CN105669367B - A kind of method for improving cumyl hydroperoxide decomposition yield - Google Patents
A kind of method for improving cumyl hydroperoxide decomposition yield Download PDFInfo
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- CN105669367B CN105669367B CN201610135698.7A CN201610135698A CN105669367B CN 105669367 B CN105669367 B CN 105669367B CN 201610135698 A CN201610135698 A CN 201610135698A CN 105669367 B CN105669367 B CN 105669367B
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Abstract
The present invention relates to a kind of method for improving phenol-acetone device cumyl hydroperoxide decomposition yield, (1) is recycled back to decomposer after level of decomposition liquid is cooled down by special distributor；(2) concentrated sulfuric acid catalyst adds from two differences and decomposes fluid circulation；(3) concentration of sulfuric acid in decomposer is reduced；(4) decomposed solution residence time, reduction decomposer reaction temperature in decomposer are improved；(5) residence time of the decomposed solution in two grades of decomposers is improved；(6) two grades of decomposition reaction temperatures are improved；(7) crude acetone column that material flash distillation recovers energy and all or part of flash distillation condensate circulation time decomposer, remainder are sent to phenol-acetone device downstream is decomposited by two grades；(8) decomposed device steam condensate is sent to the smart acetone tower or charging feed well in phenol-acetone device downstream.Present invention mainly solves the problems such as decomposition yield in existing phenol-acetone production technology is relatively low, tar accessory substance is more, rectifying charging saliferous is higher.
Description
Technical field
It is that a kind of cumyl hydroperoxide that improves is decomposed specifically the present invention relates to phenol-acetone production technical field
The method of yield.
Background technology
Phenol and acetone are all the Organic chemical products having many uses.Common production method is, the use of isopropylbenzene is original
Material, cumyl hydroperoxide is generated by the air oxidation of isopropylbenzene, and (common concentration is for cumyl hydroperoxide after concentration
Containing cumyl hydroperoxide 82% or so) decomposed under concentrated sulfuric acid catalyst catalysis and obtain benzene simultaneously after a series of purifications
Two kinds of products of phenol and acetone.Cumyl hydroperoxide, which decomposes also to have, uses solid acid as catalyst.Cumyl hydroperoxide
Decomposition be strong exothermal reaction, decomposable process can produce many kinds of accessory substances, and these accessory substances can influence the yield i.e. original decomposed
Expect the consumption of isopropylbenzene, can also influence the quality of phenol and product acetone.Generally by controlling relatively low reaction temperature, it is certain
Residence time of sulfuric acid concentration, certain water content and decomposition etc. obtains higher yield.
United States Patent (USP) US5245090 (U.S. Aristech Chemical Corporation) describes one kind and not followed
The cumyl hydroperoxide decomposition method that cyclopropanone, analytical product are largely circulated, it uses sulfuric acid as catalyst, level of decomposition
Reaction is carried out in higher temperature (77~88 DEG C), two grades of decomposition reactions at relatively low temperature (66~121 DEG C), by improving
Level of decomposition temperature, reduction by two grades of decomposition temperatures come improve cumyl hydroperoxide decomposition yield.The theory of this and the present invention
Contrast.
United States Patent (USP) US5998677 (Mitsui oiling company) describes a kind of in first-stage reactor (decomposer) discharging
It is middle to add more acetone (the product acetone produced from purification process) and with relatively low (120 DEG C) the second fractions of completion of temperature
The method of solution, the yield of decomposable process is improved by improving the energy consumption (acetone recycle) of phenol-acetone purification process.
Chinese patent CN102186799A (Sha Bai radical innovations company), which is described, a kind of uses hydroxy benzene sulfonic acid as urging
Agent, and add the cumyl hydroperoxide decomposition method of ammoniacal liquor.
Chinese patent CN101343212 (petrochina) describes the cumyl hydroperoxide point that a kind of solid acid is catalyst
Solution method.
At present, domestic and international phenol-acetone device mainly uses two kinds of cumyl hydroperoxide decomposition technique.One
Class technology is that acetone is evaporated in vacuo shifting heat, two-step method concentrated sulfuric acid catalyst decomposition technique, and the first step is cumyl hydroperoxide point
It is that 300~500ppm, operation temperature are 75~88 DEG C that solution preocess, acetone evaporated, which remove reaction heat, sulfuric acid concentration, and second step is pair
Decomposition product process, use 110~122 DEG C of tubular reactor, operation temperature.Another kind of technology is that a large amount of outer circulations of decomposed solution are moved
Heat, two-step method concentrated sulfuric acid catalyst decomposition technique, the first step is cumyl hydroperoxide decomposable process, reaction is removed in outer circulation
Heat, recycle ratio are that 25~100: 1, sulfuric acid concentration is that 30~60ppm, operation temperature are 40~70 DEG C, and second step is accessory substance point
Solution preocess, use 115~125 DEG C of tubular reactor, operation temperature.It is all reliable on various technical securities, but raw material isopropyl
The universal higher, tar growing amount of the consumption of benzene is higher, and the consumption of isopropylbenzene is above the numerical value that each technical patent business advocates.And
Evaporation is moved in pyrolysis technique, because content of acetone is higher in decomposed solution, is not easy phenol-acetone device downstream neutralization step
Desalination simultaneously causes the serious fouling of distillation system.
