CN105669367A - Method of raising decomposition yield of cumyl hydroperoxide - Google Patents
Method of raising decomposition yield of cumyl hydroperoxide Download PDFInfo
- Publication number
- CN105669367A CN105669367A CN201610135698.7A CN201610135698A CN105669367A CN 105669367 A CN105669367 A CN 105669367A CN 201610135698 A CN201610135698 A CN 201610135698A CN 105669367 A CN105669367 A CN 105669367A
- Authority
- CN
- China
- Prior art keywords
- splitter
- acetone
- decomposition
- sulfuric acid
- hydrogen phosphide
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention relates to a method for raising the decomposition yield of cumyl hydroperoxide of a phenol-acetone unit.The method includes the steps that 1, first-level decomposition liquid is recycled to a decomposer through a special distributor after being cooled; 2, a concentrated sulfuric acid catalyst is added into a decomposition liquid recycling system from two different points; 3, the concentration of sulfuric acid in the decomposer is lowered; 4, standing time of decomposition liquid in the decomposer is increased, and the reaction temperature of the decomposer is lowered; 5, standing time of the decomposition liquid in a second-level composer is increased; 6, the reaction temperature of second-level decomposition is increased; 7, flash evaporation is conducted on materials discharged through second-level decomposition to recycle energy, total or part of flash evaporation condensate liquid is recycled to the decomposer, and the remaining part is sent to a crude acetone tower on the downstream of the phenol-acetone unit; 8, part of decomposer steam condensate liquid is sent to a fine acetone tower on the downstream of the phenol-acetone unit or fed into a feeding tank.The method mainly solves the problems that by means of an existing phenol acetone production technology, the decomposition yield is low, a great number of tar by-products are generated, and a distilled fed material is high in salt content.
Description
Technical field
The present invention relates to phenol-acetone production technical field, specifically, it is a kind of method improving hydrogen phosphide cumene decomposition yield.
Background technology
Phenol and acetone are all the Organic chemical products having many uses. Common production method is, use isopropyl benzene is raw material, generating hydrogen phosphide cumene by the atmospheric oxidation of isopropyl benzene, the hydrogen phosphide cumene (common concentration is for containing hydrogen phosphide cumene about 82%) after concentrated by decomposing under concentrated sulfuric acid catalyst catalysis and obtains phenol and acetone two kinds of products after a series of purification simultaneously. Hydrogen phosphide cumene decomposes also to have and uses the solid acid as catalyzer. The decomposition of hydrogen phosphide cumene is strong exothermal reaction, and decomposition course can produce many kinds of by products, and these by products can affect the receipts rate of decomposition and the consumption of raw material isopropyl benzene, also can affect the quality of phenol and product acetone. Usually higher receipts rate is obtained by controlling the residence time etc. of lower temperature of reaction, certain sulfuric acid concentration, certain water-content and decomposition.
US Patent No. 5245090 (U.S. AristechChemicalCorporation) describes a kind of hydrogen phosphide cumene decomposition method not having acetone recycle, decomposed product to circulate in a large number, it uses sulfuric acid as catalyzer, level of decomposition reaction carries out at lower temperature (66～121 DEG C) in higher temperature (77～88 DEG C), two grades of decomposition reactions, by improving level of decomposition temperature, reduce the receipts rate that two grades of decomposition temperatures improve hydrogen phosphide cumene decomposition. The theory contrast of this and the present invention.
US Patent No. 5998677 (Mitsui You Hua company of Japan) describes one and adds more acetone (the product acetone from scavenging process produces) in A reactor (splitter) discharging and complete the method for second stage decomposition with lower temperature (120 DEG C), improves the receipts rate of decomposition course by improving the energy consumption (acetone recycle) of phenol-acetone scavenging process.
Chinese patent CN102186799A (Sha Bai radical innovations company) describes and a kind of uses hydroxy benzenesulfonic acid as catalyzer, and adds the hydrogen phosphide cumene decomposition method of ammoniacal liquor.
Chinese patent CN101343212 (PetroChina Company Limited.) describes the hydrogen phosphide cumene decomposition method that a kind of solid acid is catalyzer.
At present, domestic and international phenol-acetone device mainly use two types hydrogen phosphide cumene decomposition technique. One class technology is that acetone vacuum-evaporation moves heat, two-step approach concentrated sulfuric acid catalyst decomposition technique, the first step is hydrogen phosphide cumene decomposition course, acetone evaporated moves dereaction heat, sulfuric acid concentration is 300～500ppm, service temperature is 75～88 DEG C, and the 2nd step is by-product destruction process, uses tubular reactor, service temperature 110～122 DEG C. Another class technology is that a large amount of outer circulation of decomposed solution moves heat, two-step approach concentrated sulfuric acid catalyst decomposition technique, the first step is that hydrogen phosphide cumene decomposition course, outer circulation move dereaction heat, recycle ratio is 25～100: 1, sulfuric acid concentration is 30～60ppm, service temperature is 40～70 DEG C, and the 2nd step is by-product destruction process, uses tubular reactor, service temperature 115～125 DEG C. On various technical security all reliable, but the consumption of raw material isopropyl benzene general higher, tar growing amount is higher, isopropyl benzene consume all numerical value higher than each technical patent business advocation. And evaporate and move in pyrolysis technique, owing to acetone content in decomposed solution is higher, make phenol-acetone device downstream neutralization step be not easy except salt and the fouling causing distillation system serious.
