CN111606835A - Method for preparing ethylbenzene hydroperoxide by ethylbenzene oxidation - Google Patents
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- CN111606835A CN111606835A CN202010505289.8A CN202010505289A CN111606835A CN 111606835 A CN111606835 A CN 111606835A CN 202010505289 A CN202010505289 A CN 202010505289A CN 111606835 A CN111606835 A CN 111606835A
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 94
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 230000003647 oxidation Effects 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 16
- 238000006735 epoxidation reaction Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241001292396 Cirrhitidae Species 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- -1 ethylbenzene organic hydroperoxide Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- HDHOHQHZKXFKOS-UHFFFAOYSA-N ethylbenzene;hydrogen peroxide Chemical compound OO.CCC1=CC=CC=C1 HDHOHQHZKXFKOS-UHFFFAOYSA-N 0.000 description 1
- JRNXSPIOMZDAQR-UHFFFAOYSA-N ethylperoxybenzene Chemical compound CCOOC1=CC=CC=C1 JRNXSPIOMZDAQR-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005503 peroxidation kinetic Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing ethylbenzene hydroperoxide by ethylbenzene oxidation, which is applied to a propylene oxide/styrene co-production device and comprises the following steps: the raw material ethylbenzene and oxygen-containing gas are subjected to oxidation reaction at the reaction temperature of 135-155 ℃ and the pressure of 0.1-1.0 MPaA. The invention adopts the optimal reaction temperature and the ethylbenzene oxidation depth to control the retention time of the oxidation liquid and reduce the decomposition of the ethylbenzene hydroperoxide.
Description
Field of holding operation
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of ethylbenzene hydroperoxide in a propylene oxide and styrene co-production device.
Background
The hakon process, which is a well-known process for oxidizing propylene to propylene oxide and styrene using ethylbenzene hydroperoxide as an oxygen carrier, is now commercially available.
A typical propylene oxide/styrene co-production process includes at least the following steps:
(a) reacting ethylene with benzene to generate ethylbenzene;
(b) reacting ethylbenzene with oxygen in the oxygen-containing gas to generate ethylbenzene hydroperoxide;
(c) ethylbenzene hydroperoxide reacts with propylene to generate propylene oxide and methyl benzyl alcohol;
(d) dehydrating the methyl benzyl alcohol to generate styrene.
Theoretically, 1mol of ethylbenzene hydroperoxide and 1mol of propylene are oxidized to produce propylene oxide, and ideally, when the molar yield of propylene oxide produced by the same apparatus is the same as the molar yield of styrene and the conversion is made to a mass ratio, styrene/propylene oxide is 1.8. However, in the existing devices for producing styrene and propylene oxide by various patent manufacturers, the mass ratio of the product styrene to the product propylene oxide is 2.2-2.6. The product ratio varies because ethylbenzene hydroperoxide decomposes in step (b) and step (C) to produce methylbenzyl alcohol and acetophenone as by-products, which are converted to styrene products by treatment, but propylene oxide is produced by oxidizing propylene with ethylbenzene hydroperoxide, which means that the production of propylene oxide is reduced and the cost per ton of propylene oxide product is increased on a styrene product metering device scale. In order to maximize the efficiency of propylene oxide production, it is desirable to minimize the decomposition of ethylbenzene hydroperoxide in the overall process, particularly in the ethylbenzene oxidation step, which requires the determination of suitable ethylbenzene oxidation process conditions.
The situation of the current domestic propylene oxide/styrene co-production device is described in a text of the current state analysis and progress of the production process of propylene oxide in China, which is prepared from No. 4P 39-42 of volume 47 of 2018 in Shandong chemical industry: the process route for producing the propylene oxide is to oxidize ethylbenzene by using molecular oxygen, and generate an ethylbenzene mixed solution containing ethylbenzene organic hydroperoxide under the conditions of 0.3-0.5 MPa and 130-160 ℃, wherein the mass fraction of the ethylbenzene organic hydroperoxide is 17% ", and the mass ratio of styrene to propylene oxide obtained by the device is 1: 0.4 "(i.e., 2.5: 1).
The optimized ethylbenzene conversion rate is about 13% as shown in the publication of propylene derivative engineering at page 300 of the chemical industry press, while the content of ethylbenzene hydroperoxide in the ethylbenzene oxidation product is generally 10-12 wt%, the typical ethylbenzene peroxidation yield is 79%, and the ethylbenzene hydroperoxide is decomposed into phenethyl alcohol and acetophenone, and the total yield is about 20%.
In addition to the industrial parameters reported in these documents, many units have also studied the process for the preparation of ethylbenzene hydroperoxide by the oxidation of ethylbenzene.
The research on the reaction kinetics of ethylbenzene hydroperoxide prepared by ethylbenzene oxidation, which is carried out by P73-77 (ethylbenzene liquid phase oxidation reaction kinetics research) in 1992 in the petrochemical industry, mainly researches the influence of temperature on the reaction, and points out that the selectivity of ethylbenzene hydroperoxide can be improved by controlling the reaction temperature to be less than 145 ℃. The document, petrochemical 2010, No. 4P 411-416, free radical kinetic model research on ethylbenzene liquid phase peroxidation, proposes an ethylbenzene liquid phase peroxidation kinetic model using ethylbenzene hydroperoxide as an initiator, which is closer to industrial practice, but does not give recommended reaction process parameters.
In order to reduce the amount of ethylbenzene hydroperoxide decomposition, many reports have indicated the use of metal salts as catalysts to increase ethylbenzene hydroperoxide selectivity. Patent US4262143 of Halcon corporation proposes a method of adding sodium or potassium salts to the oxidation solution to neutralize the acid generated by the oxidation reaction, reduce the acid content in the oxidation solution, reduce the acid decomposition of ethylbenzene hydroperoxide, and improve the selectivity of ethylbenzene hydroperoxide. The document Role of ammonium salts in the liquid-phase oxidation of ethylene to hydroperoxide with molecular oxygen (Applied Catalysis A: General, Volume 294, Issue 2,10October 2005, Pages290-297) adds quaternary ammonium salts to the ethylbenzene oxidizer in higher yields than ethylbenzene hydroperoxide with hydroxide salts. In the document "Liquid-phase ethylene oxidation to hydroperoxide with barium catalysts" (Journal of Molecular Catalysis A: Chemical, Volume 227, Issues 1-2, 1March 2005, Pages 101-105), it is stated that the selectivity of ethylbenzene hydroperoxide increases when 1ppm of barium salt is added.
In addition to the above optimization process and catalyst addition, patent CN106554298 of wanhua chemical group ltd provides that the use of a multistage oxidation reaction process can effectively avoid the back-mixing problem of a horizontal reactor and improve the selectivity of the target product ethylbenzene peroxide.
Although the above-mentioned methods can improve the yield of ethylbenzene hydroperoxide, the selectivity improvement of ethylbenzene hydroperoxide does not increase monotonously to the improvement of the economic benefit of the device for the propylene oxide/styrene co-production device, and therefore, the most suitable range needs to be found out.
Disclosure of Invention
Aiming at the problem of overlarge decomposition amount of ethylbenzene hydroperoxide in the ethylbenzene oxidation step, the invention provides a method for preparing ethylbenzene hydroperoxide by ethylbenzene oxidation, which adopts the optimal reaction temperature and ethylbenzene oxidation depth to control the retention time of an oxidation liquid and reduce the decomposition of the ethylbenzene hydroperoxide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing ethylbenzene hydroperoxide by ethylbenzene oxidation is applied to a propylene oxide/styrene co-production device, and comprises the following steps: the raw material ethylbenzene and oxygen-containing gas are subjected to oxidation reaction at the reaction temperature of 135-155 ℃ and the pressure of 0.1-1.0 MPaA.
In order to better understand the process of the present invention, it is necessary to have a scientific description of the ethylbenzene oxidation process. In the literature, reported in the document "free radical dynamics model research of ethylbenzene liquid phase peroxidation" P411-416 in 2010 of petrochemical industry, the ethylbenzene oxidation reaction is a cascade reaction, the ethylbenzene oxidation reaction to ethylbenzene hydroperoxide is a 0-level reaction, the reaction rate is only related to the temperature and the reaction time, the decomposition of ethylbenzene hydroperoxide to phenethyl alcohol and acetophenone is a 2-level reaction, the reaction rate is not believed to be related to the temperature and the reaction time, and is also in a square relation with the concentration of ethylbenzene hydroperoxide, that is:
it is apparent that to obtain more ethylbenzene hydroperoxide product, it is desirable to operate at lower conversion, minimize ethylbenzene hydroperoxide concentration in the oxidation liquid, lower reaction temperature, and lower residence time to reduce decomposition reactions. The method and the device described in patent US4262143 of Halcon lower the temperature of the ethylbenzene oxidation step by step through the multi-stage oxidation reaction, lower the concentration of ethylbenzene hydroperoxide and the reaction temperature in the decomposition reaction, and effectively lower the decomposition reaction rate of the ethylbenzene hydroperoxide. However, Halcon's method reduces the EBHP decomposition scheme at a fixed oxidation depth, specifically at a fixed concentration of ethylbenzene hydroperoxide in the oxidation liquor in the effluent from the last oxidation reactor, and does not give a suitable oxidation depth, i.e., a suitable EBHP concentration, throughout the oxidation reaction sequence.
Theoretically, a shorter residence time would result in a higher ethylbenzene hydroperoxide yield, but too short a residence time would mean too low ethylbenzene conversion, which would result in a large amount of unreacted material being recycled, and the energy consumption would increase rapidly, and at the same time, the size of the oxidation reactor would also increase rapidly, so that there is a suitable oxidation depth, i.e. there is an optimum ethylbenzene hydroperoxide concentration range for the material exiting the oxidation reactor, which can provide the best economic benefit for the propylene oxide/styrene co-production plant.
Based on the above principle, as a further improvement of the present invention: and the concentration of the ethylbenzene hydroperoxide in the oxidation material formed after the oxidation reaction is finished is 6-9%.
As a preferred embodiment of the present invention: the ethylbenzene oxidation reaction is carried out by adopting a liquid phase method, a plurality of bubble reactors are used for cascade operation, the general stage number is 2-8, and the oxidation medium is air or oxygen.
As another preferred embodiment of the present invention: the ethylbenzene oxidation reaction can be a single reactor, the inside of the reactor is divided into 2-10 zones, and the reactor can be horizontal or vertical.
As a further improvement of the invention: the temperature distribution of the oxidation reaction in each stage of reactor or each stage of reaction zone is a scheme of gradually reducing the reaction temperature along with the increase of the oxidation depth, but the reaction temperature range is not more than 135-155 ℃. Because too low oxidation reaction temperature can cause too slow reaction rate, the consumption rate of oxygen in introduced air (or oxygen) is too slow, tail oxygen is easy to exceed the standard, and the oxidation tail gas can fall into an explosion range; the reaction temperature is too high, so that the reaction rate is accelerated, and the decomposition rate of the ethylbenzene hydroperoxide is improved, while the decomposition of the ethylbenzene hydroperoxide is a strong exothermic reaction, so that the temperature of the material is increased, the decomposition of the ethylbenzene hydroperoxide is promoted, and the temperature runaway which is difficult to control is easily caused.
As a further improvement of the invention: the pressure of the oxidation reaction is preferably 0.2 to 0.5 MPa. The dissolution of oxygen in liquid-phase ethylbenzene is influenced by too low pressure, the oxidation rate is reduced, the concentration of tail oxygen is possibly too high, and the tail gas falls into the explosion range; too high pressure will cause the saturation temperature of the materials in the reactor to rise, and under the condition of operating temperature, the reaction heat is difficult to be taken away by the gasification of the materials, thus causing local overheating and EBHP decomposition in the reactor.
As a preferred embodiment of the present invention: in a typical production process of propylene oxide/styrene, an ethylbenzene hydroperoxide material fed into epoxidation needs to be concentrated, and the concentration range of the ethylbenzene hydroperoxide after concentration in the invention is 30-40%. Since too low EBHP concentration reduces EBHP conversion during epoxidation, thermal decomposition of EBHP results; however, too high EBHP concentration may cause uncontrolled decomposition or even explosion during the concentration and epoxidation steps.
The concentration operation is generally carried out by adopting a rectifying tower, negative pressure operation is generally adopted in order to prevent the decomposition of the ethylbenzene hydroperoxide during the operation, and the operation pressure is generally 3-50 kPa. The single-tower rectification can be adopted, or multiple towers can be adopted, and the preferable scheme is a double-tower coupling rectification scheme, so that the distillation energy consumption is reduced.
Drawings
FIG. 1 is a process diagram of the present invention.
FIG. 2 is a graph showing the oxidation depth and the economic efficiency in each example.
Detailed Description
The processes, features and advantages of the present invention are further described in the following examples. The embodiments of the present invention are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the scope of the present invention by substituting or changing the equivalent technical solution and the inventive concept of the present invention.
Example 1
The embodiment relates to a method for preparing ethylbenzene hydroperoxide by oxidizing ethylbenzene and air, which is used for matching a 60 ten thousand ton/year styrene co-production propylene oxide device.
As shown in FIG. 1, an ethylbenzene feedstock 101 is mixed with recycled ethylbenzene 108 from a concentrating column, fed to the upper portion of a primary oxidation reactor 1, the material 103 which flows out from the primary oxidation reactor 1 after reacting with the air is sent into the secondary oxidation reactor 2, and after continuously reacting with the air, the material 104 flowing out from the bottom of the second-stage oxidation reactor 2 is sent into the third-stage oxidation reactor 3, and after continuously reacting with the air, the material 105 flowing out from the bottom of the third-stage oxidation reactor 3 is sent into the fourth-stage oxidation reactor 4, and after continuously reacting with the air, and (3) feeding the material 106 flowing out of the bottom of the four-stage oxidation reactor 4 into a concentration unit tower 6, wherein the concentration unit tower 6 adopts a two-stage coupling concentration tower, the material 107 flowing out of the bottom of the concentration tower is 35% of ethylbenzene hydroperoxide (EBHP) material and is fed into an epoxidation unit, and the circulating ethylbenzene coming out of the top of the concentration unit tower 6 returns to be fed into the oxidation reactor for continuous reaction.
Air stream 109 is divided into four parts, which are sent to four oxidation reactors respectively, oxygen in the air and ethylbenzene react and then flow out from the top of the reactor and enter a tail gas heat exchange tower 5, the cold ethylbenzene at the top of the tower is heated by tail gas and then returns to a primary oxidation reactor, the tail gas is cooled and condensed in the tower, condensate returns to the primary oxidation reactor along with the ethylbenzene, and a tail gas phase stream 110 is sent out of an oxidation unit for treatment, and is generally treated by adopting an incineration method.
Ethylbenzene is subjected to oxidation reaction in four oxidation reactors, the reaction temperature is respectively 150 ℃, 147 ℃, 144 ℃ and 141 ℃, when the reaction is stable, the retention time of newly decomposed ethylbenzene in the four oxidation reactors is 3h, and the ethylbenzene hydrogen peroxide content in a material flow 106 flowing out of the fourth oxidation reactor is 7.6%.
The logistics data for example 1 is shown in table 1.
| Number of commodity circulation | 101 | 102 | 103 | 104 | 105 | 106 | 107 | 108 | 109 | 110 |
| Temperature, C | 40 | 150 | 150 | 147 | 144 | 141 | 40 | 67 | 38 | 90 |
| Pressure, kPaA | 500 | 480 | 720 | 600 | 600 | 600 | 13 | 600 | 630 | 370 |
| Flow rate, kg/h | 35026 | 184275 | 173347 | 167462 | 162408 | 158130 | 34655 | 123490 | 15159 | 15576 |
| Ethylbenzene production | 99.8％ | 99.6％ | 97.8％ | 95.7％ | 93.6％ | 91.3％ | 61.2％ | 99.9％ | 0.0％ | 21.8％ |
| Ethylbenzene hydroperoxide | 0.0％ | 0.0％ | 1.8％ | 3.6％ | 5.6％ | 7.6％ | 35.0％ | 0.0％ | 0.0％ | 0.0％ |
| Methyl benzyl alcohol | 0.1％ | 0.0％ | 0.1％ | 0.1％ | 0.2％ | 0.3％ | 1.4％ | 0.0％ | 0.0％ | 0.0％ |
| Acetophenone | 0.0％ | 0.0％ | 0.1％ | 0.2％ | 0.3％ | 0.4％ | 1.8％ | 0.0％ | 0.0％ | 0.0％ |
| N2 | 0.0％ | 0.1％ | 0.0％ | 0.1％ | 0.1％ | 0.1％ | 0.0％ | 0.0％ | 76.2％ | 73.6％ |
| O2 | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 23.1％ | 2.6％ |
| H2O | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.7％ | 1.7％ |
| Methanol | 0.0％ | 0.1％ | 0.1％ | 0.1％ | 0.1％ | 0.0％ | 0.0％ | 0.1％ | 0.0％ | 0.2％ |
| Heavy fraction | 0.0％ | 0.0％ | 0.0％ | 0.1％ | 0.1％ | 0.1％ | 0.5％ | 0.0％ | 0.0％ | 0.0％ |
| Peroxides and their use in the preparation of pharmaceutical preparations | 0.0％ | 0.1％ | 0.1％ | 0.1％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.0％ | 0.1％ |
Table 1 shows the data of the streams of example 1
Example 2
The process flow was the same as in example 1, but the residence time was longer, the residence time of freshly ethylbenzene in the four oxidation reactors was 4h, and the ethylbenzene hydroperoxide content in the effluent stream 106 from the fourth oxidation reactor was 10.3 wt%.
Example 3
The process flow was the same as in example 1, but the residence time was longer, the residence time of freshly ethylbenzene in the four oxidation reactors was 5h, and the ethylbenzene hydroperoxide content in the effluent stream 106 from the fourth oxidation reactor was 13.2 wt%.
Example 4
The process flow was the same as in example 1, but the residence time was longer, the residence time of freshly ethylbenzene in the four oxidation reactors was 6h, and the ethylbenzene hydroperoxide content in the effluent stream 106 from the fourth oxidation reactor was 14.2 wt%.
Example 5
The process flow is the same as in example 1, but the residence time is shorter, the residence time of the freshly decomposed ethylbenzene in the four oxidation reactors is 2h, and the ethylbenzene hydroperoxide content in the effluent stream 106 from the fourth oxidation reactor is 4.9 wt%.
The above examples are compared and are shown in tables 2 to 4:
TABLE 2 productivity of PO/SM devices of examples 1-5
TABLE 3 statistics of major energy consumption changes when applied to PO/SM devices in embodiments 1-5
TABLE 4 comparison of economic benefits when applied to PO/SM devices in examples 1-5
Note: 1. when the economic benefit is calculated, the price of the propylene oxide is 10000 yuan/ton, the price of the propylene is 8000 yuan/ton, and the energy consumption is calculated according to 2.6 yuan/kg standard oil. 2. Compared with the EBHP content of 13.2% in the oxidation reactor outlet stream.
As shown in FIG. 2, it can be seen from the trend chart of the economic efficiency and the oxidation depth that the economic efficiency is the highest when the ethylbenzene hydroperoxide concentration in the outlet stream of the oxidation reactor is controlled to be 7-9 wt%.
Claims (7)
1. A method for preparing ethylbenzene hydroperoxide by ethylbenzene oxidation is applied to a propylene oxide/styrene co-production device, and is characterized by comprising the following steps: the raw material ethylbenzene and oxygen-containing gas are subjected to oxidation reaction at the reaction temperature of 135-155 ℃ and the pressure of 0.1-1.0 MPaA.
2. The process for the oxidation of ethylbenzene to produce ethylbenzene hydroperoxide as claimed in claim 1 wherein: the oxidation reaction is carried out in a cascade mode in a plurality of vertical bubble tower reactors, and the number of the reactors is 2-8.
3. The process for the oxidation of ethylbenzene to produce ethylbenzene hydroperoxide as claimed in claim 1 wherein: the oxidation reaction adopts a single reactor, and 2-10 reaction compartments are formed in the single reactor in a separated mode.
4. A process for the oxidation of ethylbenzene to produce ethylbenzene hydroperoxide according to claim 2 or claim 3 wherein: along with the advancement of the oxidation depth, the oxidation reaction temperature is gradually reduced within a control range.
5. The process for the oxidation of ethylbenzene to produce ethylbenzene hydroperoxide as claimed in claim 1 wherein: and the concentration of the ethylbenzene hydroperoxide in the oxidation material formed after the oxidation reaction is finished is 6-9%.
6. The process for the oxidation of ethylbenzene to produce ethylbenzene hydroperoxide as claimed in claim 1 wherein: the method is provided with a concentration process, wherein the oxidized material formed after the oxidation reaction is subjected to a next epoxidation process through the concentration process, and the concentration of the ethylbenzene hydroperoxide after concentration is 30-40 wt%.
7. The process for the oxidation of ethylbenzene to produce ethylbenzene hydroperoxide as claimed in claim 1 wherein: the pressure of the oxidation reaction is 0.2-0.5 MPa.
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| CN202010505289.8A CN111606835A (en) | 2020-06-05 | 2020-06-05 | Method for preparing ethylbenzene hydroperoxide by ethylbenzene oxidation |
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|---|---|---|---|---|
| US4066706A (en) * | 1975-04-21 | 1978-01-03 | Halcon International, Inc. | Preparation of ethylbenzene hydroperoxide |
| CN106554298A (en) * | 2015-09-28 | 2017-04-05 | 万华化学集团股份有限公司 | A kind of method that ethylbenzene oxidation prepares ethylbenzene hydroperoxide |
| CN109020858A (en) * | 2018-09-11 | 2018-12-18 | 中国海洋石油集团有限公司 | The method for inhibiting ethylbenzene hydroperoxide to decompose |
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| US4066706A (en) * | 1975-04-21 | 1978-01-03 | Halcon International, Inc. | Preparation of ethylbenzene hydroperoxide |
| CN106554298A (en) * | 2015-09-28 | 2017-04-05 | 万华化学集团股份有限公司 | A kind of method that ethylbenzene oxidation prepares ethylbenzene hydroperoxide |
| CN109020858A (en) * | 2018-09-11 | 2018-12-18 | 中国海洋石油集团有限公司 | The method for inhibiting ethylbenzene hydroperoxide to decompose |
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