In addition, using solid acid as the technology of cumyl hydroperoxide decomposition catalyst, its decomposable process can be generated more
Many tar, isopropylbenzene consumption is higher.This technology is not used at present.
It is too high that the present invention consumes acetone in higher and decomposed solution for raw material isopropylbenzene in existing evaporation shifting pyrolysis technique
The problem of, reduced by series of process corrective measure raw material isopropylbenzene consumption, reduction resolving cell discharging in acetone
Content.
The content of the invention
Cumyl hydroperoxide decomposition yield is improved it is an object of the invention to overcome the deficiencies of the prior art and provide one kind
Method.
The problem of existing for existing phenol-acetone device resolving cell, it is of the invention by the technique by improving decomposing system
Flow and operating condition consume acetone in high and decomposed solution to solve resolving cell raw material isopropylbenzene in existing phenol-acetone device
The problem of content is high, including increase decomposer recirculation cooler, determine new operation splitting condition, increase decomposed solution discharging flash distillation
System etc..
The purpose of the present invention is achieved through the following technical solutions：
A kind of method for improving cumyl hydroperoxide decomposition yield, it is concretely comprised the following steps：
A) the decomposition evaporation condensate liquid of the dense cumyl hydroperoxide of phenol-acetone device oxidation operation production first with circulation
Enter decomposer from the top of decomposer after mixing, cumyl hydroperoxide is decomposed into decomposer under the catalysis through persulfuric acid
Phenol and product acetone, and generate accessory substance；By controlling decomposer in appropriate sulfuric acid concentration, appropriate temperature, appropriate
Pressure, appropriate water content and operated under the appropriate residence time and obtain desired decomposition yield；
Mass fraction of the dense cumyl hydroperoxide containing cumyl hydroperoxide is 75~85%；
Accessory substance includes cumyl peroxide, tar etc.；
It is the concentrated sulfuric acid that cumyl hydroperoxide, which decomposes the catalyst used, and sulfuric acid concentration is 90~98%.Sulfuric acid at least from
Two points are added in the Decomposition Cycle system；Two points of prioritizing selection, the ratio that two points add sulfuric acid amount is 0.1~6.2: 1；
One addition point is the entrance of calorimeter；Another addition point is the outlet of decomposer recirculation cooler；
Sulfuric acid concentration in decomposer is 30~500ppmwt.Preferably 70~280ppmwt.
The operating pressure of decomposer is 360~560mmhg, and the operation temperature of decomposer is 50~86 DEG C.
Residence time of material is 3~10 minutes in decomposer.
The content that a certain amount of water adds water in decomposer, decomposer is 0.3~3%.
Acetone need not be added in decomposable process.Its feature is：To decomposition in itself, the generation of hydroxypropanone- is advantageously reduced
Amount.For Pyrogentisinic Acid's acetone device, be conducive to improving the production capacity of device, reduce the energy consumption of acetone separation.
B) the kettle liquid discharging of decomposer is divided into three strands, and first strand of material enters two grades of decomposers, and second strand of material passes through
Cool down Posterior circle and return decomposer, and mixed by distributor with decomposed solution, the 3rd strand of material merges by calorimeter with second strand
It is recycled back to decomposer；
Concentrated sulfuric acid catalyst is separately added into above-mentioned second strand and the 3rd strand of decomposed solution recycle stock；
The control of two circulation loops is the key for decomposing control；
Second stock solution liquid phase is 0.1~3: 1 for the recycle ratio for decomposing first burst of decomposed solution
Decomposed solution is 10~48 DEG C by recirculation cooler cooling extent.
Material enters the inside distributor set in decomposer, and distributor pattern is calandria or annular tube type, distributor
The material that material should be used than decomposer is more resistant to corrosion.
Distributor need to be arranged under decomposer liquid levels, and distributor is provided with the garden hole sprayed downwards, and the quantity in hole is 3
~12, jet velocity is 3~12 meter per seconds.
The characteristics of this step：The special decomposed solution circulation cooling circuit of increase, into decomposer sulfuric acid concentration it is lower, two
Point acid adding, first two eliminate in decomposer due to sulfuric acid local concentration is too high and producing more tar, latter makes decomposition
System is safer (for cumyl hydroperoxide decomposition, in order to ensure safety, it is necessary to make in system always with the presence of sulfuric acid.Make
Added with two points, even if making one point failure of system, another point can continue to add).In the prior art, sulfuric acid passes through
One point of calorimeter is added, and distributor is on liquid level, and sparger outlets sulfuric acid concentration is higher, and tar growing amount is more, Er Qieyou
Safety worries.
C) decomposer evaporated vapor sequentially passes through recirculated water and freezing water condenser condensation, and a condensate liquid part is recycled back to point
Device is solved, remainder send the smart acetone tower or rectifying feed well of phenol-acetone device；
As decomposing, downstream fine acetone tower is delivered in discharging to a part for decomposer evaporated vapor condensate liquid or rectifying is fed
Groove, the ratio that this strand of material accounts for main condenser liquid is 0~30%.
D) the Main By product peroxidating two during the kettle liquid material of decomposer discharges decomposer in two grades of decomposers is different
Propyl benzene (abbreviation DCP) is decomposed into phenol, acetone and α-methylstyrene (abbreviation AMS), while the dimethyl benzyl alcohol in decomposed solution
Suitable sulfuric acid concentration in (abbreviation DMPC) also dehydration generation α-methylstyrene, two grades of decomposers of control, suitable temperature and
The suitable residence time obtains desired reaction yield.
75~285ppm of sulfuric acid concentration in decomposing system, 80~160ppm of prioritizing selection；
Two grades of decomposers are plug flow reactor, and operation temperature is 110~166 DEG C, operating pressure is 0.46~
0.86Mpag。
Residence time of material is 0.5~6 minute in two grades of decomposers.
Two grades of decomposers are by external heating medium such as low pressure water vapor or heat-conducting oil heating；
Relative to prior art, decompose more complete, AMS yield is higher
E) the discharging feeding vacuum insulation flash tank of two grades of decomposers, utilizes the calorific value flash vaporization of two grades of decomposer dischargings
Acetone, isopropylbenzene etc., flash-off steam return to decomposer by cooling water condensation and freezing water condensation rear portion condensate liquid,
Remainder condensate liquid is sent to the rectifying feed well or crude acetone column of phenol-acetone device, the kettle liquid of vacuum insulation flash tank by
Resolving cell discharging is pumped into phenol-acetone device neutralisation unit, by the operation temperature and pressure that control vacuum insulation flash tank
To adjust the flash distillation rate of flash tank；
Vacuum insulation flash tank be vertical adiabatic flash separator, operation temperature be 70~96 DEG C, operating pressure be 350~
660mmhg。
A part for flash-off steam condensate liquid delivers to downstream crude acetone column or rectifying feed well, this stock as discharging is decomposed
The ratio that material accounts for total condensing liquid quantity is 0~100%.
Decomposed solution flash distillation rate is 8~36% in flash tank, for inlet amount.
Reclaim the heat of discharging, it is not necessary to acetone recycle (come from downstream), decompose that content of acetone in discharging is low, rectifying charging
Salt content is low.
Prioritizing selection in above-mentioned technical proposal：
It is the concentrated sulfuric acid that cumyl hydroperoxide, which decomposes the catalyst used, and the concentrated sulfuric acid at least adds the decomposition from two points and followed
In loop system.Two points of prioritizing selection, the ratio (ratio of the amount of logistics 12 and the amount of logistics 13) that two points add sulfuric acid amount is 0.1
~6.2, prioritizing selection 0.2~3.6.
Sulfuric acid concentration is 70~285ppmwt, prioritizing selection 80-160ppmwt in decomposing system.
Decomposer operating pressure is 360~560mmhg, 380~480mmhg of prioritizing selection.
Decomposer operation temperature is 50~86 DEG C, 60~72 DEG C of prioritizing selection.
It is 10~300%, prioritizing selection 38~120% that the material of decomposer, which is recycled back to, relative to the recycle ratio of main discharging.
Recirculation cooler cooling extent is 10~48 DEG C, 26~38 DEG C of prioritizing selection.
Recycle stock, which enters in decomposer, sets internal distributor, and distributor is calandria or annular tube type, is distributed equipment
The material that matter should be used than decomposer is more resistant to corrosion such as Hastelloy.The distributor need to be arranged in decomposer liquid levels it
Under, the garden hole of lower injection is opened on distributor pipe, the quantity in hole is 3-12, and prioritizing selection 4~8, jet velocity is 3~12
Meter per second, the meter per second of prioritizing selection 5~8.
A certain amount of process water adds decomposer, and the content of decomposing system water is 0.3~3%, and prioritizing selection 0.8~
1.6%.
Decomposer evaporated vapor condensate liquid a part of acetone discharging as decompose discharging deliver to downstream fine acetone tower or
Rectifying feed well, the ratio that this strand of material accounts for the main condenser liquid is 0~30%, prioritizing selection 10~20%.
Two grades of decomposers are plug flow reactor, 110~166 DEG C of operation temperature, 120~148 DEG C of prioritizing selection, behaviour
Make 0.46~0.86Mpag of pressure, 0.56~0.76Mpag of prioritizing selection.
Decomposed solution flash tank is the vertical adiabatic flash separator with demister, 70~96 DEG C of operation temperature, prioritizing selection
76~90 DEG C, 350~660mmhg of operating pressure, 380~500mmhg of prioritizing selection.
Flash-off steam condensate liquid it is some or all as decompose discharging deliver to downstream rectifying feed well or thick third
Ketone tower, the ratio that this strand of material accounts for total condensate liquid is 0~100%, prioritizing selection 45~75%.