In addition, it may also be useful to solid acid is as the technology of hydrogen phosphide cumene decomposition catalyst, and its decomposition course can generate more tar, and isopropyl benzene consumption is higher. This kind of technology does not re-use at present.
The present invention is directed to existing evaporation move that raw material isopropyl benzene consumption in pyrolysis technique is higher and in decomposed solution acetone too high problem, reduce the consumption of raw material isopropyl benzene by series of process innovative approach, reduce the content of acetone in resolving cell discharging.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of method improving hydrogen phosphide cumene decomposition yield.
For existing phenol-acetone device resolving cell Problems existing, technical process and operational condition by improving decomposing system is solved resolving cell raw material isopropyl benzene in existing phenol-acetone device and consumes the problem that in high and decomposed solution, acetone content is high by the present invention, comprises increase splitter recirculation cooler, determines new operation splitting condition, increases decomposed solution discharging flash system etc.
It is an object of the invention to be achieved through the following technical solutions:
Improving a method for hydrogen phosphide cumene decomposition yield, its concrete steps are:
A) the dense hydrogen phosphide cumene that phenol-acetone device oxidation operation is produced enters splitter from the top of splitter after first mixing with the decomposition evaporation phlegma of circulation, hydrogen phosphide cumene is decomposed into phenol and product acetone in splitter under the catalysis of persulfuric acid, and generates by product; At suitable sulfuric acid concentration, suitable temperature, suitable pressure, suitable water-content and the decomposition yield obtaining expecting under the suitable residence time, is operated by control splitter;
Dense hydrogen phosphide cumene is 75～85% containing the massfraction of hydrogen phosphide cumene;
By product comprises dicumyl peroxide, tar etc.;
It is the vitriol oil that hydrogen phosphide cumene decomposes the catalyzer used, and sulfuric acid concentration is 90～98%. Sulfuric acid at least adds this Decomposition Cycle system from two points; Prioritizing selection two points, the ratio that two points add sulfuric acid amount is 0.1～6.2: 1; An addition point is the entrance of calorimeter; Another addition point is the outlet of splitter recirculation cooler;
Sulfuric acid concentration in splitter is 30～500ppmwt. It is preferably 70～280ppmwt.
The working pressure of splitter is 360～560mmhg, and the service temperature of splitter is 50～86 DEG C.
In splitter, residence time of material is 3～10 minutes.
A certain amount of water adds splitter, and in splitter, the content of water is 0.3～3%.
Decomposition course does not need add acetone. Its feature is: to decomposition itself, is conducive to reducing the growing amount of pyruvic alcohol. Pyrogentisinic Acid's acetone device, is conducive to improving the throughput of device, reduces the energy consumption of acetone separation.
B) the still liquid discharging of splitter is divided into three strands, first strand of material enters into two grades of splitters, 2nd strand of material returns splitter through overcooling Posterior circle, and is mixed with decomposed solution by sparger, and the 3rd strand of material merges with the 2nd strand through calorimeter and loop back splitter;
Concentrated sulfuric acid catalyst adds in above-mentioned 2nd strand and the 3rd strand of decomposed solution recycle stock respectively;
The control of two circulation loops is the key decomposing control;
2nd burst of decomposed solution is 0.1～3: 1 relative to the recycle ratio of decomposition first burst of decomposed solution
Decomposed solution through recirculation cooler cooling extent be 10～48 DEG C.
Material enters in splitter the inside sparger arranged, and sparger pattern is calandria or annular tube type, and sparger material should be more corrosion-resistant than the material that splitter uses.
Sparger need to be arranged under splitter liquid levels, and sparger is provided with the hole, garden of Jet with downward flow direction, and the quantity in hole is 3～12, and jet velocity is 3～12 meters/second.
The feature of this step: increase special decomposed solution circulation cooling circuit, lower, two the some acid addings that enter splitter sulfuric acid concentration, front two eliminate produce owing to sulfuric acid partial concn is too high in splitter more tar, latter one make that decomposing system is safer (to be decomposed hydrogen phosphide cumene, in order to ensure safety, it is necessary to make system always has sulfuric acid exist. Using two points to add, even if making system point fault, another point can also continue to add). In prior art, sulfuric acid is added by calorimeter point, and sparger is on liquid level, and sparger outlet sulfuric acid concentration is higher, and tar growing amount is many, and has safety worries.
C) splitter evaporated vapor is successively through recirculated water and refrigerated water condenser condenses, and a phlegma part loops back splitter, and rest part send smart acetone tower or the rectifying feed chute of phenol-acetone device;
A part for splitter evaporated vapor phlegma delivers to downstream fine acetone tower or rectifying feed chute as decomposition discharging, and the ratio that this strand of material accounts for total condenser liquid is 0～30%.
D) the Main By product dicumyl peroxide (being called for short DCP) in splitter discharging is decomposed into phenol, acetone and alpha-methyl styrene (being called for short AMS) by the still liquid material of splitter in two grades of splitters, dimethyl benzyl alcohol in decomposed solution (being called for short DMPC) also dehydration generation alpha-methyl styrene, controls the reaction yield that sulfuric acid concentration suitable in two grades of splitters, suitable temperature and the suitable residence time obtain expectation simultaneously.
Sulfuric acid concentration 75～285ppm in decomposing system, prioritizing selection 80～160ppm;
Two grades of splitters are plug flow reactor, and service temperature is 110～166 DEG C, and working pressure is 0.46～0.86Mpag.
