阅读说明：本技术 烯基琥珀酸酐的制备方法 (Process for preparing alkenyl succinic anhydride ) 是由 施晓旦 赵锡亮 金霞朝 于 2021-07-06 设计创作，主要内容包括：本发明公开了一种烯基琥珀酸酐的制备方法。所述烯基琥珀酸酐的制备方法包括如下步骤：在催化剂存在的情况下,马来酸酐和异构烯烃在管式反应器中进行反应,即得；所述催化剂为酸性离子液体/载体的复合催化剂；所述反应的温度为160～260℃；所述反应的停留时间为2～10min。本发明的烯基琥珀酸的制备方法具有反应速率高、反应时间短、产品收率高、副产物少和产品纯度高的优点。(The invention discloses a preparation method of alkenyl succinic anhydride. The preparation method of the alkenyl succinic anhydride comprises the following steps: in the presence of a catalyst, maleic anhydride and isoolefine react in a tubular reactor to obtain the catalyst; the catalyst is a composite catalyst of acidic ionic liquid/carrier; the reaction temperature is 160-260 ℃; the residence time of the reaction is 2-10 min. The preparation method of alkenyl succinic acid has the advantages of high reaction rate, short reaction time, high product yield, few byproducts and high product purity.)

1.A method for preparing alkenyl succinic anhydride, comprising the steps of: in the presence of a catalyst, maleic anhydride and isoolefine react in a tubular reactor to obtain the catalyst; the catalyst is a composite catalyst of acidic ionic liquid/carrier; the reaction temperature is 160-260 ℃; the residence time of the reaction is 2-10 min.

2. The method of claim 1, wherein the method of producing isoolefins comprises the steps of: under the atmosphere of protective gas, carrying out isomerization reaction on terminal olefin under the action of an acid catalyst to obtain the catalyst;

the isoolefin is C_nH_2nWherein n is 14-22.

3. The process for the preparation of alkenylsuccinic anhydride according to claim 2, wherein the protective gas is an inert gas and/or nitrogen, preferably nitrogen;

and/or the temperature of the isomerization reaction is 330-370 ℃, preferably 330 ℃;

and/or, the isomerization reaction is carried out with stirring;

and/or the isomerization reaction time is 2-3 h.

4. The method of claim 1, wherein the molar ratio of the maleic anhydride to the isoolefin is 1 (1.2-2);

and/or the acidic ionic liquid is one or more of pyridinium ionic liquid, imidazolium ionic liquid, phosphate ionic liquid, sulfate ionic liquid and sulfonate ionic liquid; preferably pyridine salt ionic liquid and/or imidazole salt ionic liquid;

and/or the carrier is one or more of activated carbon, activated clay and diatomite;

and/or the particle size of the carrier is 250-350 meshes;

and/or the loading amount of the acidic ionic liquid on the carrier is 3-20%, preferably 10-15%, wherein the loading amount refers to the mass ratio of the acidic ionic liquid to the carrier;

and/or the mass ratio of the catalyst to the maleic anhydride is 0.005-0.2: 1, such as 0.01:1, 0.03:1, 0.05:1, 0.08:1, 0.1:1, or 0.15: 1.

5. The process for preparing alkenylsuccinic anhydride according to claim 1, wherein the maleic anhydride and the catalyst are preheated and mixed before being fed into the tubular reactor; wherein the preheating temperature is preferably 80-120 ℃, and more preferably 100 ℃.

6. The method of claim 1, wherein the reaction temperature is 160-180 ℃, or 180-220 ℃, or 220-240 ℃, or 240-260 ℃;

and/or the time is 8-10 min, or 4-10 min, or 3-6 min, or 2-6 min.

7. The process for the preparation of alkenyl succinic anhydride according to claim 1, wherein the reaction temperature is 160 to 180 ℃ and the residence time is 8 to 10min, such as 9 min;

or the reaction temperature is 180-220 ℃, and the residence time is 4-10 min, such as 5min, 6min, 7min, 8min or 9 min;

or the reaction temperature is 220-240 ℃, and the retention time is 3-6 min, such as 4min or 5 min;

or the reaction temperature is 240-260 ℃, and the retention time is 2-6 min, such as 3min, 4min or 5 min.

8. The method of claim 1, wherein the reaction temperature is 260 ℃ and the residence time is 2 min;

or the reaction temperature is 180 ℃, and the retention time is 10 min;

or the reaction temperature is 240 ℃, and the retention time is 6 min;

alternatively, the temperature of the reaction is 260 ℃ and the residence time is 3 min.

9. The method according to claim 1, wherein the reaction pressure is 0.3 to 0.8 MPa.

10. The method according to claim 1, wherein the tubular reactor is made of one or more of perfluoroethylene-propylene copolymer, polytetrafluoroethylene, quartz glass, silicate glass, high borosilicate glass, and silicon carbide;

and/or the tubular reactor has an internal diameter of 1 to 50mm, preferably 1 to 10mm, for example 3.7 mm.

Technical Field

The invention relates to a preparation method of alkenyl succinic anhydride.

Background

Alkenyl succinic anhydride is abbreviated as ASA and is widely applied to the fields of light industry, fine chemical industry and the like. In the paper industry, ASA, as a commonly used neutral sizing agent, can greatly improve the wear resistance, water resistance, tensile strength and the like of finished paper. In the field of fine chemicals, ASA is commonly used as a basic raw material for sizing agents, emulsifiers, lubricants and dispersants.

ASA is generally prepared by reacting an olefin with maleic anhydride in a tank reactor at elevated temperature. In the traditional batch kettle type reaction, maleic anhydride exists in a reactor in a gas form, the contact area with olefin is small, the reaction rate is slow, the reaction time is long, the higher reaction temperature and the overlong reaction time further cause that the maleic anhydride and the olefin are easy to self-polymerize, oxidize and decompose to generate a large amount of byproducts, the ASA yield is reduced, and the separated tar bottom after refining is difficult to treat.

In response to this problem, the prior art has conducted extensive research on the synthesis of ASA, mainly including the following classes: US3412111 and US3476774 reduce the formation of by-products by adding antioxidants, preferably phenothiazine, hydroquinone and sterically hindered substituted phenols; CN1609092, CN1241918 and WO9730039 prepare ASA under high pressure conditions, and inhibit the generation of byproducts to a certain extent; DEA3545133 reduces the production of by-products by adding a titanium oxide, aluminum oxide or silicon oxide catalyst and lowering the reaction temperature. Although the preparation method improves the selectivity of the reaction to a certain extent and reduces the generation of byproducts, the problems of slow reaction rate, long reaction time and low product yield still exist.

Disclosure of Invention

The invention aims to solve the technical problems of low reaction rate, long reaction time, low product yield, more byproducts and low product purity of the preparation method of ASA in the prior art, and provides a preparation method of alkenyl succinic acid. The preparation method of alkenyl succinic acid has the advantages of high reaction rate, short reaction time, high product yield, few byproducts and high product purity.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of alkenyl succinic acid, which comprises the following steps:

in the presence of a catalyst, maleic anhydride and isoolefine react in a tubular reactor to obtain the catalyst; the catalyst is a composite catalyst of acidic ionic liquid/carrier; the reaction temperature is 160-260 ℃; the residence time of the reaction is 2-10 min.

In the present invention, the isoolefin may be an internal olefin conventional in the art, preferably C_nH_2nWherein n is 14-22.

In the present invention, the process for the preparation of isoolefins may be conventional in the art and generally comprises the steps of: and under the atmosphere of protective gas, carrying out isomerization reaction on the terminal olefin under the action of an acid catalyst to obtain the catalyst.

The protective gas may be conventional in the art, and is preferably an inert gas and/or nitrogen, more preferably nitrogen.

The temperature of the isomerization reaction may be conventional in the art, and is preferably 330 to 370 ℃, and more preferably 330 ℃.

Wherein, stirring is generally carried out during the isomerization reaction.

Wherein, the time of the isomerization reaction can be conventional in the field, and is preferably 2-3 h.

In the invention, the molar ratio of the maleic anhydride to the isoolefin can be conventional in the field, and is preferably 1 (1.2-2).

In the invention, the acidic ionic liquid can be conventional in the field, and is preferably one or more of a pyridinium ionic liquid, an imidazolium ionic liquid, a phosphate ionic liquid, a sulfate ionic liquid and a sulfonate ionic liquid; more preferably a pyridine salt type ionic liquid and/or an imidazole salt type ionic liquid.

Among them, the imidazolium ionic liquid is preferably imidazole dihydrogen phosphate and/or imidazole nitrate, and more preferably 1-butyl-3-methylimidazole dihydrogen phosphate and/or 1-ethyl-3-methylimidazole nitrate.

When the acidic ionic liquid is imidazole dihydrogen phosphate and imidazole nitrate, the mass ratio of the imidazole dihydrogen phosphate to the imidazole nitrate is preferably 1 (0.5-2), and more preferably 1: 1.

Wherein, the pyridine salt ionic liquid is preferably pyridine sulfonate, and more preferably 2-methylpyridine methanesulfonate.

In the present invention, the carrier may be conventional in the art, and preferably is one or more of activated carbon, activated clay and diatomaceous earth.

In the present invention, the particle size of the carrier may be the particle size of the catalyst conventionally used in the tubular reactor, and is preferably 250 to 350 mesh.

The acidic ionic liquid/carrier in the invention refers to a catalyst prepared by loading the acidic ionic liquid on the carrier.

In the present invention, the loading amount of the acidic ionic liquid on the carrier can be conventional in the art, and generally can be 3% to 20%, and preferably 10% to 15%, where the loading amount refers to the mass ratio of the acidic ionic liquid to the carrier.

In the present invention, the preparation method of the catalyst may be conventional in the art, and is preferably an impregnation method.

The impregnation method may be performed by a method conventional in the art, and generally, the acidic ionic liquid may be mixed with the carrier.

The catalyst for catalyzing the reaction of the succinic anhydride and the isoolefine in the prior art is not suitable for a tubular reactor, and the inventor creatively loads the ionic liquid on a carrier to form the catalyst with fine granularity, can be fully and uniformly mixed with reaction raw materials, has good fluidity in the tubular reactor, can be used for catalyzing the reaction of the succinic anhydride and the isoolefine to generate the alkenyl succinic anhydride, and has reaction rate and selectivity.

In the present invention, the mass ratio of the catalyst to the maleic anhydride is preferably 0.005 to 0.2:1, for example, 0.01:1, 0.03:1, 0.05:1, 0.08:1, 0.1:1 or 0.15: 1.

The dosage of the catalyst in the invention is obtained by a great deal of experimental research of the inventor, the dosage of the catalyst is too small, the reaction rate is not obviously improved, the reaction selectivity is not obvious, the dosage of the catalyst is too high, and the tubular reactor is easy to block, thus the reaction is influenced.

In the present invention, the feeding manner of the maleic anhydride, the isoolefin and the catalyst may be conventional in the art, and generally, the maleic anhydride, the isoolefin and the catalyst may be added to the tubular reactor.

In the invention, preferably, the maleic anhydride is preheated into liquid and then added into the tubular reactor; more preferably, the maleic anhydride and the catalyst are preheated, mixed and then added to the tubular reactor.

Wherein the addition is preferably pumped at a constant flow rate using a constant flow pump.

Wherein the preheating temperature is a conventional temperature for liquefying the maleic anhydride, preferably 80-120 ℃, for example 100 ℃.

In the invention, the reaction temperature is preferably 160-180 ℃, or 180-220 ℃, or 220-240 ℃, or 240-260 ℃.

In the present invention, the reaction time is preferably 8-10 min, or 4-10 min, or 3-6 min, or 2-6 min.

In the invention, the reaction temperature is preferably 160-180 ℃, and the residence time is 8-10 min, such as 9 min.

In the invention, the reaction temperature is preferably 180-220 ℃, and the residence time is 4-10 min, such as 5min, 6min, 7min, 8min or 9 min.

