Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
  • C07C39/04—Phenol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
  • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
  • C07C409/08—Compounds containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
  • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
  • C07C409/08—Compounds containing six-membered aromatic rings
  • C07C409/10—Cumene hydroperoxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides

Definitions

• the present application relates to a process for producing phenol and ketone(s), preferably for producing phenol and acetone and/or methyl ethyl etone (MEK) .
• Phenol is an important chemical parent substance with a broad usage spectrum.
• phenol is used to produce phenol resins, bisphenol A, caprolactam, adipic acid, alkyl phenols, and plasticizers .
• phenol is manufactured by oxidizing alkylbenzene (s) to form hydroperoxide (s) followed by cleavage of the hydroperoxide (s) with an inorganic acid to form a hydroperoxide cleavage product.
• Methods of oxidation are needed which minimize the production of phenol during oxidation and which preferably also minimize the production of one or more byproducts selected from the group consisting of acetophenone (AP) , di ethylbenzyl alcohol (DMBA), and ethyl methyl benzyl carbinol (EMBA) .
• AP acetophenone
• DMBA di ethylbenzyl alcohol
• EMBA ethyl methyl benzyl carbinol
• the present invention provides a process for oxidation of alkylbenzenes to produce hydroperoxides comprising: providing an oxidation feed consisting essentially of an organic phase, said oxidation feed comprising one or more alkylbenzenes and a quantity of neutralizing base having a pH of from 8 to 12.5 in
• oxidation feed comprising up to an amount of water from 400 ppm to
• the process comprises providing an oxidation feed consisting essentially of an organic phase.
• the oxidation feed comprises one or more alkylbenzenes and a quantity of neutralizing base having a pH of from 8 to 12.5 in 1 to 10 wt.% aqueous solution.
• the quantity of neutralizing base is effective to neutralize at least a portion of acids formed during the oxidation.
• the oxidation feed comprises up to an amount of water effective to increase neutralization of acids formed during the oxidation without forming a separate aqueous phase.
• the oxidation feed is exposed to oxidation conditions effective to produce an oxidation product stream comprising one or more product hydroperoxides.
• the oxidation occurs in the presence of a neutralizing base.
• the neutralizing base maximizes the production of hydroperoxides while minimizing the production of undesirable by-products. Portions of the following description are specific to preferred embodiments, in which either s-butylbenzene, alone, or a combination of cumene and s-butylbenzene is fed to the oxidation zone.
• the neutralizing base is useful during oxidation of other alkylbenzenes, either alone or in combination.
• formic acid and acetic acid are produced as by-products from the oxidation of alkylbenzene (s) .
• Formic and acetic acids catalyze the formation of phenol, which is a poison (or inhibitor) of the main oxidation pathway to make the desired products.
• Formic and acetic acids, and hence phenol cause a reduction in the formation of desired products relative to by-products.
• the yield of hydroperoxides is increased and attendant by-product formation (e.g., AP, DMBA, EMBA) is decreased by the addition of an amount of neutralizing base to the oxidation mixture.
• Adding a neutralizing base to the oxidation mixture also neutralizes acids, such as acetic acid and formic acid, as they are formed. In this way, the acids are prevented from promoting phenol formation, and the yield of desired hydroperoxide product is maximized.
• the quantity of neutralizing base added to the oxidation mixture is sufficient under the oxidation conditions to neutralize at least a portion of acids formed.
• the quantity of neutralizing base is also insufficient to cause the neutralizing base to precipitate out of solution and/or to increase production of one or more materials selected from the group consisting of phenol and one or more byproducts selected from the group consisting of AP, DMBA and EMBA.
• Suitable neutralizing bases are those that have a pH of from 8 to 12.5 in 1 to 10 wt.% aqueous solution and include, but are not necessarily limited to alkali bases, anhydrous ammonia, and aqueous ammonia.
• preferred neutralizing bases also are effective to perform a function selected from the group consisting of increasing total hydroperoxide yield, decreasing AP formation, decreasing DMBA formation, decreasing EMBA formation, and decreasing phenol formation.
• the neutralizing base achieves one or more of the following compared to the control: increases total hydroperoxide yield by 7% or more; decreases AP formation by 20% or more; decreases EMBA and/or DMBA formation by 20% or more; and, decreases phenol content by 50% or more.
• Preferred alkali bases are alkali metal bases including, but not necessarily limited to alkali metal carbonates and alkali metal bicarbonates .
• Suitable alkali metals include, but are not necessarily limited to potassium and sodium.
• a preferred embodiment and a preferred alkali metal base is sodium carbonate.
• the amount of alkali base preferably is sufficient under the oxidation conditions to neutralize at least a portion of acids formed but insufficient to cause the alkali base to precipitate out of solution in the oxidation mixture.
• the amount of alkali base is an amount sufficient to produce a ratio of alkali base to acids of from 0.5:1 to 4:1.
• Ammonia is another preferred neutralizing base.
• the ammonia can be added as gaseous anhydrous ammonia, gaseous anhydrous ammonia along with a small water feed, or aqueous ammonia.
• the amount of ammonia preferably is insufficient to increase production of one or more materials selected from the group consisting of phenol and one or more byproducts selected from the group consisting of AP, DMBA, and EMBA.
• the amount of ammonia is sufficient to produce a molar ratio of ammonia to acids of from 0.5:1 to 6:1.
• a preferred embodiment uses aqueous ammonia.
• the total amount of water in the oxidation mixture is an amount effective to increase neutralization of acids formed during oxidation by the neutralizing base without forming a separate aqueous phase.
• the amount of water in the oxidation mixture preferably is from 400 ppm to 2 wt.%. Without limiting the application to a particular mechanism of action, including a small amount of water in the oxidation mixture is believed to improve the solubility of the base in the oxidation mixture, making the base more readily available to perform the neutralization.
• the oxidation process comprises an oxidation zone comprising one or more oxidation reactor (s).
• the oxidation reactor (s) may be batch reactor (s) or continuous reactor (s).
• the oxidation zone comprises a series of continuous reactors.
• An oxidation feed comprising one or more alkylbenzenes is fed to the oxidation reactor (s).
• the oxidation feed preferably comprises a) cumene; (b) s-butylbenzene, or (c) a combination comprising cumene and s-butylbenzene.
• the oxidation feed is oxidized by molecular oxygen, preferably air, to produce an oxidation product stream.
• the oxidation product stream comprises alkylbenzene hydroperoxide (s) corresponding to the alkylbenzene (s) in the oxidation feed.
• the oxidation product stream comprises cumene hydroperoxide.
• the oxidation product stream comprises s- butylbenzene hydroperoxide, but typically does not comprise a significant amount of cumene hydroperoxide.
• the operating conditions can be adjusted to coproduce more or less acetophenone (AP) and/or other by-products.
• the oxidation product stream comprises s- butylbenzene hydroperoxide and cumene hydroperoxide at high selectivity.
• the oxidation feed comprises a weight ratio of cumene: s-butylbenzene of from 1 : 8 to 2 : 1.
• the foregoing ratios represent from 12.5 wt.% cumene to 66.7 wt.% cumene.
• the amount of cumene is from greater than 15 wt.% to less than 30 wt.% relative to the content of s-butylbenzene.
• the predominate mechanism for the formation of the major and minor by-products is believed to be the free radical decomposition of the s-butyl-benzene hydroperoxide and (if present) the cumene hydroperoxide in the oxidation product.
• the oxidation mixture is contacted with an oxygen-containing gas under oxidation conditions comprising an oxidation temperature effective to oxidize the alkylbenzene (s) to produce the respective hydroperoxides.
• Suitable oxidation temperatures at most oxidation pressures are from 90 °C to 150 °C. Preferred temperatures will vary depending upon the type of oxidation reactor and the composition of the oxidation feed.
• the oxidation feed comprises cumene and s- butylbenzene
• conversion and selectivity to cumene hydroperoxide and s-butylbenzene hydroperoxide increases with an increase in the cumene: s-butylbenzene ratio in the oxidation feed. Conversion also increases with an increase in oxidation temperature.
• oxidation temperature can be adjusted throughout the reaction period to maximize selectivity of the oxidation reaction.
• Suitable oxidation pressures for batch reactor (s) are from 0 psig to 100 psig, preferably from 15 psig to 40 psig.
• the oxidation temperature in each oxidation reactor is selected to maximize selectivity, and will depend upon the composition of the oxidation feed.
• Suitable oxidation pressures when using continuous reactors generally are from 0 psig to 100 psig, preferably from 15 psig to 40 psig.
• a preferred oxidation temperature for a continuous reactor is from 100 °C to 115 °C.
• a preferred oxidation temperature for a continuous reactor is from 110 °C to 130 °C.
• Oxidation reaction times will vary from 5 to 25 hours.
• the oxidation reaction time in a batch reactor preferably is from 6 to 11 hours for all alkylbenzene ratios, with the oxidation temperature adjusted to maximize selectivity.
• the "reaction time” typically is referred to as the total residence time.
• the total residence time is divided between all of the continuous reactors used. For example, if 5 continuous oxidation reactors are operated in series, the residence time for each oxidation reactor is from 1 to 5 hours, with oxidation reaction temperatures for each continuous reactor chosen appropriately to achieve desired conversions.
• the total residence time can be distributed uniformly or non-uniformly between the oxidation reactors.
• Both batch reactors and continuous oxidation reactors produce a total conversion of at least 5% to the desired hydroperoxide (s) .
• total conversion is from 10% to 30%, more preferably from 15% to 25%.
• any number of continuous reactors can be employed.
• Product selectivity is increased by increasing the number of continuous reactors. For example, using two continuous reactors produces a higher yield of the desired hydroperoxide (s) than using only one continuous reactor.
• from 3 to 8 continuous reactors are used in series.
• the preferred number of reactors will vary with the alkylbenzenes in the feed. For example, where cumene is fed alone, a preferred number of reactors is four.
• the preferred number of reactors will vary with the cumene: s-butylbenzene ratio of the oxidation feed. For example, where the oxidation feed comprises a ratio of 2:1 cumene: s-butylbenzene, it is preferred to use 4 reactors. In contrast, where the oxidation feed comprises a ratio of 1:8 cumene: s-butylbenzene, it is preferred to use 5 or 6 reactors.
• the oxidation reactor is one or more continuous reactor (s)
• the continuous reactor (s) can be a variety of types, including but not necessarily limited to stirred tank reactor (s) or bubble column reactor (s).
• a standard stock oxidation mixture was prepared containing an amount of sec-butyl benzene (sBB) , and an amount of cumene effective to produce a weight ratio of sBB: cumene of 3.4:1.
• the stock oxidation mixture also contained 1% cumene hydroperoxide as an initiator.
• 300 grams of the oxidation mixture was exposed to oxidation conditions comprising a temperature of 130 °C, an oxidizing agent comprising 500 cc/min. 7% 0 2 in N 2 , and a steady pressure of 40 psig. All experiments were carried out in a 500 cc Buchi Type II reactor, with a stirring rate of 1300 rpm.
• the foregoing stock oxidation mixture was used in a control oxidation to provide a comparative example to assess the effect of ammonia on the reaction. Neither ammonia nor water was added to the control experiment. After 8 hours, the mixture contained 340 wppm formic acid, 752 wppm acetic acid, and 515 wppm phenol.
• the hydroperoxide yield in the oxidation mixture charged with ammonia but no water was 2.4% higher than in the control, while the hydroperoxide yield in the oxidation mixture charged with both ammonia and water was 8.5% higher than in the control.
• the ammonia-charged oxidation mixture exhibited an AP production 26.5% lower than in the control and a DMBA and EMBA production 29.5% lower than in the control.
• Example 2 A standard oxidation mixture was prepared containing an amount of sec-butyl benzene (sBB) and an amount of cumene effective to produce a weight ratio of sBB: cumene of 3.4:1.
• the stock oxidation mixture also contained 1% cumene hydroperoxide as an initiator.
• 300 grams of the oxidation mixture was exposed to oxidation conditions comprising a temperature of 130 °C, an oxidizing agent comprising 500 cc/min. 7% 0 2 in N 2 , and a steady pressure of 40 psig. All experiments were carried out in a 500 cc Buchi Type II reactor, with stirring rate of 1300 rpm.
• the foregoing stock oxidation mixture was used in a control oxidation to provide a comparative example to assess the effect of ammonia on the reaction. Neither ammonia nor water was added to the control experiment. After 8 hours, the mixture contained 340 wppm formic acid, 752 wppm acetic acid, and 515 wppm phenol.
• Example 3 The same standard oxidation experiment as mentioned in Example 1 and Example 2 was used as a control oxidation to provide a comparative example to assess the effect of sodium carbonate on the reaction. Neither sodium carbonate nor water was added to the control mixture. After 8 hours, the mixture contained 340 wppm formic acid, 752 wppm acetic acid and 515 wppm phenol.

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• 2004
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