In two grades of splitters, residence time of material is 0.5～6 minute.
Two grades of splitters are by indirect heating medium as low pressure water vapor or heat-conducting oil heating;
Relative to prior art, decomposing more complete, the receipts rate of AMS is higher
E) vacuum insulation flash drum is sent in the discharging of two grades of splitters, utilize the calorific value flash vaporization acetone of two grades of splitter dischargings, isopropyl benzene etc., flash distillation steam returns splitter through cooling water condensation and refrigerated water condensation rear portion phlegma, rectifying feed chute or the crude acetone column of phenol-acetone device delivered to by rest part phlegma, the still liquid of vacuum insulation flash drum delivers to phenol-acetone device neutralisation unit by resolving cell discharging pump, is regulated the flash distillation rate of flash drum by the service temperature and pressure controlling vacuum insulation flash drum;
Vacuum insulation flash drum is vertical adiabatic flash separator, and service temperature is 70～96 DEG C, and working pressure is 350～660mmhg.
A part for flash distillation steam condensate delivers to downstream crude acetone column or rectifying feed chute as decomposition discharging, and the ratio that this strand of material accounts for total condensing liquid quantity is 0～100%.
In flash drum, decomposed solution flash distillation rate is 8～36%, for charging amount.
Reclaiming the heat of discharging, it is not necessary to acetone recycle (from downstream), in decomposition discharging, acetone content is low, rectifying charging salts contg is low.
Prioritizing selection in technique scheme:
It is the vitriol oil that hydrogen phosphide cumene decomposes the catalyzer used, and the vitriol oil at least adds this Decomposition Cycle system from two points. Prioritizing selection two points, the ratio (ratio of logistics 12 amount and logistics 13 amount) that two points add sulfuric acid amount is 0.1～6.2, prioritizing selection 0.2～3.6.
In decomposing system, sulfuric acid concentration is 70～285ppmwt, prioritizing selection 80-160ppmwt.
Splitter working pressure is 360～560mmhg, prioritizing selection 380～480mmhg.
Splitter service temperature is 50～86 DEG C, prioritizing selection 60～72 DEG C.
The material looping back splitter is 10～300% relative to the recycle ratio of main discharging, prioritizing selection 38～120%. Recirculation cooler cooling extent is 10～48 DEG C, prioritizing selection 26～38 DEG C.
Recycle stock enters and arranges inner sparger in splitter, and sparger is calandria or annular tube type, and sparger material should be more corrosion-resistant such as Hastelloy than the material that splitter uses. This sparger need to be arranged in splitter under liquid levels, and distribution pipe is opened the hole, garden of Jet with downward flow direction, and the quantity in hole is 3-12, prioritizing selection 4～8, and jet velocity is 3～12 meters/second, prioritizing selection 5～8 meters/second.
A certain amount of process water adds splitter, and the content of decomposing system water is 0.3～3%, prioritizing selection 0.8～1.6%.
A part of acetone discharging of splitter evaporated vapor phlegma delivers to downstream fine acetone tower or rectifying feed chute as decomposition discharging, and the ratio that this strand of material accounts for this total condenser liquid is 0～30%, prioritizing selection 10～20%.
Two grades of splitters are plug flow reactor, service temperature 110～166 DEG C, prioritizing selection 120～148 DEG C, working pressure 0.46～0.86Mpag, prioritizing selection 0.56～0.76Mpag.
Decomposed solution flash drum is the vertical adiabatic flash separator of band scum dredger, service temperature 70～96 DEG C, prioritizing selection 76～90 DEG C, working pressure 350～660mmhg, prioritizing selection 380～500mmhg.
Part or all of flash distillation steam condensate delivers to downstream rectifying feed chute or crude acetone column as decomposition discharging, and the ratio that this strand of material accounts for total phlegma is 0～100%, prioritizing selection 45～75%.
In flash drum, decomposed solution flash distillation rate (relative to charging) is 8～36%, prioritizing selection 10～25%.
In splitter, residence time of material is 3～10 minutes, prioritizing selection 4～8 minutes.
In two grades of splitters, residence time of material is 0.5～6 minute, prioritizing selection 1～2.5 minute.
Compared with prior art, the positively effect of the present invention is:
The present invention has carried out further improvement on the basis of testing data, forms new technology. The present invention, reducing while phenol-acetone device isopropyl benzene consumes, also reduces the consumption of sulfuric acid catalyst, reduces the energy consumption of device, it is to increase the driving rate of device (decreasing the parking of distillation system).
Problem solved by the invention is the problem that in phenol-acetone device, in hydrogen phosphide cumene resolving cell raw material consumption height and decomposed solution, salts contg is high, invention is by improving existing decomposition process, design new operational condition, increase decomposed solution flash distillation facility etc., reduce the growing amount that decomposition course is coal-tar middle oil, reduce the consumption of raw material isopropyl benzene, reduce the consumption of catalyst sulfuric acid, and by reducing the content of acetone in decomposed solution, the discharging of decomposition is made more to be conducive to the follow-up neutralization of phenol-acetone device except acid and the completing of desalting process, also avoid follow-up unit acetone recycle to be returned to decompose and reduce its load (namely improve plant efficiency and reduce general facilities consumption), improve the driving rate of phenol-acetone device, reduce manufacturing cost.
