CN1061969C - Method of technical cumene hydroperoxide acidic cleavage to phenol acetone and alpha-methylstyrene - Google Patents

Abstract

Technical cumylhydroperoxide of a wide composition range is cleaved in circulating reactors of a shell and tube design at the same elevated pressure as dicumyl peroxide is cleaved in a plug flow reactor with a recirculation ratio of at least 26. The cleavage process is controlled using two calorimeters and controlling the absolute DELTA T value which is the difference in the temperature drop between the two calorimeters.

Description

Technical cumene hydroperoxide acidic cleavage is produced the method for phenol, acetone and alpha-methyl styrene

The present invention relates to use cumene (isopropyl benzene) synthesizing phenol, the method for acetone and alpha-methyl styrene (AMS).

Cumene process comprises two stages: the fs is to make oxidation of cumene become cumene hydroperoxide (CHP) with airborne oxygen, and subordinate phase is that the acidic catalyst cracking (decomposition) of CHP generates phenol and acetone.In the CHP cracking process, some useless product and phenol, acetone and AMS that is called as " phenol tar " generates together.The quantity of phenol tar depends primarily on employed CHP cleavage method, and at present best technology, its quantity is 50-60kg/t phenol, is 120-180kg/t phenol in traditional technology.

So far, many those skilled in the art are devoted to increase the selectivity of this method or improve productive rate.Yet when weighing the overall throughput of phenol-acetone production unit, output or rated output are the same with selectivity also to be-individual important index.So far also can not satisfy above-mentioned two requirements simultaneously.

Nearest technical progress is based on USP No.5, the CHP cleavage method of record in 254,751.The technical grade CHP cracking of carrying out according to this method as shown in Figure 1.This method is finished with two steps.

The-step is the CHP cracking with sulfuric acid catalysis, and this step is carried out in tubular reactor A, the B of three band shells that are cascaded, C, takes away reaction heat with the water coolant that is added in the reactor tube gap.Split product is that the ratio of 10-25/1 circulates in reaction member with internal circulating load to the CHP add-on.Sulfuric acid catalyst is added to the method for the most convenient in the reactor, be that it is joined in the circulation split product by pipeline 14, pump 2 is transported to circulation split product and catalyst sulfuric acid in the mixing tank 16, fresh technical grade CHP also is added in the mixing tank 16 by pipeline 17, and from wherein this mixture being transported to reactor A.In order to increase the selectivity of method, the water and the acetone of other quantity is added in the circulation cracking stream, depend on the add-on of CHP, the acetone that is added into calculates according to following algorithm (1): $\mathrm{Gac}=G_{\mathrm{CHP}}\×0.17\left[\mathrm{CHP}\right]+\frac{40}{G_{\mathrm{CHP}}\left[\mathrm{CHP}\right]}$ Wherein: Gac-amounts of acetone, the amount of t/hr GCHP-technical grade CHP, the weight concentration of CHP among t/hr [CHP]-technical grade CHP.

During each algorithm of listing in setting up this specification sheets, its quantity is measured with metric ton (ton or t).But, also can adopt any other weight unit to calculate as long as every kind of component is selected to use consistent identical unit of quantity.

Those skilled in the art knows that technical grade CHP is the impure cumene hydroperoxide that contains different amount impurity, and these impurity for example are DMBA, cumene, AP and other analogue, the product the when latter is oxidation of cumene, and oxidation of cumene is the first step reaction for preparing phenol from cumene.

Acetone recycle technology is crucial for the selectivity of method, selectivity is decided by three reactors (A in first workshop section in the first step in this method, B, C) temperature range in each reactor, be strict controlled under the normal atmosphere 50-62 ℃ respectively, 62-57 ℃ and 57-50 ℃, the conversion of CHP is respectively 30-60%, 25-50% and 30-10% in each reactor.Reactor A, B, C leads to atmosphere by the ventilation hole 13 of suitable design.

Because the scission reaction of CHP is a large amount of heat releases, need to use always to be not less than 30-35m than heat exchange area for PMT (Per metric ton) 100%CHP ²Reactor.Because the potentially dangerous of CHP scission reaction, in fact safer is that design is not less than 45-60m for PMT (Per metric ton) 100%CHP feed molar ratio exchange area ²Reactor.

Monitoring in the system that CHP decomposes process in the first step, is to finish by the calorimeter 3 (mini-reactor) that is contained in the particular design on last reactor outlet pipeline, temperature head (the δ T between the calorimeter entrance and exit material ₁), be the quantitative yardstick that remains in undecomposed CHP quantity in the split product.Typical δ T ₁Value is 4-16 ℃, and the amount that it is equivalent to be present in free CHP in last reactor of present method the first step is 0.6-2.3wt%.In the CHP cracking process, being present in technical grade CHP impurities in raw materials dimethyl benzyl alcohol (DMBA) can partly react with CHP simultaneously, generates intermediate two cumenyl superoxide (DCP) simultaneously.

When within the scope of CHP transformation efficiency, the CHP cracked time is from 30 seconds to 3 minutes, preferred 45 seconds to 2 minutes in above-mentioned circulation.

The cracking of the second step DCP is finished in two uniflux reactors 4 and 7 continuously, and ammonium hydroxide aqueous solution is added in first reactor 4 by pipeline 15, so that a part of sulfuric acid is transformed into NH ₄HSO ₄Therefore, the cracking of DCP is the binary catalyst (H with certain component control ratio ₂SO ₄+ NH ₄HSO ₄), under temperature 90-110 ℃, in reactor 7, to finish, the heating of product is finished by heat exchanger 6.

Reactor A in first workshop section, among B and the C, the cracking of CHP is under atmospheric pressure finished, and leads to atmosphere by the ventilation hole 13 of suitable design.In reactor 4, the cracking of DCP is under atmospheric pressure finished, and is being not less than under the 2atm in reactor 7 and is finishing.Between reactor 7 and the vaporizer 8 reducing valve 22 is housed.

A part of acetone in the split product is in normal atmosphere or be less than about under the normal atmosphere, preferably in evaporation in vaporizer 8 between the absolute pressure 500-600mmHg, residual split product leaves vaporizer and delivers to pipeline 20 from the bottom, so that further be processed into product phenol and acetone.The acetone that steams is cooled in water cooler 9 and simmer down to liquid, and liquid acetone is being advanced the reactor A of first workshop section with pump 11 pumps, is transported in the container 10 before among B and the C.

Aforesaid method had provided the method selectivity of highest level before the present invention, but also had several respects can carry out significant improvement:

1) needs jumbo reactor so that provide a large amount of heat exchange (more than 50m ²/ t 100%CHP), this will cause high equipment price and the high construction and the fund input of equipment replacement ability aspect.

2) intermediate receptacle (reactor 4) is under atmospheric pressure operated, and needs pump 5 that lysate is transported in the DCP convertor 7 of present method the 2nd step.

3), can cause in reactor 4, having the undecomposed CHP (from 0.5-2%) of volume, if H in the reduction of the 1st CHP of workshop section cracking temperature ₂SO ₄: NH ₄HSO ₄Ratio not right, danger will appear.

