CN112250610A - Method and system for concentrating alkyl peroxide - Google Patents
Method and system for concentrating alkyl peroxide Download PDFInfo
- Publication number
- CN112250610A CN112250610A CN202011051238.9A CN202011051238A CN112250610A CN 112250610 A CN112250610 A CN 112250610A CN 202011051238 A CN202011051238 A CN 202011051238A CN 112250610 A CN112250610 A CN 112250610A
- Authority
- CN
- China
- Prior art keywords
- tower
- concentration tower
- stage concentration
- stage
- liquid
- 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
- 238000000034 method Methods 0.000 title claims abstract description 70
- -1 alkyl peroxide Chemical class 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 239000007789 gas Substances 0.000 claims abstract description 51
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 239000007791 liquid phase Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000005502 peroxidation Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims description 58
- 239000012071 phase Substances 0.000 claims description 25
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 11
- 239000010865 sewage Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000002978 peroxides Chemical class 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 238000007872 degassing Methods 0.000 claims description 4
- IQSWASBUPOHAPT-UHFFFAOYSA-N OCC(P(O)(O)=O)P(O)(O)=O.[Na].[Na].[Na].[Na] Chemical compound OCC(P(O)(O)=O)P(O)(O)=O.[Na].[Na].[Na].[Na] IQSWASBUPOHAPT-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- CVIKLBFHCCGYHS-UHFFFAOYSA-N [Na].[Na].OCC(P(O)(O)=O)P(O)(O)=O Chemical compound [Na].[Na].OCC(P(O)(O)=O)P(O)(O)=O CVIKLBFHCCGYHS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012141 concentrate Substances 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
- C07C407/006—Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a system for concentrating alkyl peroxide, which are used for concentrating the alkyl peroxide, in particular to the concentration of cyclohexyl hydroperoxide in cyclohexane oxidation liquid, and comprise the steps of cooling the oxidation liquid, recovering heat, performing primary concentration, performing secondary concentration and performing a vacuum system. In the process of producing chemical products by oxidizing organic hydrocarbons, the gas containing molecular oxygen oxidizes the organic hydrocarbons to generate an oxidizing liquid of substances such as hydrocarbon-based hydrogen oxide and the like, the conversion rate of peroxidation reaction is low, and a large amount of organic hydrocarbons are circulated greatly in the subsequent treatment process, so that the energy consumption is high and the method is uneconomical. The invention concentrates the alkyl hydrogen oxide, can reduce a large amount of liquid phase organic hydrocarbon circulation in the subsequent process, greatly reduces the energy consumption, simultaneously takes effect on the equipment size of the subsequent process, and has good technical development and practical significance.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a method and a system for concentrating alkyl peroxide.
Background
In the process of producing chemical products by oxidizing organic hydrocarbons, the conversion rate of peroxidation is low, and a large amount of organic hydrocarbons are circulated in the subsequent treatment process, so that the energy consumption is high and the method is uneconomical.
The preparation of cyclohexanol and cyclohexanone is carried out by oxidizing cyclohexane with molecular oxygen-containing gas to generate cyclohexane oxidizing liquid containing cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, treating cyclohexane oxidizing liquid to decompose cyclohexyl hydroperoxide to generate cyclohexanol and cyclohexanone, distilling out unreacted cyclohexane for cyclic use, and rectifying reaction product for several times to obtain cyclohexanol and cyclohexanone. However, the conversion rate of the cyclohexane oxidation reaction is low, a large amount of cyclohexane is circulated in the subsequent process, and the energy consumption is large.
Disclosure of Invention
The invention provides an improvement on the technology for producing cyclohexanol or cyclohexanone by oxidizing cyclohexane, and the improvement increases the concentration of cyclohexyl hydroperoxide, can reduce a large amount of cyclohexane circulation in subsequent processes, greatly reduces energy consumption, and has good technical development and practical significance.