Decomposed solution flash distillation rate (relative to charging) is 8~36%, prioritizing selection 10~25% in flash tank.
Residence time of material is 3~10 minutes, prioritizing selection 4~8 minutes in decomposer.
Residence time of material is 0.5~6 minute, prioritizing selection 1~2.5 minute in two grades of decomposers.
Compared with prior art, the positive effect of the present invention is：
The present invention has carried out further improvement on the basis of test data, forms new technology.The present invention is in reduction
While phenol-acetone device isopropylbenzene is consumed, the consumption of sulfuric acid catalyst is also reduced, the energy consumption of device is reduced, improves
The driving rate (parking for reducing distillation system) of device.
Problem solved by the invention be in phenol-acetone device cumyl hydroperoxide resolving cell consumption of raw materials it is high and
The problem of salt content is high in decomposed solution, invention is by improving the new operating condition of existing decomposition process, design, increase decomposed solution
Facility etc. is flashed, to reduce the growing amount of tar in decomposable process, the consumption of raw material isopropylbenzene is reduced, reduction catalyst sulfuric acid
Consumption, and removed by reducing the content of acetone in decomposed solution, the discharging of decomposition is more beneficial for follow-up neutralize of phenol-acetone device
The completion of acid and desalting process, also avoids subsequent cell from returning acetone recycle and decomposes and reduce its load and (improve device efficiency
With the consumption of reduction public work), the driving rate of phenol-acetone device is improved, manufacturing cost is reduced.
The main difference of the present invention and prior art：The lower sulfuric acid concentration of decomposing system (generation of reduction tar), point
Device lower temperature (generation of reduction tar) is solved, increases decomposed solution circulating cooling (dilute sulphuric acid, the reduction (relative to prior art)
Decomposer temperature, the generation of reduction tar), sparger outlets part sulfuric acid concentration is lower (generation of reduction tar), decomposer steam
Condensate liquid part is sent out as analytical product and (can be used for the acetone for producing low methanol content), and two grades are decomposed higher temperature
(cumyl peroxide, dimethyl benzyl alcohol decompose more complete), increase decomposed solution flash system (reclaims heat, eliminates acetone production
Product circulation, reduction rectifying charging salt content).
Brief description of the drawings：
Fig. 1 cumyl hydroperoxide decomposition technique flow charts are shown in.
Mark in accompanying drawing for：
R-1 is decomposer, and R-2 is two grades of decomposers, and P-1 is decomposer discharging pump, and P-2 is resolving cell discharging pump, E-1
For Decomposition Cycle cooler, E-2 is decomposes steam condenser, and E-3 is decomposed tail gas condenser, and E-4 is flash-off steam condenser,
E-5 is exhaust gas of flash evaporation condenser, and M-1 is calorimeter, and V-1 is flash tank.
1 is dense cumyl hydroperoxide solution, and 2 be process adjustments water, and 3 be acetone discharging, and 4 be reflux acetone, and 5 be not coagulate
Property tail gas, 6 be chilled water, and logistics 7 is recirculated water, is discharged based on 8, and 9 be main recycle stock, and 10 be low discharge material, and 11 is follow
Ring cooling water, 12 be sulfuric acid I, and 13 be sulfuric acid II, and 14 be flash distillation refluxer, and 15 be not coagulate for flash distillation discharging condensate liquid, 16
Property gas, 17 be the second chilled water, 18 be recirculated cooling water, 19 be steam or conduction oil, 20 be decomposed solution, and 21 be resolving cell
Discharging.
Embodiment
A kind of embodiment for the method for improving cumyl hydroperoxide decomposition yield of the present invention presented below.
Accompanying drawing and explanation：Cumyl hydroperoxide decomposition technique flow chart is shown in accompanying drawing 1.Procedure declaration：
In phenol-acetone device, technique productions are raw material using isopropylbenzene, while producing two kinds of products of phenol and acetone.It is different
Propyl benzene first pass through oxidation generation cumyl hydroperoxide, cumyl hydroperoxide be decomposed under sulfuric acid catalysis phenol, acetone and
Other accessory substances, decomposed solution obtains phenol and third by neutralizing a series of purification process such as deacidification desalination, rectifying, catalytic treatment
Ketone.
Raw material isopropylbenzene generates cumyl hydroperoxide first in oxidation unit by the dioxygen oxidation in air, aoxidizes out
The concentration of cumyl hydroperoxide is generally 20~36% in material (being referred to as oxidation solution), and (pressure is generally pressure oxidation
It is that (pressure is generally nearly atmospheric pressure oxidation containing cumyl hydroperoxide 20~26% that 0.3Mpag) oxidation solution concentration is relatively low in technique
0.03Mpag) oxidation solution concentration is more a height of in technique contains cumyl hydroperoxide 28~36%.Oxidation solution is entering resolving cell
The preceding concentration that cumyl hydroperoxide is improved by being concentrated in vacuo, the concentration of dense oxidation solution is generally 78~85%.
Dense cumyl hydroperoxide solution 1 is entered in decomposer after being mixed with reflux acetone 4 by decomposer R-1 tops, by
The decomposer for being pumped into resolving cell of oxidation unit；The vacuum system condensed water that rectification cell is reclaimed is used as process adjustments water 2
Decomposer is pumped into by rectification cell, the composition of regulation water is aqueous 98.71%, acetone 1.06%, phenol 0.23%；Concentration is
98% concentrated sulfuric acid is divided to two strands (being specially sulfuric acid I12 and sulfuric acid II13) to send into decomposer circulation pipe by decomposer discharging pump P-1
It is interior；
Cumyl hydroperoxide be decomposed into decomposer under sulfuric acid catalysis phenol, acetone, cumyl peroxide and
Other byproducts.Cumyl hydroperoxide is decomposed into Fast exothermic reaction, evaporation and decomposed solution circulation of the reaction heat by acetone
Cooler E-1 is removed.Acetone of decomposer evaporation etc. comes out at the top of decomposer, and sequentially passing through recirculated water 7, (temperature is generally 30
DEG C) decomposed solution steam condenser E-2 and (temperature is generally 0 DEG C) the decomposed tail gas condenser of chilled water 6 E-3 condensation, incoagulability tail
Gas 5 goes vacuum system, and the most reflux acetone of condensate liquid is recycled back to decomposer, and small part acetone discharging 3 is used as decomposition discharging
One of be sent to the smart acetone tower or rectifying feed well in device downstream.
The liquid discharging of decomposer is divided into three strands by pumping out.First burst of discharging is main recycle stock 9, through supercooling
After the cooling of water 11 (temperature is generally 30 DEG C) cooler decomposer is recycled back to together with after main sulfuric acid II mixing.Second strand goes out
Expect for low discharge material logistics 10, major cycle logistics is incorporated to after calorimeter is mixed with sulfuric acid I, passed in and out by measuring calorimeter
The temperature change of material controls the degree of decomposition to observe.8 are discharged based on 3rd burst of discharging, first pass around two grades of the heating of steam 19
The byproduct cumyl peroxide of decomposable process is decomposed into phenol, acetone and α-methylstyrene by decomposer, and oxidation is produced
Byproduct dimethyl benzyl alcohol be dehydrated in two grades of decomposers generation α-methylstyrene.
The decomposed solution 20 of two grades of decomposers is sent directly into flash tank V-1, flash vaporization a part of acetone therein and isopropyl
The components such as benzene.The steam flashed off sequentially passes through recirculated water 18 (temperature is generally 30 DEG C) flash-off steam condenser E-4 and second
(temperature is generally 0 DEG C) the exhaust gas of flash evaporation condenser of chilled water 17 E-5 is condensed, and incoagulability tail gas 16 goes vacuum system, flash distillation backflow
The part of condensate liquid 14 is recycled back to decomposer, and another part flash distillation discharging condensate liquid 15 is sent under device as one of discharging is decomposed
The rectifying feed well or crude acetone column of trip.The decomposition discharging 21 of flash tank is sent to device downstream by resolving cell discharging pump P-2
Neutralisation unit.
Embodiment 1
The dense cumyl hydroperoxide solution that phenol-acetone device oxidation unit comes contains cumyl hydroperoxide
81.92%th, isopropylbenzene 14.33%, dimethyl benzyl alcohol 3.36%, acetophenone 0.39%, decomposition list is pumped into by oxidation unit
The decomposer R-1 of member；The vacuum system condensed water that rectification cell is reclaimed is pumped into decomposition as process adjustments water by rectification cell
Device, the composition of process adjustments water is aqueous 98.71%, acetone 1.06%, phenol 0.23%；Concentration is divided to two for 98% concentrated sulfuric acid
Stock ((being specially sulfuric acid II13 and sulfuric acid I12)) is sent into decomposer circulation pipe by decomposer discharging pump pump P-1；Hydrogen peroxide is different
Propyl benzene issues solution exothermic reaction estranged in sulfuric acid catalyst, and decomposer temperature is 62 DEG C, pressure is 426mmhg, and sulfuric acid concentration is
100ppm, it is 1% to decompose water content, and heat of reaction makes a large amount of acetone and a small amount of isopropylbenzene, α-methylstyrene in decomposer
Deng evaporation, this strand of steam condensate liquid after condenser is condensed largely is recycled back to decomposer, and acetone discharging is used as resolving cell
One product pass out to the smart acetone tower or rectifying feed well of phenol-acetone device, the ratio that acetone discharging accounts for total condensate liquid is
1: 10, incoagulability tail gas 5 send vacuum system；Decomposer kettle liquid is by pumping out, a part (circulation major cycle material and low discharge thing
Material), another part send into two grades of decomposers, the ratio of cyclic part logistics and cleared-out material is 0.76: 1；Two grades of decomposers are used
1.0Mpag low-pressure steams are heated, in two grades of decomposers temperature be 136 DEG C, pressure be 0.72Mpag；Two grades of decomposer dischargings enter
Flash tank flash separation, flash-off steam goes decomposer, another part to remove downstream phenol-acetone dress by condensed in two stages rear portion
The rectifying feed well or crude acetone column put, the ratio of flash distillation discharging condensate liquid and flash distillation refluxer is 0.5: 1, flash distillation
Bath temperature degree is 86 DEG C, pressure is 450mmhg, and flash tank kettle liquid is discharged by resolving cell is pumped into the neutralization list of phenol-acetone device
Member.
Each logistics composition (mass fraction) table of 1 embodiment of table 1
In table, code name CHP represents cumyl hydroperoxide, and code name AMS represents α-methylstyrene, and code name DMPC represents two
Xylyl alcohol, code name DCP represents cumyl peroxide.
Embodiment 2
In embodiment 1, for the device in 200,000 tons of phenol-acetone/years of production capacity, the ratio of two strands of sulfuric acid is 10: 1
(being specially sulfuric acid II13 and sulfuric acid I12), recirculation cooler outlet temperature is 52 DEG C, into the flow of calorimeter) it is 1.6m3/
H, calorimeter sulphuric acid is 1kg/h, and decomposer interior circulation distributor uses calandria, and nozzle inside diameter is 6mm, hole number
For 6.
Save 2529 tons/year of isopropyl benzene raw materials, 91 tons/year of sulfuric acid (concentration 98%) raw material, caustic soda (concentration 32%) raw material
229 tons/year, 656110 tons/year of recirculated water, 3568 tons/year of steam.
Embodiment 3
In embodiment 1, for the device in 350,000 tons of phenol-acetone/years of production capacity, the ratio of two strands of sulfuric acid is 16: 1
((being specially sulfuric acid II13 and sulfuric acid I12)), recirculation cooler outlet temperature is 56 DEG C, and calorimeter flow is 2.6m3/ h, calorimetric
Device sulphuric acid is 1.7kg/h, and decomposer interior circulation distributor uses calandria, and nozzle inside diameter is 7mm, and hole number is 8
It is individual.
Save 4492 tons/year of isopropyl benzene raw materials, 158 tons/year of sulfuric acid (concentration 98%) raw material, caustic soda (concentration 32%) raw material
406 tons/year, 1173170 tons/year of recirculated water, 6331 tons/year of steam.
Embodiment 4
Existing resolving cell is improved, and decomposes steam condensate and flash-off steam condensate liquid not as product discharge, i.e., third
Ketone discharging 3 is zero with the flash distillation discharging flow of condensate liquid 15.
The dense cumyl hydroperoxide solution that phenol-acetone device oxidation unit comes contains cumyl hydroperoxide
81.92%th, isopropylbenzene 14.33%, dimethyl benzyl alcohol 3.36%, acetophenone 0.39%, decomposition list is pumped into by oxidation unit
The decomposer of member；The vacuum system condensed water that rectification cell is reclaimed is pumped into decomposer as process adjustments water by rectification cell,
The composition of process adjustments water is aqueous 98.71%, acetone 1.06%, phenol 0.23%；Concentration is divided to two strands of (tools for 98% sulfuric acid
Body is sulfuric acid I12 and sulfuric acid II13) by being pumped into decomposer circulation pipe；Cumyl hydroperoxide occurs under sulfuric acid catalyst
Decomposition caused heat release reacts, and decomposer temperature is 65 DEG C, pressure is 460mmhg, and sulfuric acid concentration is 100ppm, and it is 1% to decompose water content,
Heat of reaction evaporates a large amount of acetone and a small amount of isopropylbenzene, α-methylstyrene in decomposer etc., and this strand of steam is by condensation
All divide after device condensation and be recycled back to decomposer, incoagulability tail gas send vacuum system；Decomposer kettle liquid is sent out by pump P-1, a part
Circulation (circulation major cycle material and low discharge material), another part send into two grades of decomposer R-2, cyclic part logistics and cleared-out
The ratio of material is 0.68: 1；Two grades of decomposers are heated using 1.0Mpag low-pressure steams, and temperature is 128 DEG C, pressure in two grades of decomposers
Power is 0.72Mpag；Two grades of decomposer dischargings 20 enter flash tank flash separation, and steam is all recycled back to after condensed in two stages
Decomposer, flash tank temperature is 83 DEG C, pressure is 430mmhg, and flash tank kettle liquid is pumped into phenol-acetone by resolving cell discharging
The neutralisation unit of device.
Each logistics composition (mass fraction) table of 2 embodiment of table 4
In table, code name CHP represents cumyl hydroperoxide, and code name AMS represents α-methylstyrene, and code name DMPC represents two
Xylyl alcohol, code name DCP represents cumyl peroxide.
Embodiment 5
In embodiment 4, for the device in 200,000 tons of phenol-acetone/years of production capacity, the ratio of two strands of sulfuric acid is 10: 1
(being specially sulfuric acid II13 and sulfuric acid I12), recirculation cooler outlet temperature is 56 DEG C, and calorimeter flow is 2.6m3/ h, calorimeter
Sulphuric acid is 1.6kg/h, and decomposer interior circulation distributor uses calandria, and nozzle inside diameter is 6mm, and hole number is 8.
Save 2480 tons/year of isopropyl benzene raw materials, 91 tons/year of sulfuric acid (concentration 98%) raw material, caustic soda (concentration 32%) raw material
229 tons/year, 637000 tons/year of recirculated water, 3464 tons/year of steam.
Embodiment 6
In embodiment 4, for the device in 350,000 tons of phenol-acetone/years of production capacity, the ratio of two strands of sulfuric acid is 16: 1
(being specially sulfuric acid II13 and sulfuric acid I12), recirculation cooler outlet temperature is 59 DEG C, and calorimeter flow is 4.5m3/ h, calorimeter
Sulphuric acid is 2.6kg/h, and decomposer interior circulation distributor uses calandria, and nozzle inside diameter is 7mm, and hole number is 10
It is individual.
Save 4400 tons/year of isopropyl benzene raw materials, 158 tons/year of sulfuric acid (concentration 98%) raw material, caustic soda (concentration 32%) 406
Ton/year, 1139220 tons/year of recirculated water, 6146 tons/year of steam.
Embodiment 7
Decomposer steam condensate is sent out not as resolving cell product, and flash tank steam condensate is all single as decomposing
First product is sent out.
The dense cumyl hydroperoxide solution that phenol-acetone device oxidation unit comes contains cumyl hydroperoxide
81.92%th, isopropylbenzene 14.33%, dimethyl benzyl alcohol 3.36%, acetophenone 0.39%, decomposition list is pumped into by oxidation unit
The decomposer R-1 of member；The vacuum system condensed water that rectification cell is reclaimed is pumped into decomposition as process adjustments water by rectification cell
Device, the composition of regulation water is aqueous 98.71%, acetone 1.06%, phenol 0.23%；Concentration is divided to two strands of ((tools for 98% sulfuric acid
Body is sulfuric acid II13 and sulfuric acid I12)) by being pumped into decomposer circulation pipe；Cumyl hydroperoxide is issued in sulfuric acid catalyst
Solution exothermic reaction estranged, decomposer temperature is 66 DEG C, pressure is 460mmhg, and sulfuric acid concentration is 100ppm, decomposes water content and is
1%, heat of reaction evaporates a large amount of acetone and a small amount of isopropylbenzene, α-methylstyrene in decomposer etc., and this strand of steam passes through
Condensate liquid is all recycled back to decomposer after condenser condensation, and incoagulability tail gas 5 send vacuum system；Decomposer kettle liquid is sent by pump P-1
Go out, part circulation (circulation major cycle material and low discharge material), another part send into two grades of decomposers, cyclic part logistics
Ratio with cleared-out material is 1: 1；Two grades of decomposers are heated using 1.0Mpag low-pressure steams, and temperature is 128 in two grades of decomposers
DEG C, pressure be 0.72Mpag；Two grades of decomposer dischargings 20 enter flash tank flash separation, steam condensate liquid after condensed in two stages
The rectifying feed well or crude acetone column of downstream phenol-acetone device are all removed, incoagulability tail gas 16 send vacuum system, flash tank
Temperature is 80 DEG C, pressure is 410mmhg, and flash tank kettle liquid is discharged by resolving cell is pumped into the neutralization list of phenol-acetone device
Member.
Each logistics composition (mass fraction) table of 3 embodiment of table 7
In table, code name CHP represents cumyl hydroperoxide, and code name AMS represents α-methylstyrene, and code name DMPC represents two
Xylyl alcohol, code name DCP represents cumyl peroxide.
Embodiment 8
In embodiment 7, for the device in 200,000 tons of phenol-acetone/years of production capacity, the ratio of two strands of sulfuric acid is 10: 1
((being specially sulfuric acid II13 and sulfuric acid I12)), recirculation cooler outlet temperature is 58 DEG C, and calorimeter flow is 2.6m3/ h, calorimetric
Device sulphuric acid is 1.6kg/h, and decomposer interior circulation distributor uses calandria, and nozzle inside diameter is 6mm, and hole number is 8
It is individual.
Save 2487 tons/year of isopropyl benzene raw materials, 91 tons/year of sulfuric acid (concentration 98%) raw material, caustic soda (concentration 32%) raw material
229 tons/year, 668850 tons/year of recirculated water, 3637 tons/year of steam.
Embodiment 9
In embodiment 7, for the device in 350,000 tons of phenol-acetone/years of production capacity, the ratio of two strands of sulfuric acid is 16: 1
((being specially sulfuric acid II13 and sulfuric acid I12)), recirculation cooler outlet temperature is 55 DEG C, and calorimeter flow is 4.5m3/ h, calorimetric
Device sulphuric acid is 2.6kg/h, and decomposer interior circulation distributor uses calandria, and nozzle inside diameter is 7mm, and hole number is 10
It is individual.
Save 4413 tons/year of isopropyl benzene raw materials, 158 tons/year of sulfuric acid (concentration 98%) raw material, caustic soda (concentration 32%) raw material
406 tons/year, 1196180 tons/year of recirculated water, 6453 tons/year of steam.
Embodiment 1 is the blanket of embodiment 2 and 3, and the amount specifically reduced is listed in embodiment 2 and 3.The also class of embodiment 4 and 7
Seemingly.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make some improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (9)
1. a kind of method for improving cumyl hydroperoxide decomposition yield, it is characterised in that it is concretely comprised the following steps：
A) the dense cumyl hydroperoxide of phenol-acetone device oxidation operation production is first mixed with the decomposition evaporation condensate liquid circulated
Enter decomposer from the top of decomposer afterwards, cumyl hydroperoxide be decomposed into decomposer under the catalysis of sulfuric acid phenol and
Acetone, and generate accessory substance；
Added acetone is not needed in decomposable process；
B) the kettle liquid discharging of decomposer is divided into three strands, and first strand of material enters two grades of decomposers, and second strand of material is through supercooling
Posterior circle returns decomposer, and is mixed by distributor with decomposed solution, and the 3rd strand of material merges by calorimeter with second strand of material
It is recycled back to decomposer；
Concentrated sulfuric acid catalyst is separately added into above-mentioned second strand and the 3rd strand of decomposed solution recycle stock；
c）Decomposer evaporated vapor sequentially passes through recirculated water and freezing water condenser condensation, and a condensate liquid part is recycled back to decomposition
Device, remainder send the smart acetone tower or rectifying feed well of phenol-acetone device；
D) the Main By product cumyl peroxide during two grades of decomposers discharge decomposer liquid is decomposed into phenol, acetone
And α-methylstyrene, while the dimethyl benzyl alcohol in decomposed solution is also dehydrated generation α-methylstyrene；
E) the discharging feeding vacuum insulation flash tank of two grades of decomposers, utilizes the calorific value flash vaporization point of two grades of decomposer dischargings
From acetone and isopropylbenzene, flash-off steam returns to decomposer by cooling water condensation and freezing water condensation rear portion condensate liquid, its
Waste cold lime set is sent to the rectifying feed well or crude acetone column of phenol-acetone device, and the kettle liquid of vacuum insulation flash tank is single by decomposing
Member discharging is pumped into phenol-acetone device neutralisation unit.
2. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step a）In, the operating pressure of decomposer is 360~560mmHg, and the operation temperature of decomposer is 50~86 DEG C；Thing in decomposer
It is 3~10 minutes to expect the residence time.
3. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step a）In, it is the concentrated sulfuric acid that cumyl hydroperoxide, which decomposes the catalyst used, and sulfuric acid concentration is 90~98%；Sulfuric acid at least from
Two points are added in the Decomposition Cycle system；The ratio that two points add sulfuric acid amount is 0.1~6.2:1；One addition point is amount
The entrance of hot device；Another addition point is the outlet of decomposer recirculation cooler；
Sulfuric acid concentration in decomposer is 30~500ppmwt；
The content of water is 0.3~3% in decomposer.
4. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step b）In, second strand of material is 0.1~3 relative to the recycle ratio of first strand of material is decomposed:1；Decomposed solution passes through circulating cooling
Device cooling extent is 10~48 DEG C.
5. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step b）In, material enters the distributor set in decomposer, and distributor pattern is calandria or annular tube type, distributor material
The material that should be used than decomposer is more resistant to corrosion；
Distributor need to be arranged under decomposer liquid levels, and distributor is provided with the garden hole sprayed downwards, and the quantity in hole is 3~12
Individual, jet velocity is 3~12 meter per seconds.
6. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step c）In, as decomposing, downstream fine acetone tower is delivered in discharging to a part for decomposer evaporated vapor condensate liquid or rectifying is fed
Groove, the ratio that this strand of material accounts for main condenser liquid is 0~30%.
7. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step d）In, two grades of decomposers are plug flow reactor, and operation temperature is 110~166 DEG C, operating pressure is 0.46~
0.86MPaG。
8. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step d）In, residence time of material is 0.5~6 minute in two grades of decomposers.
9. a kind of method for improving cumyl hydroperoxide decomposition yield as claimed in claim 1, it is characterised in that described
Step e）In, vacuum insulation flash tank is vertical adiabatic flash separator, and operation temperature is 70~96 DEG C, and operating pressure is 350
~660mmHg；Decomposed solution flash distillation rate is 8~36% in flash tank.
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| 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 |
| CN109534952A (en) * | 2018-12-17 | 2019-03-29 | 实友化工（扬州）有限公司 | A kind of phenol preparation method can reduce by-product tar yield |
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| CN1639097A (en) * | 2002-07-19 | 2005-07-13 | 桑诺克公司(R&M) | Decomposition of cumene oxidation product |
| US7141700B1 (en) * | 2005-08-19 | 2006-11-28 | Uop Llc | Decomposition of cumene hydroperoxide |
| US7141701B1 (en) * | 2005-08-19 | 2006-11-28 | Uop Llc | Decomposition of cumene hydroperoxide |
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