CN114082383A - Method and device for improving epoxidation reaction stability - Google Patents
Method and device for improving epoxidation reaction stability Download PDFInfo
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- CN114082383A CN114082383A CN202111613434.5A CN202111613434A CN114082383A CN 114082383 A CN114082383 A CN 114082383A CN 202111613434 A CN202111613434 A CN 202111613434A CN 114082383 A CN114082383 A CN 114082383A
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Abstract
The invention discloses a method for improving the stability of epoxidation reaction, which comprises the steps of adsorbing a material containing organic hydrocarbon peroxide to ensure that the chroma of the material is less than 5Gardner, and then introducing the material into an epoxidation reactor. The application also discloses a device for improving the epoxidation reaction stability of the method. By the adoption of the method and the device, the stability of the material inlet and outlet pressure of the reactor during the epoxidation reaction can be improved, and the continuous production can be smoothly carried out.
Description
Technical Field
The invention relates to a method and a device for improving the stability of epoxidation reaction.
Background
The production method of olefin oxide mainly comprises the steps of oxidation, epoxidation and the like, wherein organic hydrocarbon and oxygen are subjected to oxidation reaction to generate an organic hydrocarbon peroxide crude product, and then the crude product enters an epoxidation reaction stage after treatment processes of alkali washing, water washing and the like.
In the epoxidation reaction stage, in order to ensure the safety and continuity of production, the pressure difference between materials entering and flowing out of the reactor is required to be less than 0.1MPa, but in the actual production process, the phenomenon of overlarge pressure difference fluctuation or rapid increase often occurs, when the pressure difference exceeds 0.1MPa, potential safety hazards exist, the reaction needs to be stopped, the blockage of a catalyst bed layer of the epoxidation reactor is cleared, the catalyst is replaced, and the time and resources are wasted.
Disclosure of Invention
In order to improve the stability of the material inlet and outlet pressure of the reactor during the epoxidation reaction and ensure the smooth continuous production, the application firstly provides a method for improving the stability of the epoxidation reaction, which comprises the steps of adsorbing the material containing organic hydrocarbon peroxide to ensure that the chromaticity of the material is less than 5Gardner, and then introducing the material into the epoxidation reactor.
The inventor finds that in the prior art, after the crude product of the organic hydrocarbon peroxide is subjected to treatment processes such as alkali washing, water washing and the like, a large amount of colored substances, salts, organic acids and the like are still contained, wherein the colored substances are generally between 7 and 12Gardner, and the substances can adversely affect the stability of an epoxidation reactor, and particularly, if the colored substances are not effectively treated, the pressure difference of an inlet and an outlet of the epoxidation reactor fluctuates greatly, so that continuous production is difficult. It has been found that the stability of the epoxidation reactor can be maintained continuously at a high level by treating the feed by adsorption and maintaining the color of the feed at < 5 Gardner. The reason for this may be that the colored substances are corrosive to the catalyst, the catalyst is broken after corrosion to cause a rapid increase in the pressure in the reactor, and the removal of the colored substances can avoid the corrosion of the catalyst.
To enhance the optimization of the epoxidation reactor stability, it is further preferred that the color of the feed is 4 Gardner.
Further, in the adsorption treatment, the adsorbent used is at least one of silica gel, silicate, clay, zeolite, alumina, or activated carbon.
The organic hydrocarbon peroxide is a strong oxidizing substance, when the temperature is too high, a violent decomposition reaction can occur, particularly cumene hydroperoxide can be decomposed when the temperature is over 120 ℃ under the normal pressure without an adsorbent, but when the adsorbent is available, the decomposition temperature can be obviously reduced, even the decomposition can be carried out at room temperature.
By adopting the adsorbent, the adsorbent has a good adsorption effect on impurities such as organic acid, salts, colored substances and the like, and can be used for adsorption operation at a wide temperature range of 10-95 ℃, so that the organic peroxide oxide cannot be decomposed in the process, and the safety is high. Above-mentioned adsorbent is at the working process, and the adsorption heat is difficult for piling up, can discharge the adsorbent fast, enters into material on every side, avoids the inside too high temperature that leads to because the adsorption heat piles up of adsorbent, initiates peroxide decomposition. Further, when the main impurities are colored substances, the adsorbent is preferably activated carbon or clay.
Further, the specific surface of the adsorbentThe product is more than or equal to 100m2(ii) in terms of/g. The contact area between the material and the adsorption particles is favorably increased, so that the adsorption efficiency is increased, and the further optimization is 100-500 m2/g。
The inventors found in the research that part of the adsorbent does not react with CHP when the specific surface area is small, and does not greatly affect the temperature rise of the system, but when the specific surface area is large, the adsorption heat is increased, the temperature rise of the system is rapid, and the CHP decomposition reaction is easily induced. However, the adsorption efficiency is affected due to the small specific surface area, so that the preferable specific surface area is 100-500 m for improving the adsorption efficiency and reducing the risk of CHP decomposition2/g。
Further, the adsorbent forms an adsorbent layer, and the porosity of the adsorbent layer is 65 to 87%.
The porosity mainly influences the macroscopic flow rate of materials, and the adsorbent layer with high porosity is adopted, so that adsorption heat can be emitted from the adsorbent and enters the external material of the adsorbent, and the internal temperature of the adsorbent is prevented from being rapidly increased. When the porosity is too small, the flow rate of the material is reduced, which causes too large temperature rise of the material, and the material tends to be decomposed.
In addition, under the porosity, the adsorption pressure is favorably reduced, when the porosity is too low, the flow rate of the material can be ensured only by high pressure, so that the adsorption pressure is increased, and under high adsorption pressure, peroxide has the risk of decomposition.
However, when the porosity is too high, the material speed is too fast, so that the adsorbent is in a fast adsorption state for a long time, the adsorption heat in the adsorbent cannot be released quickly, the temperature in the adsorbent is too high, and the peroxide is decomposed. If reduce the material speed, then can reduce the production efficiency of absorption unit, therefore appropriate void fraction not only can guarantee absorbent normal clear, can also guarantee that the adsorption heat can be discharged smoothly from the adsorbent to enter into the material, avoid the high temperature in the adsorbent.
And the porosity is too high, so that part of materials directly pass through the adsorbent layer through gaps among the adsorbents, the contact between the materials and the adsorbents is insufficient, and the adsorption effect is poor. By adopting the porosity, both the adsorption effect and the prevention of decomposition of the organic hydrocarbon peroxide can be achieved.
Although the particle size of the adsorbent used in the present application is 5 to 1500 mesh, it is preferable to use an adsorbent having an average particle size of 50 to 600 mesh in the present application in order to reduce the pressure inside the adsorbent layer.
Further, in order to prevent decomposition of the organic hydrocarbon peroxide, the pressure during the adsorption treatment is not more than 2.0MPa, preferably 0 to 2.0MPa, more preferably 0.02 to 1.0MPa, and still more preferably 0.02 to 0.5 MPa.
In addition, in the adsorption treatment, it is preferable that the height of the adsorbent layer is 100 to 1500mm, the superficial flow rate is 0.025 to 1.56cm/s, and the adsorption temperature is 15 to 20 ℃.
Further, in the lift process, the organic hydrocarbon peroxide-containing material is first subjected to a dehydration treatment before the adsorption treatment. That is, the organic hydrocarbon peroxide-containing material is subjected to dehydration treatment and adsorption treatment in order that the color of the material is less than 5Gardner, and then introduced into the epoxidation reactor.
The dehydration treatment is mainly to remove substances such as water and the like in the materials, and specifically, methods such as coalescence, distillation and the like can be adopted, and the reduced pressure distillation method is preferred in the invention in view of convenience in operation. In the process of dehydration reason, can get rid of moisture on the one hand, prevent adsorbent corrosion damage, guarantee adsorption process's serialization, on the other hand can also carry out the concentration to the material with balanced adsorption rate, improves adsorption efficiency.
Further, after dehydration treatment, the water content in the material containing the organic hydrocarbon peroxide is less than or equal to 1 wt%. Under the condition of the moisture content, the service life of the adsorbent can be ensured, and the adsorbent is prevented from losing, so that the continuity and the high efficiency of the epoxidation process can be ensured.
Further, the lifting method further comprises concentration treatment, and after the concentration treatment, the proportion of the organic hydrocarbon peroxide in the material containing the organic hydrocarbon peroxide is 30-80 wt%. The concentration treatment and the dehydration treatment are not in sequence, but because the boiling point of the solvent is lower than that of water, the concentration treatment is preferably carried out after the dehydration treatment. After the organic hydrocarbon peroxide-containing material is subjected to dehydration treatment, concentration treatment and adsorption treatment in sequence, the chromaticity of the material is less than 5 Gardner.
When the organic hydrocarbon peroxide in the material after the dehydration treatment and the concentration treatment accounts for 30-80 wt% of the material, the adsorption speed is favorably considered, and the decomposition of the organic hydrocarbon peroxide is prevented. The improvement of the mass fraction of the organic hydrocarbon peroxide is beneficial to improving the adsorption efficiency, under the condition that the yield of the organic hydrocarbon peroxide is not changed, the higher the concentration of the organic hydrocarbon peroxide in the material is, the less the total amount of the material needing adsorption treatment is, the shorter the time needed for adsorption is, but the higher the concentration is, the organic hydrocarbon peroxide is easily decomposed, and the mass fraction of the organic hydrocarbon peroxide is more preferably 48-60 wt%.
The present invention also provides a device for improving the stability of an epoxidation reactor, the device being used in any one of the above-mentioned methods, the device comprising an adsorber, an adsorbent layer disposed in the adsorber, the adsorbent layer being formed from an adsorbent having a specific surface area of 100m or more2The adsorbent layer has a porosity of 65 to 87%. By utilizing the lifting device, the chromaticity of the materials can be smoothly made to be less than 5Gardner, so that the pressure difference can be kept to be continuously stable in the epoxidation reaction process.
In the present application, the formation of the adsorber may specifically be a fixed bed, a moving bed or a fluidized bed, and the adsorber preferably employs a fixed bed type adsorption tower. In the application, the adsorber adopts an upper feeding method, and in order to prevent the adsorbent from being scattered by the impact of the material, a feeding and shunting device is preferably arranged at the upper part of the adsorbent layer, and the shunting device preferably adopts a distributor or ceramic balls, wherein the distributor can adopt a shower head type, an impact type, a pagoda type, a porous calandria type, a porous coil type, an overflow disc type and an overflow groove type, and preferably adopts an overflow disc type. The diameter of the porcelain ball is preferably 1-20 mm. In order to improve the stability of the adsorbent layer, a support device is preferably arranged at the lower part of the adsorbent layer, and the support device is preferably a ceramic ball or a filter screen, wherein the mesh number of the filter screen is larger than that of the adsorbent, so that the adsorbent is prevented from losing.
Further, in order to ensure the continuity and high efficiency of the adsorption process, the lifting device also comprises dewatering and concentration equipment, and the dewatering equipment and the concentration equipment are both positioned in the front passage of the adsorber. The material passes through the dehydration equipment and the concentration equipment and then enters the absorber, and the dehydration equipment preferably adopts a negative pressure distillation dehydration tower, so that the moisture in the material is reduced to less than or equal to 1 wt%, the loss of the adsorbent is prevented, and simultaneously, the content of organic hydrocarbon peroxide in the material can be correspondingly improved. The concentration equipment preferably adopts a falling film evaporator.
The dehydration equipment and the concentration equipment are not in sequence, but because the boiling point of the solvent is lower than that of water, the dehydration equipment is preferably arranged in a front passage with the concentration equipment, even if the material containing the organic hydrocarbon peroxide passes through the dehydration equipment, the concentration equipment and the adsorber in sequence.
When the organic hydrocarbon peroxide in the material accounts for 30-80 wt% of the material after concentration treatment, the adsorption speed is favorably considered, and the decomposition of the organic hydrocarbon peroxide is prevented.
Further, in order to improve the efficiency of the adsorption treatment, it is preferable that the adsorbent used in each adsorber be at least two of silica gel, silicate, clay, zeolite, alumina, and activated carbon.
Overall, the combined advantages of the present application are:
(1) the long-term stability of the epoxidation reactor in the continuous production process can be kept, and the pressure difference between the inlet and the outlet of the epoxidation reactor is still less than 0.1MPa after the continuous production is over 140 hours;
(2) the corrosion to the adsorbent is low, and the continuity of the control process can be ensured;
(3) the dosage of the adsorbent is small, and the adsorption efficiency is high;
(4) can prevent the decomposition of organic hydrocarbon peroxide, has a wider safe temperature range of 10-95 ℃, and has high safety coefficient;
(5) has good effect of removing colored substances, salts and alkali liquor.
Drawings
Fig. 1 is a schematic structural view of an embodiment of a lifting device.
Fig. 2 is a schematic structural view of another embodiment of the lifting device.
Detailed Description
The content of the colored substances is expressed by using a colorimetric method, and the detection method refers to a method for measuring the color of the transparent liquid (Gardner color) according to the national standard GB/T22295-2008.
The pressures in the present invention are all absolute pressures.
The following first describes the lifting device:
referring to fig. 1, a 1# lift device, which is a first embodiment of a lift device for improving the stability of an epoxidation reaction, includes a first adsorption tower 12 in the form of a fixed bed, i.e., an adsorber. The 1# lifting device is used to reduce the chroma of the material to < 5 Gardner.
A support grid 13 is arranged at the lower part in the first adsorption tower 12, ceramic balls 16 with the diameter of 3-5 mm are stacked on the support grid 13 to be used as a cushion layer, the support grid and the ceramic balls jointly form a support device, an adsorbent layer 14 formed by an adsorbent is arranged on the ceramic balls, and an overflow disc 15 is arranged at the top part in the first adsorption tower to uniformly distribute an entering material on the adsorbent layer and avoid impacting the adsorbent layer.
The outlet of the first booster pump 11 is communicated with the feed inlet at the top of the first adsorption tower, and the discharge outlet at the bottom of the first adsorption tower is communicated with the feed inlet at the top of the first epoxidation reactor 17. Namely, the first adsorption tower is positioned in the front of the first epoxidation reactor, so that the materials can enter the first epoxidation reactor 17 after being treated by the No. 1 lifting device for epoxidation reaction.
The first propylene tank 18 is connected to a first feed pipe 19 of the first epoxidation reactor.
Referring to fig. 2, a second embodiment of the 2# lift device, which is an epoxidation reactivity lift device, includes a second adsorption tower 22 in the form of a fixed bed, i.e., an adsorber, and the second adsorption tower has the same structure as the first adsorption tower.
The 2# lifting device also comprises a negative pressure distillation dehydration tower 32 and a falling film evaporator 33, wherein the negative pressure distillation dehydration tower 32 is dehydration equipment, and the falling film evaporator 33 is concentration equipment. The falling film evaporator 33 is located between the negative pressure distillation dehydration column 32 and the second adsorption column 22.
The second booster pump A31 is communicated with a first material inlet 321 in the middle of the negative pressure distillation dehydration tower 32 through a refrigerant channel of the preheater 311, a steam outlet 323 for discharging water steam is arranged at the top of the dehydration tower 32, a first material outlet 322 at the bottom of the negative pressure distillation dehydration tower 32 is communicated with a second material inlet 331 in the middle of the falling film evaporator, and a solvent outlet 333 for discharging solvent steam is arranged at the top of the falling film evaporator. The second material outlet 332 at the bottom of the film evaporator is communicated with the liquid storage tank 35 through a heat medium channel of the condenser 34, the liquid storage tank 35 is communicated with the feed inlet at the top of the second adsorption tower 22 through a second booster pump B21, and the discharge outlet at the bottom of the second adsorption tower is communicated with the feed inlet at the top of the second epoxidation reactor 27.
The second propylene tank 28 is connected to the second feed 29 of the second epoxidation reactor.
The 2# lifting device is used for reducing the chroma of the material to be less than 5Gardenr, reducing the moisture in the material to be less than or equal to 1 wt%, and improving the mass fraction of the organic hydrocarbon peroxide to be 30-80 wt%.
In the following examples, cumene hydroperoxide containing material was used as a treatment target, but the present invention can be applied to organic hydrocarbon peroxide containing materials, for example, ethylbenzene hydroperoxide containing material with the same effect.
In each of the following examples, the cumene hydroperoxide containing material had a composition of 22 wt% cumene hydroperoxide and 73 wt% cumene, 1 wt% dimethylbenzyl alcohol, 1 wt% alpha-methylstyrene, 100mg/kg organic acid, 2.0 wt% moisture, 12mg/kg sodium ions, and a small amount of other impurities, color 8Gardner, based on 100 wt%.
The epoxidation process adopted in the embodiment of the invention is as follows:
the cumene hydroperoxide solution and propylene are conveyed into an epoxidation fixed bed reactor through a pump, epoxidation reaction is carried out under the action of a titanium silicon molecular sieve catalyst to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol reaction liquid, the reaction liquid is separated to obtain a pure product of propylene oxide, the reaction temperature is 120 ℃, the reaction pressure is 5.5MPaG, and the linear velocity is 3 cm/s.
Example 1
The adsorbent layer in the first adsorption tower 12 was formed of activated carbon using a # 1 lift device, the average particle size of the adsorbent was 50 mesh, and the average specific surface area of the adsorbent was 300m2The void ratio of the adsorbent layer reaches 87 percent, and the height of the adsorbent layer is 1000 mm.
During production, materials are pumped into a first adsorption tower 12 by a first booster pump 11, the pressure in the adsorption process is 1.0MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.17cm/s, and the materials discharged from the bottom of the first adsorption tower 12 enter a first epoxidation reactor 17 for epoxidation.
Example 2
The adsorbent layer in the first adsorption tower 12 is formed by a mixture of zeolite and activated clay by using a No. 1 lifting device, the average particle size of the adsorbent is 600 meshes, and the average specific surface area of the adsorbent is 250m2The void ratio of the adsorbent layer reaches 65 percent, and the height of the adsorbent layer is 1500 mm. In particular to
During production, materials are pumped into a first adsorption tower 12 by a first booster pump 11, the pressure in the adsorption process is 2.0MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.25cm/s, and the materials discharged from the bottom of the first adsorption tower 12 enter a first epoxidation reactor 17 for epoxidation.
Example 3
The adsorbent layer in the first adsorption tower 12 is formed by a mixture of magnesium silicate and activated carbon by adopting a No. 1 lifting device, the average particle size of the adsorbent is 300 meshes, and the average specific surface area of the adsorbent is 450m2The void ratio of the adsorbent layer reaches 80 percent, and the height of the adsorbent layer is 1500 mm.
During production, materials are pumped into a first adsorption tower 12 by a first booster pump 11, the pressure in the adsorption process is 2.0MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.25cm/s, and the materials discharged from the bottom of the first adsorption tower 12 enter a first epoxidation reactor 17 for epoxidation.
Example 4
The adsorbent layer in the second adsorption tower 22 was formed of activated carbon using a # 2 lift device, the average particle size of the adsorbent was 100 mesh, and the average specific surface area of the adsorbent was 250m2The porosity of the adsorbent layer is 87%, and the height of the adsorbent layer is 150 mm.
During production, materials are pumped into a preheater by a second booster pump A31, and are dehydrated and concentrated by a negative pressure distillation dehydration tower 32 and a falling film evaporator 33 in sequence after being preheated, wherein the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, and the pressure is 6-10 kPa. The temperature in the falling-film evaporator is 90-95 ℃, the pressure is 1-2 kPa, steam in the negative pressure distillation dehydration tower is discharged through a steam discharge port 323, a solvent in the falling-film evaporator is discharged through a solvent discharge port 333, and a material subjected to dehydration and concentration is discharged from a second material outlet 332, condensed to 20 ℃ through a condenser 34 and then enters a liquid storage tank 35. The second booster pump B21 pumps the materials in the liquid storage tank 35 into the second adsorption tower 22 for adsorption, the adsorption pressure in the second adsorption tower 22 is 0.02MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.025cm/s, and the materials discharged from the bottom of the second adsorption tower 22 enter the second epoxidation reactor 27 for epoxidation.
Example 5
The adsorbent layer in the second adsorption tower 22 was formed of silica gel using a 2# lift device, the average particle size of the adsorbent was 500 mesh, and the average specific surface area of the adsorbent was 100m2The void ratio of the adsorbent layer reaches 70 percent, and the height of the adsorbent layer is 180 mm.
During production, materials are pumped into a preheater by a second booster pump A31, and are dehydrated and concentrated by a negative pressure distillation dehydration tower 32 and a falling film evaporator 33 in sequence after being preheated, wherein the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, and the pressure is 6-10 kPa. The temperature in the falling-film evaporator is 90-95 ℃, the pressure is 1-2 kPa, steam in the negative pressure distillation dehydration tower is discharged through a steam discharge port 323, a solvent in the falling-film evaporator is discharged through a solvent discharge port 333, and a material subjected to dehydration and concentration is discharged from a second material outlet 332, condensed to 20 ℃ through a condenser 34 and then enters a liquid storage tank 35. The second booster pump B21 pumps the materials in the liquid storage tank 35 into the second adsorption tower 22 for adsorption, the adsorption pressure in the second adsorption tower 22 is 0.3MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.30cm/s, and the materials discharged from the bottom of the second adsorption tower 22 enter the second epoxidation reactor 27 for epoxidation.
Example 6
By using the # 2 lift device, the adsorbent layer in the second adsorption tower 22 was formed of a mixture of zeolite and activated clay, the average particle size of the adsorbent was 550 mesh, the average specific surface area of the adsorbent was 150m2/g, the porosity of the adsorbent layer was 65%, and the height of the adsorbent layer was 100 mm.
During production, materials are pumped into a preheater by a second booster pump A31, and are dehydrated and concentrated by a negative pressure distillation dehydration tower 32 and a falling film evaporator 33 in sequence after being preheated, wherein the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, and the pressure is 6-10 kPa. The temperature in the falling-film evaporator is 90-95 ℃, the pressure is 1-2 kPa, steam in the negative pressure distillation dehydration tower is discharged through a steam discharge port 323, a solvent in the falling-film evaporator is discharged through a solvent discharge port 333, and a material subjected to dehydration and concentration is discharged from a second material outlet 332, condensed to 20 ℃ through a condenser 34 and then enters a liquid storage tank 35. The second booster pump B21 pumps the materials in the liquid storage tank 35 into the second adsorption tower 22 for adsorption, the adsorption pressure in the second adsorption tower 22 is 0.8MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 1.56cm/s, and the materials discharged from the bottom of the second adsorption tower 22 enter the second epoxidation reactor 27 for epoxidation.
Example 7
The adsorbent layer in the second adsorption tower 22 was formed of aluminum silicate using a # 2 lift device, the average particle size of the adsorbent was 150 mesh, and the average specific surface area of the adsorbent was 400m2The porosity of the adsorbent layer is 85% and the height of the adsorbent layer is 400 mm.
During production, materials are pumped into a preheater by a second booster pump A31, and are dehydrated and concentrated by a negative pressure distillation dehydration tower 32 and a falling film evaporator 33 in sequence after being preheated, wherein the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, and the pressure is 6-10 kPa. The temperature in the falling-film evaporator is 90-95 ℃, the pressure is 1-2 kPa, steam in the negative pressure distillation dehydration tower is discharged through a steam discharge port 323, a solvent in the falling-film evaporator is discharged through a solvent discharge port 333, and a material subjected to dehydration and concentration is discharged from a second material outlet 332, condensed to 20 ℃ through a condenser 34 and then enters a liquid storage tank 35. The second booster pump B21 pumps the materials in the liquid storage tank 35 into the second adsorption tower 22 for adsorption, the adsorption pressure in the second adsorption tower 22 is 1.5MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.68cm/s, and the materials discharged from the bottom of the second adsorption tower 22 enter the second epoxidation reactor 27 for epoxidation.
Example 8
The adsorbent layer in the second adsorption tower 22 is formed by a mixture of alumina and acid clay by using a No. 2 lifting device, the average particle size of the adsorbent is 200 meshes, and the average specific surface area of the adsorbent is 200m2The void ratio of the adsorbent layer reaches 75 percent, and the height of the adsorbent layer is 350 mm.
During production, materials are pumped into a preheater by a second booster pump A31, and are dehydrated and concentrated by a negative pressure distillation dehydration tower 32 and a falling film evaporator 33 in sequence after being preheated, the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, the pressure in the negative pressure distillation dehydration tower is 6-10 kPa, the temperature in the falling film evaporator is 90-95 ℃, the pressure in the falling film evaporator is 1-2 kPa, steam in the negative pressure distillation dehydration tower is discharged through a steam discharge port 323, solvent in the falling film evaporator is discharged through a solvent discharge port 333, and the materials after dehydration and concentration are condensed to 20 ℃ through a condenser 34 and enter a liquid storage tank 35. The second booster pump B21 pumps the materials in the liquid storage tank 35 into the second adsorption tower 22 for adsorption, the adsorption pressure in the second adsorption tower 22 is 1.0MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.55cm/s, and the materials discharged from the bottom of the second adsorption tower 22 enter the second epoxidation reactor 27 for epoxidation.
Example 9
The adsorbent layer in the second adsorption tower 22 is formed by a mixture of magnesium silicate and activated carbon by using a No. 2 lifting device, the average particle size of the adsorbent is 200 meshes, and the average particle size of the adsorbent is flatThe average specific surface area is 450m2The void ratio of the adsorbent layer reaches 80 percent, and the height of the adsorbent layer is 140 mm.
During production, materials are pumped into a preheater by a second booster pump A31, and are dehydrated and concentrated by a negative pressure distillation dehydration tower 32 and a falling film evaporator 33 in sequence after being preheated, the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, the pressure in the negative pressure distillation dehydration tower is 6-10 kPa, the temperature in the falling film evaporator is 90-95 ℃, the pressure in the falling film evaporator is 1-2 kPa, steam in the negative pressure distillation dehydration tower is discharged through a steam discharge port 323, solvent in the falling film evaporator is discharged through a solvent discharge port 333, and the materials after dehydration and concentration are condensed to 20 ℃ through a condenser 34 and enter a liquid storage tank 35. The second booster pump B21 pumps the materials in the liquid storage tank 35 into the second adsorption tower 22 for adsorption, the adsorption pressure in the second adsorption tower 22 is 0.5MPa, the adsorption temperature is 15-20 ℃, the empty tower flow rate is 0.68cm/s, and the materials discharged from the bottom of the second adsorption tower 22 enter the second epoxidation reactor 27 for epoxidation.
Comparative example 1
This example was carried out in substantially the same manner as example 1, except that the feed was fed directly to the first epoxidation reactor 17 without being subjected to adsorption treatment by the first adsorption column 12.
Comparative example 2
In this embodiment, the same as example 1 is adopted, but the material is not subjected to adsorption treatment by the first adsorption tower 12, but is subjected to alkali washing and water washing in sequence, wherein in the alkali washing, the material is mixed and stirred with a 0.2 wt% sodium hydroxide aqueous solution, and then is layered, and an oil phase is obtained after a water phase is removed; in the water washing, the oil phase and pure water are mixed, then the layering is carried out, after the water phase is removed, the oil phase is sent into a first epoxidation reactor for epoxidation reaction.
Comparative example 3
The adsorbent of the second adsorption tower has a specific surface area of 60m by using a No. 2 lifting device2Silica/g, the porosity of the adsorbent layer was 70%, and the height of the adsorbent layer was 80 mm. Pumping the material into a 2# lifting device for dehydration and concentration treatmentAnd (3) the temperature in the negative pressure distillation dehydration tower is 80-85 ℃, the pressure is 6-10 kPa, the temperature in the falling film evaporator is 90-95 ℃, the pressure is 1-2 kPa, then the adsorption treatment is carried out under 0.3MPa, the empty tower flow rate in the second adsorption tower is 0.68cm/s, and after the completion, the material is pumped into a second oxidation reactor to carry out the epoxidation reaction.
Comparative example 4
The adsorbent of the second adsorption tower has a specific surface area of 200m by using a No. 2 lifting device2Acid clay/g, the porosity of the adsorbent layer was 50%, and the height of the adsorbent layer was 1000 mm. And pumping the material into a No. 2 lifting device for dehydration and concentration treatment, wherein the temperature in a negative pressure distillation dehydration tower is 80-85 ℃, the pressure is 6-10 kPa, the temperature in a falling film evaporator is 90-95 ℃, the pressure is 1-2 kPa, then performing adsorption treatment under the pressure of 3.5MPa, the adsorption temperature is 15-20 ℃, the empty tower flow velocity in a second adsorption tower is 0.68cm/s, and pumping the material into a second epoxidation reactor for epoxidation reaction after the completion.
Table 1 characterization of the results of the examples
Table 2 characterization of comparative example results
TABLE 3 epoxidation reactor stability control Effect
As can be seen from tables 1, 2 and 3, the technical scheme of the invention can realize better reactor stability effect and better impurity removal effect. Comparative example 1 is a cumene hydroperoxide-containing material used in the examples of the present invention without any treatment, and it can be seen from the characterization results that if it is directly added to an epoxidation reactor, the reactor pressure difference is large and it is difficult to maintain the continuity of production; comparative example 2 adopts an alkali washing and water washing method to remove impurities, but the treated material still causes larger change of the pressure difference of the reactor after entering the epoxidation reactor; comparative example 3 adopts an adsorbent different from the technical scheme of the invention, but under the same operation conditions, a better reactor stabilizing effect is not achieved, and the pressure difference of the reactor is increased more quickly; the comparative example 4 has too high adsorption pressure, and part of organic hydrocarbon peroxide is decomposed in the adsorption process, so that the temperature of the adsorption column is increased rapidly, and the material is blackened and cannot be used.
Claims (10)
1. The method for improving the stability of the epoxidation reaction is characterized in that a material containing organic hydrocarbon peroxide is subjected to adsorption treatment to ensure that the chroma of the material is less than 5Gardner, and then the material is introduced into an epoxidation reactor.
2. The method according to claim 1, wherein the adsorbent used in the adsorption treatment is at least one selected from silica gel, silicate, clay, zeolite, alumina, and activated carbon.
3. The lifting method according to claim 2, wherein the adsorbent has a specific surface area of 100m or more2/g。
4. The lift method of claim 3, wherein the adsorbent forms an adsorbent layer having a porosity of 65-87%.
5. The lifting method according to any one of claims 1 to 4, characterized in that the pressure during the adsorption treatment is < 2.0 MPa.
6. The lifting method according to any one of claims 1 to 4, wherein the organic peroxide-containing material is first subjected to a dehydration treatment before the adsorption treatment.
7. The lifting method according to claim 6, wherein the organic hydrocarbon peroxide-containing material has a moisture content of 1 wt.% or less after the dehydration treatment.
8. The lifting method according to claim 6, wherein a concentration treatment is further performed, and after the concentration treatment, the proportion of the organic hydrocarbon peroxide in the organic hydrocarbon peroxide-containing material is 30 to 80 wt%.
9. The device for improving the stability of epoxidation reaction, which is used in the method for improving the stability of epoxidation reaction according to any one of claims 1 to 8, comprises an adsorber in which an adsorbent layer is disposed, the adsorbent layer being formed of an adsorbent having a specific surface area of 100m or more2The adsorbent layer has a porosity of 65 to 87%.
10. The lift device of claim 9, further comprising a dewatering device and a concentrating device, both located in a front pass of the adsorber.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171399A (en) * | 1996-07-19 | 1998-01-28 | 恩尼彻姆公司 | Process of preparation of epoxides from olefins |
| CN1405160A (en) * | 2001-08-02 | 2003-03-26 | 拜尔公司 | Method for preparing olefin oxide from olefin |
| CN1484635A (en) * | 2000-12-27 | 2004-03-24 | ���ʿ����о�����˾ | Process for preparing organic hydroperoxide having a reduced amount of contaminants |
| JP2006219479A (en) * | 2005-01-14 | 2006-08-24 | Sumitomo Chemical Co Ltd | Method for producing propylene oxide |
| CN101103010A (en) * | 2005-01-14 | 2008-01-09 | 住友化学株式会社 | Method for producing propylene oxide |
| CN102333586A (en) * | 2009-02-16 | 2012-01-25 | 圣戈本陶瓷及塑料股份有限公司 | Vessel containing fluid distribution media |
| CN102826957A (en) * | 2012-08-30 | 2012-12-19 | 宁夏宝塔石化集团有限公司 | Method for removing basic nitrogen from methanol used as benzene-ethanol alkylation reaction raw material |
| RU2012134380A (en) * | 2012-08-10 | 2014-02-20 | Общество с ограниченной ответственностью "Научно-исследовательский и проектно-конструкторский институт химического машиностроения" (ООО "ЛЕННИИХИММАШ") | ADSORBER VERTICAL WITH A FIXED LAYER OF AN ADSORBENT |
| CN104109139A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Epoxypropane synthesis method |
| CN106039765A (en) * | 2016-06-29 | 2016-10-26 | 天津市天元机械制造有限公司 | Multi-layer liquid adsorption tank |
| CN205683774U (en) * | 2016-06-03 | 2016-11-16 | 湖北雄鹰石化设备发展有限公司 | A kind of multi-nozzle distributor |
| CN205759874U (en) * | 2016-06-29 | 2016-12-07 | 天津市天元机械制造有限公司 | A kind of layered adsorption tank |
| CN106957719A (en) * | 2017-04-21 | 2017-07-18 | 南通海珥玛科技股份有限公司 | A kind of discoloration method of deoxidation industry oil |
| CN111606834A (en) * | 2020-05-21 | 2020-09-01 | 常州瑞华化工工程技术股份有限公司 | Concentration method of ethylbenzene hydroperoxide |
| CN114100544A (en) * | 2021-12-27 | 2022-03-01 | 红宝丽集团泰兴化学有限公司 | Apparatus and method for treating organic hydrocarbon peroxide |
-
2021
- 2021-12-27 CN CN202111613434.5A patent/CN114082383B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171399A (en) * | 1996-07-19 | 1998-01-28 | 恩尼彻姆公司 | Process of preparation of epoxides from olefins |
| CN1484635A (en) * | 2000-12-27 | 2004-03-24 | ���ʿ����о�����˾ | Process for preparing organic hydroperoxide having a reduced amount of contaminants |
| CN1405160A (en) * | 2001-08-02 | 2003-03-26 | 拜尔公司 | Method for preparing olefin oxide from olefin |
| JP2006219479A (en) * | 2005-01-14 | 2006-08-24 | Sumitomo Chemical Co Ltd | Method for producing propylene oxide |
| CN101103010A (en) * | 2005-01-14 | 2008-01-09 | 住友化学株式会社 | Method for producing propylene oxide |
| CN102333586A (en) * | 2009-02-16 | 2012-01-25 | 圣戈本陶瓷及塑料股份有限公司 | Vessel containing fluid distribution media |
| RU2012134380A (en) * | 2012-08-10 | 2014-02-20 | Общество с ограниченной ответственностью "Научно-исследовательский и проектно-конструкторский институт химического машиностроения" (ООО "ЛЕННИИХИММАШ") | ADSORBER VERTICAL WITH A FIXED LAYER OF AN ADSORBENT |
| CN102826957A (en) * | 2012-08-30 | 2012-12-19 | 宁夏宝塔石化集团有限公司 | Method for removing basic nitrogen from methanol used as benzene-ethanol alkylation reaction raw material |
| CN104109139A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Epoxypropane synthesis method |
| CN205683774U (en) * | 2016-06-03 | 2016-11-16 | 湖北雄鹰石化设备发展有限公司 | A kind of multi-nozzle distributor |
| CN106039765A (en) * | 2016-06-29 | 2016-10-26 | 天津市天元机械制造有限公司 | Multi-layer liquid adsorption tank |
| CN205759874U (en) * | 2016-06-29 | 2016-12-07 | 天津市天元机械制造有限公司 | A kind of layered adsorption tank |
| CN106957719A (en) * | 2017-04-21 | 2017-07-18 | 南通海珥玛科技股份有限公司 | A kind of discoloration method of deoxidation industry oil |
| CN111606834A (en) * | 2020-05-21 | 2020-09-01 | 常州瑞华化工工程技术股份有限公司 | Concentration method of ethylbenzene hydroperoxide |
| CN114100544A (en) * | 2021-12-27 | 2022-03-01 | 红宝丽集团泰兴化学有限公司 | Apparatus and method for treating organic hydrocarbon peroxide |
Non-Patent Citations (11)
| Title |
|---|
| （苏）卡弗达诺夫: "《普通燃料化学工艺学》", 30 April 1958, 北京：高等教育出版社, pages: 240 - 241 * |
| 于剑昆等: "用异丙苯过氧化氢作氧化剂合成环氧丙烷的新技术(待续)", 《化学推进剂与高分子材料》, no. 05, 25 September 2007 (2007-09-25) * |
| 华东化工学院等: "《基本有机化工工艺学》", 31 January 1981, 北京：化学工业出版社, pages: 230 * |
| 唐波等: "《化学工业 化工卷》", 30 April 2007, 济南：山东科学技术出版社, pages: 71 * |
| 姚仲鹏等: "《空气净化原理、设计与应用》", 30 September 2014, 北京：中国科学技术出版社, pages: 153 - 154 * |
| 汪世龙: "《蛋白质化学》", 上海：同济大学出版社 * |
| 汪世龙: "《蛋白质化学》", 上海：同济大学出版社, pages: 179 * |
| 赵亚平等: "《中国石油和化工行业发展研究报告》", 28 February 2008, 郑州：河南科学技术出版社, pages: 163 * |
| 邹安丽等: "《化工机器与设备》", 30 June 1991, 北京：化学工业出版社, pages: 288 - 293 * |
| 高希: "Aspen技术环氧丙烷制备工艺的模拟及优化", 《化工管理》 * |
| 高希: "Aspen技术环氧丙烷制备工艺的模拟及优化", 《化工管理》, no. 09, 21 March 2020 (2020-03-21) * |
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