The object of the invention can be achieved by the following measures:
a process for the concentration of a hydrocarbyl peroxide, the process comprising the steps of:
1) cooling the oxidizing liquid and recovering heat: cooling the oxidizing liquid from the peroxidation process to recover waste heat;
2) primary concentration: mixing the cooled oxidation liquid with an oxide stabilizer with the mass flow of 0.0001-0.08% of the oxidation liquid, carrying out a first-stage concentration tower, partially returning the first-stage concentration after the gas phase at the upper part of the first-stage concentration is cooled, and returning the residual liquid-phase hydrocarbon to the oxidation reaction process;
3) secondary concentration: the liquid phase after the first-stage concentration enters a second-stage concentration step, the gas-phase cyclohexane at the upper part of the second-stage concentration step is partially returned to the second-stage concentration step after condensation, the residual liquid-phase hydrocarbon returns to the peroxidation step, the discharge of the second-stage concentration liquid phase is the concentrated alkyl peroxide solution, and the next step is carried out;
4) a vacuum system: two-stage concentration is carried out in a vacuum system, condensate flows back to return to the first-stage concentration after cooling of first-stage concentration tail gas, non-condensable gas and second-stage concentration tail gas are converged and further cooled, the condensate returns to the second-stage concentration, the non-condensable tail gas is sent to a concentration tower vacuum system, the concentration vacuum system uses liquid-phase hydrocarbon as sealing liquid, the tail gas is treated by removing the tail gas, the sealing liquid is recycled to an oil phase oxidation reaction system, and oily sewage is treated by removing the sewage.
The technical scheme of the invention is as follows: the material of the hydrocarbon-based peroxide is C4-C20 chain hydrocarbon or naphthenic hydrocarbon peroxide, and preferably: the material of the alkyl peroxide is cyclohexyl hydrogen peroxide concentration of cyclohexane oxidation liquid: preferably: the peroxide stabilizer is one or two of hydroxyethylidene diphosphonic acid tetrasodium or hydroxyethylidene diphosphonic acid disodium.
A system for carrying out the above-described hydrocarbon-based peroxide concentration process, which comprises:
the system comprises a primary concentration tower, wherein an output pipeline of an oxidation liquid in an oxidation reaction process is connected with the middle part of the primary concentration tower, and an output end at the top of the primary concentration tower is connected with a reflux tank of the primary concentration tower through a reboiler of a secondary concentration tower;
the output end of the bottom of the first-stage concentration tower is connected with the middle part of the second-stage concentration tower, the output end of the top of the second-stage concentration tower is connected with a reflux tank of the second-stage concentration tower through a condenser of the second-stage concentration tower, and the output end of the bottom of the second-stage concentration tower is connected with a decomposition reaction process through a cyclohexyl hydrogen peroxide concentrated solution cooler;
the output end of the top of the second-stage concentration tower reflux tank is sequentially connected with a concentration tower vacuum pump and a concentration tower sealing liquid tank through a concentration tower tail gas condenser, and the output end of the bottom of the concentration tower sealing liquid tank is connected with the bottom end of the second-stage concentration tower reflux tank.
In the above-mentioned chemical solution enrichment system: the system comprises a primary concentration tower, wherein an output pipeline of an oxidation liquid in an oxidation reaction process is connected with the middle part of the primary concentration tower through an oxidation liquid degassing tank tail gas condenser.
In the above-mentioned chemical solution enrichment system: one output end of the first-stage concentration tower reflux tank is connected with the upper part of the first-stage concentration tower, and the other output end of the first-stage concentration tower reflux tank is connected with the output end of the second-stage concentration tower reflux tank through a first-stage concentration tower aftercooler.
In the above-mentioned chemical solution enrichment system: the lower part of the first-stage concentration tower is provided with a reboiler of the first-stage concentration tower.
In the above-mentioned chemical solution enrichment system: one output end at the bottom of the reflux tank of the second-stage concentration tower is connected with the upper part of the second-stage concentration tower, and the other output end is connected with the oxidation reaction process.
In some specific embodiments: a method for realizing the concentration of the alkyl peroxide by using the system, which comprises the following steps:
and cooling the oxidizing liquid from the oxidation reaction process in an oxidizing liquid cooler, mixing the oxidizing liquid with a peroxide stabilizer accounting for 0.0001-0.08% of the mass flow of the oxidizing liquid, and feeding the mixture into the middle part of a primary concentration tower. The lower part of the first-stage concentration tower is provided with a reboiler. And the gas-phase cyclohexane from the top of the first-stage concentration tower is used as a heat source of a reboiler of the second-stage concentration tower, is cooled and then enters a reflux tank of the first-stage concentration tower, part of the gas-phase cyclohexane flows back to the top of the first-stage concentration tower through a reflux pump of the first-stage concentration tower, and the rest cyclohexane returns to the oxidation reaction process.
The liquid phase at the bottom of the first-stage concentration tower enters the middle part of the second-stage concentration tower. And condensing gas-phase cyclohexane at the top of the secondary concentrating tower by a secondary concentrating tower condenser, then feeding the condensed gas-phase cyclohexane into a secondary concentrating tower reflux tank, partially refluxing the condensed gas-phase cyclohexane to the top of the secondary concentrating tower by a secondary concentrating tower reflux pump, and returning the rest cyclohexane to the oxidation reaction process. And the concentrated cyclohexyl hydrogen peroxide liquid from the bottom of the secondary concentration tower is cooled by a cyclohexyl hydrogen peroxide concentrated liquid cooler and then is pumped to the decomposition reaction process by a tower kettle of the secondary concentration tower.
Tail gas of a first-stage concentration tower reflux tank is cooled by a first-stage concentration tower after passing through a first-stage concentration tower aftercooler, condensate flows back to the first-stage concentration tower reflux tank, non-condensable gas and tail gas of a second-stage concentration tower reflux tank are converged and sent to a tail gas condenser of a concentration tower for cooling, the condensate flows back to a second-stage concentration tower reflux tank, and the non-condensable tail gas is sent to a vacuum pump of the concentration tower.
Cyclohexane is used as sealing liquid for a vacuum pump of the concentration tower, tail gas of the vacuum pump is delivered to a sealed tank of the concentration tower, tail gas in the tank is treated by removing the tail gas, an oil phase in the tank is treated by a reflux pump of a second-level concentration tower, and oily sewage is treated by removing sewage.
The method comprises the following steps: the operation pressure of the first-stage concentration tower at the top of the tower is 0.03-0.05 MPa, the operation temperature of the top of the tower is 70-80 ℃, the operation pressure of the bottom of the tower is 0.04-0.05 MPa, and the operation temperature of the top of the tower is 90-100 ℃.
The method comprises the following steps: the tower top operating pressure of the secondary concentration tower is 0.01-0.02 MPa, and the operating temperature is 68-73 ℃; the operation pressure at the bottom of the tower is 0.01-0.02 MPa, and the operation temperature is 48-54 ℃.
The technical scheme of the invention is as follows: the cyclohexyl hydrogen peroxide secondary concentration system has the advantages that the addition of the stabilizer can improve the operation safety, the cyclohexyl hydrogen peroxide concentration can reduce a large amount of cyclohexane circulation in subsequent procedures, the energy consumption is greatly reduced, the temperature in the whole process is easy to control, the separation process is simple, and the cyclohexyl hydrogen peroxide secondary concentration system has good technical development and practical significance.
The pressure or pressure in the present invention is absolute pressure or absolute pressure unless otherwise specified.
Has the advantages that: in the process of producing chemical products by oxidizing organic hydrocarbons, the gas containing molecular oxygen oxidizes the organic hydrocarbons to generate an oxidizing liquid of substances such as hydrocarbon-based hydrogen oxide and the like, the conversion rate of peroxidation reaction is low, and a large amount of organic hydrocarbons are circulated greatly in the subsequent treatment process, so that the energy consumption is high and the method is uneconomical. The invention concentrates the alkyl hydrogen oxide, can reduce a large amount of liquid phase organic hydrocarbon circulation in the subsequent process, greatly reduces the energy consumption, simultaneously takes effect on the equipment size of the subsequent process, and has good technical development and practical significance.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
FIG. 2 is a schematic diagram of a two-stage concentration process for a cyclohexyl hydroperoxide concentration system of the present invention.
