CN113454064B - Method for producing organic peroxides - Google Patents
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- CN113454064B CN113454064B CN202080015750.XA CN202080015750A CN113454064B CN 113454064 B CN113454064 B CN 113454064B CN 202080015750 A CN202080015750 A CN 202080015750A CN 113454064 B CN113454064 B CN 113454064B
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Abstract
The present invention relates to a process for producing an organic peroxide and separating, purifying and concentrating sulfuric acid from an aqueous effluent of said organic peroxide production process.
Description
The present invention relates to an acid catalyzed process for producing 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 amounts of sulfate-containing waste streams.
It is an object of the present invention to reduce these sulfate containing waste streams.
From CN101857563 and CN 108658824, recycling of streams in a process for producing organic peroxides from alcohols or ketones is known. CN101857563 and CN 108658824 disclose a process for preparing tert-butyl hydroperoxide by reacting tert-butanol with hydrogen peroxide in the presence of sulfuric acid, wherein part of the mother liquor is recycled as solvent for the newly added reactants to be reused. To avoid infinite dilution of the process stream, only a portion of the mother liquor is recycled. Because only a portion of the mother liquor is recycled to the process, only a portion of the sulfuric acid and unreacted hydrogen peroxide and tertiary butanol are reused. In fact, a large portion of the sulfuric acid used will eventually become a waste stream in the disclosed process.
The object of further reducing the sulfate containing waste stream has been achieved by the process of the present invention comprising the steps of purifying, concentrating and reusing the sulfuric acid stream originating from the organic peroxide production process.
The sulfuric acid stream comprises peroxide: hydrogen peroxide, residues of generated organic peroxides, or combinations thereof. The sulfuric acid stream also contains other organic species. For reuse, the sulfuric acid must be purified from the organic residue. It is also necessary to concentrate the sulfuric acid to a concentration required for its reuse. Furthermore, peroxide residues have to be removed from the stream, as not all process steps using the purified and recycled stream allow the presence of peroxide residues.
The method for producing an organic peroxide according to the present invention comprises the steps of:
a. reacting an alcohol or ketone with hydrogen peroxide to form a reaction mixture comprising:
an organic phase comprising an organic peroxide, and
an aqueous phase comprising (i) at least 5% by weight of H 2 SO 4 And (ii) H 2 O 2 And/or residues of the organic peroxide,
b. the aqueous phase is separated from the organic phase,
c. optionally adding H to the aqueous phase 2 O 2 And/or removing any residual organic compounds from the aqueous phase,
d. obtaining a catalyst comprising 5-60 wt.% H 2 SO 4 And 0.3 to 35% by weight of H 2 O 2 And (2) an aqueous phase of
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 H 2 O 2 Removing part of the water and allowing H of the aqueous mixture to flow 2 SO 4 The concentration is increased by at least 7 weight percent to a concentration in the range of 12-95 weight percent.
Quite unexpectedly, it is possible to concentrate the sulfuric acid containing stream by a simple step, i.e. step e) above, wherein water is evaporated. As known to those skilled in the art, when an alcohol or ketone is reacted with hydrogen peroxide in the presence of sulfuric acid, the formation of acetone peroxide cannot be prevented. Acetone peroxide has a risk of solidification in a water evaporation step 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 a level that would cause safety problems.
It should be noted that US 4,168,274 and GB1501356 disclose a process involving the recycling of a sulfuric acid waste stream, wherein a concentration step of the sulfuric acid solution is present. However, these documents relate to the preparation of peracids by reacting an organic acid with hydrogen peroxide in the presence of sulfuric acid. When the peracid is prepared by reacting an acid with hydrogen peroxide, acetone peroxide is not formed, as is known to those skilled in the art, as opposed to reacting an alcohol or ketone with hydrogen peroxide.
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 coke-oven plants, the production of aluminium sulphate from bauxite, the production of dye solutions, the production of hydrogen via the sulphur-iodine cycle (Bunsen reaction), as industrial cleaning solution or as 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.
An 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 be produced by one particular organic peroxide production process, but may also be a mixture of aqueous phases produced by two or more different organic peroxide production processes.
H is increased in step e by heating the aqueous phase 2 SO 4 The concentration does not look as simple. H present in the phase 2 O 2 Will decompose, which will lead to significant oxygen formation and thus pressure build up. In addition, the oxygen, together with volatile organics, can 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-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 the 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.
Reaction in step a) at H 2 SO 4 In the presence of a catalyst.
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% by weight or more).
The term "cyclic ketone peroxide" includes dimeric cyclic ketone peroxides and trimeric cyclic ketone peroxides. These peroxides have the following structure:
wherein R is 1 -R 6 Independently selected from hydrogen, C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl groups, which groups may include linear or branched alkyl moieties; and R is 1 -R 6 Optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxyl, nitrile and amido groups.
Preferred cyclic ketone peroxides are 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane (3 MEK-cp) and mixtures comprising 3MEK-cp and at least one peroxide satisfying the formula
Wherein R is 1 To R 3 Independently selected from alkyl and alkoxyalkyl groups, said groups having from 2 to 5 carbon atoms, R 1 +R 2 +R 3 The total number of carbon-plus-oxygen atoms of (2) is in the range of 7-15. The term alkoxyalkyl refers to a compound having the formula-C n H 2n -O-C m H 2m+1 Wherein n and m are both at least 1.
Trioxepanes have the formula
Wherein R is 1 、R 2 And R is 3 Independently selected from hydrogen and substituted or unsubstituted hydrocarbyl groups, and optionally the group R 1 、R 2 And R is 3 To form a ring structure. Preferably, R 1 、R 2 And R is 3 Independently selected from hydrogen and substituted or unsubstituted C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl groups, which may include linear or branched alkyl moieties, with R 1 、R 2 And R is 3 May be linked to form a (substituted) cycloalkyl ring; r is R 1 -R 3 The optional substituent or substituents on each of (a) is/are selected from hydroxy, alkoxy, linear or branched alk (en) yl, aryloxy, halogen, carboxylic acid, ester, carboxyl, nitrile and amide groups.
Preferably, R 1 And R is 3 Selected from lower alkyl groups, more preferably C 1 -C 6 Alkyl groups such as methyl, ethyl and isopropyl, most preferably methyl and ethyl. R is R 2 Preferably selected from hydrogen, methyl, ethyl, isopropyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclohexyl, phenyl, CH 3 C(O)CH 2 -、C 2 H 5 OC(O)CH 2 -、HOC(CH 3 ) 2 CH 2 -sum of
Wherein R is 4 Independently selected from the group consisting of 1-3 Any one of the groups of the given compounds. 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, 3-tetramethylbutyl hydroperoxide and 1, 1-dimethylbutyl hydroperoxide.
If a monohydric alcohol is used in step a of the process, dialkyl peroxide or hydroperoxide is produced, depending on the amount of hydrogen peroxide and sulfuric acid concentration. For the production of dialkyl peroxides, aqueous sulfuric acid solutions having a concentration of at least 30% by weight are 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, 3-tetramethylbutanol.
If a diol is used in step a of the process, a di-hydroperoxide is produced, which can be reacted further with a monohydric alcohol again in the presence of sulfuric acid to produce a di-dialkyl peroxide. In the latter reaction, aqueous sulfuric acid solutions having a concentration of at least 10% by weight are 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.
To obtain dimeric or trimeric cyclic ketone peroxides, the ketone is reacted with hydrogen peroxide in the presence of 20-75% by weight of aqueous sulfuric acid and an inert diluent (phlegmatiser). Examples of suitable ketones are linear, branched or cyclic C 3 -C 13 Ketones, most preferably C 3 -C 7 Ketones. 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 glycol (diol) with hydrogen peroxide in the presence of 20-60 wt% aqueous sulfuric acid to form a glycol hydroperoxide. Subsequently, the glycol hydroperoxide is reacted with a ketone or aldehyde again in the presence of sulfuric acid (10-60 wt% aqueous solution) to form trioxepan. This method 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 separators, centrifuges or continuous (plate) separators (step b).
The organic peroxide is usually washed with water or an aqueous alkaline solution.
The aqueous phase will contain (i) H 2 SO 4 And (ii) H 2 O 2 And/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 darkening or accumulating 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 preferably at least 20 wt% and most preferably at least 30 wt% H 2 SO 4 . Preferably not more than 60% by weight of H 2 SO 4 。
In addition to H 2 SO 4 In 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.% H 2 O 2 。
To decompose at least part of H 2 O 2 Removing part of the water and removing H 2 SO 4 The concentration is increased by at least 7 weight percent to a concentration in the range of 12-95 weight percent, preferably 50-95 weight percent, more preferably 70-95 weight percent and most preferably 75-85 weight percent, and the aqueous mixture is heated to a temperature in the range of 20-300 ℃, preferably 30-250 ℃, even more preferably 50-200 ℃ and most preferably 100-200 ℃ at a pressure of 0.001-1 bar, preferably 0.01-1 bar (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.
Undesirably concentrate to 96 wt.% or more of H 2 SO 4 Because this requires distillation of SO 3 And 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 H 2 O 2 Stripping volatile organic components at a temperature of the decomposition temperature of (c). Suitable temperatures range from 30 to 120 ℃. The pressure may be atmospheric pressure, but is preferably lower to avoid an explosive atmosphere during the process.
If the hydrogen peroxide concentration of the aqueous mixture is relatively high (about 2 wt.% or more), its decomposition will result in a significant oxygen flow. Distillation at atmospheric pressure is preferred in view of safety issues.
Reduced pressure distillation should be considered if the peroxide concentration is low, or becomes low during the process. It is also possible to first carry out atmospheric distillation and then vacuum distillation.
The aqueous distillate removed during step e is condensed in a condenser and subsequently collected in a vessel.
Due to the decomposition of hydrogen peroxide, the distillate will contain a large amount of oxygen. The oxygen does not condense in the condenser and in order to ensure safe processing, the oxygen concentration of the distillate needs to be kept below the flash point. Preferably, the oxygen concentration in the gas phase is kept below 30% by volume, preferably below 8% by volume.
This can be achieved by introducing nitrogen or air into the system thereby diluting the oxygen. More preferably, nitrogen or air stream is added to the distillate prior to entering the condenser, or when present in the condenser.
Step e may be performed batchwise, semi-continuously or continuously. In larger batch processes, the temperature should be carefully controlled to prevent dangerous situations. Furthermore, in a batch process most of the gas is formed at the beginning of the process, which may beResulting in 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 CO 2 The formation rate of (c) will be more stable to almost completely stable 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 H 2 SO 4 And H 2 O 2 The remaining part of the aqueous phase of (a) is fed into the batch reactor and (part of) the concentrated acid is withdrawn intermittently. 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, are 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 may be separated from the aqueous effluent by filtration or centrifugation and contains a major amount of sulfuric acid, hydrogen peroxide, a minor amount of glycols, and various organic byproducts.
The dihydroperoxide is then reacted with t-butanol, again catalyzed by high concentration 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 byproducts.
The combined aqueous effluent contains about 10-50 wt% H 2 SO 4 And about 5 to 20 wt% H 2 O 2 . By stripping with a stream of air followed by distillation to destroy a major part of H 2 O 2 And increase H 2 SO 4 Concentration of water obtained fromThe organics were removed from the phase. Thereafter, further distillation under reduced pressure may be carried out to further increase H 2 SO 4 Concentration.
The resulting purified and concentrated H 2 SO 4 Can be used for 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 method involves the production of di-tert-butyl peroxide or di-tert-amyl peroxide. According to this embodiment, t-butanol or t-amyl alcohol is reacted with hydrogen peroxide in the presence of 30-78 wt% aqueous sulfuric acid to form di-t-butyl peroxide or di-t-amyl peroxide, respectively.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separators or continuous (plate) separators.
The aqueous phase contains 5-70 wt% H 2 SO 4 0.1 to 10% by weight of tert-butanol or tert-amyl alcohol and 0.1 to 5% by weight of organic peroxide.
Hydrogen peroxide is then added to the aqueous phase to produce an aqueous phase having a hydrogen peroxide concentration of 0.3 to 20 wt.%, preferably 0.3 to 10 wt.% and most preferably 0.3 to 5 wt.%. The mixture is then preferably stirred at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-210 ℃ optionally under reduced pressure to destroy and/or remove organic residues and increase the sulfuric acid concentration.