In the invention, the reaction temperature can be 220-240 ℃, and the retention time can be 3-6 min, such as 4min or 5 min.

In the invention, the reaction temperature can be 240-260 ℃, and the retention time can be 2-6 min, such as 3min, 4min or 5 min.

In a preferred embodiment of the invention, the reaction temperature is 260 ℃ and the residence time is 2 min.

In a preferred embodiment of the present invention, the reaction temperature is 180 ℃ and the residence time is 10 min.

In a preferred embodiment of the present invention, the reaction temperature is 240 ℃ and the residence time is 6 min.

In a preferred embodiment of the present invention, the reaction temperature is 260 ℃ and the residence time is 3 min.

The inventor of the invention makes a great deal of research on the applicable temperature and residence time of the ionic liquid/carrier catalyst, and finds that the higher the reaction temperature and the longer the residence time, the more easily the side reaction occurs to generate a tar substrate; the temperature is too low or the residence time is too short, and the conversion rate of raw materials and the yield of products are not high. The inventor obtains the proper reaction temperature and residence time through a large number of experiments, and the reaction rate is high, the product yield is high, the tar content is low, and the product quality is high within the reaction temperature and residence time range of the invention.

In the present invention, the reaction pressure is preferably 0.3 to 0.8 MPa. The pressure of the reaction can be achieved by adjusting a back pressure valve.

In the invention, maleic anhydride and isoolefine react in a tubular reactor, and when the reaction temperature is lower than the boiling point of the maleic anhydride, the maleic anhydride is in a liquid phase and is more uniformly mixed with the isoolefine; when the reaction temperature exceeds the boiling point of the maleic anhydride, the maleic anhydride is in a gas phase, but in the limited space of the tubular reactor, the liquid in the tubular reactor flows in a trickle mode, the contact area of the maleic anhydride gas and isoolefine is larger, the mixture is more uniform, and the reaction rate is greatly improved under the catalytic action of the ionic liquid catalyst.

In the present invention, the material of the tubular reactor may be conventional in the art, and is preferably one or more of perfluoroethylene propylene copolymer, polytetrafluoroethylene, quartz glass, silicate glass, high borosilicate glass, and silicon carbide.

In the present invention, the inner diameter of the tubular reactor may be conventional in the art, and is preferably 1 to 50mm, more preferably 1 to 10mm, for example 3.7 mm.

In the present invention, the tubular reactor is preferably cleaned before use.

Wherein, the cleaning can be carried out by adopting a method which is conventional in the field, and generally, dilute alkali liquor is added and heated, and the mixture is discharged and then is washed by water.

The heating temperature can be conventional in the art, and is preferably 40-80 ℃.

The heating time can be conventional in the art, and is preferably 40-80 min, and more preferably 60 min.

In the present invention, preferably, the preparation method of the alkenyl succinic anhydride further comprises: and (3) carrying out solid-liquid separation on the reaction product to obtain a crude product, and purifying the crude product to obtain the refined alkenyl succinic anhydride.

Wherein, the solid-liquid separation can be carried out by adopting a method which is conventional in the field, and is preferably filtration.

Wherein, the purification can be carried out by adopting the conventional method in the field, and the reduced pressure distillation is preferred.

The reduced pressure distillation may be carried out by a method conventional in the art.

On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows:

(1) the reaction rate is high, the reaction time is short, the reaction time can be 2-10 min, and the reaction time is greatly shortened compared with a kettle type reaction;

(2) the product yield is high, the ASA yield can be higher than 75 percent, and in a preferred embodiment, the ASA yield can be as high as 79.71 percent;

(3) the product quality is high, the purity of the obtained ASA product can be higher than 99%, and the color is light yellow;

(4) the side reaction is less, the tar generation amount is less, and the tar yield can be lower than or close to 1%;

(5) the reaction temperature is lower and can be lower than 200 ℃, and the energy consumption is reduced.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The isomerized olefins were all produced by INEOS Oligomers (inc.) with a purity of greater than 99%. With C from example 1₁₄H₂₈For example, it is given by C₁₄H₂₈Mainly (the mass percent is generally more than 70 percent), and the total content of isoolefine is more than 99 percent;

the maleic anhydride manufacturer is Shanghai Kayin chemical company Limited, and the purity is 99 percent;

the ionic liquid/carrier composite catalyst is produced by Linzhou Keneng materials science and technology limited company;

the manufacturer of the solid super acid is Nanjing chemical, and the model is HZ-280.

The tubular reactors or stirred tank reactors used in the following examples and comparative examples were cleaned as follows before use:

adding the dilute alkali liquor into a tubular reactor or a reaction kettle with a stirrer, heating to 40-80 ℃, preserving heat for 1h, discharging the dilute alkali liquor, and washing with water.

Example 1

0.25g of 2-methylpyridine methanesulfonate ion/activated carbon catalyst (with a load of 10%) and 50g of maleic anhydride were mixed, added into a molten liquid tank, preheated to 80 ℃, and then fed into a tubular reactor (with an inner diameter of 3.7mm), and 150g of isomerized olefin (C) was simultaneously fed at a constant flow rate through a constant flow pump₁₄H₂₈) Pumped into a tubular reactor. The temperature is controlled at 260 ℃ through heat conducting oil of the shell layer, a back pressure valve is adjusted, the pressure is controlled at 0.8MPa, and the retention time is 2 min. After the reaction is finished, the materials are separated from the crude product by a filter screen. And transferring the obtained crude product to a reduced pressure distillation device for crude product purification, wherein the fraction is ASA.

Example 2

1g of 1-butyl-3-methylimidazolium dihydrogenphosphate/kieselguhr catalyst (15% loading) was mixed with 50g of maleic anhydride and added to a melt tank and preheated to 120 ℃. 248g of isomerized olefin (C) were pumped at a constant flow rate through a constant flow pump₁₆H₃₂And C₁₈H₃₆Of 1: 1) was pumped into a tubular reactor (internal diameter of 3.7 mm). Controlling the temperature at 180 ℃ through heat conducting oil of a shell layer, adjusting a back pressure valve, controlling the pressure at 0.3Mpa, keeping the pressure for 10min, and obtaining the ASA by the other steps and conditions which are the same as those of the example 1.

Example 3

1g of 1-ethyl-3-methylimidazole nitrate/activated clay catalyst (loading 10%) and 50g of maleic anhydride were mixed, added to a molten liquid tank and preheated to 100 ℃. 275g of isomerized olefin (C) were pumped at a constant flow rate through a constant flow pump₂₂H₄₄) Pumped into a tubular reactor (internal diameter of3.7 mm). The temperature is controlled at 240 deg.C by heat conducting oil of shell layer, backpressure valve is adjusted, pressure is controlled at 0.5Mpa, and residence time is 6 min. The other steps and conditions were the same as in example 1 to obtain ASA.

Example 4

Cleaning the tubular reactor. 0.5g of 1-ethyl-3-methylimidazole nitrate/activated clay (loading: 10%) and 0.5g of 1-butyl-3-methylimidazole dihydrogen phosphate/diatomaceous earth (loading: 15%) were mixed with 60g of maleic anhydride, and the mixture was charged into a molten liquid tank and preheated to 100 ℃. 240g of isomerized olefin (C) were fed at a constant flow rate through a constant flow pump₁₈H₃₆) Pumped into a tubular reactor (internal diameter 3.7 mm). Controlling the temperature at 260 ℃ through heat conducting oil of a shell layer, adjusting a back pressure valve, controlling the pressure at 0.5Mpa, keeping the pressure for 3min, and obtaining the ASA by the other steps and conditions which are the same as those of the example 1.

Comparative example 1

275g of isomerized olefin (C)₂₂H₄₄) Adding into a reaction kettle, stirring and mixing. 0.5g of 2-methylpyridine methanesulfonate/activated carbon (the load is 10%) and 50g of maleic anhydride are mixed, preheated to 100 ℃, and then dropwise added into a reaction kettle within 2-3 hours. Heating to 230 ℃, and reacting for 8 hours at constant temperature. The separation and purification steps were the same as in example 1 to obtain ASA.

Comparative example 2

0.25g of 2-methylpyridine methanesulfonate ion/activated carbon catalyst (with a loading of 10%) and 50g of maleic anhydride were mixed, added to a melt tank and preheated to 80 ℃, and then introduced into a tubular reactor (with an inner diameter of 3.7 mm). While 150g of isomerized olefin (C) was fed at a constant flow rate through a constant flow pump₁₄H₂₈) Pumped into the reactor. The temperature is controlled at 270 ℃ through heat conducting oil of the shell layer, a back pressure valve is adjusted, the pressure is controlled at 0.8MPa, and the retention time is 2 min. The other steps are the same as the example 1, and the ASA is obtained.

Comparative example 3

0.5g of solid superacid (HZ-280) was reacted with 275g of isomerized olefin (C)₂₂H₄₄) Adding into a reaction kettle, stirring and mixing. Mixing 50g of maleic anhydride, preheating to 100 ℃, and dripping within 2-3 hoursAdding into a reaction kettle. Heating to 230 ℃, and reacting for 8 hours at constant temperature. The separation and purification steps were the same as in example 1 to obtain ASA.

Effects of the embodiment

ASA yield

The yields of alkenyl succinic anhydrides of examples 1 to 4 and comparative example 1 were calculated based on the amount of maleic anhydride charged, and the results are shown in Table 1.

ASA purity

The purity of the products obtained in examples 1 to 4 and comparative example 1 was measured by gas chromatography and nuclear magnetic resonance, and the results are shown in table 1. The gas chromatography peak time, substance and content of ASA obtained in example 2 are shown in table 2.

ASA Density characterization

The densities of the alkenyl succinic anhydrides obtained in examples 1 to 4 and comparative example 1 were measured by an automatic bench density densitometer, and the results are shown in Table 1.

As can be seen from Table 1, the alkenyl succinic anhydrides obtained in examples 1 to 4 all had densities in the range of 0.93 to 0.97g/cm3, and were high in quality.

ASA viscosity characterization

The density of the alkenyl succinic anhydrides obtained in examples 1 to 4 and comparative example 1 was measured by a viscometer, and the results are shown in Table 1.

As can be seen from Table 1, the alkenyl succinic anhydrides obtained in examples 1 to 4 all have viscosities in the range of 130 to 150cps, and the viscosities are moderate.

ASA appearance

The alkenyl succinic anhydrides obtained in examples 1 to 4 and comparative example 1 were visually recognized as appearance, and it was found that they were amber transparent liquids.

5. By-product tar yield

After the crude products obtained in examples 1-4 and comparative example 1 were purified by vacuum distillation, the ASA product and the tar byproduct were obtained, and the yield of the tar byproduct was calculated by the amount of isoolefin fed, and the results are shown in table 1.

TABLE 1 ASA characterization results of each example and comparative example

Table 2 comparative table of ASA gas chromatography

As shown in Table 1, in the examples 1-4, the ASA yield is higher than 78% in the reaction time of 2-10 min, the ASA yield is higher than that in the comparative examples 1-3, the reaction time is greatly shortened compared with that in the comparative examples 1 and 3, and the reaction efficiency is greatly improved; the reaction temperature of comparative example 2 was 270 c, side reactions were significantly increased at reaction temperatures outside the scope of the present invention, and the product yield was reduced.

The product purity of the ASA obtained in the examples 1-4 is higher than 99% and higher than that of the products in the comparative examples 1-3, and if the product purity of the comparative examples 1-3 is further improved through reduced pressure distillation, the yield is further reduced, and meanwhile, the flow and the energy consumption are increased.

The yield of the byproduct tar in the embodiments 1 to 4 is lower than or close to 1 percent and far lower than that in the comparative examples 1 to 3, which shows that the ASA modified by the method has high selectivity, less side reaction and less byproduct generation, and reduces the treatment difficulty of the tar substrate.

As shown in Table 2, the purity of alkenyl succinic anhydride in the product obtained in example 2 was 99.8%.