In the figure: t-0201 is a first-stage concentration tower, T-0202 is a second-stage concentration tower, E-0201 is an oxidized liquid degassing tank tail gas condenser, E-0202 is a first-stage concentration tower reboiler, E-0203 is a second-stage concentration tower reboiler, E-0204 is a first-stage concentration tower after-cooler, E-0205 is a second-stage concentration tower condenser, E-0206 is a concentration tower tail gas condenser, E-0207 is a cyclohexyl hydrogen peroxide concentrate cooler, V-0201 is a first-stage concentration tower reflux tank, V-0202 is a second-stage concentration tower reflux tank, V-0203 is a concentration tower sealed liquid tank, P-0201 is a first-stage concentration tower reflux pump, P-0202 is a second-stage concentration tower reflux pump, P-0203 is a concentration tower vacuum pump, and P-0204 is a second-stage concentration tower kettle pump.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
As shown in figures 1-2, the oxidation liquid concentration system comprises a primary concentration tower T-0201, and an output pipeline of oxidation liquid in an oxidation reaction process is connected with the middle part of the primary concentration tower T-0201 through an oxidation liquid degassing tank tail gas condenser. The output end of the top of the first-stage concentration tower T-0201 is connected with a first-stage concentration tower reflux tank V-0201 through a second-stage concentration tower reboiler E-0203; one output end of the first-stage concentration tower reflux tank V-0201 is connected with the upper part of the first-stage concentration tower T-0201, and the other output end of the first-stage concentration tower reflux tank V-0201 is connected with the output end of the second-stage concentration tower reflux tank V-0202 through a first-stage concentration tower aftercooler E-0204. The lower part of the first-level concentration tower T-0201 is provided with a first-level concentration tower reboiler E-0202.
The output end of the bottom of the first-stage concentration tower T-0201 is connected with the middle part of the second-stage concentration tower T-0202, the output end of the top of the second-stage concentration tower T-0202 is connected with a reflux tank V-0202 of the second-stage concentration tower through a second-stage concentration tower condenser E-0205, and the output end of the bottom of the second-stage concentration tower T-0202 is connected with a decomposition reaction process through a cyclohexyl hydrogen peroxide concentrated solution cooler E-0207;
the output end of the top of the second-stage concentration tower reflux tank V-0202 is sequentially connected with a concentration tower vacuum pump P-0203 and a concentration tower sealing liquid tank V-0203 through a concentration tower tail gas condenser E-0206, and the output end of the bottom of the concentration tower sealing liquid tank V-0203 is connected with the bottom end of the second-stage concentration tower reflux tank V-0202. One output end at the bottom of the secondary concentration tower reflux tank V-0202 is connected with the upper part of the secondary concentration tower T-0202, and the other output end is connected with the oxidation reaction process.
Example 1
As shown in FIGS. 1 to 2, the compressed air 7966Nm contains 211462kg/h cyclohexane and 21% oxygen mole fraction3The reaction temperature is controlled to be 165 ℃, the reaction pressure is 1.35MPa, the gas phase at the top of the reactor is discharged at 62548kg/h, the cyclohexyl hydrogen peroxide solution at the bottom is discharged at 160298kg/h, and the concentration of the cyclohexyl hydrogen peroxide, the cyclohexanone, the cyclohexanol and the cyclohexane in the liquid phase is respectively 3.50 wt%, 2.34 wt%, 2.80 wt% and 91.36 wt%.
The oxidation liquid from the oxidation reaction process enters an oxidation liquid cooler E-0201 to be cooled to 105 ℃, and then is mixed with 4.5kg/h of oxide stabilizer, namely the hydroxyethylidene diphosphonic acid tetrasodium, and enters the middle part of a first-stage concentration tower T-0201. The reboiler E-0204 is arranged at the lower part of the first-stage concentration tower T-0201, the operation pressure at the top of the tower is 0.04MPa, the operation temperature at the top of the tower is 75 ℃, the operation pressure at the bottom of the tower is 0.045MPa, and the operation temperature at the top of the tower is 95 ℃. And gas-phase cyclohexane coming out of the top of the first-stage concentration tower T-0201 is used as a heat source of a reboiler E-0203 of the second-stage concentration tower, is cooled to 65 ℃, enters a first-stage concentration tower reflux tank V-0201, partially reflows to the top of the first-stage concentration tower T-0201 through a first-stage concentration tower reflux pump P-0201, and the rest cyclohexane returns to the oxidation reaction process.