4) a spot of ammoniacal liquor of accurate measurement and H ₂SO ₄Be difficult to apply so that keep correct ratio, the metering out of true is at H ₂SO ₄Under the incomplete situation that neutralizes, can produce the AMS dimer and form the phenol mixture, at H ₂SO ₄In excessive and under the situation DCP is transformed not exclusively.The productive rate of desired product all can reduce in both cases, and " phenol tar " output can raise naturally.

5) be present in H in the split product ₂SO ₄And NH ₄HSO ₄, can cause that the acidic catalyst character of these catalyzer increases 4-7 doubly, and its concentration can increase side reaction continuation in this container, and because the selectivity that has reduced method of by product simultaneously in container 8 during acetone evaporated.The NH of above-mentioned low dosage ₄OH has worsened this situation, and causes producing the raw material cumene of 1 ton of phenol loss 10-20kg, and the output of AMS also can drop to 60% of theoretical amount.

6) with very weak an acidic catalyst (H ₂SO ₄+ NH ₄HSO ₄) operation DCP cracking reactor 7, the reactor volume of having relatively high expectations promptly needs 0.8m to this reactor feeding quantity per ton ³Be 0.4-0.5m to charging capacity reactor volume per ton in/t and the method for the present invention ³It is very disadvantageous that/t compares.

7) join acetone in the CHP cracking apparatus by above-mentioned algorithm (1), will cause higher energy requirement to be used for it and concentrate, and need to improve the equipment of heat-exchange capacity, this also causes adding large equipment cost substantial contribution for regulating compensation.

On the contrary, the present invention has improved the throughput of this method equipment, reduces volume of equipment when accusing new installation by building and can reduce capital contribution, and simplified technology, but still kept high method selectivity.

The method of prior art is represented with Fig. 1.Method of the present invention is represented with Fig. 2.

The cleavage step of CHP and DCP is in placed in-line reactor in the method for the invention, finishes under uniform pressure.Wherein the pressure in the reactor is about 2-10atm.Preferred pressure is about 3-5atm.CHP is added in the circulation loop of cleavage reaction product of sulfur acid catalyzer.The same with the method for prior art, sulfuric acid catalyst normally is added in the circulation loop by pipeline 14, and technical grade CHP is added into by pipeline 17, and mixes mutually with the CHP lysate that is circulating in mixing tank 16.In art methods, reactor A, B and C lead to atmosphericly, but in the method for the invention, pipeline 21 is linked to reactor A, B, C and 7 top, and keep all reactors to be co-located under the identical higher pressure.Because four all reactor A, B, C and 7 is under the identical pressure, and deleted reactor 4 in the method for the invention, being presented at the ammonia soln that adds by pipeline 15 in the art methods of Fig. 1, is to join in the pipeline that enters vaporizer 8 after reducing valve 22 in the method.Though adding ammoniacal liquor before near vaporizer 8 as shown in Figure 2 is most convenient, and not having ammonia really is present in the reactor 7, but as long as do not have ammonia in the reactor 7, add the implantation site after reactor 7 time, all inessential after being added in before the reducing valve 22 still.

In the present invention, the investment of pump and reactor 4 is unwanted, and this is because the first step of present method all was designed to operate under identical higher pressure with second step.The first step of the present invention reaction is than carrying out under the higher temperature of art methods, and this higher temperature requirement uses higher pressure, so that the boiling point of reduction lysate.The pressure in the high pressure of the inventive method the first step and second step is identical, does not therefore need to use pump.

Along with the cracking of CHP, the heat that the is discharged reactor A of present method the first step the 1st workshop section, the water coolant among B and the C is taken away.The reactant speed of circulation is no less than about 26: 1 to the weight ratio of CHP feeding rate, but no more than about 40: 1, preferred about 26: 1 to about 35: 1.

According to method of the present invention, join the acetone in present method the 1st step the 1st workshop section's reactor A, and it to the ratio of the industrial CHP quantity that adds for cracking by following algorithm (II) calculating: $\mathrm{Gac}=G_{\mathrm{CHP}}\×0.125\left[\mathrm{CHP}\right]+\frac{35}{G_{\mathrm{CHP}}\left[\mathrm{CHP}\right]}$ Wherein: Gac-is the amounts of acetone that cracking adds, and t/hr GCHP-is the amount of the technical grade CHP of cracking adding, the weight concentration of CHP among t/hr [CHP]-technical grade CHP.

This formula is applicable to the most common industrial CHP that can buy, and for example the CHP weight concentration is approximately from the technical grade CHP of 74%-92%.

The wideer algorithm that is applicable to wider scope is found, and provides control to use the more basis of the method for the technical grade CHP raw material of wide region.

Algorithm (III) is as follows:

Wherein: Gac-is the amounts of acetone that cracking adds, and t/hr GCHP-is the amount of the technical grade CHP of cracking adding, the CHP weight concentration of t/hr [CHP]-technical grade CHP.DMBA weight concentration among [DMBA]-technical grade CHP.Cumene weight concentration among [cumene]-technical grade CHP.The weight concentration of methyl phenyl ketone (AP) among [AP]-technical grade CHP.

Above-mentioned algorithm expands application of the present invention to CHP concentration and is low to moderate 40% weight and high CHP raw material to about 98% weight, preferably about 50-90%, and 60-85% more preferably from about, but above-mentioned algorithm also can be used for using the method for any CHP concentration.

In the present invention, the higher conversion of high temperature and CHP is used in the first step of CHP decomposition course.The transformation efficiency scope of reactor A .B and C is controlled at 55-78% respectively, 60-94% and 90-98%, and the total conversion rate of CHP is near complete in the present invention.Calorimeter 3 (mini-reactor) is contained in the exit of reactor C, and it can pass through above-mentioned δ T ₁Value indicates the total transforming degree of CHP.δ T ₁Representative value be from about 0.4-2.1 ℃, at pressure under about 3 to 4 normal atmosphere, reactor A, the representative temperature scope of B and C is respectively 57-82 ℃, 65-82 ℃ and 57-70 ℃.

Concentration at reactor exit CHP remains on 0.1-0.45wt%, preferred 0.2-0.4wt%, and the cracking time of CHP in the method for the invention, used the total specific surface of heat exchange to be 17-25m from 17 seconds to 28 seconds ²The reactor of/t 100%CHP.

The lysate that comes out from reactor C enters reactor 7 by well heater 6, and this moment, DCP and DMBA were converted to required product.

For 98% DCP and the transformation efficiency of DMBA are provided in reactor 7, the water of sufficient amount is added in the motionless mixer 19 on the reaction C product outlet line by pipeline 20.The content of water is controlled in and is no more than 3wt% in split product, preferred 1.3-2.0wt%.

The degree that control DCP and DMBA decompose behind water and split product hybrid position, be to realize by the temperature head (δ T2) that in system, monitors second mini-reactor 12 (calorimeter), mini-reactor 12 is connected in parallel on the reactor A that connects the 1st step of present method the 1st workshop section, and B and C are to the pipeline of reactor 7.Temperature in the mini-reactor 12 is in entrance and exit two place's Be Controlled.