In another embodiment, the method involves the production of a hydroperoxide. 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 separators or continuous (plate) separators.
The aqueous phase contains 5-60 wt% H 2 SO 4 1-25 wt% of H 2 O 2 0.1-20 wt% of tertiary alcohol and 0.1-5 wt% of organic peroxide.
Hydrogen peroxide is then optionally added to the aqueous phase, and then stirred, optionally under reduced pressure, preferably at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-210 ℃, to destroy and/or remove organic residues and increase the sulfuric acid concentration.
In another embodiment, the method involves the production of trimeric cyclic ketone peroxides.
According to this embodiment, the ketone is reacted with hydrogen peroxide in the presence of 20-95 wt% aqueous sulfuric acid to form a trimeric cyclic ketone peroxide.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separators or continuous (plate) separators.
The aqueous phase contains 20-70 wt% H 2 SO 4 1-25% H 2 O 2 0.1-20 wt.% ketone and 0.1-10 wt.% organic peroxide.
Hydrogen peroxide is then optionally added to the aqueous phase, and then stirred, optionally under reduced pressure, preferably at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-210 ℃, to destroy and/or remove organic residues and increase the sulfuric acid concentration.
In another embodiment, the method involves the production of trioxepan.
According to this embodiment, the ketone is reacted with the hydroxyl hydroperoxide in the presence of 20 to 95 weight percent aqueous sulfuric acid to form trioxepan.
The organic and aqueous phases may be separated by gravity, centrifugation, liquid/liquid separators or continuous (plate) separators.
The aqueous phase contains 10-70 wt% H 2 SO 4 0.1-20 wt.% ketone and 0.1-20 wt.% organic peroxide.
Hydrogen peroxide is then optionally added to the aqueous phase, and then stirred, optionally under reduced pressure, preferably at a temperature in the range of 50-250 ℃, more preferably 80-220 ℃, most preferably 100-210 ℃, to destroy and/or remove organic residues and increase the sulfuric acid concentration.
Examples
Example 1
70% by weight aqueous hydrogen peroxide (121.6 g) was added to the jacketed reactor. The reactor was cooled to 5 ℃. Then 78 wt% aqueous sulfuric acid (157.5 g) was added to the reactor over 20 minutes while the temperature of the mixture was controlled below 10 ℃. After the addition of sulfuric acid, the mixture was cooled to 5 ℃. Solid 2, 5-dimethyl-2, 5-dihydroxyhexane (36.6 g,0.25 mol) was added to the mixture at a rate to maintain the temperature below 10 ℃.
After the addition of 2, 5-dimethyl-2, 5-dihydroxyhexane, the temperature was raised to 25℃and maintained at that temperature for 1 hour. The temperature was then reduced to 5 ℃ and 200mL of water was added. After stirring for 2 min, the reaction mixture was filtered and washed with cold water. Solid 2, 5-dimethyl-2, 5-dihydroperoxy hexane was obtained in 78% yield. 471g containing 26% H 2 SO 4 Is combined with the acid layer of the next step.
Tert-butanol (88 wt%, in water, 143g,1.7 mol) was added dropwise (20 min) to a stirred sulfuric acid solution (78 wt%, 104.7g,0.83 mol) in a jacketed reactor maintained at 15 ℃.2, 5-Dimethylhexane-2, 5-dihydroperoxide (54 g,0.20 mol) obtained in the previous step was added over 20 minutes, after which the temperature was raised to 40℃and maintained at that temperature for up to four hours.
The reaction produces a bilayer mixture; the layers were separated by draining the aqueous layer. The organic layer contained 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane in 70% yield.
The aqueous layer was diluted with 150g of water and tert-butanol was removed by distillation at 100 mbar. 276g obtained containing 30% by weight of H 2 SO 4 Is combined with the aqueous phase of the first step, thereby forming a mixture comprising 27 wt.% H 2 SO 4 And 9 wt% H 2 O 2 Is a water phase of (a) a (b).
The aqueous phase was fed 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 between 135-140 ℃ by heating with an external oil bath at atmospheric pressure. The Vigreux column was connected to a condenser (20 ℃) and a vessel to collect condensate. Air was fed to the condenser to dilute the oxygen content in the gas phase to 25% by volume. At 5 g/minThe aqueous phase was fed to the Vigreux column at a rate of 2.65 g/min resulting in condensate formation. No solids (any compounds such as diacetone peroxide) were observed in the equipment, acid or distillate. In steady state, 2.35g of colorless concentrated acid were pumped from the three-necked vessel per minute. H of concentrated acid 2 SO 4 Content of 58.3% and H 2 O 2 The content was 1.8%.
In the second concentration step, the concentrated acid of the previous step is added to 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-necked glass vessel was connected to the condenser and vessel to collect condensate. Concentrated acid was added at a rate of 2 g/min and 0.6 g of condensate was obtained per minute. In steady state, 1.4g of colorless concentrated acid was pumped from the three-necked vessel per minute. No solids (any compounds such as diacetone peroxide) were observed in the equipment, acid or distillate. H of concentrated acid 2 SO 4 The content of H is 83 wt% 2 O 2 The content is less than 0.5 percent. The acid was diluted to 78 wt% with water and can be reused as described above to prepare 2, 5-dimethylhexane-2, 5-di-hydrogen peroxide.
Example 2
900g of 70% by weight H are introduced into a 2.5 liter reactor 2 SO 4 And 600g of 30% by weight H 2 O 2 The reactor was fitted with 3 baffles, turbine wheels, thermometer and cooling jackets. Tert-butanol (700 g) was added over 1 hour to maintain the temperature in the range of 35-40 ℃. The mixture was heated to 45 ℃ and stirred at that temperature for 1 hour. After which the mixture was cooled to 30 ℃ and allowed to separate. The sulfuric acid concentration of the 1.520g aqueous layer was 41 wt%. The organic layer was washed with bicarbonate solution and contained 668g of di-tert-butyl peroxide, 99.4% purity and 96% yield.
Addition of H to the aqueous layer 2 O 2 (102 g,30 wt%). The resulting mixture was fed (rate: 500 ml/h) into a 100ml heated vessel operating at 93℃and 100-150 mbar. The water vapor is sent to a condenser. Delivering acid exiting the vessel to multiple compartment evaporationA reactor, wherein the temperature is increased to 157 ℃ at a pressure of 100-150 mbar. The colorless acid from the final compartment was cooled to room temperature and H was taken from 2 SO 4 The content was 74% by weight. No solids (any compounds such as diacetone peroxide) were observed in the equipment, acid or distillate. Diluted with water to 70 wt% H 2 SO 4 The acid can then be reused to prepare di-tert-butyl peroxide according to the procedure described above.
Claims (24)
1. A process for producing an organic peroxide comprising the steps of:
a. reacting an alcohol or ketone with hydrogen peroxide to form a reaction mixture comprising:
an organic phase comprising an organic peroxide, and
an aqueous phase comprising (i) at least 5% by weight of H 2 SO 4 And (ii) H 2 O 2 And/or residues of the organic peroxide,
b. the aqueous phase is separated from the organic phase,
c. adding H to the aqueous phase 2 O 2 And/or removing any residual organic compounds from the aqueous phase,
d. obtaining a catalyst comprising 5-60 wt.% H 2 SO 4 And 0.3 to 35% by weight of H 2 O 2 And (2) an aqueous phase of
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 H 2 O 2 Removing part of the water and allowing H of the aqueous mixture to flow 2 SO 4 The concentration is increased by at least 7 weight percent to a concentration in the range of 12-95 weight percent.
2. The process according to claim 1, wherein at least part of the aqueous phase resulting from step e is recycled to step a.
3. The process of any one of claims 1-2, wherein the aqueous phase of step d comprises 0.5-35 wt% H 2 O 2 。
4. A process according to claim 3, wherein the aqueous phase of step d comprises 1-35 wt% H 2 O 2 。
5. The process of claim 4 wherein the aqueous phase of step d comprises from 2 to 35 wt.% H 2 O 2 。
6. The process of claim 5 wherein the aqueous phase of step d comprises from 2 to 25 wt.% H 2 O 2 。
7. The process of any one of claims 1-2, wherein the aqueous phase of step d comprises 10-60 wt% H 2 SO 4 。
8. The process of claim 7 wherein the aqueous phase of step d comprises 20-55 wt.% H 2 SO 4 。
9. The process of claim 8 wherein the aqueous phase of step d comprises 30-50 wt.% H 2 SO 4 。
10. The process of any one of claims 1-2, wherein H of the aqueous mixture produced by step e 2 SO 4 H having a concentration of 50-95 wt% 2 SO 4 Concentration.
11. The process of claim 10 wherein H of the aqueous mixture produced by step e 2 SO 4 H with a concentration of 70-95 wt% 2 SO 4 Concentration.
12. The process of claim 11 wherein H of the aqueous mixture produced by step e 2 SO 4 H with a concentration of 75-85 wt% 2 SO 4 Concentration.
13. The process of any one of claims 1-2, wherein step e comprises stripping the volatile organic components at a temperature in the range of 30-120 ℃.
14. The process of any one of claims 1-2, wherein step e comprises distillation at atmospheric pressure followed by distillation at a pressure below atmospheric pressure.
15. The process according to any one of claims 1-2, wherein step e comprises distillation and wherein the oxygen content in the gas phase of the distillate is kept below 30 vol.% by adding nitrogen or air.
16. The process according to claim 15, wherein step e comprises distillation and wherein the oxygen content in the gas phase of the distillate is maintained below 8% by volume by adding nitrogen or air.
17. The method according to any one of claims 1-2, wherein step e is performed in a semi-continuous or continuous mode.
18. The process according to any one of claims 1-2, wherein the organic peroxide produced is selected from the group consisting of dialkyl peroxides, cyclic ketone peroxides, trioxepanes, and aliphatic hydroperoxides.
19. The method of claim 18, wherein the organic peroxide is a dialkyl peroxide selected from the group consisting of: 2, 2-di (tert-butylperoxy) butane, dicumyl peroxide, di (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, di-tert-butyl peroxide, di-tert-amyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -3-hexyne and tert-butylcumyl peroxide.
20. The method of claim 19, wherein the organic peroxide is a dialkyl peroxide 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.
21. The method of claim 18, wherein the organic peroxide is an aliphatic hydroperoxide selected from the group consisting of: tert-butyl hydroperoxide, tert-amyl hydroperoxide, hexanediol hydroperoxide, 2, 5-dimethyl-2, 5-dihydroperoxy hexane, 2, 5-dimethyl-2, 5-dihydroperoxy-3-hexyne, 1, 3-tetramethylbutyl hydroperoxide and 1, 1-dimethylbutyl hydroperoxide.
22. The method of claim 18, wherein the organic peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxycyclononane or a mixture of cyclic ketone peroxides comprising 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxycyclononane.
23. The process according to any one of claims 1-2, wherein in step a an alcohol is reacted with hydrogen peroxide, the alcohol being selected from the group consisting of t-butanol, t-amyl alcohol and 1, 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.
24. The process according to any one of claims 1-2, wherein in step a ketone is reacted with hydrogen peroxide, said ketone being 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.
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| EP15088375 | 2019-02-22 | ||
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| PCT/EP2020/052464 WO2020169322A1 (en) | 2019-02-22 | 2020-01-31 | Process for producing an organic peroxide |
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| CN117304087B (en) * | 2023-09-20 | 2024-03-05 | 淄博正华助剂股份有限公司 | Preparation method of 1, 3-tetramethylbutyl hydroperoxide |
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| GB1501356A (en) * | 1975-04-30 | 1978-02-15 | Bayer Ag | Process for the continuous preparation of organic solutions of percarboxylic acids |
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| CN108658824A (en) * | 2018-07-23 | 2018-10-16 | 常熟市滨江化工有限公司 | A method of preparing the mixture containing tert-butyl hydroperoxide using recycling t-butanol solution |
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| US4168274A (en) * | 1975-02-04 | 1979-09-18 | Interox Chemicals Limited | Production of a peracid and an oxirane |
| GB1501356A (en) * | 1975-04-30 | 1978-02-15 | Bayer Ag | Process for the continuous preparation of organic solutions of percarboxylic acids |
| CN101857563A (en) * | 2010-06-13 | 2010-10-13 | 江苏强盛化工有限公司 | Preparation method for mixture containing tert-butyl hydroperoxide |
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