The liquid phase at the bottom of the first-stage concentration tower T-0201 enters the middle part of the second-stage concentration tower T-0202. The operation pressure of the top of the second-stage concentration tower T-0202 is 0.012MPa, and the operation temperature is 71 ℃; the operation pressure at the bottom of the tower is 0.016MPa, and the operation temperature is 52 ℃. And condensing gas-phase cyclohexane on the top of the second-stage concentration tower T-0202 to 50 ℃ through a second-stage concentration tower condenser E-0205, then feeding the condensed gas-phase cyclohexane into a second-stage concentration tower reflux tank V-0202, partially refluxing the condensed gas-phase cyclohexane to the top of the second-stage concentration tower T-0202 through a second-stage concentration tower reflux pump P-0202, and returning the rest cyclohexane to the oxidation reaction process.
The concentration of the concentrated cyclohexyl hydrogen peroxide solution from the bottom of the second-stage concentration tower T-0202 is 10.5 wt%, and the cyclohexyl hydrogen peroxide solution is cooled to 40 ℃ by a cyclohexyl hydrogen peroxide concentrated solution cooler E-0207 and then sent to the decomposition reaction process by a second-stage concentration tower kettle pump P-0204.
Tail gas of a first-stage concentration tower reflux tank V-0201 is cooled to 42 ℃ through a first-stage concentration tower aftercooler E-0204, then condensate flows back to the first-stage concentration tower reflux tank V-0201, non-condensable gas and tail gas of a second-stage concentration tower reflux tank V-0202 are converged and sent to a tail gas condenser E-0206 of the concentration tower to be cooled to 10 ℃, then condensate flows back to a second-stage concentration tower reflux tank V-0202, and the non-condensable tail gas is sent to a concentration tower vacuum pump P-0203. Cyclohexane is used as sealing liquid for a concentration tower vacuum pump P-0203, tail gas of the vacuum pump enters a concentration tower sealing tank V-0203, tail gas in the tank is removed for tail gas treatment, an oil phase in the tank is removed for a secondary concentration tower reflux pump P-0202, and oily sewage is removed for sewage treatment.
The concentrated oxidizing solution from the oxidizing solution concentration step and 320kg/h of 20 wt% sodium hydroxide aqueous solution enter a decomposition reactor, and react under the action of the sodium hydroxide aqueous solution to generate cyclohexanone, cyclohexanol and water. The material after the decomposition reaction is a mixture of cyclohexanol and cyclohexanone containing alkali liquor, and enters an alkali liquor separator, and the alkali liquor is separated under the action of sedimentation and recycled to the decomposition reactor. And (3) feeding the material after alkali liquor separation into a cyclohexane recovery tower, controlling the operation pressure in the tower to be 0.011MPa, the operation temperature at the top of the tower to be 51 ℃, the operation temperature at the bottom of the tower to be 113 ℃, circulating the top fraction into cyclohexane and returning to the peroxidation process, and obtaining 16015g/h bottom fraction which is cyclohexanol and cyclohexanone.
Comparative example 1
As shown in FIGS. 1 to 2, the compressed air 7966Nm contains 211462kg/h cyclohexane and 21% oxygen mole fraction3The reaction temperature is controlled to be 165 ℃, the reaction pressure is 1.35MPa, the gas phase at the top of the reactor is discharged at 62548kg/h, the cyclohexyl hydrogen peroxide solution at the bottom is discharged at 160298kg/h, and the concentration of the cyclohexyl hydrogen peroxide, the cyclohexanone, the cyclohexanol and the cyclohexane in the liquid phase is respectively 3.50 wt%, 2.34 wt%, 2.80 wt% and 91.36 wt%. The conversion rate of cyclohexane oxidation reaction is very low.