As long as the residence time of split product in calorimeter 12 changes into phenol for DCP and DMBC, total conversion of acetone and AMS is competent, and the structure of calorimeter 12 is not important.In general this can flow by the low speed of split product slip-stream and reach.

The temperature control of this method is finished by temperature head (δ T), and δ T is the δ T of the 1st calorimeter ₁δ T with the 2nd calorimeter ₂Between difference, the absolute value of this δ T maintains in the 0.2-3 ℃ of scope.

In order to get rid of the chemical loss in the acetone evaporated process when product enters vaporizer 8, neutralization reagent alkali is added into by pipeline 18, and its quantity neutralisation of sulphuric acid fully becomes neutral salt (vitriol).Na ₂CO ₃, NH ₄OH, NaOH also can be used as neutralization reagent, and the ammoniacal liquor of 1-10wt% concentration is better.

Method of the present invention has the following advantages:

1) scope of application of method is wideer, and it can adopt more the technical grade CHP of wide region CHP concentration (40-98% weight), and high working (machining) efficiency is arranged.

2) need not a large amount of fund inputs and can make equipment capacity improve 2-2.5 doubly, when output was high, selectivity still kept maximum value (the AMS productive rate is the 78-80% of theoretical amount).

3) reduced 50-60% by the investment of the new cracking apparatus built, this be because:

A) the CHP scission reaction occurs in (17-25m in the reactor of low ratio heat exchange area ²And the ratio heat exchange area of traditional reactor is 40-60m/t CHP), ²/ t CHP.

B) the DCP scission reaction takes place in a reactor rather than in two reactors, because two reactors can operate under same pressure, thereby two reactors can intensively turn to an equipment.

4) owing to reduced the quantity of acetone recycle, and from process, save pump 5, thereby reduced energy consumption in operation.

5) saved in the DCP cleavage step and added ammonia, only added water, so just simplified H ₂SO ₄The control of acidic catalyst performance.

6) by δ T=δ T ₂-δ T ₁Process control the CHP cracking process has been simplified, all automatically help the selectivity of the method for having kept in CHP cleavage stages and DCP cleavage stages.

7) before the acetone evaporated device fully in and H ₂SO ₄Unwanted side reaction has been got rid of in help.

In addition, in the existing method leakage of lower boiling acetone by connecting the 1st workshop section reactor A, B and C and the DCP cracking reactor in present method of realization novel process be excluded.

Of the present inventionly elaborated, but be not subjected to the restriction of these examples, and compared with the comparative example 1 who represents prior art by following embodiment 2-14.

Comparing embodiment 1

Use art methods shown in Figure 1, with the technical grade CHP that following wt% forms, be added to continuously in the reactor unit of being made up of the tubular reactor of three band shells, its total reaction capacity is 10.08m ³:

Cumene hydroperoxide 82.500wt%

Cumene 12.721wt%

Dimethyl benzyl alcohol 4.325wt%

Methyl phenyl ketone 0.453wt%

Per hour 26 tons of technical grade CHP are added to the CHP reactor A, and among B and the C, according to the calculating of algorithm (1), the acetone of 5492kg/h is added into, and the sulfuric acid of 16kg/h amount is added in the above-mentioned reactor, and the split product that circulates therein.For scission reaction, it is 1254m that the total heat of reactor is transmitted the surface ², this heat passage value of ratio that is equivalent to 100%CHP per ton is 58m ²/ t CHP.

The residence time in the CHP cracking reactor is 74 seconds.Temperature on each reactor outlet pipeline is respectively 58 ℃, and 55 ℃ and 50 ℃, each reactor exit CHP transformation efficiency is respectively 38%, 73% and 85%, temperature reduction value (the δ T in the mini-reactor 3 ₁) be 5.6 ℃, CHP mixes with 1: 16 the ratio (recycle ratio is 16) and the lysate of reaction in the cracking reactor ingress, and 10kg sulfuric acid is added in the circulation loop.

The cracking of DCP is to finish in two uniflux reactors of non-stop run at low temperatures, and first temperature of reactor is 58 ℃, and second is 93 ℃.33.8kg/h ammonia soln be added in first reactor with 5wt% concentration, so will be 50% for the sulfuric acid degree of neutralization that sulfuric acid is transformed into monoammonium sulfate.

CHP cracking and DCP cracking in two uniflux reactors in three band package line reactors are to carry out under different pressure, in CHP cracking reactor and first reactor of DCP cracked is normal atmosphere, and the pressure of second reactor of DCP cracked is 3-5atm.

The residence time in the DCP cracking reactor is respectively to stop 420 seconds in reactor 4, stops 2030 seconds in reactor 7.

Acetone is transported in the cracking apparatus by pump 11 from container 10, and above-mentioned acetone is evaporated from the reaction lysate of DCP under decompression in vaporizer 8, is condensed into liquid in water cooler 9.

The total overall reaction result who appears in the reactor is:

Phenol-13174.5kg/h (productive rate 99.2%)

Acetone-8084.5kg/h (productive rate 98.9%)

Alpha-methyl styrene-54.5kg/t phenol (is considered the DMBA of adding, the product of AMS

Rate be theoretical amount 73.4%)

Phenol tar output-59.2kg/t phenol

Cumene consumption-1333kg/t phenol

In present embodiment and embodiment subsequently, the consumption figures of cumene only is the effect for comparative descriptions the inventive method, and the present invention only relates to the part of whole phenol processes.When not counted cumene in total process and consume as other cumene reclaimer operation of the part among the present invention, clean cumene consumption is just lower, is generally 1307-1310kg/t.

Embodiment 2

The output that this embodiment of the present invention illustrates rate ratio embodiment 1 is high 2.3 times.Method of the present invention in present embodiment and following examples is finished according to Fig. 2 is described.All reactors of present embodiment are all operated under identical pressure, and all the working pressure of system is 4kg/cm ²

Per hour 60 tons technical grade CHP is added in the CHP cracking reactor, and its composition is same as embodiment 1.The cracking of technical grade CHP is to carry out under the following conditions, and recycle ratio is 26/1, and the temperature of each reactor inlet is respectively 68 ℃, 67 ℃ and 60 ℃, and the accumulation CHP transformation efficiency in each reactor is respectively 62%, 94% and 98%.

Spissated acetone is according to the calculating of formula II from container 10, is added to (the 1st workshop section) in the cracking apparatus with the speed of 6890kg/h: $G_{\mathrm{ac}}=G_{\mathrm{CHP}}\×0.125\left[\mathrm{CHP}\right]+\frac{35}{G_{\mathrm{CHP}}\left[\mathrm{CHP}\right]}$ Wherein Gac is an amounts of acetone, G _CHPBe the amount of technical grade CHP, both represent with t/hr that all 1 ton (t) equals 1000 kilograms (kg) herein.[CHP] is the concentration of CHP among the technical grade CHP, represents temperature drop-out value δ T in the mini-reactor 3 of cracking apparatus with wt% ₁=0.4 ℃.

By entering the pipeline of DCP cracking reactor 7, add entry with the speed of 482kg/h, making the concentration of water in the reactor exit split product is 1.63wt%, the cracking time is 485 seconds.

In split product and the mixed position of water, mini-reactor 12 (calorimeter) is installed, measure temperature reduction value (the δ T between outlet and the inlet herein ₂).Process control is actually to reduce by absolute temperature and realizes,

δT=δT ₂-δT ₁=0.65℃

Ammonia soln is added in the product inlet pipeline that enters acetone evaporated device 8 by pipeline 18 with the speed of 10%wt concentration and 145kg/h, so that get rid of the chemical loss of required product in acetone evaporated device 8.

Consequently:

Phenol-30431.2kg/h (productive rate 99.5%)

Acetone-18769.7kg/h (productive rate 98.5%)

Alpha-methyl styrene-58.5kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-54.2kg/t phenol

Cumene consumption-1328kg/t phenol

Embodiment 3

The present embodiment explanation is reducing the reactor A of capacity, the process of the present invention of carrying out among B and the C, and these reactor A, B and C are the heat transfer surface of attenuating and the heat exchanger of low specific surface.This process is finished according to the route described in the embodiment 2, but the equipment that uses in embodiment 3 is:

The volumetric ratio embodiment 1 of CHP cracking reactor system is little 2.8 times,

The surface ratio embodiment 1 of body series heat exchanger is little 3.5 times,

The specific surface of DCP cracked heat exchanger is littler 3 times than embodiment 1 described similar value.

The technical grade CHP that forms identical 26t/hr with embodiment 1 is added in the CHP cracking reactor, 9.3kg/hr sulfuric acid be added to by the CHP cracking reactor (A in the 1st workshop section, B, C) in the circulation loop of Zu Chenging, the cracking of technical grade CHP is to carry out reactor A under the following conditions, the temperature of B and C outlet is respectively 79 ℃, 75 ℃ and 69 ℃, the CHP transformation efficiency is respectively 77%, 96% and 98%.

The acetone recycle of the 4312kg/h that calculates by the formula II among the embodiment 2 is added to the CHP cracking apparatus from container 10.

The residence time of reaction product is 638 seconds in DCP cracking reactor 7.

Consequently:

Phenol-13185.3kg/h (productive rate 99.4%)

Acetone-8075.4kg/h (productive rate 98.8%)

Alpha-methyl styrene-58.02 kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-55.03kg/t phenol

Cumene consumption-1329kg/t phenol

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁=0.34 ℃.

Absolute temperature difference δ T=δ T ₂-δ T ₁=0.66 ℃

Concentration is that the ammonia soln of 10%wt is added in the product inlet pipeline of acetone evaporated device 8 with the speed of 63kg/h, so that get rid of the chemical loss of desired product in the acetone evaporated device, so the transforming degree that acid is transformed into ammonium sulfate in acetone evaporated device 8 is 100%.

Embodiment 4

The present embodiment explanation is confirmed as 25m at the heat exchange specific surface ²The reactor A of/t 100%CHP among B and the C, is implemented situation of the present invention.

The technical grade CHP of the 26t/h that composition is determined by embodiment 1 is added in the CHP cracking reactor, and recycle ratio is 26/1.9.3kg/h sulfuric acid be added in the circulation loop of forming by CHP cracking reactor A, B and C, the cracking of CHP is respectively in reactor A, B and C temperature out are 67 ℃, carry out under 66 ℃ and 61 ℃, the CHP transformation efficiency is respectively 62%, 87% and 94%.

Calculate with the formula II that proposes among the embodiment 2, with the acetone of the rate loop of 4312kg/h, join the cracking apparatus of CHP from container 10.

The time that reaction product stops in DCP cracking reactor 7 is 640 seconds.

Consequently obtain following quantity:

Phenol-13188.5kg/h (productive rate 99.3%)

Acetone-8078.9kg/h (productive rate 98.8%)

Alpha-methyl styrene-58.5kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-53.9kg/t phenol

Cumene consumption-1328kg/t phenol

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁=1.26 ℃, mini-reactor 12 is contained in water and is added in the reaction product circulation loop outlet afterwards, and the temperature reduction value in the mini-reactor 12 is 1.98 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.72 ℃

Concentration is the ammonia soln of 10%wt, speed with 63kg/h is passed through pipeline 18, be added in the product inlet line of leading to acetone evaporated device 8, so that get rid of the chemical loss of desired product in acetone evaporated device 8, so the transforming degree that sulfuric acid is transformed into ammonium sulfate in the acetone evaporated device is 100%.

Embodiment 5

Present embodiment illustrates each cracking apparatus than adding technical grade CHP under the lower velocity, and under high recycle ratio situation the fabulous selectivity of the inventive method.

Composition joins in the CHP cracking reactor by the technical grade CHP of the 22t/h of embodiment 1 regulation, and recycle ratio is 35, adds the sulfuric acid of 7.2kg/h in the circulation loop of being made up of CHP cracking reactor A, B and C.The cracking of technical grade CHP is in reactor A, and B and C temperature out are respectively 72 ℃, carries out under 78 ℃ and 67 ℃, and the CHP transformation efficiency is respectively 65%, 92% and 97%.

By the 4192kg/hr acetone recycle that formula II among the embodiment 2 calculates, from container 10, be added to the cracking apparatus (the 1st workshop section) of CHP.

The residence time of reaction product in DCP cracking reactor 7 is 865 seconds.

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁=0.82 ℃

Be installed in the mini-reactor 12 after the device of reaction product circulation loop exit water supply, the temperature depreciation is 1.68 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.86 ℃

Concentration is 10% the ammonia soln speed with 48kg/h, be added in the product inlet pipeline that enters acetone evaporated device 8, avoiding the chemical loss of desired product in the acetone evaporated device, so that the transforming degree that sulfuric acid becomes ammonium sulfate is 100% in acetone evaporated device 8.

The result obtains the product of following quantity:

Phenol-11156.4 kg/h (productive rate 99.4%)

Acetone-6815.7kg/h (productive rate 98.5%)

Alpha-methyl styrene-58.1kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-55.14kg/t phenol

Cumene consumption-1328kg/t phenol

Embodiment 6

The present embodiment explanation adds under the technical grade CHP situation high selectivity of the inventive method with the moderate speed at each cracking apparatus.

Composition is added in the CHP cracking reactor by the technical grade CHP of the 35t/h of embodiment 1 regulation, and recycle ratio is 26, adds the sulfuric acid of 11.80kg/h in the circulation loop of being made up of the CHP cracking reactor.The cracking of technical grade CHP is in reactor A, and B and C temperature out are respectively 74 ℃, carries out under the situation of 71 ℃ and 65 ℃, and the CHP transformation efficiency is respectively 70%, 93% and 97%.

The speed that calculates according to the formula II among the embodiment 2 is that the acetone recycle of 4821kg/h is added to CHP cracking apparatus (the 1st workshop section) from container 10.

The residence time of reaction product in DCP cracking reactor 7 is 487 seconds.

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁=0.64 ℃, be installed in the mini-reactor 12 of reaction product after the device that supplies water in the circulation loop exit, the temperature depreciation is 1.92 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 1.72 ℃

Concentration is 10% the ammonia soln speed with 80kg/h, be added to the product inlet pipeline that enters acetone evaporated device 8 by pipeline 18, so that prevent the chemical loss of required product in the acetone evaporated device, so that the transforming degree that sulfuric acid becomes ammonium sulfate is 100% in the acetone evaporated device.

The gained result is as follows:

Phenol-17751kg/h (productive rate 99.4%)

Acetone-10906kg/h (productive rate 98.5%)

Alpha-methyl styrene-58.6 kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-54.14kg/t phenol

Cumene consumption-1328kg/t phenol

Embodiment 7

Present embodiment illustrates each cracking apparatus under the medium feed rate of technical grade CHP, the reproducibility of present method high selectivity.In the present embodiment, in fact the concentration of technical grade CHP be higher than the concentration among comparing embodiment 1 and the embodiment 2-6.

The technical grade CHP of the 35t/h of following composition is added in the CHP cracking reactor.

CHP 91.5％(wt)

Cumene 2.0% (wt)

DMBA 5.5％(wt)

Methyl phenyl ketone 1.0% (wt)

Recycle ratio is 26, adds the sulfuric acid of 9.3kg/h in the response circuit of being made up of CHP cracking reactor A, B and C.The cracking of technical grade CHP is respectively 71 ℃ in the reactor outlet temperature, finishes under the situation of 67 ℃ and 61 ℃, and the CHP transformation efficiency is respectively 75%, 94% and 98%.

The speed that calculates by the formula II among the embodiment 2 is the acetone recycle of 4444kg/h, is added to the CHP cracking apparatus from container 10.

The residence time of reactor product in DCP cracking reactor 7 is 640 seconds.

In the mini-reactor 3 of cracking apparatus, temperature drop-out value δ T ₁=0.49 ℃, the temperature reduction value that is installed in the mini-reactor 12 in the circulation loop exit after the reactor product pipeline adds water is 1.38 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.89 ℃

Concentration is 10% the ammonia soln speed with 63kg/h, be added to the product source line that leads to acetone evaporated device 8, preventing the chemical loss of desired product in acetone evaporated device 8, so that the transforming degree that sulfuric acid becomes ammonium sulfate is 100% in the acetone evaporated device.

Obtain following result:

Phenol-14610.2kg/h (productive rate 99.4%)

Acetone-8972.3kg/h (productive rate 98.5%)

Alpha-methyl styrene-56.6kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-62.51kg/t phenol

Cumene consumption-1335kg/t phenol

The foregoing description explanation is having under the fabulous reproducible various reaction conditionss, technical grade CHP when the feed rate of different levels, the high selectivity of present method.

Embodiment 8

Present embodiment and following embodiment (9-14) are by the preferred embodiment of the inventive method, explanation increases by 2.3 times than the output of embodiment 1, it uses the formula III to calculate the amounts of acetone that adds, and explanation has the utmost point widely under the situation of concentration range 40-98% at technical grade CHP, and it also is effective using this embodiment.With embodiment 2 relatively, this method is finished under the situation of the preparation that need not to change equipment.All reactors are all operated under uniform pressure in the inventive method, so all reactors are coupled to each other by the top, system's total pressure is 4kg/cm ²

Concentrated acetone from container 10 is added in the cracking apparatus with the speed 6890kg/h that calculates by following calculation formula III:

Wherein: Gac-is the amounts of acetone that cracking adds, t/h GCHP-is the technical grade CHP amount that cracking adds, the weight concentration of methyl phenyl ketone among weight concentration [the AP]-technical grade CHP of cumene among weight concentration [cumene]-technical grade CHP of DMBA among weight concentration [DMBA]-technical grade CHP of CHP among t/h [CHP]-technical grade CHP

The technical grade CHP of 60t/h is added among CHP cracking reactor A, B and the C, and its composition is identical with embodiment 1.21.3kg/h sulfuric acid also be added in this reactor, the cracking of technical grade CHP is respectively under 68 ℃, 67 ℃ and 60 ℃ at reactor inlet temperature with 26/1 recycle ratio to be carried out, and is equivalent to CHP transformation efficiency 59%, 94%, 98%.

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁=0.4 ℃.

Water passes through pipeline 20 and motionless mixer 19 with the speed of 455kg/h, is added in the product feeding pipe line that enters DCP cracking reactor 7, and water is 1.58% (wt) in the concentration of reactor exit in split product to cause, and the cracking time is 485 seconds.

The 2nd mini-reactor 12 (calorimeter) is installed on the position after mixed pyrolysis product and water, and the temperature of measuring its outlet and ingress reduces δ T ₂, process control is worth by the absolute temperature reduction in fact to be finished:

δT=δT ₂-δT ₁=0.62℃

Concentration is 10% ammonia soln, pass through pipeline 18 with linear velocity 141kg/h, be added to the product inlet pipeline that enters acetone evaporated device 8, so that get rid of the chemical loss of desired product in acetone evaporated device 8, the transforming degree that causes acid to become ammonium sulfate is 100% in acetone evaporated device 8.

Obtain following result:

Phenol-30434.1kg/h (productive rate 99.5%)

Acetone-18774.8kg/h (productive rate 98.5%)

Alpha-methyl styrene-58.4kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 78.9%)

Phenol tar output-54.0kg/t phenol

Cumene consumption-1328kg/t phenol

Embodiment 9

The inventive method that the present embodiment explanation is implemented when reactor capacity reduces, reduce on the thermoconverter surface of this reactor, and therefore the specific surface of heat exchanger is low.This process is carried out according to embodiment 8 described routes, but present embodiment equipment used such as following:

The volume ratio embodiment 1 of CHP cracking reactor system is little 2.8 times,

Body series thermoconverter surface area ratio embodiment 1 is little 3.5 times,

The specific surface of DCP cracking heat exchanger is littler 3 times than embodiment 1 described analog value,

Form technical grade CHP, be added in CHP cracked A, B and the C reactor, add the sulfuric acid of 9.3kg/h in the circulating system of forming by CHP cracking reactor A, B and C (the 1st workshop section) as the 26t/h of embodiment 1 defined.The cracking of technical grade CHP is to be respectively that 73 ℃, 70 ℃ and 65 ℃ of following situations are finished in reactor A, B and C temperature out, is 66%, 90%, 96% corresponding to the CHP transformation efficiency.

By the 4312kg/h acetone of the calculating of the formula III among the embodiment 8, by being added to CHP cracking apparatus (the 1st workshop section) in the container 10.

The residence time of reaction product in DCP cracking reactor 7 is 630 seconds.

Obtain following result:

Phenol-13183.2kg/h (productive rate 99.4%)

Acetone-8072.5kg/h (productive rate 98.8%)

Alpha-methyl styrene-58.02kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 78.4%)

Phenol tar output-55.43kg/t phenol

Cumene consumption-1329kg/t phenol

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁It is 0.95 ℃.

Absolute temperature difference δ T=δ T ₂-δ T ₁=0.58 ℃

Concentration is 10% the ammonia soln speed with 63kg/h, be added in the acetone evaporated device 8 product inlet pipelines by pipeline 18, so that get rid of the chemical loss of desired product in acetone evaporated device 8, so that the transforming degree that sulfuric acid changes into ammonium sulfate 8 is 100% in the acetone evaporated device.

Embodiment 10

The present embodiment explanation is 25m in the specific surface area based on 100%CHP, heat exchange ²In the reactor of/t, the method for being implemented of the present invention.Composition is added in the CHP cracking reactor by the technical grade CHP of the 26t/h of embodiment 1 regulation, and recycle ratio is 26, adds the sulfuric acid of 9.3kg/h in the circulation loop of being made up of CHP cracking reactor A, B and C.The cracking of technical grade CHP is respectively under 67 ℃, 66 ℃ and 60 ℃ in A, B and C reactor outlet temperature to be carried out, and is respectively 62%, 82% and 90% corresponding to the CHP transformation efficiency.

The acetone of the 4313kg/h that is calculated by the formula III among the embodiment 8 joins the CHP cracking apparatus from container 10.

The residence time of reactor product in DCP cracking reactor 7 is 640 seconds.

The gained result data is as follows:

Phenol-13188.4kg/h (productive rate 99.3%)

Acetone-8082.9kg/h (productive rate 98.8%)

Alpha-methyl styrene-50.1kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.8%)

Phenol tar output-52.9kg/t phenol

Cumene consumption-1327kg/t phenol

In the mini-reactor 3 of cracking apparatus, temperature reduction value δ T ₁Be 2.17 ℃, δ T in the temperature reduction value in the mini-reactor 12 that is contained in the circulation loop exit after reactor product supplies water ₂=3.11 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.94 ℃

Concentration is 10% the ammonia soln speed with 63kg/h, be added to the product inlet pipeline of acetone evaporated device 8 by pipeline 18, to prevent the chemical loss of desired product in the acetone evaporated device, the consequently sour transforming degree that becomes ammonium sulfate is 100% in the acetone evaporated device.

Embodiment 11

Present embodiment illustrates each cracking apparatus under lower feed rate of technical grade CHP and higher recycle ratio situation, the high selectivity of the inventive method.

Composition is added among CHP cracking reactor A, B and the C by the technical grade CHP of the 22t/h of embodiment 1 regulation.Recycle ratio is 35.The sulfuric acid that in the circulation loop of forming by CHP cracking reactor A, B and C, adds 8.3kg/h.The cracking of technical grade CHP is respectively to carry out under 72 ℃, 78 ℃ and 67 ℃ in reactor A, B and C temperature out, and the CHP transformation efficiency is corresponding to be 68%, 94% and 98%.

The speed that is calculated by embodiment 8 formula III is the acetone of 4191.4kg/h, is added to CHP cracking apparatus (the 1st workshop section) from container 10.

The residence time of reactor product in DCP cracking reactor 7 is 737 seconds.

Temperature reduction value δ T in the mini-reactor 3 of cracking apparatus ₁=0.39 ℃, the temperature reduction value that is contained in the mini-reactor 12 on the circulation loop outlet position after reaction product supplies water is 0.99 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.6 ℃

Concentration is 10% the ammonia soln speed with 55.1kg/h, be added to by pipeline 18 in the product inlet pipeline of acetone evaporated device 8, so that get rid of the chemical loss of desired product in the acetone evaporated device, thus acid to become the transforming degree of ammonium sulfate in acetone evaporated device 8 be 100%.

Obtain following result:

Phenol-11159.1kg/h (productive rate 79.4%)

Acetone-6821.8kg/h (productive rate 98.5%)

Alpha-methyl styrene-57.8 kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 78%)

Phenol tar output-55.6kg/t phenol

Cumene consumption-1328kg/t phenol

Embodiment 12

Present embodiment illustrates that each cracking apparatus adds under the technical grade CHP situation selectivity of the inventive method under the moderate speed.

Composition is added among CHP cracking reactor A, B and the C by the 35t/h r technical grade CHP of embodiment 1 regulation.Recycle ratio is 26.The sulfuric acid that adds 13.1kg/h in the circulation loop of forming by CHP cracking reactor A, B and C.The cracking of technical grade CHP is respectively to carry out under 73 ℃, 71 ℃ and 66 ℃ in reactor A, B and C temperature out, is 55%, 82% and 91% corresponding to the CHP transformation efficiency.

The speed that calculates according to the formula III among the embodiment 8 is the acetone recycle of 6410kg/h, is added to cracking apparatus (the 1st workshop section) from container 10.

Reaction product residence time in DCP cracking reactor 7 is 467 seconds.

In mini-reactor 3, temperature reduction value δ T ₁=2.09 ℃, in the mini-reactor 12 in the circulation loop outlet that is installed on after reaction product supplies water, temperature reduction value is 3.04 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.95 ℃

Concentration is 10% the ammonia soln speed with 88.7kg/h, be added in the product inlet pipeline of acetone evaporated device 8, so that get rid of the chemical loss of required product in acetone evaporated device 8, so that the sour transforming degree that becomes ammonium sulfate is 100% in the acetone evaporated device.

Obtain following result:

Phenol-17752.4kg/h (productive rate 99.4%)

Acetone-1 0904.3kg/h (productive rate 99.1%)

Alpha-methyl styrene-58.9kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 79.67%)

Phenol tar output-53.84kg/t phenol

Cumene consumption-1328kg/t phenol

The foregoing description 12 illustrates the CHP cracking apparatus under the situation that the inventory that higher level is arranged is passed through, practicality of the present invention (being that 35t/h and 26t/h compare)

When following embodiment illustrates the technical grade CHP raw material that uses different CHP concentration, practicality of the present invention.CHP is dense in the embodiment 13 explanation raw materials, and CHP is poorer in the embodiment 14 explanation raw materials.

Embodiment 13

The embodiment of this technical grade CHP is in order to the high selectivity of explanation the inventive method under high density CHP situation.

The 26t/hr technical grade CHP of following composition is added among CHP cracking reactor A, B and the C:

CHP 91.5％(wt)

Cumene 2.0% (wt)

DMBA 5.5％(wt)

Methyl phenyl ketone 1.0% (wt)

Recycle ratio is 26, adds the sulfuric acid of 9.3kg/h in the circulation loop of being made up of CHP cracking reactor A, B and C.The cracking of technical grade CHP is 72.5 ℃ in reactor A, B and C temperature out, carries out under 68 ℃ and 61 ℃, and be 78%, 96% and 98% corresponding to the CHP transformation efficiency.

The speed of calculating according to the formula III among the embodiment 8 is the acetone recycle of 4444kg/h, is added to CHP cracking apparatus (the 1st workshop section) from container 10.

The residence time of reaction product in reactor 7 is 642 seconds.

In the mini-reactor 3 of cracking apparatus. temperature reduction value δ T ₁Be 0.36 ℃, in the mini-reactor 12 that is installed on the circulation loop outlet place after reaction product supplies water, temperature reduction value is 1.46 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 1.1 ℃

Concentration is 10% ammonia soln, with the speed of 63kg/h, is added in the acetone evaporated device 8 product source lines, so that get rid of the chemical loss of required product in acetone evaporated device 8, so that the sour transforming degree that becomes ammonium sulfate is 100% in the acetone evaporated device.

The result obtains following data:

Phenol-14607.4 kg/h (productive rate 99.3%)

Acetone-8975kg/h (productive rate 99.9%)

Alpha-methyl styrene-64.8 kg/t phenol (is considered the DMBA of adding, AMS

Productive rate be theoretical amount 77.33%)

Phenol tar output-69.36kg/t phenol

Cumene consumption-1342kg/t phenol

Embodiment 14

The high selectivity of present embodiment explanation the inventive method under lower concentration CHP situation.

The 26t/hr technical grade CHP of following composition is added among CHP cracking reactor A, B and the C:

CHP 67％(wt)

Cumene 28.6% (wt)

DMBA 4％(wt)

Methyl phenyl ketone 0.4% (wt)

Recycle ratio is 26, in the circulation loop of forming by CHP cracking reactor A, B and C as the sulfuric acid of 11.8kg/h.The cracking of CHP is respectively 69 ℃ in reactor A, B and C temperature out, carries out under 63 ℃ and 62 ℃, and the CHP transformation efficiency should be 68%, 96% and 98% mutually.

The speed that calculates according to formula III among the embodiment 8 is that the acetone recycle of 2376kg/h joins CHP scission reaction equipment (the 1st workshop section) from container 10.

The residence time of reaction product in DCP cracking reactor 7 is 516 seconds.

Temperature reduction value δ T in mini-reactor 3 ₁Be 1.58 ℃, in the mini-reactor 12 in the circulation loop outlet that is installed on after reaction product supplies water, temperature reduction value is 2.04 ℃.

Absolute temperature difference (δ T=δ T ₂-δ T ₁) be 0.46 ℃

Concentration is 10% the ammonia soln speed with 79kg/h, be added to the product inlet pipeline of acetone evaporated device 8 by pipeline 18, so that get rid of the chemical loss of required product in acetone evaporated device 8, so that the sour transforming degree that becomes ammonium sulfate is 100% in acetone evaporated device 8.

Obtain following result:

Phenol-14402kg/h (productive rate 99.2%)

Acetone-8833kg/h (productive rate 98.9%)

Alpha-methyl styrene-67kg/t phenol (is considered and is added DMBA, AMS

Productive rate be theoretical amount 79.9%)

Phenol tar output-79.9kg/t phenol

Cumene consumption-1331kg/t phenol

Below be the inventive method and USP No.5.254, the comparison of 751 methods operation.

With USP No.5,254,751 method is compared, it is faster that cleavage method of the present invention carries out speed, and more " reliably ", in the methods of the invention three reactor A, B and C are littler, and are operation under higher temperature (and elevated pressures are to reduce boiling point)

Temperature ℃

A B C pressure 68-79 78-65 of the present invention 69-60 3-4atmUS 5,254,751 50-62 62-57 57-50 1atm

CHP transformation efficiency by three reactors is different from USP NO.5,254,751.In the methods of the invention, leave first reactor after the C liver raw material of higher per-cent is fallen by reaction consumes, in fact do not have unreacted CHP to come out, the δ T of calorimeter from reactor C ₁, be controlled at very low value (＜1 ℃).

% CHP transformation efficiency wt%CHP

A B C calorimeter 3 the present invention 75 90 98 0.2US 5,254,751 45 75 88 1.0

In the methods of the invention, in reactor A, B and C, use higher recycle ratio (2 6: 1-4 0: 1) so that the CHP raw material obtains extra dilution, so under very fast rate of cleavage, can keep safe operation.The CHP concentration that adds reactor A is 2.5-3wt%, and at USP No.5, in 254,751 methods, this numerical value is 4.5-5wt%.CHP residence time in the 1st step of the present invention is 17-28 second, and at US 5,254, is 50-60 second in 751 the method.

For the first step reaction, the concentration of sulfuric acid, water and acetone comes down to identical in two kinds of methods, and the concentration of sulfuric acid catalyst all is 300ppm in both cases.

In the methods of the invention, the outlet of the 1st step and the 2nd step is associated in together, and therefore two steps are to operate under the pressure of same raising, have so just saved the investment of pump and other equipment.

The foregoing description, experiment with expected result be with laying down a definition and illustrating of the present inventionly, be not the present invention only will be limited on the concrete those disclosed parameter of institute.Therefore by conscientiously reading this specification sheets, can make many improvement of above-mentioned record, but as following claims defined, these all should can be regarded as scope of the present invention and content.

The data of embodiment are taken notes in following table:

Embodiment #	The add-on CHP l/hr of technical grade CHP	The volume CHP DCP m of cracking reactor 3	Heat exchange area and total specific surface area m 2 m 2/t CHP	Residence time CHP DCP sec sec in cracking reactor	Recycle ratio	Acetone recycle flow velocity kg/hr	7 ℃ of temperature DCP CHP AB C in the cracking reactor
								1	26	10.08 16	1254 58	74 2040	16	5192	58 55 50 93
2	60	10.08 16	1254 25	21.4 485	26	6893	68 67 60 99
								3	26	3.6 7	360 17	18 638	26	4312	79 75 69 95
4	26	4.5 7	540 25	22 6400	26	4312	67 66 61 96
								5	22	4.5 7	540 25	28 865	35	4192	72 78 67 93
6	35	4.5 7	540 19	16.8 487	26	48821	74 71 65 96
								7	26	4.5 7	540 23	22 640	26	4444	71 67 61 94
8	60	10.08 16	1254 25	21 485	26	6898	68 67 60 99
								9	26	3.8 7	360 17	18 638	26	4312	73 70 65 95
10	26	4.5 7	540 25	22 640	26	4313	67 65 63 96
								11	22	4.5 7	540 25	28 737	35	4191	72 78 67 93
12	35	4.5 7	540 19	168 467	26	6410	73 71 65 96
								13	26	4.5 7	540 23	22 640	26	4444	72 68 61 94
14	26	4.5 7	540 23	22 516	26	2376	69 63 62 96

* in embodiment 1, the pressure among CHPP cracking reactor A, B and the C is normal atmosphere, and the pressure in DCP cracking reactor 7 is 3atm.* in embodiment 2-14, among CHP cracking reactor A, B and the C and the pressure in the DCP cracking reactor 7 all are 4atm.

Embodiment #	The transformation efficiency A B C % of CHP in the reactor	The 1st 2nd ℃ of temperature head in the mini-reactor	Temperature head between mini-reactor ℃	H in the DCP cracking reactor 2SO 4Degree of neutralization %	The concentration wt.% of water in the DCP cracking reactor	The productive rate % theoretical value of AMS behind the DCP cracking reactor	The productive rate % theoretical value of AMS behind vaporizer
								1	38 73 85	56	-	25	1.38	80.3	73.4
2	62 96 98	0.40 1.05	0.65	100	1.63	79.9	79.9
								3	77 96 98	0.34 4.0	0.56	100	1.68	78.8	78.8
4	62 87 94	1.26 1.98	0.72	100	1.55	79.9	79.9
								5	65 92 97	0.82 1.68	0.86	100	1.68	79.3	79.3
6	70 93 97	0.64 1.91	1.27	100	1.58	79.6	79.6
								7	75 94 98	0.49 1.38	0.89	100	1.67	79.6	79.6
8	59 94 98	0.40 1.58	0.62	100	1.58	78.9	78.9
								9	66 90 96	0.95 1.53	0.58	100	1.68	78.4	78.4
10	62 82 90	2.17 3.11	0.94	100	1.55	79.8	79.8
								11	68 94 98	0.39 0.99	0.6	100	1.68	78.0	78.0
12	55 82 91	2.09 3.04	0.95	100	1.58	79.6	79.6
								13	78 96 98	0.36 1.46	1.10	100	1.67	77.3	77.3
14	68 96 98	1.58 2.04	0.40	100	1.50	79.9	79.5

* in embodiment 1, the pressure among CHP cracking reactor A, B and the c is normal atmosphere, and the pressure in DCP cracking reactor 7 is 3atm.* in embodiment 2-14, among CHP cracking reactor A, B and the c and the pressure in the DCP cracking reactor 7 all are 4atm.

Claims (12)

1. improved method of producing phenol and acetone from cumene, this method comprises acidic catalyst cracking technical grade cumenyl hydrogen peroxide and cracking two cumenyl superoxide, improvement wherein comprises: be higher than in first reactor under the atmospheric pressure, cracking technical grade cumenyl hydrogen peroxide, obtain the lysate of cumenyl hydrogen peroxide, contain two cumenyl superoxide in this lysate, and in second reactor in being higher than under the atmospheric uniform pressure, therefore cracking two cumenyl superoxide do not need pump and compensation equipment that cumenyl hydrogen peroxide lysate is transported to two cumenyl superoxide cracking reactors from cumenyl hydrogen peroxide cracking reactor.

2. according to the process of claim 1 wherein that the pressure in cumenyl hydrogen peroxide cracking reactor and the two cumenyl superoxide cracking reactors is about 2-10 normal atmosphere.

3. according to the method for claim 2, wherein said pressure is about 3-5 normal atmosphere.

4. according to the method for claim 1, wherein the cumenyl hydrogen peroxide carries out cracking in a multiple reaction device, described multiple reaction device is several tubular recirculation reactors of the band shell that is cascaded, and two cumenyl superoxide are to carry out cracking in a uniflux reactor.

5, according to the method for claim 4, wherein the cumenyl hydrogen peroxide is cracking in three following reactors of temperature range:

First reactor: from about 57 ℃ to about 82 ℃.

Second reactor: from about 65 ℃ to about 82 ℃.

The 3rd reactor: from about 57 ℃ to about 70 ℃.

6. according to the method for claim 4, it is characterized in that described temperature range is:

First reactor: from about 67 ℃ to about 79 ℃.

Second reactor: from about 63 ℃ to about 78 ℃.

The 3rd reactor: from about 60 ℃ to about 69 ℃.

7. according to the method for claim 1, wherein after second reactor, pressure is reduced to is about normal atmosphere or lower, the acetone that is present in the lysate is partly evaporated, concentrate and send back to first reactor, and before partial acetone is evaporated but lysate leave after second reactor, ammoniacal liquor is added in the lysate, therefore residual acid catalyst is become neutral salt.

8. according to the method for claim 1, it is characterized in that technical grade cumenyl hydrogen peroxide raw material, contain the cumenyl hydrogen peroxide of about 74%wt, and be recycled to the acetone in the cumenyl hydrogen peroxide cracking reactor, calculate according to following formula to about 92%wt: $\mathrm{Gac}=G_{\mathrm{CHP})}\×0.125\left[\mathrm{CHP}\right]+\frac{35}{G_{\mathrm{CHP}}\left[\mathrm{CHP}\right]}$ Wherein: Gac is the amounts of acetone that adds for cracking, ton/hour, GCHP is the amount for the technical grade cumenyl hydrogen peroxide of cracking adding, ton/hour, and [CHP] is the weight concentration of cumenyl hydrogen peroxide in the technical grade cumenyl hydrogen peroxide.

9. according to the process of claim 1 wherein in the cumenyl hydrogen peroxide lysate, contain the cumenyl hydrogen peroxide of 40-98%wt and be recycled to acetone in the cumenyl hydrogen peroxide cracking reactor, calculate according to following formula:

Wherein: Gac is the amounts of acetone that adds for cracking, ton/hour, G _CHPBe amount for the technical grade cumenyl hydrogen peroxide of cracking adding, ton/hour, [CHP] is the weight concentration of cumenyl hydrogen peroxide in the technical grade cumenyl hydrogen peroxide.[DMBA] is that the weight concentration [cumene] of dimethyl benzyl alcohol in the technical grade cumenyl hydrogen peroxide is that the weight concentration [AP] of cumene in the technical grade cumenyl hydrogen peroxide is the weight concentration of methyl phenyl ketone in the technical grade cumenyl hydrogen peroxide.

10. according to the method for claim 1, wherein a part of cumenyl hydrogen peroxide lysate passes through circulation line, be recycled to the cumenyl hydrogen peroxide reactor, there is first calorimeter of gangway to be parallel on the above-mentioned circulation line, part round-robin cumenyl hydrogen peroxide lysate is by above-mentioned calorimeter, the temperature of this part is determined in the ingress and the exit of above-mentioned first calorimeter, obtain first temperature gap, second has the calorimeter of entrance and exit to be parallel on the pipeline that connects cumenyl hydrogen peroxide cracking reactor and two cumenyl peroxide catalyzed cracking reactors, and be to be in water to be added to cumenyl hydrogen peroxide split product position afterwards, a part is sent to the cumenyl hydrogen peroxide lysate of two cumenyl superoxide cracking reactors, entrance and exit by above-mentioned second calorimeter, and the temperature of measuring this part in the inlet and the exit of this second calorimeter, obtain second temperature head, absolute difference between first and second temperature head, i.e. δ T=δ T ₂-δ T ₁, scope be within about 0.2 ℃-3 ℃.

11. according to the process of claim 1 wherein a part of cumenyl hydrogen peroxide lysate by first reactor cycles, its recycle ratio is the cumenyl hydrogen peroxide of the circulation lysate of about 20-40 deal than a adding that weighs.

12. according to the method for claim 11, wherein said ratio is the cumenyl hydrogen peroxide of the heavy circulation lysate of the about 26-35 part adding heavier than portion.

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