CN113636914B - Treatment method for propylene epoxidation recovery of alcohol solvent - Google Patents
Treatment method for propylene epoxidation recovery of alcohol solvent Download PDFInfo
- Publication number
- CN113636914B CN113636914B CN202111073576.7A CN202111073576A CN113636914B CN 113636914 B CN113636914 B CN 113636914B CN 202111073576 A CN202111073576 A CN 202111073576A CN 113636914 B CN113636914 B CN 113636914B
- Authority
- CN
- China
- Prior art keywords
- alcohol solvent
- hydrogen peroxide
- propylene
- catalyst
- epoxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a treatment method for propylene epoxidation recovery alcohol solvent, which comprises a coupling treatment method for performing hydrogen peroxide removal pretreatment and hydrogenation purification on the propylene epoxidation recovery alcohol solvent. The coupling treatment method has the characteristics of strong raw material adaptability, high risk resistance, high operation elasticity of a main device, high impurity removal rate, long service life of a catalyst and the like, is favorable for the performance of a hydrogenation purification unit, is particularly suitable for the optimization of industrial application and industrial devices, improves the production capacity of the device, and prolongs the service life of the hydrogenation purification catalyst.
Description
Technical Field
The invention relates to a treatment method for propylene epoxidation recovery alcohol solvent, in particular to a coupling treatment method for performing hydrogen peroxide removal pretreatment and hydrogenation purification on the propylene epoxidation recovery alcohol solvent.
Background
With the development of petrochemical industry and fine chemical industry, propylene oxide has become the second largest derivative of propylene and is an important petrochemical intermediate. The method takes hydrogen peroxide as an oxidant, takes low-carbon alcohol as a solvent, and adopts a titanium-silicon molecular sieve to catalyze propylene to synthesize propylene oxide by epoxidation, thereby meeting the requirements of green chemistry and atomic economy development concept and being a green new process with great development prospect. In this process, the solvent is generally recycled and subjected to purification treatment.
The propylene epoxide to propylene oxide process produces carbonyl compound, acetal (ketone) compound, nitrogen compound and other impurities in the reaction stage, and in the alcohol solvent high temperature rectification recovery stage, unreacted hydrogen peroxide and organic peroxide compound further oxidize solvent and other matters and produce carbonyl compound and other impurities. Some of these impurities, such as formaldehyde, acetaldehyde, propionaldehyde, acetone, methyl formate, dimethoxymethane, 1-dimethoxyethane, 1-dimethoxypropane, 2-dimethoxypropane, acetonitrile, nitromethane, nitroethane, etc., are difficult to separate from the alcohol solvent and the product propylene oxide by rectification, thus resulting in a decrease in the purity of the recycled alcohol solvent and an increase in the accumulation of impurities in the product propylene oxide, which affects the quality of the product. At the same time, these impurities can also lead to deactivation of the epoxidation catalyst, affecting catalyst life, product yield, etc. Therefore, it is particularly important to purify the recovered alcohol solvent to remove impurities and hydrogen peroxide therefrom, which is an important component of the propylene epoxide to propylene oxide process.
The removal of residual hydrogen peroxide from olefin and hydrogen peroxide epoxidation reaction products, chinese patent ZL01814048.3 and USP7,138,534 disclose a continuous process for the manufacture of propylene oxide by first feeding the epoxidation products of propylene and hydrogen peroxide to a distillation column to remove propylene and propylene oxide from the top of the column, and then feeding the bottoms of the distillation column containing methanol, water, epoxidation reaction byproducts and hydrogen peroxide to a fixed bed reactor containing a group viii metal or metal oxide catalyst to remove hydrogen peroxide at a temperature of 80 to 90 ℃ and under alkaline conditions without removing other impurities.
CN 1294125C discloses a method for hydrofining a recovered solvent for olefin epoxidation reaction, wherein the active components of the catalyst are Ru, rh, pd, pt, ag, ir, fe, cu, co and Ni, and the carrier is active carbon and SiO 2 、TiO 2 、ZrO 2 、Al 2 O 3 Carbonyl compounds such as formaldehyde and acetaldehyde can be substantially removed and hydrogen peroxide can be removed under the reaction conditions of 0.5-30MPa and 80-150 ℃. CN 110354858A discloses an alcohol solvent hydrofining catalyst in olefin epoxidation reaction process, a preparation method and application thereof, wherein the catalyst comprises Ni as an active ingredient, mn or Fe as an auxiliary ingredient, C as well as alumina carrier as the rest, the catalyst has a volume ratio of hydrogen to alcohol solvent of 20-500 at 70-150 ℃ and 0.5-5MPa,the liquid hourly space velocity is 1-10h -1 The catalyst has good hydrogenation effect on various impurities in the recovered alcohol solvent under the condition of good hydrogenation activity and high impurity removal rate, and the catalyst is continuously used for 4000 hours without obvious deactivation.
In summary, there has not been disclosed a coupling treatment method for performing hydrogen peroxide removal pretreatment and hydrogenation purification on an alcohol solvent recovered from an olefin epoxidation reaction.
The existing method adopts the metal or metal oxide of the VIII family as the catalyst, only hydrogen peroxide is removed, other impurities are not removed, and the method can influence the service life of the epoxidation catalyst and the product quality; under the condition of hydrogen, a catalyst containing Ni and the like is adopted for hydrogenation and impurity removal, and partial auxiliary agents are added to improve the oxidation resistance and hydrogenation activity of the catalyst, but oxidation of a strong oxidant hydrogen peroxide and the like to the catalyst active component Ni and the like cannot be avoided, namely slow deactivation of the catalyst cannot be avoided, the hydrogen peroxide concentration in a material to be hydrogenated is strictly limited in practical industrial application, and the oxidation deactivation of the hydrogenation catalyst by high-concentration hydrogen peroxide is more serious under abnormal working conditions. These factors have prompted more rational methods for the recovery of alcohol solvents in industrial applications.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a coupling treatment method for carrying out hydrogen peroxide removal pretreatment and hydrogenation purification on a propylene epoxidation recovery alcohol solvent, which overcomes the oxidation passivation of an oxidant hydrogen peroxide on a catalyst active component Ni and the like, has longer catalyst service life, stronger catalyst shock resistance and higher impurity removal effect, and has larger operation elasticity, thus being particularly suitable for industrial application and optimization of industrial devices.
The invention aims at realizing the following technical scheme:
a method for treating a propylene epoxidation recovery alcohol solvent comprises a treatment method for coupling hydrogen peroxide removal pretreatment and hydrogenation purification of the propylene epoxidation recovery alcohol solvent.
The recovered alcohol solvent is the solution remained after propylene oxide is removed from the mixture obtained by propylene epoxidation.
The hydrogen peroxide removal pretreatment comprises reducing agent treatment and/or catalyst catalytic hydrogen peroxide removal treatment.
The reducing agent treatment is that hydrazine hydrate and/or derivatives thereof are mixed with a recovered alcohol solvent, and the mixture is treated for 2 to 20 minutes at the temperature of between 30 and 110 ℃ to remove part of hydrogen peroxide.
The reducing agent treatment temperature is preferably 70-110 ℃.
The catalytic hydrogen peroxide removal treatment of the catalyst is to contact the recovered alcohol solvent with the catalyst and remove hydrogen peroxide under the conditions of 70-120 ℃ and 0.1-4.0 MPa.
The catalyst is a shaped catalyst prepared by loading one or more oxides of manganese oxide, copper oxide and ferric oxide on an alumina and/or silica and/or active carbon carrier.
When the hydrogen peroxide removal pretreatment is carried out by adopting a catalytic hydrogen peroxide removal method, the alcohol solvent is recycled before pretreatment and mixed with a certain amount of nitrogen or the discharged material after pretreatment is mixed with a certain amount of nitrogen, and a gas-liquid separator is additionally arranged at the rear of the mixture to safely remove oxygen-containing noncondensable gas.
The hydrogenation purification refers to the steps that the recovered alcohol solvent is contacted with a catalyst with a catalytic hydrofining function, and the recovered alcohol solvent is subjected to purification treatment under the condition of hydrogen.
The beneficial effects of the invention are mainly as follows:
(1) In the existing hydrogenation purification method, the active component of the hydrogenation catalyst is a metal simple substance, the hydrogenation agent is inactivated by oxidation, the hydrogenation reduction reaction of hydrogen peroxide (or other organic peroxides) and the reaction of the active component of the hydrogen peroxide oxidation hydrogenation catalyst are competing reactions in the hydrogenation process, and the inactivation of the hydrogenation agent is accelerated when the concentration of hydrogen peroxide in the propylene epoxidation recovery alcohol solvent is higher; the method has the advantages that the alcohol solvent is recycled through propylene epoxidation to carry out hydrogen peroxide removal pretreatment, so that the concentration of hydrogen peroxide in materials to be subjected to hydrogenation purification is greatly reduced, the hydrogen peroxide comprises most of organic peroxide, the oxidation passivation of a strong oxidant-peroxide on the catalyst in the subsequent hydrogenation purification process is effectively inhibited, the service life of the hydrogenation catalyst is greatly prolonged, and the performance of the hydrogenation purification unit catalyst is favorably exerted.
(2) The pretreated propylene epoxidation recovery alcohol solvent is further purified, and the precursors of all impurities affecting the product quality and the activity of the epoxidation catalyst can be more effectively reduced through the hydrogenation agent which exerts the hydrogenation activity to the greatest extent.
(3) The coupling treatment method for carrying out the hydrogen peroxide removal pretreatment and the hydrogenation purification on the propylene epoxidation recovery alcohol solvent can obviously improve the raw material adaptability of the treatment process, has stronger shock resistance, and has higher operation elasticity and better application effect for the main device in practical application.
(4) The coupling treatment method for carrying out the hydrogen peroxide removal pretreatment and the hydrogenation purification on the propylene epoxidation recovery alcohol solvent can partially reduce the loading amount of the catalyst of the hydrogenation purification unit and improve the economic benefit of the device.
Compared with the existing processing method, the coupling processing method has the following advantages: the device has strong adaptability of raw materials, high risk resistance and high operation elasticity of the main device, is favorable for the performance of the hydrogenation purification unit, has the characteristics of long service life of the catalyst, high impurity removal rate and the like, and is particularly suitable for industrial application and optimization and promotion of industrial devices.
Drawings
FIG. 1 shows the effect of the treatment process according to the invention compared with the long-period comparative test of the treatment process for direct hydropurification
Detailed Description
The present invention will be described in detail with reference to examples and comparative examples. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example 1
The method comprises the following steps of (1) carrying out hydrogen peroxide removal pretreatment on a propylene epoxidation recovery alcohol solvent:
loading 5.0 g of inert alumina supported manganese oxide catalyst into a fixed bed stainless steel reactor with a diameter of 12mm and a length of 90cmIn the reactor, quartz sand is filled at the upper end and the lower end of the reactor, and a catalyst is filled in the middle of the reactor, so that the catalyst is ensured to be in a constant temperature zone of the reactor (the reactor is used in the following examples and the filling modes are consistent if no special description exists). At a reaction temperature of 70 ℃, a reaction pressure of 0.1MPa and a space velocity of 10h -1 Under the condition of (1) conveying propylene epoxidation recovery alcohol solvent (wherein the mass percent of hydrogen peroxide in the solvent is 0.5 percent and the mass percent of acetaldehyde is 0.5 percent) by a syringe pump, entering a reactor for hydrogen peroxide removal treatment, leading the hydrogen peroxide conversion rate to be more than or equal to 95.2 percent, leading the discharged material to be mixed with nitrogen, carrying out sampling analysis after flash evaporation for removing non-condensable gas, and collecting the mixture for subsequent treatment.
The method comprises the steps of (1) carrying out hydrogenation purification on a propylene epoxidation recovery alcohol solvent after hydrogen peroxide removal pretreatment:
5.0 g of a commercially available hydrogenation catalyst (active component: ni) was charged into a fixed bed stainless steel reactor having a diameter of 12mm and a length of 90cm, and both ends of the reactor were charged with quartz sand and the catalyst was charged in the middle to ensure that the catalyst was in a constant temperature zone of the reactor (the reactor was used in the following examples, and the charging manner was uniform, unless otherwise specified). In the reactor, firstly, catalyst reduction is carried out, then, the treated olefin epoxidation is carried out to recycle alcohol solvent for hydrogenation purification, the evaluation device is continuously operated for 800 hours, sampling analysis is carried out, and the compositions before and after hydrogenation reaction are shown in table 1.
Wherein, the catalyst reduction conditions: the temperature is 400 ℃, the pressure is 0.5MPa, the reducing atmosphere is pure hydrogen, and the reducing time is 10 hours; the alcohol solvent hydrogenation purification conditions include: the temperature is 85 ℃, the pressure is 1.5MPa, the volume ratio of hydrogen to alcohol solvent is 80, and the liquid hourly space velocity is 5.0h -1 。
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 1.
Example 2
And (3) performing a dehydrogen peroxide pretreatment test on the propylene epoxidation recovery alcohol solvent.
Propylene epoxidation recovery alcohol solvent with hydrazine hydrate addedIn the amount of hydrazine hydrate/H 2 O 2 Calculated by the method of (mol ratio) =2, the mixture is uniformly mixed and reacted for 2min under the conditions of normal pressure and the reaction temperature of 110 ℃, and the hydrogen peroxide removal rate is 99.3%. The removal rate of the pretreated hydrogen peroxide is high, and the residual quantity of the hydrogen peroxide and the organic peroxide is small.
Example 3
The method comprises the following steps of (1) carrying out hydrogen peroxide removal pretreatment on a propylene epoxidation recovery alcohol solvent:
propylene epoxidation recovery alcohol solvent is added with hydrazine hydrate, and the addition amount of the hydrazine hydrate is calculated according to the ratio of hydrazine hydrate to H 2 O 2 Calculated by the method of (mol ratio) =2, the mixture is uniformly mixed and reacted for 20min under the conditions of normal pressure and reaction temperature of 30 ℃, and the hydrogen peroxide removal rate is 99.1%.
The method comprises the steps of (1) carrying out hydrogenation purification on a propylene epoxidation recovery alcohol solvent after hydrogen peroxide removal pretreatment:
the same hydrogenation catalyst was used and the catalyst loading, reduction and recovery of the alcohol solvent was performed in the same manner as in example 1.
The evaluation device was continuously operated for 800 hours, and the composition before and after hydrogenation reaction was sampled and analyzed as shown in Table 1.
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 1.
Comparative example 1
Directly carrying out hydrogenation purification treatment on the propylene epoxidation recovered alcohol solvent, adopting the same hydrogenation catalyst, and filling, reducing and recovering the catalyst and carrying out hydrogenation purification on the alcohol solvent in the same manner as in example 1.
The propylene epoxidation recovery alcohol solvent was subjected to hydrogenation purification in the prepared reactor, and the evaluation apparatus was continuously operated for 800 hours, and the composition before and after the hydrogenation reaction was analyzed by sampling and shown in Table 1.
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 1.
TABLE 1 raw materials, composition after hydrogenation and hydrogenation effect
* Comprises unknown components, undetectable components, etc
As can be seen from the data in Table 1, when the device is operated for 800 hours, the removal rate of hydrogen peroxide is 100 percent; the removal rate coupling treatment method of acetaldehyde is 100%, and the direct hydrogenation purification is reduced to 80%; the removal rate coupling treatment method of the dimethoxyethane is about 32.95-35.8 percent, and the direct hydrogenation purification is reduced to 2.27 percent; the removal rate coupling treatment method of the dimethoxy propane is about 30.57 to 33.12 percent, and the direct hydrogenation purification is reduced to 5.73 percent; the acetone removal rate coupling treatment method is about 78.57-82.14%, and the direct hydrogenation purification is about 67.86%; the removal rate coupling treatment method of acetonitrile is 80 percent, and the direct hydrogenation purification is reduced to 50 percent; the removal rates of nitromethane, nitroethane and nitropropane are all 100%; in addition, the common formaldehyde method in the material is hard to characterize, the formaldehyde removal rate is generally similar to that of formaldehyde, and residual formaldehyde reacts with methanol in a subsequent system to generate dimethoxy methane, the boiling point of the material is close to that of propylene oxide and can enter a propylene oxide product, the product quality is affected, and the purity of the propylene oxide product is higher after the coupling treatment method is adopted. The treated propylene epoxidation recovery alcohol solvent is further subjected to rectification separation, and the data in the table 1 shows that after the coupling treatment of hydrogen peroxide pretreatment and hydrogenation purification is adopted, the purity of the finally obtained methanol solvent is higher and is more than 99.5%, so that the recycling of the solvent is facilitated.
In conclusion, the coupling treatment method adopting hydrogen peroxide pretreatment and hydrogenation purification has better treatment effect on the propylene epoxidation recovery alcohol solvent than direct hydrogenation purification treatment; on the other hand, in the two treatment modes under the condition of achieving the same treatment effect, the loading amount of the hydrogenation agent is lower by adopting a coupling process; or the service life of the hydrogenating agent is longer under the condition of the same loading amount of the hydrogenating agent.
Example 4
The method comprises the following steps of (1) carrying out hydrogen peroxide removal pretreatment on a propylene epoxidation recovery alcohol solvent:
5.0 g of active carbon supported manganese oxide catalyst, the catalyst loading mode is as follows: as in example 1.
At a reaction temperature of 120 ℃, a reaction pressure of 4.0Mpa and a space velocity of 10h -1 Under the condition of (1) conveying propylene epoxidation recovery alcohol solvent (wherein the mass percentage of hydrogen peroxide in the solvent is 1.5% and the mass percentage of acetaldehyde is 0.5%) by a syringe pump, entering a reactor for hydrogen peroxide removal treatment, wherein the hydrogen peroxide removal rate is more than or equal to 94.8%, introducing nitrogen into discharge for mixing, and carrying out sampling analysis after flash evaporation for removing non-condensable gas, and collecting for subsequent treatment.
The method comprises the steps of (1) carrying out hydrogenation purification on a propylene epoxidation recovery alcohol solvent after hydrogen peroxide removal pretreatment:
the hydrogenation purification mode of catalyst filling, reduction and recovery of alcohol solvent: same as in example 1
The recovered alcohol solvent after the treatment was subjected to hydrogenation purification in the prepared reactor, and the evaluation apparatus was continuously operated for 800 hours, and the composition before and after the hydrogenation reaction was analyzed by sampling and shown in Table 2.
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 2.
Example 5
The method comprises the following steps of (1) carrying out hydrogen peroxide removal pretreatment on a propylene epoxidation recovery alcohol solvent:
5.0 g of active carbon supported manganese oxide catalyst, the catalyst loading mode is as follows: as in example 1.
At a reaction temperature of 120 ℃, a reaction pressure of 4.0Mpa and a space velocity of 10h -1 Under the condition of (1) conveying propylene epoxidation recovery alcohol solvent (wherein the mass percent of hydrogen peroxide in the solvent is 1.5% and the mass percent of acetaldehyde is 0.5%) by a syringe pump, mixing with 0.17L/min nitrogen, then feeding the mixture into a reactor for hydrogen peroxide removal treatment, wherein the hydrogen peroxide removal rate is more than or equal to 91.3%, and carrying out sampling analysis after flash evaporation and non-condensable gas removal on discharge, and collecting the mixture for subsequent treatment.
The method comprises the steps of (1) carrying out hydrogenation purification on a propylene epoxidation recovery alcohol solvent after hydrogen peroxide removal pretreatment:
the same hydrogenation catalyst is adopted, and the hydrogenation purification mode of filling, reducing and recovering the alcohol solvent is adopted: as in example 1.
The recovered alcohol solvent after the treatment was subjected to hydrogenation purification in the prepared reactor, and the evaluation apparatus was continuously operated for 800 hours, and the composition before and after the hydrogenation reaction was analyzed by sampling and shown in Table 2.
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 2.
Comparative example 2
Directly carrying out hydrogenation purification treatment on the propylene epoxidation recovered alcohol solvent, adopting the same hydrogenation catalyst, and filling, reducing and recovering the catalyst in the hydrogenation purification mode of the alcohol solvent: as in example 1.
The propylene epoxidation recovery alcohol solvent was subjected to hydrogenation purification in the prepared reactor, and the evaluation apparatus was continuously operated for 800 hours, and the composition before and after the hydrogenation reaction was analyzed by sampling and shown in Table 2.
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 2.
TABLE 2 raw materials, composition after hydrogenation and hydrogenation effect
* Comprises unknown components, undetectable components and the like, and the # recovered alcohol solvent is mixed with nitrogen and then subjected to hydrogen peroxide removal pretreatment
From the data in table 2, under the condition that the concentration of hydrogen peroxide in the raw material is increased from 0.5% to 1.5%, after the device is operated for 800 hours, the removal rate of impurities such as acetaldehyde, dimethoxyethane, dimethoxypropane, acetone, acetonitrile and the like in the coupling treatment method of hydrogen peroxide pretreatment and hydrogenation purification is superior to the removal rate of direct hydrogenation purification treatment, and the advantages are more obvious; the treated propylene epoxidation recovery alcohol solvent is further subjected to rectification separation, and the data in the table 2 show that after the coupling treatment of hydrogen peroxide pretreatment and hydrogenation purification is adopted, the purity of the finally obtained methanol solvent is higher and is more than 99.5%, so that the recycling of the solvent is facilitated. In conclusion, the coupling treatment method of hydrogen peroxide pretreatment and hydrogenation purification is adopted, so that the treatment effect is better, the service life of the hydrogenation agent is longer, and the purity of the recovered methanol solvent product is higher.
The removal rate of impurities such as acetaldehyde, dimethoxyethane, dimethoxypropane, acetone, acetonitrile and the like in the coupling treatment method of carrying out the hydrogen peroxide removal pretreatment and the hydrogenation purification after the alcohol solvent is recycled and the nitrogen is better than the removal rate of impurities of direct hydrogenation purification treatment, but slightly lower than the removal rate of impurities of the coupling treatment method of introducing nitrogen flash evaporation and hydrogenation purification after the hydrogen peroxide removal pretreatment.
Example 6
The method comprises the following steps of (1) carrying out hydrogen peroxide removal pretreatment on a propylene epoxidation recovery alcohol solvent:
100.0 g of the silica-supported manganese oxide catalyst was charged into a slurry bed reactor having a capacity of 2000mL, which was a coupling device for separation of the reaction from the catalyst, and continuous and stable operation was achieved. At a reaction temperature of 80 ℃, a reaction pressure of 1.0Mpa and a space velocity of 10h -1 Under the condition of (1) conveying propylene epoxidation recovery alcohol solvent (wherein the mass percent of hydrogen peroxide in the solvent is 0.5% and the mass percent of acetaldehyde is 0.5%) by a syringe pump, entering a reactor for hydrogen peroxide removal treatment, introducing nitrogen into a discharge, mixing, carrying out flash evaporation for non-condensable gas removal, then carrying out sampling analysis, wherein the hydrogen peroxide removal rate is more than or equal to 98.3%, and collecting materials for subsequent treatment.
The method comprises the steps of (1) carrying out hydrogenation purification on a propylene epoxidation recovery alcohol solvent after hydrogen peroxide removal pretreatment:
the same hydrogenation catalyst is adopted, and the hydrogenation purification mode of filling, reducing and recovering the alcohol solvent is adopted: as in example 1.
The recovered alcohol solvent after the treatment was subjected to hydrogenation purification in the prepared reactor, and the evaluation apparatus was continuously operated for 800 hours, and the composition before and after the hydrogenation reaction was analyzed by sampling and shown in Table 3.
The hydrogenated recovered alcohol solvent obtained in the previous step was subjected to rectification separation at normal pressure, and a fraction having a distillation range of 64 to 65℃was collected to obtain a recovered methanol solvent having the purity shown in Table 3.
Comparative case see comparative example 1.
TABLE 3 raw materials, composition after hydrogenation and hydrogenation effect
* Comprises unknown components, undetectable components, etc
As can be seen from the data in Table 3, the removal rate of impurities such as acetaldehyde, dimethoxyethane, dimethoxypropane, acetone and acetonitrile is better than that of the direct hydrogenation purification treatment by adopting the coupling treatment method of slurry bed manganese oxide dehydrogen peroxide pretreatment and hydrogenation purification to treat propylene for epoxidation and recovering alcohol solvent; the treated olefin epoxidized alcohol solvent is further subjected to rectification separation, and the data in the table 3 show that after the coupling treatment of hydrogen peroxide pretreatment and hydrogenation purification is adopted, the purity of the finally obtained methanol solvent is higher and is more than 99.5%, so that the recycling of the solvent is facilitated. In a word, the coupling method provided by the invention has better effect of treating propylene epoxidation to recover the alcohol solvent.
The test methods of example 1 and comparative example 1 were used to conduct long-period comparative tests on the treatment effects of both the fixed bed manganese oxide dehydrogen peroxide pretreatment + hydrogenation purification coupling treatment method and the direct hydrogenation purification treatment method, and the test results are shown in table 4 and fig. 1.
Table 4 coupled treatment and direct hydrotreatment comparative data
As can be seen from Table 4 and FIG. 1, the recovery of alcohol solvent by epoxidation of propylene by direct hydrogenation purification method, the removal rate of acetaldehyde starts to decrease after about 500 hours, and the removal rate of acetaldehyde decreases to 80.1% when the device is operated for 892 hours; the coupling treatment method of hydrogen peroxide removal pretreatment and hydrogenation purification is adopted to treat propylene epoxidation to recycle alcohol solvent, when the device is operated for 2116 hours, the removal rate of acetaldehyde starts to decrease, and the removal rate of acetaldehyde is 99.6%; further, the coupling treatment method has the treatment effect far superior to that of the direct hydrogenation purification method, has longer service life of the catalyst and higher impurity removal rate, and particularly has the advantages of being capable of efficiently removing hydrogen peroxide and organic peroxide by introducing a hydrogen peroxide removal pretreatment unit and having more outstanding advantages when treating harsher propylene epoxidation to recycle alcohol solvent.
Claims (5)
1. A method for treating propylene epoxidation recovery alcohol solvent comprises a treatment method for coupling hydrogen peroxide removal pretreatment and hydrogenation purification of the propylene epoxidation recovery alcohol solvent; the catalyst is a formed catalyst prepared by loading one or more oxides of manganese oxide, copper oxide and ferric oxide on an alumina and/or silica and/or active carbon carrier.
2. The method for treating a recovered alcohol solvent for epoxidation of propylene according to claim 1, wherein said recovered alcohol solvent is a solution remaining after removal of propylene oxide from a mixture obtained by epoxidation of propylene.
3. The method for treating a propylene epoxidation recovery alcohol solvent according to claim 1, characterized in that: the catalytic hydrogen peroxide removal treatment is to recycle alcohol solvent to contact with the catalyst and to remove hydrogen peroxide under the conditions of the temperature of 70-120 ℃ and the pressure of 0.1-4.0 MPa.
4. A process for the epoxidation of propylene to recover an alcohol solvent according to claim 1 or 3, characterized in that: when the hydrogen peroxide removal pretreatment is carried out by adopting a catalytic hydrogen peroxide removal method, the alcohol solvent is recycled before pretreatment and mixed with a certain amount of nitrogen or the discharged material after pretreatment is mixed with a certain amount of nitrogen, and a gas-liquid separator is additionally arranged at the rear of the mixture to safely remove oxygen-containing noncondensable gas.
5. The method for treating a propylene epoxidation recovery alcohol solvent according to claim 1, characterized in that: the hydrogenation purification refers to the steps that the recovered alcohol solvent is contacted with a catalyst with a catalytic hydrofining function, and the recovered alcohol solvent is subjected to purification treatment under the condition of hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111073576.7A CN113636914B (en) | 2021-09-14 | 2021-09-14 | Treatment method for propylene epoxidation recovery of alcohol solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111073576.7A CN113636914B (en) | 2021-09-14 | 2021-09-14 | Treatment method for propylene epoxidation recovery of alcohol solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113636914A CN113636914A (en) | 2021-11-12 |
| CN113636914B true CN113636914B (en) | 2024-04-12 |
Family
ID=78425734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111073576.7A Active CN113636914B (en) | 2021-09-14 | 2021-09-14 | Treatment method for propylene epoxidation recovery of alcohol solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113636914B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649858A (en) * | 2002-05-02 | 2005-08-03 | 德古萨股份公司 | Process for the epoxidation of olefins |
| CN104926606A (en) * | 2014-03-21 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | Method for purifying recycle alcohol solvent of olefin epoxidation process and olefin epoxidation method |
| CN110354858A (en) * | 2019-08-23 | 2019-10-22 | 湖南长岭石化科技开发有限公司 | A kind of alcoholic solvent Hydrobon catalyst of epoxidation reaction of olefines process and its preparation method and application |
-
2021
- 2021-09-14 CN CN202111073576.7A patent/CN113636914B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649858A (en) * | 2002-05-02 | 2005-08-03 | 德古萨股份公司 | Process for the epoxidation of olefins |
| CN104926606A (en) * | 2014-03-21 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | Method for purifying recycle alcohol solvent of olefin epoxidation process and olefin epoxidation method |
| CN110354858A (en) * | 2019-08-23 | 2019-10-22 | 湖南长岭石化科技开发有限公司 | A kind of alcoholic solvent Hydrobon catalyst of epoxidation reaction of olefines process and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113636914A (en) | 2021-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100814310B1 (en) | Epoxy Reaction Method of Olefin | |
| KR102138648B1 (en) | A process for refining propylene oxide | |
| KR20050086795A (en) | Process for the purification of crude propene oxide | |
| CN110354858B (en) | Alcohol solvent hydrofining catalyst in olefin epoxidation reaction process and preparation method and application thereof | |
| JP4718186B2 (en) | Olefin epoxidation process | |
| CN103172596B (en) | Propylene oxide refining method | |
| JP2005526844A5 (en) | ||
| WO2018205244A1 (en) | Process for the epoxidation of propene | |
| TW201730168A (en) | Process for the epoxidation of propene | |
| CN113636914B (en) | Treatment method for propylene epoxidation recovery of alcohol solvent | |
| CN101341139B (en) | Propylene oxide purification and recovery | |
| CN113651777B (en) | Reaction rectification formaldehyde removal process | |
| CN112694455B (en) | System and method for hydrogenation removal of aldehydes and ketones | |
| CN113968830B (en) | Separation method of epoxypropane stream and separation method of epoxidation reaction product and propylene epoxidation method | |
| CN113968829B (en) | Propylene epoxidation method and epoxidation system | |
| CN113968772B (en) | Purification method and apparatus, mixture stream treatment method and apparatus, method for producing epoxide and epoxidation reaction system | |
| EP4107141B1 (en) | Process for preparing alkylene glycol mixture from a carbohydrate source with decreased selectivity for polyol side products | |
| CN112694454A (en) | Method and system for processing crude propylene oxide material | |
| CN119192100A (en) | Method for preparing propylene oxide and device for preparing propylene oxide | |
| EP4166545B1 (en) | Process for making propene oxide | |
| CN115385768B (en) | Method for producing cumene, method for producing propylene oxide, and cumene and propylene oxide obtained thereby | |
| CN114634467B (en) | Method for removing impurities in epoxypropane | |
| TW202246225A (en) | Process for the epoxidation of propene | |
| CN113968831A (en) | Propylene oxide refining method, method for separating propylene oxide stream, method for separating epoxidation reaction product, and method for epoxidizing propylene | |
| WO2025027195A1 (en) | Process for the production of n-methylmorpholine having low hazen color number |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 414012 Lu Kou Zhen Chang Lian Long Kou, Yunxi District, Yueyang City, Hunan Province (opposite to Chang Lian hospital) Applicant after: Hunan Changlian New Material Technology Co.,Ltd. Address before: 414000 Changlian Longkou, Lukou Town, Yunxi District, Yueyang City, Hunan Province (opposite to Changlian hospital) Applicant before: HUNAN CHANGLING PETROCHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |