, need to be added, which makes the recycled sulfuric acid suitable for reuse in the peroxide production process.
In a more preferred embodiment, at least part of the aqueous phase resulting from step e is recycled to step a.
The aqueous phase treated in steps c, d and e may result from one particular organic peroxide production process, but may also be a mixture of aqueous phases resulting from two or more different organic peroxide production processes.
Increasing H in step e by heating the aqueous phase2SO4The concentration is not as simple as it looks. H present in said phase2O2Can decompose which can lead to significant oxygen formation and thus pressure build-up. In addition, the oxygen together with the volatile organic compounds may form a flammable and potentially explosive mixture.
The alcohol used in step a) of the embodiment is selected from the group consisting of t-butanol, t-amyl alcohol, 1,3, 3-tetramethylbutanol, 2, 5-dimethyl-2, 5-hexanediol, 2-methyl-2, 4-pentanediol, 2, 5-dimethyl-2, 5-dihydroxy-3-hexyne, 1, 3-bis (isopropanol) benzene, and 1, 4-bis (isopropanol) benzene.
The ketone used in step a) of an embodiment is selected from the group consisting of acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl hexyl ketone, methyl heptyl ketone, diethyl ketone, ethyl propyl ketone, ethyl amyl ketone, methyl octyl ketone, methyl nonyl ketone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3, 5-trimethylcyclohexanone.
The reaction of step a) is carried out in H2SO4In the presence of oxygen.
Suitable organic peroxides which can be produced according to the process of the present invention are dialkyl peroxides, cyclic ketone peroxides, trioxepanes and aliphatic hydroperoxides.
Specific examples of dialkyl peroxides are 2, 2-di (t-butylperoxy) butane, dicumyl peroxide, di (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, di-t-amyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne and t-butylcumyl peroxide.
Preferred dialkyl peroxides are 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, di-t-amyl peroxide and di-t-butyl peroxide. The production of these peroxides requires relatively concentrated sulfuric acid solutions (30 wt% or higher).
The term "cyclic ketone peroxide" includes dimeric cyclic ketone peroxides and trimeric cyclic ketone peroxides. These peroxides have the following structure:
wherein R is1-R6Independently selected from hydrogen, C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20Alkaryl groups, which groups may include linear or branched alkyl moieties; and R is1-R6Each of which may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxy, nitrile and amido.
Preferred cyclic ketone peroxides are 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane (3MEK-cp) and mixtures comprising 3MEK-cp and at least one peroxide satisfying the formula
Wherein R is1To R3Independently selected from alkyl and alkoxyalkyl groups having 2 to 5 carbon atoms, R1+R2+R3The total number of carbon plus oxygen atoms of (a) is in the range of 7 to 15. The term alkoxyalkyl means a compound having the formula-CnH2n-O-CmH2m+1Wherein n and m are both at least 1.
The trioxepanes have the formula
Wherein R is1、R2And R3Independently selected from hydrogen and substituted or unsubstituted hydrocarbyl, and optionally a group R1、R2And R3Are connected to form a ring structure. Preferably, R1、R2And R3Independently selected from hydrogen and substituted or unsubstituted C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20Alkylaryl groups, which groups may include linear or branched alkyl moieties, with R1、R2And R3May be linked to form a (substituted) cycloalkyl ring; r1-R3Is selected from the group consisting of hydroxy, alkoxy, linear or branched alk (en) yl, aryloxy, halogen, carboxylic acid, ester, carboxy, nitrile and amide groups.
Preferably, R1And R3Selected from lower alkyl, more preferably C1-C6Alkyl groups such as methyl, ethyl and isopropyl, most preferably methyl and ethyl. R2Preferably selected from hydrogen, methyl, ethyl, isopropyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclohexyl, phenyl, CH3C(O)CH2-、C2H5OC(O)CH2-、HOC(CH3)2CH2-and
wherein R is4Independently selected from for R1-3Any one of the groups of the given compound. Another preferred trioxepane is:
specific examples of aliphatic hydroperoxides are tert-butyl hydroperoxide, tert-amyl hydroperoxide, hexanediol hydroperoxide, 2, 5-dimethyl-2, 5-dihydroperoxy hexane, 2, 5-dimethyl-2, 5-dihydroperoxy-3-hexyne, and 1,1,3, 3-tetramethylbutyl hydroperoxide and 1, 1-dimethylbutyl hydroperoxide.
If a monohydric alcohol is used in step a of the process, dialkyl peroxides or hydroperoxides are produced, depending on the amount of hydrogen peroxide and the sulfuric acid concentration. For the production of dialkyl peroxides, an aqueous solution of sulfuric acid having a concentration of at least 30% by weight is generally required; for the production of hydroperoxides, concentrations of between 10 and 30% by weight are generally used.
Examples of suitable monoalcohols are tert-butanol, tert-amyl alcohol and 1,1,3, 3-tetramethylbutanol.
If a dihydric alcohol is used in step a of the process, a di-hydroperoxide is produced which can be further reacted with a monohydric alcohol again in the presence of sulfuric acid to form the bis-dialkyl peroxide. In the latter reaction, an aqueous solution of sulfuric acid having a concentration of at least 10% by weight is preferably used.
Examples of diols are 2, 5-dimethyl-2, 5-hexanediol, 2, 5-dimethyl-2, 5-dihydroxy-3-hexyne, 1, 3-bis (isopropanol) benzene and 1, 4-bis (isopropanol) benzene.
In order to obtain dimeric or trimeric cyclic ketone peroxides, in the range from 20 to 75% by weight% aqueous sulfuric acid and inert diluent (phlegmatizer) are reacted with the ketone and hydrogen peroxide. Examples of suitable ketones are linear, branched or cyclic C3-C13Ketones, most preferably C3-C7A ketone. Examples of suitable ketones are acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl hexyl ketone, methyl heptyl ketone, diethyl ketone, ethyl propyl ketone, ethyl amyl ketone, methyl octyl ketone, methyl nonyl ketone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3, 5-trimethylcyclohexanone, and mixtures thereof.
Trioxepanes are obtained by reacting a diol (diol) with hydrogen peroxide in the presence of a 20-60% by weight aqueous sulfuric acid solution to form a diol hydroperoxide. Subsequently, the diol hydroperoxide is reacted again with the ketone or aldehyde in the presence of sulfuric acid (10-60% by weight aqueous solution) to form trioxepane. This process is described in WO 2006/066984.
A suitable example of a diol is 2-methyl-2, 4-pentanediol.
The organic peroxide formed will be present in the organic layer of the resulting biphasic reaction mixture and may be separated by conventional techniques, such as gravity, liquid/liquid separator, centrifuge or continuous (plate) separator (step b).
The organic peroxide is usually washed with water or an aqueous alkaline solution.
The aqueous phase will contain (i) H2SO4And (ii) H2O2And/or residual organic peroxide. The aqueous phase may also contain additional organics. In preferred embodiments, it is desirable to substantially remove and/or destroy these organics to prevent them from blackening or building up the aqueous mixture to undesirable levels.
In a preferred embodiment, these organics are more completely removed and/or destroyed by (vacuum) distillation (step e) or by adding (additional) amounts of hydrogen peroxide to the aqueous mixture (step c).
The aqueous phase of step d preferably comprises at least 5 wt.%, preferably at least 10 wt.%, more preferablyPreferably at least 20 wt.% and most preferably at least 30 wt.% of H2SO4. Preferably containing not more than 60 wt.% of H2SO4。
Except for H2SO4In addition, other acids may be present in the aqueous phase.
The aqueous phase of step d comprises 0.3-35 wt.%, preferably 0.5-35 wt.%, more preferably 1-35 wt.%, even more preferably 2-35 wt.% and most preferably 2-25 wt.% of H2O2。
In order to decompose at least part of H2O2Removing part of water and removing H2SO4The concentration is increased by at least 7 weight percent to a concentration in the range of 12-95 weight-%, preferably 50-95 weight-%, more preferably 70-95 weight-% and most preferably 75-85 weight-%, and the aqueous mixture is heated at a pressure of 0.001-1 bar, preferably 0.01-1 bar, to a temperature in the range of 20-300 ℃, preferably 30-250 ℃, even more preferably 50-200 ℃ and most preferably 100-200 ℃ (step e).
It should be noted that the temperature of the aqueous phase formed in step b is typically in the range of 0-20 c, preferably 0-10 c, since peroxide production processes are typically carried out at low temperatures.
It is undesirable to concentrate to 96 wt.% H or more2SO4Since this requires distillation of SO3And then dissolved.
The heating is preferably carried out in one or more distillation and/or heating steps.
In a preferred embodiment, the heating step involves heating at a temperature below H2O2At a decomposition temperature of (a) is stripping volatile organic components. A suitable temperature range is 30-120 ℃. The pressure may be atmospheric, but is preferably lower to avoid an explosive atmosphere during the process.
If the aqueous mixture has a relatively high hydrogen peroxide concentration (about 2 wt% or higher), its decomposition will result in a large oxygen stream. Distillation at atmospheric pressure is preferred in view of safety concerns.
If the peroxide concentration is low, or becomes low during the process, reduced pressure distillation is contemplated. It is also possible to carry out atmospheric distillation first and then vacuum distillation.
The aqueous distillate removed during step e was condensed in a condenser and subsequently collected in a vessel.
The distillate will contain a large amount of oxygen due to the decomposition of hydrogen peroxide. Oxygen does not condense in the condenser and in order to ensure safe processing it is necessary to maintain the oxygen concentration of the distillate below the flash point. Preferably, the oxygen concentration in the gas phase is kept below 30 vol%, preferably below 8 vol%.
This can be achieved by introducing nitrogen or air into the system thereby diluting the oxygen. More preferably, nitrogen or air streams are added to the distillate prior to entering the condenser, or when present in the condenser.
Step e may be carried out batchwise, semi-continuously or continuously. In large volume batch processes, the temperature should be carefully controlled to prevent hazardous conditions. Furthermore, most of the gases formed at the start of the process in a batch process may result in the formation of a very concentrated oxygen stream. In the case of a concentrated oxygen stream, it is difficult to control the nitrogen stream so that the mixture remains below the flash point. However, in (semi-) continuous operation, oxygen and CO2The rate of formation of (a) will be more stable to almost complete stability and the oxygen concentration will be more easily controlled. Heating a first portion of the aqueous phase to boiling point in a batch reactor in a semi-continuous mode; then will contain H2SO4And H2O2The remaining part of the aqueous phase of (a) is fed to the batch reactor and (part of) the concentrated acid is intermittently withdrawn. In this way, the rate of oxygen formation and organic stripping is also more efficient and can be better controlled. Continuous or semi-continuous operation is preferred.
In a specific embodiment, the process involves the production of 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane or 2, 5-di-tert-butylperoxy-2, 5-di (tert-butylperoxy) -3-hexyne. These peroxides are usually prepared in two steps. In a first step, 2, 5-dimethyl-2, 5-hexanediol, 2, 5-dimethyl-2, 5-dihydroxy-3-hexyne, respectively, is reacted with hydrogen peroxide in the presence of sulfuric acid to form 2, 5-dihydroperoxy-2, 5-dimethylhexane, 2, 5-dihydroperoxy-2, 5-dimethyl-3-hexyne, respectively. An excess of high concentration hydrogen peroxide (e.g., 70 wt.% aqueous solution) is typically required, including relatively large amounts of high concentration sulfuric acid (e.g., 70-95 wt.% aqueous solution). The dihydroperoxide can be separated from the aqueous effluent by filtration or centrifugation and contains large amounts of sulfuric acid, hydrogen peroxide, small amounts of glycols and various organic by-products.
The dihydroperoxide is then reacted with t-butanol, again catalyzed by a high concentration of sulfuric acid (e.g., 60-90 wt% aqueous solution) to form the desired peroxide. The aqueous effluent from this step, which may also be obtained by gravity separation or centrifugation, will contain sulfuric acid and organic by-products.
The combined aqueous effluent contains about 10-50 wt.% H2SO4And about 5-20 wt% H2O2. By stripping with an air stream, followed by distillation to destroy most of the H2O2And increase H2SO4Concentration, organic matter can be removed from the resulting aqueous phase. Thereafter, further distillation under reduced pressure may be carried out to further increase H2SO4And (4) concentration.
The resulting purified and concentrated H2SO4Can be used in various processes. In a preferred embodiment, it is reused in the first and/or second step of the peroxide production process.
In another specific embodiment, the process involves the production of di-t-butyl peroxide or di-t-amyl peroxide. According to this embodiment, t-butanol or t-amyl alcohol, respectively, is reacted with hydrogen peroxide in the presence of 30 to 78 weight percent aqueous sulfuric acid to form di-t-butyl peroxide or di-t-amyl peroxide.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separator or continuous (plate) separator.
The aqueous phase contains 5-70 wt.% of H2SO40.1 to 10% by weight of tert-butanol or tert-amyl alcohol and 0.1 to 5% by weight of an organic peroxide.
Hydrogen peroxide is then added to the aqueous phase, resulting in an aqueous phase with a hydrogen peroxide concentration of 0.3-20 wt.%, preferably 0.3-10 wt.% and most preferably 0.3-5 wt.%. The mixture is then preferably stirred at a temperature in the range of 50-250 deg.C, more preferably 80-220 deg.C, most preferably 100-210 deg.C, optionally under reduced pressure, to destroy and/or remove organic residues and increase the sulfuric acid concentration.
In another embodiment, the process relates to the production of hydroperoxides. According to this embodiment, a tertiary alcohol or substituted olefin is reacted with hydrogen peroxide in the presence of sulfuric acid (5-95 wt% aqueous solution) to form a tertiary alkyl hydroperoxide.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separator or continuous (plate) separator.
The aqueous phase contains 5-60 wt.% of H2SO41-25% by weight of H2O20.1-20 wt.% tertiary alcohol and 0.1-5 wt.% organic peroxide.
Hydrogen peroxide is then optionally dosed into the aqueous phase and then optionally stirred under reduced pressure, preferably at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-.
In another embodiment, the process relates to the production of trimeric cyclic ketone peroxides.
According to this embodiment, the ketone is reacted with hydrogen peroxide in the presence of a 20-95 wt% aqueous sulfuric acid solution to form a trimeric cyclic ketone peroxide.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separator or continuous (plate) separator.
The aqueous phase comprises 20-70 wt.% of H2SO41-25% of H2O20.1 to 20% by weight of a ketone and 0.1 to 10% by weight of an organic peroxide.
Hydrogen peroxide is then optionally dosed into the aqueous phase and then optionally stirred under reduced pressure, preferably at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-.
In another embodiment, the method involves the production of trioxepanes.
According to this embodiment, the ketone is reacted with a hydroxy hydroperoxide in the presence of a 20 to 95% by weight aqueous solution of sulfuric acid to form trioxepane.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separator or continuous (plate) separator.
The aqueous phase contains 10-70% by weight of H2SO40.1 to 20 wt.% of a ketone and 0.1 to 20 wt.% of an organic peroxide.
Hydrogen peroxide is then optionally dosed into the aqueous phase and then optionally stirred under reduced pressure, preferably at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-.
Examples
Example 1
70 wt% aqueous hydrogen peroxide (121.6g) was added to the jacketed reactor. The reactor was cooled to 5 ℃. A78 wt% aqueous solution of sulfuric acid (157.5g) was then fed to the reactor over 20 minutes while controlling the temperature of the mixture to below 10 ℃. After addition of sulfuric acid, the mixture was cooled to 5 ℃. Solid 2, 5-dimethyl-2, 5-dihydroxyhexane (36.6g,0.25mol) was added to the mixture at a rate that maintained the temperature below 10 ℃.
After addition of 2, 5-dimethyl-2, 5-dihydroxyhexane, the temperature was raised to 25 ℃ and held at this temperature for 1 hour. The temperature was then reduced to 5 ℃ and 200mL of water was added. After stirring for 2 minutes, the reaction mixture was filtered and washed with cold water. 2, 5-dimethyl-2, 5-dihydroperoxy hexane was obtained as a solid in a yield of 78%. 471g of the catalyst contained 26% of H2SO4The aqueous phase of (a) was combined with the acid layer of the next step.
Tert-butanol (88% by weight in water, 143g,1.7mol) was added dropwise (20 minutes) to a stirred solution of sulfuric acid (78% by weight, 104.7g,0.83mol) in a jacketed reactor maintained at 15 ℃.2, 5-dimethylhexane-2, 5-dihydroperoxide (54g,0.20mol) obtained in the preceding step was added over 20 minutes, after which the temperature was raised to 40 ℃ and kept at this temperature for up to four hours.
The reaction produced a two-layer mixture; the layers were separated by draining the aqueous layer. The organic layer contained 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane in a yield of 70%.
The aqueous layer was diluted with 150g of water and the tert-butanol was removed by distillation at 100 mbar. 276g obtained containing 30 wt% H2SO4Is combined with the aqueous phase of the first step, thereby forming a mixture comprising 27 wt% H2SO4And 9 wt% H2O2The aqueous phase of (a).
The aqueous phase was dosed just below the top of a glass Vigreux column mounted on a three-necked glass vessel. The vessel was stirred and the temperature was maintained at 135-140 ℃ by heating with an external oil bath at atmospheric pressure. The Vigreux column was connected to a condenser (20 ℃ C.) and a container to collect the condensate. Air was fed to the condenser to dilute the oxygen content in the gas phase to 25 vol%. The aqueous phase was dosed to the Vigreux column at a rate of 5 g/min, resulting in the formation of a condensate at a rate of 2.65 g/min. No solids (any compounds such as diproprione peroxide) were observed in the equipment, acid or distillate. At steady state, 2.35g of colorless concentrated acid was pumped out of the three-necked vessel per minute. H of concentrated acid2SO4Content 58.3% and H2O2The content is 1.8%.
In the second concentration step, the concentrated acid of the previous step was dosed into a three-necked glass vessel. The vessel was stirred and heated with an external oil bath to maintain the temperature at about 162 ℃ and connected to a vacuum system at a pressure of 70-120 mbar. A three-neck glass vessel was connected to the condenser and vessel to collect the condensate. The concentrated acid was dosed at a rate of 2 g/min and 0.6 g of condensate was obtained per minute. At steady state, 1.4g of colorless concentrated acid was pumped out of the three-necked vessel per minute. No solids (any compounds such as diproprione peroxide) were observed in the equipment, acid or distillate. H of concentrated acid2SO4Content 83 wt.%, H2O2The content is less than 0.5 percent. The acid was diluted with water to 78 wt% and may be weighed as described aboveIt is used for preparing 2, 5-dimethyl hexane-2, 5-di-hydroperoxide.
Example 2
To a 2.5 liter reactor was added 900g of 70 wt% H2SO4And 600g of 30% by weight H2O2The reactor was equipped with 3 baffles, a turbine impeller, a thermometer and a cooling jacket. Tert-butanol (700g) was added over 1 hour to maintain the temperature in the range of 35-40 ℃. The mixture was heated to 45 ℃ and stirred at this temperature for 1 hour. The mixture was thereafter cooled to 30 ℃ and allowed to separate. The sulfuric acid concentration of the 1.520g aqueous layer was 41% by weight. The organic layer was washed with bicarbonate solution and contained 668g of di-tert-butyl peroxide in 99.4% purity and 96% yield.
Adding H to the aqueous layer2O2(102g,30 wt%). The resulting mixture was dosed (rate: 500 ml/h) into a 100ml heated vessel operating at 93 ℃ and 100 and 150 mbar. The water vapor was sent to a condenser. The acid exiting the vessel was sent to a multi-compartment evaporator where the temperature was raised to 157 ℃ at a pressure of 100-. The colourless acid from the last compartment was cooled to room temperature and its H2SO4The content was 74% by weight. No solids (any compounds such as diproprione peroxide) were observed in the equipment, acid or distillate. Diluted to 70% by weight of H with water2SO4Thereafter, the acid may be reused to prepare di-tert-butyl peroxide according to the procedure described above.
Claims (15)
1. A process for producing an organic peroxide, comprising the steps of:
a. reacting an alcohol or ketone with hydrogen peroxide, thereby forming a reaction mixture comprising:
an organic phase comprising an organic peroxide, and
-an aqueous phase comprising (i) at least 5% by weight of H2SO4And (ii) H2O2And/or organic peroxide residues,
b. the aqueous phase is separated from the organic phase,
c. optionally to the waterAddition of H to phase2O2And/or removing any residual organic compounds from the aqueous phase,
d. obtaining a catalyst containing 5-60 wt% of H2SO4And 0.3-35 wt% of H2O2An aqueous phase of (A), and
e. heating the aqueous phase of step d at a temperature in the range of 20-300 ℃ and a pressure of 0.001 to 1 bar, thereby decomposing at least part of the H2O2Removing part of the water and subjecting the aqueous mixture to H2SO4The concentration is increased by at least 7 weight percent to a concentration in the range of 12-95 weight percent.
2. The process of claim 1, wherein at least a portion of the aqueous phase resulting from step e is recycled to step a.
3. The process according to any of the preceding claims, wherein the aqueous phase of step d comprises 0.5-35 wt.%, preferably 1-35 wt.%, more preferably 2-35 wt.% and most preferably 2-25 wt.% of H2O2。
4. The process according to any of the preceding claims, wherein the aqueous phase of step d comprises 10-60 wt. -%, preferably 20-55 wt. -%, and most preferably 30-50 wt. -% of H2SO4。
5. The process of any one of the preceding claims, wherein the H of the aqueous mixture resulting from step e2SO4The concentration has a H content of 50-95 wt.%, preferably 70-95 wt.% and most preferably 75-85 wt.%2SO4And (4) concentration.
6. The process according to any one of the preceding claims, wherein step e comprises stripping volatile organic components at a temperature in the range of 30-120 ℃.
7. The process of any one of the preceding claims, wherein step e comprises distillation at atmospheric pressure followed by distillation at a pressure below atmospheric pressure.
8. The process according to any of the preceding claims, wherein step e comprises distillation and wherein the oxygen content in the gas phase of the distillate is kept below 30 vol.%, preferably below 8 vol.%, by adding nitrogen or air.
9. The process according to any one of the preceding claims, wherein step e is carried out in a semi-continuous or continuous mode.
10. The process according to any one of the preceding claims, wherein the organic peroxide produced is selected from the group consisting of dialkyl peroxides, cyclic ketone peroxides, trioxepanes and aliphatic hydroperoxides.
11. The process of claim 10, wherein the organic peroxide is a dialkyl peroxide selected from the group consisting of: 2, 2-di (t-butylperoxy) butane, dicumyl peroxide, di (t-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, di-t-amyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne and t-butylcumyl peroxide, and is preferably selected from the group consisting of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne, di-t-amyl peroxide and di-t-butyl peroxide.
12. The process of claim 10, wherein the organic peroxide is an aliphatic hydroperoxide selected from the group consisting of: t-butyl hydroperoxide, t-amyl hydroperoxide, hexylene glycol hydroperoxide, 2, 5-dimethyl-2, 5-dihydroperoxy hexane, 2, 5-dimethyl-2, 5-dihydroperoxy-3-hexyne, 1,3, 3-tetramethylbutyl hydroperoxide and 1, 1-dimethylbutyl hydroperoxide.
13. The process of claim 10, wherein the organic peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane or a mixture of cyclic ketone peroxides comprising 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxynonane.
14. The process of any one of claims 1-12, wherein in step a an alcohol selected from the group consisting of tert-butanol, tert-amyl alcohol, and 1,1,3, 3-tetramethylbutanol, 2, 5-dimethyl-2, 5-hexanediol, 2, 5-dimethyl-2, 5-dihydroxy-3-hexyne, 1, 3-bis (isopropanol) benzene, and 1, 4-bis (isopropanol) benzene is reacted with hydrogen peroxide.
15. The process of any one of claims 1-10 and 13, wherein in step a ketone selected from the group consisting of acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl hexyl ketone, methyl heptyl ketone, diethyl ketone, ethyl propyl ketone, ethyl amyl ketone, methyl octyl ketone, methyl nonyl ketone, cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3, 5-trimethylcyclohexanone, and mixtures thereof, is reacted with hydrogen peroxide.
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