The main difference point of the present invention and prior art: the sulfuric acid concentration (reducing tar to generate) that decomposing system is lower, the temperature (reducing tar to generate) that splitter is lower, increase (relative to prior art) decomposed solution circulating cooling (dilute sulphuric acid, reduce splitter temperature, reduce tar to generate), sparger outlet local sulfuric acid concentration lower (reducing tar to generate), splitter steam condensate part is sent (acetone that may be used for producing low methanol content) as analytical product, two grades are decomposed higher temperature (dicumyl peroxide, dimethyl benzyl alcohol decomposes more complete), increase decomposed solution flash system and (reclaim heat, elimination product acetone circulates, reduce rectifying charging salts contg).
Accompanying drawing illustrates:
Fig. 1 hydrogen phosphide cumene decomposition technique schema is shown in.
Being labeled as in accompanying drawing:
R-1 is splitter, R-2 is two grades of splitters, P-1 is splitter discharging pump, and P-2 is resolving cell discharging pump, and E-1 is Decomposition Cycle water cooler, E-2 is for decomposing steam condenser, E-3 is decomposed tail gas condenser, and E-4 is flash distillation steam condenser, and E-5 is exhaust gas of flash evaporation condenser, M-1 is calorimeter, and V-1 is flash drum.
1 is dense hydrogen phosphide cumene solution, and 2 is process adjustments water, and 3 is acetone discharging, 4 is backflow acetone, 5 cannot not being solidifying property tail gas, 6 is refrigerated water, and logistics 7 is recirculated water, 8 is main discharging, 9 is major cycle material, and 10 is little flow material, and 11 is recirculated cooling water, 12 is sulfuric acid I, 13 is sulfuric acid II, and 14 is flash distillation refluxer, and 15 is flash distillation discharging phlegma, 16 is non-condensable gases, 17 is the 2nd refrigerated water, and 18 is recirculated cooling water, and 19 is steam or thermal oil, 20 is decomposed solution, and 21 is resolving cell discharging.
Embodiment
The embodiment of a kind of method improving hydrogen phosphide cumene decomposition yield of the present invention is below provided.
Accompanying drawing and explanation: hydrogen phosphide cumene decomposition technique schema is shown in accompanying drawing 1. Process explanation:
In phenol-acetone device, explained hereafter uses isopropyl benzene to be raw material, produces phenol and acetone two kinds of products simultaneously. Isopropyl benzene first generates hydrogen phosphide cumene through peroxidation, hydrogen phosphide cumene is decomposed into phenol, acetone and other by product under sulfuric acid catalysis, and decomposed solution is removed a series of scavenging process such as salt, rectifying, catalytic treatment through neutralization except acid and obtained phenol and acetone.
First raw material isopropyl benzene generates hydrogen phosphide cumene by the dioxygen oxidation in air in oxidation unit, in oxidation discharging (being called oxidation solution), the concentration of hydrogen phosphide cumene is generally 20～36%, in pressure oxidation (pressure is generally 0.3Mpag) technique, oxidation solution concentration is lower for containing hydrogen phosphide cumene 20～26%, in nearly atmospheric pressure oxidation (pressure is generally 0.03Mpag) technique, oxidation solution concentration is higher for containing hydrogen phosphide cumene 28～36%.Oxidation solution improves the concentration of hydrogen phosphide cumene before entering resolving cell by vacuum concentration, and the concentration of dense oxidation solution is generally 78～85%.
Dense hydrogen phosphide cumene solution 1 enters in splitter by splitter R-1 top after mixing with backflow acetone 4, by the splitter being pumped into resolving cell of oxidation unit; The vacuum system water of condensation that rectification cell reclaims is pumped into splitter as process adjustments water 2 by rectification cell, and the composition regulating water is moisture 98.71%, acetone 1.06%, phenol 0.23%; Concentration be 98% the vitriol oil divide two strands (being specially sulfuric acid I12 and sulfuric acid II13) to send in splitter circulation tube by splitter discharging pump P-1;
Hydrogen phosphide cumene is decomposed into phenol, acetone, dicumyl peroxide and other byproduct in splitter under sulfuric acid catalysis. Hydrogen phosphide cumene is decomposed into quick thermopositive reaction, and reaction heat is moved out by the evaporation of acetone and decomposed solution recirculation cooler E-1. The acetone of splitter evaporation etc. are from splitter top out, successively through recirculated water 7 (temperature is generally 30 DEG C) decomposed solution steam condenser E-2 and the condenser E-3 condensation of refrigerated water 6 (temperature is generally 0 DEG C) decomposed tail gas, not solidifying property tail gas 5 goes vacuum system, the backflow acetone recycle of phlegma major part returns splitter, and smart acetone tower or the rectifying feed chute in device downstream is delivered in small part acetone discharging 3 as decomposing one of discharging.
The liquid discharging of splitter is by pumping out, and is divided into three strands. First burst of discharging is major cycle material 9, loops back splitter together with after mixing with main sulfuric acid II after supercooled water 11 (temperature is generally 30 DEG C) water cooler cools. 2nd burst of discharging is little flow material logistics 10, is incorporated to major cycle logistics with sulfuric acid I after calorimeter mixes, and observes the degree of control decomposition by measuring the temperature variation of calorimeter input and output material. 3rd burst of discharging is main discharging 8, the byproduct dicumyl peroxide of decomposition course is decomposed into phenol, acetone and alpha-methyl styrene by the two grades of splitters first heated through steam 19, and the byproduct dimethyl benzyl alcohol that oxidation produces dewaters in two grades of splitters and generates alpha-methyl styrene.
The decomposed solution 20 of two grades of splitters directly sends into flash drum V-1, the flash vaporization component such as a part of acetone and isopropyl benzene wherein. The steam flashed off is successively through recirculated water 18 (temperature is generally 30 DEG C) flash distillation steam condenser E-4 and the 2nd refrigerated water 17 (temperature is generally 0 DEG C) exhaust gas of flash evaporation condenser E-5 condensation, not solidifying property tail gas 16 goes vacuum system, flash distillation refluxer 14 part loops back splitter, and rectifying feed chute or the crude acetone column in device downstream delivered to by another part flash distillation discharging phlegma 15 as decomposing one of discharging. The decomposition discharging 21 of flash drum delivers to the neutralisation unit in device downstream by resolving cell discharging pump P-2.
Embodiment 1
The dense hydrogen phosphide cumene solution that phenol-acetone device oxidation unit comes contains hydrogen phosphide cumene 81.92%, isopropyl benzene 14.33%, dimethyl benzyl alcohol 3.36%, methyl phenyl ketone 0.39%, by the splitter R-1 being pumped into resolving cell of oxidation unit; The vacuum system water of condensation that rectification cell reclaims is pumped into splitter as process adjustments water by rectification cell, and the composition of process adjustments water is moisture 98.71%, acetone 1.06%, phenol 0.23%; Concentration be 98% the vitriol oil divide two strands ((being specially sulfuric acid II13 and sulfuric acid I12)) to send in splitter circulation tube by splitter discharging pump pump P-1;Hydrogen phosphide cumene issues solution thermopositive reaction estranged at sulfuric acid catalyst, splitter temperature is 62 DEG C, pressure is 426mmhg, sulfuric acid concentration is 100ppm, water of decomposition content is 1%, heat of reaction makes a large amount of acetone in splitter and a small amount of isopropyl benzene, alpha-methyl styrenes etc. evaporate, this burst of steam phlegma major part after condenser condenses loops back splitter, acetone discharging passes out to smart acetone tower or the rectifying feed chute of phenol-acetone device as one product of resolving cell, it is 1: 10 that acetone discharging accounts for the ratio of total phlegma, not solidifying property tail gas 5 send vacuum system, splitter still liquid is by pumping out, and a part (circulation major cycle material and little flow material), another part send into two grades of splitters, and the ratio of circulation part logistics and cleared-out material is 0.76: 1, two grades of splitters use the heating of 1.0Mpag low-pressure steam, in two grades of splitters temperature be 136 DEG C, pressure be 0.72Mpag, two grades of splitter dischargings enter flash drum flash separation, flash distillation steam goes splitter, another part to go rectifying feed chute or the crude acetone column of downstream phenol-acetone device through condensed in two stages rear portion, the ratio of flash distillation discharging phlegma and flash distillation refluxer is 0.5: 1, flash drum temperature is 86 DEG C, pressure is 450mmhg, and flash drum still liquid is delivered to the neutralisation unit of phenol-acetone device by resolving cell discharging pump.
Each logistics composition (mass fraction) table of table 1 embodiment 1
In table, code name CHP represents hydrogen phosphide cumene, and code name AMS represents alpha-methyl styrene, and code name DMPC represents dimethyl benzyl alcohol, and code name DCP represents dicumyl peroxide.
Embodiment 2
In embodiment 1, for the device in 200,000 tons of phenol-acetone/years of throughput, the ratio of the sulfuric acid of two strands is 10: 1 (being specially sulfuric acid II13 and sulfuric acid I12), and recirculation cooler temperature out is 52 DEG C, enters the flow of calorimeter) it is 1.6m3/ h, calorimeter sulfuric acid add-on is 1kg/h, and splitter internal recycle sparger adopts calandria, and nozzle inside diameter is 6mm, and hole number is 6.
Save isopropyl benzene raw material 2529 tons/year, sulfuric acid (concentration 98%) raw material 91 tons/year, caustic soda (concentration 32%) raw material 229 tons/year, recirculated water 656110 tons/year, steam 3568 tons/year.
Embodiment 3
In embodiment 1, for the device in 350,000 tons of phenol-acetone/years of throughput, the ratio of the sulfuric acid of two strands is 16: 1 ((being specially sulfuric acid II13 and sulfuric acid I12)), and recirculation cooler temperature out is 56 DEG C, and calorimeter flow is 2.6m3/ h, calorimeter sulfuric acid add-on is 1.7kg/h, and splitter internal recycle sparger adopts calandria, and nozzle inside diameter is 7mm, and hole number is 8.
Save isopropyl benzene raw material 4492 tons/year, sulfuric acid (concentration 98%) raw material 158 tons/year, caustic soda (concentration 32%) raw material 406 tons/year, recirculated water 1173170 tons/year, steam 6331 tons/year.
Embodiment 4
Existing resolving cell improves, and decomposition steam condensate and flash distillation steam condensate be not all as product discharge, and namely acetone discharging 3 and flash distillation discharging phlegma 15 flow are zero.
The dense hydrogen phosphide cumene solution that phenol-acetone device oxidation unit comes contains hydrogen phosphide cumene 81.92%, isopropyl benzene 14.33%, dimethyl benzyl alcohol 3.36%, methyl phenyl ketone 0.39%, by the splitter being pumped into resolving cell of oxidation unit; The vacuum system water of condensation that rectification cell reclaims is pumped into splitter as process adjustments water by rectification cell, and the composition of process adjustments water is moisture 98.71%, acetone 1.06%, phenol 0.23%;Concentration be 98% sulfuric acid divide two strands (being specially sulfuric acid I12 and sulfuric acid II13) by being pumped in splitter circulation tube; Hydrogen phosphide cumene issues solution thermopositive reaction estranged at sulfuric acid catalyst, splitter temperature is 65 DEG C, pressure is 460mmhg, sulfuric acid concentration is 100ppm, water of decomposition content is 1%, heat of reaction makes a large amount of acetone in splitter and a small amount of evaporation such as isopropyl benzene, alpha-methyl styrene, this strand of steam loops back splitter whole dividing after condenser condenses, and solidifying property tail gas send vacuum system; Splitter still liquid is sent by pump P-1, and part circulation (circulation major cycle material and little flow material), another part send into two grades of splitter R-2, and the ratio of circulation part logistics and cleared-out material is 0.68: 1; Two grades of splitters use the heating of 1.0Mpag low-pressure steam, in two grades of splitters temperature be 128 DEG C, pressure be 0.72Mpag; Two grades of splitter dischargings 20 enter flash drum flash separation, and steam all loops back splitter after condensed in two stages, and flash drum temperature is 83 DEG C, pressure is 430mmhg, and flash drum still liquid is delivered to the neutralisation unit of phenol-acetone device by resolving cell discharging pump.
Each logistics composition (mass fraction) table of table 2 embodiment 4
In table, code name CHP represents hydrogen phosphide cumene, and code name AMS represents alpha-methyl styrene, and code name DMPC represents dimethyl benzyl alcohol, and code name DCP represents dicumyl peroxide.
Embodiment 5
In embodiment 4, for the device in 200,000 tons of phenol-acetone/years of throughput, the ratio of the sulfuric acid of two strands is 10: 1 (being specially sulfuric acid II13 and sulfuric acid I12), and recirculation cooler temperature out is 56 DEG C, and calorimeter flow is 2.6m3/ h, calorimeter sulfuric acid add-on is 1.6kg/h, and splitter internal recycle sparger adopts calandria, and nozzle inside diameter is 6mm, and hole number is 8.
Save isopropyl benzene raw material 2480 tons/year, sulfuric acid (concentration 98%) raw material 91 tons/year, caustic soda (concentration 32%) raw material 229 tons/year, recirculated water 637000 tons/year, steam 3464 tons/year.
Embodiment 6
In embodiment 4, for the device in 350,000 tons of phenol-acetone/years of throughput, the ratio of the sulfuric acid of two strands is 16: 1 (being specially sulfuric acid II13 and sulfuric acid I12), and recirculation cooler temperature out is 59 DEG C, and calorimeter flow is 4.5m3/ h, calorimeter sulfuric acid add-on is 2.6kg/h, and splitter internal recycle sparger adopts calandria, and nozzle inside diameter is 7mm, and hole number is 10.
Save isopropyl benzene raw material 4400 tons/year, sulfuric acid (concentration 98%) raw material 158 tons/year, 406 tons/year, caustic soda (concentration 32%), recirculated water 1139220 tons/year, steam 6146 tons/year.
Embodiment 7
Splitter steam condensate is not sent as resolving cell product, and flash drum steam condensate is all sent as resolving cell product.
The dense hydrogen phosphide cumene solution that phenol-acetone device oxidation unit comes contains hydrogen phosphide cumene 81.92%, isopropyl benzene 14.33%, dimethyl benzyl alcohol 3.36%, methyl phenyl ketone 0.39%, by the splitter R-1 being pumped into resolving cell of oxidation unit; The vacuum system water of condensation that rectification cell reclaims is pumped into splitter as process adjustments water by rectification cell, and the composition regulating water is moisture 98.71%, acetone 1.06%, phenol 0.23%; Concentration be 98% sulfuric acid divide two strands ((being specially sulfuric acid II13 and sulfuric acid I12)) by being pumped in splitter circulation tube; Hydrogen phosphide cumene issues solution thermopositive reaction estranged at sulfuric acid catalyst, splitter temperature is 66 DEG C, pressure is 460mmhg, sulfuric acid concentration is 100ppm, water of decomposition content is 1%, heat of reaction makes a large amount of acetone in splitter and a small amount of evaporation such as isopropyl benzene, alpha-methyl styrene, this strand of steam phlegma after condenser condenses all loops back splitter, and not solidifying property tail gas 5 send vacuum system;Splitter still liquid is sent by pump P-1, and part circulation (circulation major cycle material and little flow material), another part send into two grades of splitters, and the ratio of circulation part logistics and cleared-out material is 1: 1; Two grades of splitters use the heating of 1.0Mpag low-pressure steam, in two grades of splitters temperature be 128 DEG C, pressure be 0.72Mpag; Two grades of splitter dischargings 20 enter flash drum flash separation, steam phlegma after condensed in two stages all goes rectifying feed chute or the crude acetone column of downstream phenol-acetone device, not solidifying property tail gas 16 send vacuum system, flash drum temperature is 80 DEG C, pressure is 410mmhg, and flash drum still liquid is delivered to the neutralisation unit of phenol-acetone device by resolving cell discharging pump.
Each logistics composition (mass fraction) table of table 3 embodiment 7
In table, code name CHP represents hydrogen phosphide cumene, and code name AMS represents alpha-methyl styrene, and code name DMPC represents dimethyl benzyl alcohol, and code name DCP represents dicumyl peroxide.
Embodiment 8
In embodiment 7, for the device in 200,000 tons of phenol-acetone/years of throughput, the ratio of the sulfuric acid of two strands is 10: 1 ((being specially sulfuric acid II13 and sulfuric acid I12)), and recirculation cooler temperature out is 58 DEG C, and calorimeter flow is 2.6m3/ h, calorimeter sulfuric acid add-on is 1.6kg/h, and splitter internal recycle sparger adopts calandria, and nozzle inside diameter is 6mm, and hole number is 8.
Save isopropyl benzene raw material 2487 tons/year, sulfuric acid (concentration 98%) raw material 91 tons/year, caustic soda (concentration 32%) raw material 229 tons/year, recirculated water 668850 tons/year, steam 3637 tons/year.
Embodiment 9
In embodiment 7, for the device in 350,000 tons of phenol-acetone/years of throughput, the ratio of the sulfuric acid of two strands is 16: 1 ((being specially sulfuric acid II13 and sulfuric acid I12)), and recirculation cooler temperature out is 55 DEG C, and calorimeter flow is 4.5m3/ h, calorimeter sulfuric acid add-on is 2.6kg/h, and splitter internal recycle sparger adopts calandria, and nozzle inside diameter is 7mm, and hole number is 10.
Save isopropyl benzene raw material 4413 tons/year, sulfuric acid (concentration 98%) raw material 158 tons/year, caustic soda (concentration 32%) raw material 406 tons/year, recirculated water 1196180 tons/year, steam 6453 tons/year.
Embodiment 1 is the blanket of embodiment 2 and 3, and the concrete amount reduced is listed in embodiment 2 and 3. Embodiment 4 and 7 is also similar.
The above is only the preferred embodiment of the present invention; it is noted that for those skilled in the art, without departing from the inventive concept of the premise; can also making some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (10)
1. one kind is improved the method for hydrogen phosphide cumene decomposition yield, it is characterised in that, its concrete steps are:
A) the dense hydrogen phosphide cumene that phenol-acetone device oxidation operation is produced enters splitter from the top of splitter after first mixing with the decomposition evaporation phlegma of circulation, hydrogen phosphide cumene is decomposed into phenol and acetone in splitter under the catalysis of sulfuric acid, and generates by product;
Decomposition course does not need added acetone;
B) the still liquid discharging of splitter is divided into three strands, first strand of material enters into two grades of splitters, 2nd strand of material returns splitter through overcooling Posterior circle, and is mixed with decomposed solution by sparger, and the 3rd strand of material merges with the 2nd strand of material through calorimeter and loop back splitter;
Concentrated sulfuric acid catalyst adds in above-mentioned 2nd strand and the 3rd strand of decomposed solution recycle stock respectively;
C) splitter evaporated vapor is successively through recirculated water and refrigerated water condenser condenses, and a phlegma part loops back splitter, and rest part send smart acetone tower or the rectifying feed chute of phenol-acetone device;
D) the Main By product dicumyl peroxide in splitter liquid discharging is decomposed into phenol, acetone and alpha-methyl styrene by two grades of splitters, and simultaneously the dimethyl benzyl alcohol in decomposed solution also dewaters generation alpha-methyl styrene;
E) vacuum insulation flash drum is sent in the discharging of two grades of splitters, utilize calorific value flash vaporization acetone and the isopropyl benzene of two grades of splitter dischargings, flash distillation steam returns splitter through cooling water condensation and refrigerated water condensation rear portion phlegma, rectifying feed chute or the crude acetone column of phenol-acetone device delivered to by all the other phlegmas, and the still liquid of vacuum insulation flash drum delivers to phenol-acetone device neutralisation unit by resolving cell discharging pump.
2. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterised in that, described step a) in, the working pressure of splitter is 360～560mmhg, and the service temperature of splitter is 50～86 DEG C; In splitter, residence time of material is 3～10 minutes.
3. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterised in that, described step a) in, hydrogen phosphide cumene decompose use catalyzer be the vitriol oil, sulfuric acid concentration is 90～98%; Sulfuric acid at least adds this Decomposition Cycle system from two points; Prioritizing selection two points, the ratio that two points add sulfuric acid amount is 0.1～6.2: 1; An addition point is the entrance of calorimeter; Another addition point is the outlet of splitter recirculation cooler;
Sulfuric acid concentration in splitter is 30～500ppmwt;
In splitter, the content of water is 0.3～3%.
4. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterised in that, at described step b) in, the 2nd strand of material is 0.1～3: 1 relative to the recycle ratio of decomposition first strand of material; Decomposed solution through recirculation cooler cooling extent be 10～48 DEG C.
5. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterized in that, at described step b) in, material enters in splitter the sparger arranged, sparger pattern is calandria or annular tube type, and sparger material should be more corrosion-resistant than the material that splitter uses;
Sparger need to be arranged under splitter liquid levels, and sparger is provided with the hole, garden of Jet with downward flow direction, and the quantity in hole is 3～12, and jet velocity is 3～12 meters/second.
6. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterized in that, at described step c) in, a part for splitter evaporated vapor phlegma delivers to downstream fine acetone tower or rectifying feed chute as decomposition discharging, and the ratio that this strand of material accounts for total condenser liquid is 0～30%.
7. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterized in that, in described steps d) in, two grades of splitters are plug flow reactor, service temperature is 110～166 DEG C, and working pressure is 0.46～0.86Mpag.
8. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterised in that, in described steps d) in, in two grades of splitters, residence time of material is 0.5～6 minute.
9. a kind of method improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, it is characterized in that, at described step e) in, vacuum insulation flash drum is vertical adiabatic flash separator, service temperature is 70～96 DEG C, and working pressure is 350～660mmhg;In flash drum, decomposed solution flash distillation rate is 8～36%.
10. a kind of device improving hydrogen phosphide cumene decomposition yield as claimed in claim 1, comprise splitter unit, two grades of splitter unit and decomposed solution flash drum unit, it is characterized in that, described splitter unit comprises splitter and the recirculation cooler of vacuum operating, splitter is connected with recirculation cooler by Decomposition Cycle pump and forms circulation loop, affiliated decomposed solution flash drum unit comprises the adiabatic flash groove of vacuum operating, and flash drum is connected with tail cooler by condenser.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610135698.7A CN105669367B (en) | 2016-03-10 | 2016-03-10 | A kind of method for improving cumyl hydroperoxide decomposition yield |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610135698.7A CN105669367B (en) | 2016-03-10 | 2016-03-10 | A kind of method for improving cumyl hydroperoxide decomposition yield |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105669367A true CN105669367A (en) | 2016-06-15 |
| CN105669367B CN105669367B (en) | 2017-09-19 |
Family
ID=56307405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610135698.7A Active CN105669367B (en) | 2016-03-10 | 2016-03-10 | A kind of method for improving cumyl hydroperoxide decomposition yield |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105669367B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7464211B2 (en) | 2020-12-21 | 2024-04-09 | エルジー・ケム・リミテッド | Method for producing α-methylstyrene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5245090A (en) * | 1992-09-11 | 1993-09-14 | Aristech Chemical Corporation | Two-stage cleavage of cumene hydroperoxide |
| CN1639097A (en) * | 2002-07-19 | 2005-07-13 | 桑诺克公司(R&M) | Decomposition of cumene oxidation product |
| CN101268032A (en) * | 2005-08-19 | 2008-09-17 | 环球油品公司 | Decomposition of cumene hydroperoxide |
| CN101268031A (en) * | 2005-08-19 | 2008-09-17 | 环球油品公司 | Decomposition of cumene hydroperoxide |
-
2016
- 2016-03-10 CN CN201610135698.7A patent/CN105669367B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5245090A (en) * | 1992-09-11 | 1993-09-14 | Aristech Chemical Corporation | Two-stage cleavage of cumene hydroperoxide |
| CN1639097A (en) * | 2002-07-19 | 2005-07-13 | 桑诺克公司(R&M) | Decomposition of cumene oxidation product |
| CN101268032A (en) * | 2005-08-19 | 2008-09-17 | 环球油品公司 | Decomposition of cumene hydroperoxide |
| CN101268031A (en) * | 2005-08-19 | 2008-09-17 | 环球油品公司 | Decomposition of cumene hydroperoxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105669367B (en) | 2017-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107739301B (en) | Polymethoxy dimethyl ether synthesis system and process | |
| CN202808649U (en) | Systemic device for preparing polyoxymethylene dimethyl ether | |
| CN105669367A (en) | Method of raising decomposition yield of cumyl hydroperoxide | |
| CN110467595A (en) | A kind of no sulfuric acid process metaformaldehyde synthesizer and its synthesis route | |
| CN103333080A (en) | Quadruple-effect method for rectifying and recycling waste water containing DMF (dimethyl formamide) | |
| CN111233690A (en) | DMAc thermal coupling refining and recycling system and method | |
| CN105884586B (en) | A kind of method and device thereof of methanol gas phase dewatering preparing dimethy ether device combined production of methanol sodium | |
| CN105669383A (en) | Method for removing acid in phenol-acetone device decomposition liquid | |
| CN111995489B (en) | System and method for treating tail gas of ethylbenzene oxidation reaction | |
| CN212102640U (en) | System for preparing acetic anhydride by acetic acid cracking-ketene method | |
| CN103524478A (en) | Device and method for shortening ketalation time in ibuprofen synthesis process | |
| CN108083984A (en) | For glyphosate solvent and the method for by-product recovery | |
| CN207435077U (en) | A kind of processing system of acrylonitrile recycling tower bottoms | |
| CN112694163A (en) | Method for quenching waste water of catalytic wet-type acrylonitrile oxidation device | |
| CN102504852B (en) | Improved Litwin coal tar processing technic | |
| CN214781576U (en) | Caprolactam rearrangement heat energy cyclic utilization device | |
| CN112920018B (en) | Method for producing mixture of cyclohexanol and cyclohexanone by oxidizing cyclohexane | |
| CN106316792B (en) | The device and method of methanol and ethyl alcohol is recycled from stalk sugar hydrocrackates | |
| CN211972183U (en) | Acetic anhydride production system | |
| CN107473294A (en) | A kind of handling process and processing system of acrylonitrile recovery tower tower bottoms | |
| CN113842852A (en) | Process and system for annual production of 20 ten thousand tons of methylamine | |
| CN100352796C (en) | Process of preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in near critical water | |
| CN111848482A (en) | Separation method of cyclohexanone oxime gas phase reaction rearrangement product | |
| CN214299944U (en) | Equipment for producing cyclohexanol and cyclohexanone mixture by cyclohexane oxidation | |
| CN215975598U (en) | Device for refining cyclohexanone by cyclohexanol dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |