CN114656333A - Improved method for producing phenol/acetone - Google Patents
Improved method for producing phenol/acetone Download PDFInfo
- Publication number
- CN114656333A CN114656333A CN202210451851.2A CN202210451851A CN114656333A CN 114656333 A CN114656333 A CN 114656333A CN 202210451851 A CN202210451851 A CN 202210451851A CN 114656333 A CN114656333 A CN 114656333A
- Authority
- CN
- China
- Prior art keywords
- chp
- phenol
- cumene
- acetone
- cumene hydroperoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 108
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims abstract description 229
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 31
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 37
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940032330 sulfuric acid Drugs 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 38
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000013021 overheating Methods 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 68
- 239000000047 product Substances 0.000 description 20
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 16
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000004811 liquid chromatography Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 description 8
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002063 nanoring Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- XDTRNDKYILNOAP-UHFFFAOYSA-N phenol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC=C1 XDTRNDKYILNOAP-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- 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
- C07C407/00—Preparation of peroxy compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an improved method for producing phenol/acetone, which comprises the following operation steps of (1) oxidizing cumene under the condition of taking oxygen or air as an oxidant to generate Cumene Hydroperoxide (CHP) to obtain cumene oxidation reaction liquid; (2) the cumene oxidation reaction liquid and the acid solution are synchronously introduced into a mixer for mixing without concentration, and then enter a tubular continuous flow reactor for the decomposition reaction of the Cumene Hydroperoxide (CHP). The high-efficiency mixing of a reaction system is realized through the micro mixer, the high-efficiency heat transfer and the stability of the mixing system are realized through the tubular reactor filled with the component, the local overheating is avoided, the decomposition stability of the Cumene Hydroperoxide (CHP) is ensured, and the safety of the preparation of the phenol/acetone is improved. Realizes the decomposition reaction of the Cumene Hydroperoxide (CHP) by directly taking the cumene oxidizing solution as the raw material, and reduces the equipment investment cost and the energy consumption.
Description
Technical Field
The invention relates to a production method of phenol/acetone, in particular to an improved method for preparing phenol/acetone by using cumene as a raw material and through cumene oxidation and Cumene Hydroperoxide (CHP) decomposition.
Background
Phenol is an organic chemical raw material widely used, and the main preparation method is an isopropyl benzene method. The reaction route for producing phenol by the cumyl method is shown in formula 1, benzene and propylene are firstly subjected to alkylation reaction to generate cumyl; cumene Hydroperoxide (CHP) is generated by oxidizing cumene in a liquid phase, the conversion rate of the Cumene Hydroperoxide (CHP) needs to be kept at a lower level to ensure the selectivity of the Cumene Hydroperoxide (CHP), and the mass concentration of the Cumene Hydroperoxide (CHP) after reaction is about 24 percent; then, Cumene Hydroperoxide (CHP) is concentrated through a concentration process to obtain a Cumene Hydroperoxide (CHP) solution with the concentration of about 80 percent, and other components are mainly cumene and dimethyl benzyl alcohol (DMPC); the concentrated Cumene Hydroperoxide (CHP) is catalyzed and decomposed by sulfuric acid to obtain phenol and acetone. Compared with other production processes, the production process of the cumben method for producing the phenol/acetone has the advantages of good product quality, low cost, very small equipment corrosion and very small environmental pollution. By this method, phenol and acetone can be obtained simultaneously at a ratio of 1: 0.6 in continuous production process, and α -methylstyrene (AMS) as byproduct can be produced continuously.
At present, all processes for preparing phenol acetone from cumene comprise the following important steps: (1) cumene is oxidized to Cumene Hydroperoxide (CHP); (2) concentrating the cumene hydroperoxide reaction liquid to obtain higher-concentration Cumene Hydroperoxide (CHP); (3) decomposing Cumene Hydroperoxide (CHP) and dimethyl benzyl alcohol (DMPC) under the acid catalysis condition to obtain phenol/acetone and alpha-methyl styrene (AMS); (4) neutralizing the acid catalyst in the reaction product and separating the salt therefrom; (5) and (4) separating and purifying reaction products.
Due to the low mass transfer efficiency between cumene and the catalyst, a large amount of cumene in the system affects the efficiency of the Cumene Hydroperoxide (CHP) decomposition reaction. Therefore, before Cumene Hydroperoxide (CHP) is decomposed, cumene oxidation reaction liquid needs to be concentrated to obtain high-concentration Cumene Hydroperoxide (CHP) (80-85%), and at the moment, cumene with the residue of less than 15% in the cumene oxidation reaction liquid ensures the high-efficiency proceeding of the Cumene Hydroperoxide (CHP) decomposition reaction, but in the concentration process of the cumene oxidation reaction liquid, due to the characteristic of poor stability of the Cumene Hydroperoxide (CHP), a higher vacuum degree is needed in the concentration process to avoid the thermal decomposition of the Cumene Hydroperoxide (CHP) to generate byproducts as far as possible, on the other hand, the Cumene Hydroperoxide (CHP) has strong oxidizing property, so that the operation risk of the concentration process is increased, and the process also obviously increases the energy consumption.
Patent CN102992961A discloses a rectification process by vacuum reaction using cumene oxidation reaction solution without concentration as raw material, however, the catalyst loaded in the reaction section is solid acid ion exchange resin, which is easy to remove sulfonic acid group in Cumene Hydroperoxide (CHP) decomposition, so that the stability of Cumene Hydroperoxide (CHP) decomposition reaction is poor; on the other hand, in the decomposition process of Cumene Hydroperoxide (CHP), the reaction is violent, the heat release is large (252 kJ/mol), and the danger coefficient is extremely high, so that a large amount of acetone circulation is needed in the reaction process to take away the heat, and the heat accumulation is prevented. Since cumene has a boiling point of 152 ℃, efficient removal of large amounts of heat cannot be achieved at reaction temperatures (about 80 ℃). The problem of local overheating of a catalytic bed layer in the reactive distillation process is difficult to effectively solve.
In view of the defects of the existing phenol preparation process, the inventor develops a method for producing phenol/acetone based on years of practical experience and professional knowledge in the design and manufacture of the product, skillfully utilizes a chemical mechanism, continuously researches and innovates in practice, omits a concentration process by optimizing the preparation process, ensures the decomposition stability of Cumene Hydroperoxide (CHP), solves the problem of local overheating in the reaction process, and improves the safety of phenol/acetone preparation.
Disclosure of Invention
The invention mainly aims to provide a method for producing phenol/acetone, which omits the concentration process by optimizing the preparation process, ensures the decomposition stability of Cumene Hydroperoxide (CHP), solves the problem of local overheating in the reaction process and improves the safety of phenol/acetone preparation.
The technical purpose of the invention is realized by the following technical scheme:
the method for producing phenol/acetone provided by the invention comprises the following operation steps:
(1) oxidizing cumene under the condition of taking oxygen or air as an oxidant to generate Cumene Hydroperoxide (CHP) to obtain cumene oxidation reaction liquid;
(2) the cumene oxidation reaction liquid and an acid solution are synchronously introduced into a mixer for mixing without concentration, and then enter a tubular continuous flow reactor for decomposition reaction of Cumene Hydroperoxide (CHP). The safety risk in the concentration process of the cumene oxidizing solution is avoided, and the safety of the process is improved. Meanwhile, the premixing of the mixer ensures the sufficient mixing of the system, avoids the over-high local concentration caused by the uneven distribution of the acid catalyst during the decomposition reaction of the Cumene Hydroperoxide (CHP), and simultaneously ensures the decomposition stability of the Cumene Hydroperoxide (CHP) and improves the safety of the preparation of phenol/acetone by controlling the concentration and the content of the acid solution.
Preferably, in the cumene oxidation reaction solution in the step (1), the concentration of Cumene Hydroperoxide (CHP) is 19.5 to 32.8%. In order to ensure the selectivity of oxidizing cumene to Cumene Hydroperoxide (CHP), the conversion rate of cumene needs to be controlled at a low level, generally 15-35%, in the oxidation process. When the conversion rate of the oxidation reaction is more than 35%, the selectivity of the Cumene Hydroperoxide (CHP) is obviously reduced, the conversion rate of the cumene in the application is about 18.5-32%, and the high selectivity of the Cumene Hydroperoxide (CHP) generated by oxidizing the cumene is ensured.
Meanwhile, the cumene oxidation reaction liquid is directly subjected to acid catalytic decomposition without concentration, and compared with the prior art, the method avoids the concentration process of the cumene oxidation reaction liquid, shortens the process flow, reduces the equipment investment cost and energy consumption, and improves the preparation safety.
Preferably, the mixer in the step (2) is a micromixer. The reaction system mainly comprises cumene and Cumene Hydroperoxide (CHP), has poor compatibility with a catalyst acid solution, and can ensure the full mixing of the system by adopting a high-efficiency micro mixer. When the reaction mixed liquid enters the tubular reactor for reaction, local overheating can be avoided, the thermal decomposition reaction of Cumene Hydroperoxide (CHP) is reduced, and the reaction selectivity is improved.
Preferably, the inner diameter of the tubular continuous flow reactor in the step (2) is 0.5-30 mm. The small inner diameter and the filled member in the reactor can effectively improve the heat transfer efficiency and the mixing efficiency of the reaction liquid, ensure the uniformity of the reaction system and avoid local overheating in the reactor.
Preferably, any inert filling material of Raschig rings, pall rings, Natt rings or eight-four inner arc rings is filled in the tubular continuous flow reactor, so that the mass transfer and heat transfer effects can be enhanced.
Preferably, the acid solution in the step (2) is a mixed solution of an acid A and a solvent B, the acid A is one or a mixture of sulfuric acid, benzenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid, and the solvent B is acetone, phenol or a mixture of acetone and phenol. This avoids the introduction of new impurities and ensures sufficient dispersibility. On the other hand, the method can avoid the removal of acidic substances and ensure the stability of the decomposition reaction of the Cumene Hydroperoxide (CHP).
Preferably, the mass concentration of the acid A is 1-10%. If the concentration of the acid A is too low, a large amount of solvent B can be introduced, and the subsequent separation load is increased; too high a concentration of acid A may affect its dispersibility in the system, resulting in the formation of by-products.
Preferably, the amount of the acid A is 0.5 to 5.0 ‰ of Cumene Hydroperoxide (CHP). The acid A is used as a catalyst, and the dosage of the acid A is too low, so that the efficiency of the decomposition reaction of the Cumene Hydroperoxide (CHP) is influenced; if the dosage is too high, the decomposition rate of Cumene Hydroperoxide (CHP) can be rapidly increased, so that the heat release is rapidly increased, and when the reaction heat cannot be effectively removed, the system can be locally overheated, thereby affecting the selectivity of the reaction.
Preferably, the reaction residence time in the mixer in the step (2) is 80-300 s, and the reaction temperature is 80-140 ℃. Compared with the acid catalytic decomposition reaction of Cumene Hydroperoxide (CHP) with a fast speed, the side reaction rates of acetone condensation-dehydration to generate Mesityl Oxide (MO), the reaction of acetone and Cumene Hydroperoxide (CHP) to generate Hydroxyacetone (HA) and the polymerization of alpha-methyl styrene (AMS) and the like are slow, but the retention time is too long, so that more side products are generated; when the reaction temperature is higher than 140 ℃, the side reaction of generating Acetophenone (ACP) by the thermal decomposition of Cumene Hydroperoxide (CHP) can be obviously increased, the product yield is influenced, and the difficulty and the energy consumption of the subsequent separation of each component can be increased; too low a reaction temperature and too short a residence time will affect the efficiency of the Cumene Hydroperoxide (CHP) decomposition reaction. The method ensures the complete conversion of the Cumene Hydroperoxide (CHP) in a reaction system by controlling the temperature and time of the reaction, improves the selectivity of phenol/acetone, and reduces the difficulty of the subsequent separation.
In conclusion, the invention has the following beneficial effects:
(1) according to the improved method for producing phenol/acetone, cumene oxidation reaction liquid directly enters a decomposition stage without being concentrated, the current situation that phenol is prepared by the prior art and must be concentrated is changed, and the content of cumene in a reaction system reaches 60-78%. In existing production plants and processes, such high cumene contents hinder the removal of the large amounts of heat released during the Cumene Hydroperoxide (CHP) decomposition reaction, and at the same time lead to low reaction efficiencies due to the poor compatibility of cumene with the acid catalyst system. The invention realizes the high-efficiency mixing of the reaction system through the micro mixer, and realizes the high-efficiency heat transfer and the stability of the mixing system through the tubular continuous flow reactor filled with the component; meanwhile, by setting the appropriate amount of the acid catalyst, the decomposition of the Cumene Hydroperoxide (CHP) is kept at a certain speed, the reaction heat is effectively removed, the local overheating of the system is avoided, and the decomposition reaction efficiency of the Cumene Hydroperoxide (CHP) is improved; ensures the decomposition stability of the Cumene Hydroperoxide (CHP) and improves the safety of the preparation of phenol/acetone.
(2) During the decomposition of Cumene Hydroperoxide (CHP), the composition of the system can significantly influence the selectivity of the decomposition reaction of the Cumene Hydroperoxide (CHP). According to the invention, the cumene oxidation reaction liquid is not concentrated, the concentration of Cumene Hydroperoxide (CHP) in the reaction system is 19.5-32.8%, other components are mainly cumene and dimethyl benzyl alcohol (DMPC), and side reactions of the Cumene Hydroperoxide (CHP) generated by thermal decomposition into dimethyl benzyl alcohol (DMPC) and Acetophenone (ACP) can be obviously inhibited due to the high cumene content; improves the selectivity of the decomposition of the Cumene Hydroperoxide (CHP) to generate the phenol/acetone, and reduces the difficulty and the energy consumption of the subsequent separation of each component.
(3) In addition to the selectivity of the target product, the content of acetone-derived by-products such as Mesityl Oxide (MO) and Hydroxyacetone (HA) significantly increases the difficulty of product separation and energy consumption in the phenol/acetone production process. In the invention, acetone, phenol or a mixture of acetone and phenol are used as a solvent to prepare an acid solution, so that other impurities are prevented from being introduced in the acid catalytic decomposition process, the purity of the product is improved, on the other hand, the introduction of a large amount of solvent is avoided by setting a proper mass concentration, the generation of byproducts such as isopropylidene acetone (MO), Hydroxy Acetone (HA) and the like is reduced, meanwhile, the complete conversion of Cumene Hydroperoxide (CHP) in a reaction system is ensured by controlling the temperature and time of the reaction, the generation of the isopropylidene acetone (MO) and the Hydroxy Acetone (HA) is further reduced, and the yield of alpha-methyl styrene (AMS) is improved.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the embodiments, features and effects of the method for producing phenol/acetone according to the present invention are described in detail below.
In the examples of the present invention, commercially available material sources are as follows:
example 1
Under the conditions of a reaction temperature of 100 ℃, a Cumene Hydroperoxide (CHP) initiator addition amount of 5 percent and vigorous stirring, oxygen is continuously introduced into 1000mL of cumene reaction liquid, the oxygen flow rate is 80mL/min, and after 8 hours of reaction, the cumene oxidation reaction liquid with the Cumene Hydroperoxide (CHP) concentration of 24.6 percent, the cumene concentration of 71.5 percent and the dimethyl benzyl alcohol (DMPC) content of 2.5 percent is obtained.
The obtained cumene oxidation reaction liquid is used as a raw material, the raw material and an acid solution are fully mixed in a micro mixer, the mass concentration of an acetone solution of sulfuric acid is 2%, and the flow rate is controlled so that the use amount of the sulfuric acid is 2.0 per mill of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 99.4%, and the yield of alpha-methylstyrene (AMS) was 99.2%.
Example 2
Under the conditions of a reaction temperature of 100 ℃, a Cumene Hydroperoxide (CHP) initiator addition amount of 5 percent and vigorous stirring, oxygen is continuously introduced into 1000mL of cumene reaction liquid, the oxygen flow rate is 80mL/min, and after 5 hours of reaction, the cumene oxidation reaction liquid with the Cumene Hydroperoxide (CHP) concentration of 19.5 percent, the cumene concentration of 77.6 percent and the dimethyl benzyl alcohol (DMPC) content of 2.0 percent is obtained.
The obtained cumene oxidation reaction liquid is used as a raw material, the raw material and an acid solution are fully mixed in a micro mixer, the mass concentration of an acetone solution of sulfuric acid is 2%, and the flow rate is controlled so that the use amount of the sulfuric acid is 2.0 per mill of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 140 ℃, and the retention time is 80 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 98.4%, and the yield of alpha-methylstyrene (AMS) was 99.2%.
Example 3
Under the conditions that the reaction temperature is 100 ℃, the addition amount of a Cumene Hydroperoxide (CHP) initiator is 8 percent, and vigorous stirring is carried out, oxygen is continuously introduced into 1000mL of cumene reaction liquid, the flow rate of the oxygen is 80mL/min, and after 6 hours of reaction, the cumene oxidation reaction liquid with the Cumene Hydroperoxide (CHP) concentration of 32.8 percent, the cumene concentration of 60.3 percent and the dimethyl benzyl alcohol (DMPC) content of 3.3 percent is obtained.
The obtained cumene oxidation reaction solution is used as a raw material, the raw material and an acid solution are fully mixed in a micro mixer, the mass concentration of the acetone solution of the methanesulfonic acid is 1%, and the flow rate is controlled so that the dosage of the methanesulfonic acid is 5.0 per mill of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 99.4%, and the yield of alpha-methylstyrene (AMS) was 99.2%.
Example 4
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the acetone solution of sulfuric acid had a mass concentration of 10%, and the flow rate was controlled so that the amount of sulfuric acid used was 0.5% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 0.5mm, and no member is filled; the reaction temperature is 80 ℃, and the retention time is 300 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the products phenol and alpha-methyl styrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 94.4%, and the yield of alpha-methylstyrene (AMS) was 89.2%.
Example 5
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the acetone solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid used was 2.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 30mm, and eight-four inner arc rings are filled; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 99.4%, and the yield of alpha-methylstyrene (AMS) was 99.2%.
Example 6
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the phenol solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid used was 2.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 110 ℃, and the retention time is 100 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 99.2%, and the yield of alpha-methylstyrene (AMS) was 97.3%.
Example 7
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the acetone solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid was 2.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and a nano ring is filled; the reaction temperature is 120 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 98.3%, and the yield of alpha-methylstyrene (AMS) was 92.7%.
Example 8
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the mass concentration of the acetone solution of benzenesulfonic acid was 5%, and the flow rate was controlled so that the amount of sulfuric acid was 3.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 98.4%, and the yield of alpha-methylstyrene (AMS) was 91.3%.
Comparative example 1
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the acetone solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid used was 2.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and no member is filled; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 88.2%, and the yield of alpha-methylstyrene (AMS) was 90.1%.
Comparative example 2
The cumene oxidation reaction solution of example 1 was used as a raw material, the acetone solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid was 2.0% o of Cumene Hydroperoxide (CHP). Directly entering a tubular reactor for reaction without mixing, wherein the inner diameter of the tubular reactor is 26mm, and filling pall rings; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 90.5%, and the yield of alpha-methylstyrene (AMS) was 92.2%.
Comparative example 3
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the acetone solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid used was 10.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 110 ℃, and the retention time is 120 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the product phenol and alpha-methylstyrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 94.3%, and the yield of alpha-methylstyrene (AMS) was 95.1%.
Comparative example 4
The cumene oxidation reaction solution in example 1 was used as a raw material, and the raw material and an acid solution were thoroughly mixed in a micro mixer, the acetone solution of sulfuric acid had a mass concentration of 2%, and the flow rate was controlled so that the amount of sulfuric acid used was 2.0% o of Cumene Hydroperoxide (CHP). The mixed raw materials enter a tubular reactor for reaction, the inner diameter of the tubular reactor is 26mm, and pall rings are filled in the tubular reactor; the reaction temperature is 150 ℃, and the retention time is 80 s; the reaction product was passed through a cooling coil water bath and flowed out of the reactor in a high dispersed phase continuous flow regime.
Cumene Hydroperoxide (CHP) was titrated by iodometry and the products phenol and alpha-methyl styrene (AMS) were analyzed by liquid chromatography. The conversion of Cumene Hydroperoxide (CHP) was 100%, the selectivity to phenol was 90.8%, and the yield of alpha-methylstyrene (AMS) was 96.2%.
Description of the Performance results
As shown in the above examples 1 to 8, the preparation method of the present invention realizes a Cumene Hydroperoxide (CHP) decomposition reaction directly using a cumene oxidizing solution as a raw material, avoids a safety risk during a Cumene Hydroperoxide (CHP) concentration process, and improves the safety of the process; meanwhile, the concentration process of the cumene oxidizing solution is avoided, and the equipment investment cost and the energy consumption are reduced; greatly reduces the thermal decomposition side reaction of the Cumene Hydroperoxide (CHP), improves the decomposition selectivity of the Cumene Hydroperoxide (CHP), and reduces the separation difficulty and the energy consumption.
Comparative example 1 with respect to example 1, it was found that the selectivity of phenol and the yield of alpha-methylstyrene (AMS) were decreased, wherein the selectivity of phenol was decreased by 11.2% and the yield of alpha-methylstyrene (AMS) was decreased by 9.1%, compared to example 1, in which no member was filled in the tubular reactor, indicating that the mass transfer and heat transfer effects can be enhanced by filling the inert packing material in the tubular continuous flow reactor. When no member is filled, heat cannot be well removed, so that the heat transfer efficiency and the mixing efficiency of reaction liquid are influenced, the side reaction of generating the Acetophenone (ACP) by the thermal decomposition of the Cumene Hydroperoxide (CHP) is obviously increased, and the product yield is influenced.
Compared with the embodiment 1, the inventor finds that the cumene oxidation reaction liquid and the acetone solution of the sulfuric acid are not fully mixed, so that the acid catalyst is unevenly distributed, the local overheating is obvious, the reaction safety is seriously influenced, meanwhile, the selectivity of the phenol is reduced by 8.9 percent, the yield of the alpha-methyl styrene (AMS) is reduced by 7 percent, the difference of the results of the full mixing with the embodiment 1 is obvious, the full mixing of the reaction mixed liquid is proved, the local overheating can be avoided, the thermal decomposition reaction of the Cumene Hydroperoxide (CHP) can be reduced, and the reaction selectivity is improved.
Comparative example 3 the amount of sulphuric acid used was 10.0% o of Cumene Hydroperoxide (CHP) compared to example 1. The dosage is 5 times of the dosage of sulfuric acid in example 1, however, the selectivity of phenol is reduced by 5.1%, and the yield of alpha-methyl styrene (AMS) is reduced by 4.1%, which indicates that the dosage of the acid catalyst needs to be kept in a certain range, and the dosage of the acid catalyst is too high, so that the decomposition rate of Cumene Hydroperoxide (CHP) is too high, the reaction heat release speed is accelerated, heat cannot be removed in time, the increase of thermal decomposition side reactions is caused, the selectivity of products is influenced, and the danger of the reaction is also increased.
Comparative example 4 compared to example 1, the reaction temperature was 150 ℃, and it was found that the selectivity for phenol was decreased by 8.6%, the yield of α -methylstyrene (AMS) was decreased by 3%, and the side reaction of Cumene Hydroperoxide (CHP) thermally decomposed to dimethyl benzyl alcohol (DMPC) and Acetophenone (ACP) was significantly enhanced when the reaction temperature was increased to 150 ℃, thereby decreasing the selectivity for phenol/acetone decomposition of Cumene Hydroperoxide (CHP).
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. An improved process for the production of phenol/acetone characterized by: comprises the following operation steps of the following steps of,
(1) oxidizing cumene under the condition of taking oxygen or air as an oxidant to generate Cumene Hydroperoxide (CHP) to obtain cumene oxidation reaction liquid;
(2) the cumene oxidation reaction liquid and an acid solution are synchronously introduced into a mixer for mixing without concentration, and then enter a tubular continuous flow reactor for decomposition reaction of Cumene Hydroperoxide (CHP).
2. The improved process for the production of phenol/acetone according to claim 1, characterized in that: the Cumene Hydroperoxide (CHP) concentration in the cumene oxidation reaction liquid generated in the step (1) is 19.5-32.8%.
3. The improved phenol/acetone production process according to claim 2, wherein: the mixer in the step (2) is a micro mixer.
4. The improved process for the production of phenol/acetone according to claim 2, characterized in that: the inner diameter of the tubular continuous flow reactor in the step (2) is 0.5-30 mm.
5. The improved process for the production of phenol/acetone according to claim 4, characterized in that: any inert filling material of Raschig rings, pall rings, Natt rings or eight-four inner arc rings is filled in the tubular continuous flow reactor.
6. The improved process for the production of phenol/acetone according to any one of claims 2 to 5, wherein: the acid solution in the step (2) is a mixed solution of an acid A and a solvent B, the acid A is one or a mixture of sulfuric acid, benzenesulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid, and the solvent B is acetone, phenol or a mixture of acetone and phenol.
7. The improved process for the production of phenol/acetone according to claim 6, characterized in that: the mass concentration of the acid A is 1-10%.
8. The improved process for the production of phenol/acetone according to claim 7, characterized in that: the dosage of the acid A is 0.5-5.0 per mill of Cumene Hydroperoxide (CHP).
9. The improved process for the production of phenol/acetone according to any one of claims 2 to 5, wherein: the reaction residence time in the mixer in the step (2) is 80-300 s, and the reaction temperature is 80-140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210451851.2A CN114656333A (en) | 2022-04-27 | 2022-04-27 | Improved method for producing phenol/acetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210451851.2A CN114656333A (en) | 2022-04-27 | 2022-04-27 | Improved method for producing phenol/acetone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114656333A true CN114656333A (en) | 2022-06-24 |
Family
ID=82036381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210451851.2A Pending CN114656333A (en) | 2022-04-27 | 2022-04-27 | Improved method for producing phenol/acetone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114656333A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240417A (en) * | 1996-12-15 | 2000-01-05 | 伊拉国际有限公司 | Improved method for producing phenol and acetone from cumol |
| JP2004352674A (en) * | 2003-05-30 | 2004-12-16 | Mitsui Chemicals Inc | Method for producing phenol |
| KR20130025503A (en) * | 2011-09-02 | 2013-03-12 | 주식회사 엘지화학 | Method for preparing phenol, acetone and alpha methyl styrene |
| CN103562168A (en) * | 2011-07-15 | 2014-02-05 | Lg化学株式会社 | Method of preparing cumyl alcohol and method of preparing phenol, acetone and alpha-methyl styrene |
| CN109180437A (en) * | 2018-09-06 | 2019-01-11 | 常州大学 | The method that cumyl hydroperoxide decomposition prepares phenol in tubular type continuous flow reactor |
-
2022
- 2022-04-27 CN CN202210451851.2A patent/CN114656333A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1240417A (en) * | 1996-12-15 | 2000-01-05 | 伊拉国际有限公司 | Improved method for producing phenol and acetone from cumol |
| JP2004352674A (en) * | 2003-05-30 | 2004-12-16 | Mitsui Chemicals Inc | Method for producing phenol |
| CN103562168A (en) * | 2011-07-15 | 2014-02-05 | Lg化学株式会社 | Method of preparing cumyl alcohol and method of preparing phenol, acetone and alpha-methyl styrene |
| KR20130025503A (en) * | 2011-09-02 | 2013-03-12 | 주식회사 엘지화학 | Method for preparing phenol, acetone and alpha methyl styrene |
| CN109180437A (en) * | 2018-09-06 | 2019-01-11 | 常州大学 | The method that cumyl hydroperoxide decomposition prepares phenol in tubular type continuous flow reactor |
| US20200079714A1 (en) * | 2018-09-06 | 2020-03-12 | Changzhou University | PROCESS FOR ACID-CATALYZED DECOMPOSITION OF ARYL a- HYDROPEROXIDE WITH CONTINUOUS FLOW TUBULAR REACTOR |
Non-Patent Citations (2)
| Title |
|---|
| （苏）金采斯等: "石油化学合成工艺学基础 下", 中国工业出版社, pages: 403 * |
| 张丽君;高焕新;胥明;: "异丙苯氧化制过氧化异丙苯反应工艺优化", 化学反应工程与工艺, no. 03, pages 92 - 98 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100937463B1 (en) | Decomposition of cumene hydroperoxide | |
| CN103896740B (en) | A kind of method producing cresol | |
| EP0406050B1 (en) | Process for the preparation of phenols | |
| JP4012255B2 (en) | An improved method for producing phenol and acetone from cumene | |
| JP3769050B2 (en) | Method for producing phenol | |
| US10954180B2 (en) | Process for acid-catalyzed decomposition of aryl α-hydroperoxide with continuous flow tubular reactor | |
| KR20080037723A (en) | Decomposition of cumene hydroperoxide | |
| KR100658952B1 (en) | Process for preparing phenol and acetone by acid-catalyzed cleavage of cumene hydroperoxide | |
| EP2089358B1 (en) | Process for the liquid phase oxidation of ethylbenzene into ethylbenzene hydroperoxide | |
| JP3864558B2 (en) | Method for producing dihydric phenol and its production equipment | |
| EP1732869A1 (en) | Process for producing phenol | |
| CN114656333A (en) | Improved method for producing phenol/acetone | |
| RU2404954C2 (en) | Method of producing phenol and acetone | |
| CN112457176B (en) | Method for continuously producing hexafluoroacetone | |
| JP5185623B2 (en) | Continuous process for the production of phenol from benzene in a fixed bed reactor. | |
| EP1809589B1 (en) | A method to obtain visually pure bisphenol a | |
| EP2271607B1 (en) | Method for producing phenol and acetone | |
| EP3186216B1 (en) | The optimization of o-sulfonated phenol production for cumene hydroperoxide cleavage | |
| CN115557841B (en) | Preparation method of 1-nitroanthraquinone compound | |
| CN113461494B (en) | Method for synthesizing benzenediol by hydroxylation of phenol and hydrogen peroxide | |
| SK14342000A3 (en) | Process for the preparation of phenol | |
| CN108633275B (en) | Process for purifying phenol | |
| RU2316535C2 (en) | Method of production of phenols | |
| CN118667147A (en) | Combined process for directly producing PPO from benzene | |
| JPH01100136A (en) | Production of alpha-methylstyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220624 |