If the cyclohexyl hydroperoxide solution is not concentrated, 160298kg/h enters the decomposition process;
if the cyclohexyl hydroperoxide solution is concentrated to 10.5 wt%, only about 53433kg/h enters the decomposition process, the concentrated and separated material is cyclohexane, about 106865kg/h of cyclohexane returns to the oxidation reaction process after being concentrated, and 73% of cyclohexane is reduced and enters the subsequent processes. The cyclohexyl hydrogen peroxide solution is concentrated to 10.5 wt%, the material entering the decomposition reaction is reduced by about 67%, the equipment volume of the subsequent process can be reduced by 67% under the condition of the same retention time of the material, and the energy consumption of a mechanical pump can be reduced by 67%, so that the equipment size is reduced, the arrangement space is reduced, and the investment cost of the subsequent process is reduced.
Claims (10)
1. A process for concentrating a hydrocarbyl peroxide, characterized by: the method comprises the following steps:
1) cooling the oxidizing liquid and recovering heat: cooling the oxidizing liquid from the peroxidation process to recover waste heat;
2) primary concentration: mixing the cooled oxidation liquid with an oxide stabilizer with the mass flow of 0.0001-0.08% of the oxidation liquid, carrying out a first-stage concentration tower, partially returning the first-stage concentration after the gas phase at the upper part of the first-stage concentration is cooled, and returning the residual liquid-phase hydrocarbon to the oxidation reaction process;
3) secondary concentration: the liquid phase after the first-stage concentration enters a second-stage concentration step, the gas-phase cyclohexane at the upper part of the second-stage concentration step is partially returned to the second-stage concentration step after condensation, the residual liquid-phase hydrocarbon returns to the peroxidation step, the discharge of the second-stage concentration liquid phase is the concentrated alkyl peroxide solution, and the next step is carried out;
4) a vacuum system: two-stage concentration is carried out in a vacuum system, condensate flows back to return to the first-stage concentration after cooling of first-stage concentration tail gas, non-condensable gas and second-stage concentration tail gas are converged and further cooled, the condensate returns to the second-stage concentration, the non-condensable tail gas is sent to a concentration tower vacuum system, the concentration vacuum system uses liquid-phase hydrocarbon as sealing liquid, the tail gas is treated by removing the tail gas, the sealing liquid is used for recycling an oil phase and is subjected to a deoxidation reaction process, and oily sewage is treated by removing the sewage.
2. The process for producing cyclohexanol and cyclohexanone according to claim 1, characterized in that: the material of the hydrocarbon-based peroxide is C4-C20 chain hydrocarbon or naphthenic hydrocarbon peroxide, and preferably: the material of the alkyl peroxide is cyclohexyl hydrogen peroxide concentration of cyclohexane oxidation liquid: preferably: the peroxide stabilizer is one or two of hydroxyethylidene diphosphonic acid tetrasodium or hydroxyethylidene diphosphonic acid disodium.
3. A system for carrying out the hydrocarbon based peroxide concentration process of claim 1, wherein: the system is as follows:
the oxidized liquid concentration system comprises a first-stage concentration tower (T-0201), an output pipeline of oxidized liquid in an oxidation reaction process is connected with the middle part of the first-stage concentration tower (T-0201), and the output end of the top of the first-stage concentration tower (T-0201) is connected with a first-stage concentration tower reflux tank (V-0201) through a second-stage concentration tower reboiler (E-0203);
the output end of the bottom of the first-stage concentration tower (T-0201) is connected with the middle part of the second-stage concentration tower (T-0202), the output end of the top of the second-stage concentration tower (T-0202) is connected with a reflux tank (V-0202) of the second-stage concentration tower through a condenser (E-0205) of the second-stage concentration tower, and the output end of the bottom of the second-stage concentration tower (T-0202) is connected with a decomposition reaction process through a cyclohexyl hydrogen peroxide concentrated solution cooler (E-0207);
the output end of the top of the second-stage concentration tower reflux tank (V-0202) is sequentially connected with a concentration tower vacuum pump (P-0203) and a concentration tower sealing liquid tank (V-0203) through a concentration tower tail gas condenser (E-0206), and the output end of the bottom of the concentration tower sealing liquid tank (V-0203) is connected with the bottom end of the second-stage concentration tower reflux tank (V-0202).
4. The system of claim 3, wherein: an output pipeline of the oxidation liquid in the oxidation reaction process is connected with the middle part of the first-stage concentration tower (T-0201) through an oxidation liquid degassing tank tail gas condenser.
5. The system of claim 3, wherein: one output end of the first-stage concentration tower reflux tank (V-0201) is connected with the upper part of the first-stage concentration tower (T-0201), and the other output end of the first-stage concentration tower reflux tank (V-0201) is connected with the output end of the second-stage concentration tower reflux tank (V-0202) through a first-stage concentration tower aftercooler (E-0204).
6. The system of claim 3, wherein: the lower part of the first-stage concentration tower (T-0201) is provided with a first-stage concentration tower reboiler (E-0202).
7. The system of claim 3, wherein: one output end at the bottom of the secondary concentration tower reflux tank (V-0202) is connected with the upper part of the secondary concentration tower (T-0202), and the other output end is connected with the oxidation reaction process.
8. A method of effecting hydrocarbon peroxide concentration using the system of claim 3, wherein: the method comprises the following steps:
the oxidation liquid from the oxidation reaction process enters an oxidation liquid cooler for cooling, then is mixed with a very small amount of peroxide stabilizer and enters the middle part of a first-stage concentration tower. The lower part of the first-stage concentration tower is provided with a reboiler. And the gas-phase cyclohexane from the top of the first-stage concentration tower is used as a heat source of a reboiler of the second-stage concentration tower, is cooled and then enters a reflux tank of the first-stage concentration tower, part of the gas-phase cyclohexane flows back to the top of the first-stage concentration tower through a reflux pump of the first-stage concentration tower, and the rest cyclohexane returns to the oxidation reaction process.
The liquid phase at the bottom of the first-stage concentration tower enters the middle part of the second-stage concentration tower. And condensing gas-phase cyclohexane at the top of the secondary concentrating tower by a secondary concentrating tower condenser, then feeding the condensed gas-phase cyclohexane into a secondary concentrating tower reflux tank, partially refluxing the condensed gas-phase cyclohexane to the top of the secondary concentrating tower by a secondary concentrating tower reflux pump, and returning the rest cyclohexane to the oxidation reaction process. And the concentrated cyclohexyl hydrogen peroxide liquid from the bottom of the secondary concentration tower is cooled by a cyclohexyl hydrogen peroxide concentrated liquid cooler and then is pumped to the decomposition reaction process by a tower kettle of the secondary concentration tower.
Tail gas of a first-stage concentration tower reflux tank is cooled by a first-stage concentration tower after passing through a first-stage concentration tower aftercooler, condensate flows back to the first-stage concentration tower reflux tank, non-condensable gas and tail gas of a second-stage concentration tower reflux tank are converged and sent to a tail gas condenser of a concentration tower for cooling, the condensate flows back to a second-stage concentration tower reflux tank, and the non-condensable tail gas is sent to a vacuum pump of the concentration tower.
Cyclohexane is used as sealing liquid for a vacuum pump of the concentration tower, tail gas of the vacuum pump is delivered to a sealed tank of the concentration tower, tail gas in the tank is treated by removing the tail gas, an oil phase in the tank is treated by a reflux pump of a second-level concentration tower, and oily sewage is treated by removing sewage.
9. The method of claim 8, wherein: the operation pressure of the first-stage concentration tower at the top of the tower is 0.03-0.05 MPa, the operation temperature of the top of the tower is 70-80 ℃, the operation pressure of the bottom of the tower is 0.04-0.05 MPa, and the operation temperature of the top of the tower is 90-100 ℃.
10. The method of claim 8, wherein: the tower top operating pressure of the secondary concentration tower is 0.01-0.02 MPa, and the operating temperature is 68-73 ℃; the operation pressure at the bottom of the tower is 0.01-0.02 MPa, and the operation temperature is 48-54 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011051238.9A CN112250610A (en) | 2020-09-29 | 2020-09-29 | Method and system for concentrating alkyl peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011051238.9A CN112250610A (en) | 2020-09-29 | 2020-09-29 | Method and system for concentrating alkyl peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112250610A true CN112250610A (en) | 2021-01-22 |
Family
ID=74233914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011051238.9A Pending CN112250610A (en) | 2020-09-29 | 2020-09-29 | Method and system for concentrating alkyl peroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250610A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN203763884U (en) * | 2014-04-21 | 2014-08-13 | 太仓塑料助剂厂有限公司 | Secondary distillation and concentration device of cumyl hydroperoxide |
| CN107488099A (en) * | 2017-08-10 | 2017-12-19 | 中石化南京工程有限公司 | A kind of method for producing expoxy propane and cyclohexanol |
| CN111606834A (en) * | 2020-05-21 | 2020-09-01 | 常州瑞华化工工程技术股份有限公司 | Concentration method of ethylbenzene hydroperoxide |
-
2020
- 2020-09-29 CN CN202011051238.9A patent/CN112250610A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627541A (en) * | 2012-03-28 | 2012-08-08 | 肖藻生 | Technology for preparing hexanaphthene and cyclohexanone through cyclohexane oxidation and device thereof |
| CN203763884U (en) * | 2014-04-21 | 2014-08-13 | 太仓塑料助剂厂有限公司 | Secondary distillation and concentration device of cumyl hydroperoxide |
| CN107488099A (en) * | 2017-08-10 | 2017-12-19 | 中石化南京工程有限公司 | A kind of method for producing expoxy propane and cyclohexanol |
| CN111606834A (en) * | 2020-05-21 | 2020-09-01 | 常州瑞华化工工程技术股份有限公司 | Concentration method of ethylbenzene hydroperoxide |
Non-Patent Citations (3)
| Title |
|---|
| 候慧珠 等主编: "《过程控制技术》", 31 December 2012 * |
| 熊楚安 等: "《化工原理实训教程》", 31 July 2008 * |
| 赵海红: "《化学工程与工艺专业实验》", 28 February 2017 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106588536B (en) | Preparation method and system of cyclohexanone | |
| CN111302899B (en) | Ammonia and tertiary butanol recovery device and method in cyclohexanone ammoximation production process | |
| CN102256939B (en) | Multistage cumene oxidation | |
| CN107879998B (en) | Sectional type epoxypropane preparation method | |
| CN206232628U (en) | A kind of production system of cyclohexanone | |
| CN210084997U (en) | Device for recycling cyclohexanone ammoximation device wastewater | |
| CN105293606A (en) | Recovery system and recovery method of oily waste liquor in cyclohexanol production process | |
| CN112745208A (en) | Cyclohexanone recovery and separation process and system | |
| CN107987037B (en) | Method for preparing epoxypropane in unit mode | |
| CN112250610A (en) | Method and system for concentrating alkyl peroxide | |
| CN109195934A (en) | The method for preparing butadiene | |
| CN112142566B (en) | Method for producing cyclohexanol and cyclohexanone | |
| CN113559540A (en) | Stripping method and stripping device for ethylene oxide | |
| CN107488099B (en) | A method of producing propylene oxide and cyclohexanol | |
| CN112010728A (en) | Alkali washing and water washing method | |
| CN211733856U (en) | Oxidation tower for preparing hydrogen peroxide by anthraquinone process | |
| CN212102637U (en) | Ammonia and tert-butyl alcohol recovery device in cyclohexanone ammoximation production process | |
| CN108033868B (en) | System and method for separating and recovering propylene in process of producing epoxypropane by HPPO method | |
| CN112174790A (en) | Reinforcing system and process for producing cyclohexanone by cyclohexane oxidation method | |
| CN217409757U (en) | Cumene hydroperoxide concentrating device | |
| CN216972384U (en) | Device for recovering and purifying propylene in propylene oxide production process | |
| CN111608910B (en) | Application and system of Roots liquid ring vacuum pump unit in ammoximation process production | |
| RU2661867C2 (en) | Continuous process for the production of purified cyclohexanone | |
| CN214763389U (en) | Rectification energy-saving device in cyclohexanone oxime production process by cyclohexanone ammoximation method | |
| CN117427688A (en) | Catalyst system for producing trimellitic anhydride and continuous process |
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: 20210122 |
|
| RJ01 | Rejection of invention patent application after publication |