CN115124431B - Preparation method of di-and polyamines of diphenylmethane series with low N-methyl impurity content - Google Patents
Preparation method of di-and polyamines of diphenylmethane series with low N-methyl impurity content Download PDFInfo
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- CN115124431B CN115124431B CN202210768526.9A CN202210768526A CN115124431B CN 115124431 B CN115124431 B CN 115124431B CN 202210768526 A CN202210768526 A CN 202210768526A CN 115124431 B CN115124431 B CN 115124431B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Abstract
The present invention relates to a process for the production of diamines and polyamines of the diphenylmethane series having a low N-methyl impurity content. The method comprises the steps of preparing a mixture (DAM) of di-and polyamines of the diphenylmethane series by carrying out condensation reaction and dehydration of part of aniline and formaldehyde, salifying part of aniline and an acidic catalyst, and then mixing the part of aniline and the acidic catalyst for carrying out transposition reaction. According to the invention, the reaction quality can be improved, the generation of N-methyl impurities can be reduced, and high-quality di-amine and polyamine of diphenylmethane series can be obtained.
Description
Technical Field
The present invention relates to the preparation of di-and polyamines of the diphenylmethane series, and in particular to a process for the preparation of di-and polyamines (DAM) of the diphenylmethane series of high quality with low N-methyl impurity content, which process involves a process for the production of DAM with low macromolecular impurity content by salt formation reaction with condensation.
Background
The di-and polyamines (DAM) of the diphenylmethane series are understood to mean the following types of amines and mixtures of amines:
here, n represents a natural number of 0 or more, and n=0 is referred to as diaminodiphenylmethane, abbreviated as diamine; n is n>At 0, the polyamine-based diphenylmethane is referred to as polyamine, and the two types of mixtures are referred to as diamines and polyamines of the diaminodiphenylmethane series. Wherein NH in DAM 2 The derived products being diisocyanates of the diaminodiphenylmethane series, polyisocyanates of the diaminodiphenylmethane series or polyiminopolyphenylene polymethylene polyisocyanates of the diaminodiphenylmethane series, or products derived from the substitution of the groups entirely by NCO groupsThe list of di-and polyisocyanates (hereinafter MDI) which are used for the production of polyurethanes.
Methods for the preparation of DAM are generally well known in the art and are described in A number of published patents and publications, such as U.S. Pat. No. 2009/024777, EP-A-451442 and WO-A-99/40059, where DAM is prepared by A continuous, semi-continuous or discontinuous reaction process, typically using aniline to react with hydrochloric acid to form aniline acid salt, then formaldehyde is added to the reactor to form DAM acid salt, the organic phase is separated from the inorganic phase by neutralization and water washing to give crude DAM, the DAM is purified, and the monomeric or polymeric MDI is formed by phosgenation.
In the traditional large-scale industrial production process, side reactions easily occur in the DAM preparation process, N-methyl DAM impurities are generated, N-methyl DAM impurities generate N-methyl acyl chloride and other impurities in the downstream phosgenation process, and the activity of downstream polyurethane products is influenced. Therefore, reducing the content of the byproduct N-methyl DAM in the DAM preparation process plays a key role in improving the quality of polyurethane products.
At present, research has been made at home and abroad to reduce N-methyl impurities in DAM by changing process parameters by adding formaldehyde step by step, adding DAM into recovered aniline and the like and improving the selectivity of the transposition rearrangement reaction by a catalyst, and as described in US7528283, the impurity in the product is reduced by adding 0.01-1wt% of DAM into recovered aniline; CN200980121586.4 reacts with aminal by using solid acidic silica catalyst and ion exchange resin catalyst based on styrene-divinylbenzene copolymer to prepare 4,4' -methylenedianiline with low impurity content; CN 107827756A performs a metathesis reaction in a fixed bed metathesis reactor loaded with a novel catalyst after reacting aniline, formaldehyde and an acidic catalyst to form a reaction mixture of polyaminobenzyl aniline salts, and reduces the N-methyl DAM impurity content by rearrangement. The above-described manner controls the amount of N-methyl-type DAM impurity generated to some extent, but there are complicated steps in the production operation process, and the catalyst production process is expensive due to the initial cost of the selected catalyst or because of the short catalyst life, which limits the large-scale use of the process to some extent.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing a DAM having a low N-methyl impurity content, which reduces the impurity content of N-methyl DAM by reducing the possibility of a side reaction process in which a proton-carrying schiff base reacts with formaldehyde to form a precursor of N-methyl compound by adding schiff base to a salt product of aniline after a partial aniline reacts with hydrochloric acid or a solid acid to form a schiff base in a condensation reaction and dehydration process, thereby improving MDI product quality.
In order to achieve the above object, the present invention provides a process for producing diamines and polyamines of the diphenylmethane series, comprising the steps of:
a) Dividing aniline into two parts, mixing part of aniline with formaldehyde to perform condensation reaction to obtain a mixture containing Schiff base, and removing water in the mixture;
b) Reacting another part of aniline with hydrochloric acid or solid acid to obtain aniline salts;
c) Adding the mixture dehydrated in the step a) into the aniline salt obtained in the step b) in a reactor, fully stirring and mixing, and further carrying out transposition reaction to obtain a mixture containing di-amine and polyamine of diphenylmethane series;
d) The mixture obtained in step c) is worked up to give a refined DAM.
The preparation of aniline and formaldehyde mentioned in step a) is known to the person skilled in the art, and in principle aniline or formaldehyde can be prepared by any desired method. The formaldehyde is preferably in the form of an aqueous solution, the mass fraction of the formaldehyde is 20-55%, preferably 30-40%, the molar ratio of the formaldehyde to the aniline is 0.2-0.8, preferably 0.3-0.6, and the aniline refers to the total aniline amount mixed with formaldehyde and hydrochloric acid or solid acid;
the molar ratio of aniline mixed with formaldehyde in step a) to total aniline amount is 0.5-0.9, preferably 0.7-0.8;
the condensation reaction temperature of aniline and formaldehyde in step a) is 40-80 ℃, preferably 50-70 ℃ and the reaction time is 1-2 hours;
the mixing in the step a) is preferably carried out by adopting one or more modes of multi-point addition, spray addition and dropwise addition of formaldehyde;
the dehydration process in step a) comprises removing the water produced by the condensation reaction by means of a phase separator or by means of distillation;
the molar ratio of hydrochloric acid or solid acid to aniline in step b) is from 0.2 to 0.5, preferably from 0.3 to 0.4, aniline referring to the total aniline amount mixed with formaldehyde and hydrochloric acid or solid acid;
the reaction temperature of the aniline and the hydrochloric acid or the solid acid in the step b) is 20-60 ℃, preferably 30-40 ℃ and the reaction time is 10-30min, preferably solid acid is adopted;
the reactor for the mixing and transposition reaction of the condensation reaction and the salification reaction products in step c) is preferably a fixed bed reactor, the transposition reaction temperature is 90-140 ℃, preferably 100-115 ℃ and the reaction time is 1-5h;
in step d), the post-treatment step comprises a step of removing water and organic phase;
in step d), if hydrochloric acid is used in step b), a step of neutralizing the mixture by adding a base thereto and separating phases is further included before the step of removing the organic phase.
In step d), the step of removing the water and organic phase comprises resin adsorption, distillation, preferably vacuum distillation.
The invention also provides a preparation method of the solid acid for salification and transposition reaction, which comprises the following steps of firstly synthesizing a carbonaceous precursor by a hydrothermal carbonization method, and synthesizing the carbonaceous solid acid after sulfonation of the carbonaceous precursor:
(1) Under the protection of inert atmosphere, biomass, natural raw materials or carbon sources such as polycyclic aromatic hydrocarbon are carbonized in a reaction kettle by adopting water as a solvent, and grinding, washing, suction filtration and drying are carried out to obtain a carbonaceous precursor;
(2) And (3) continuously carrying out sulfonation reaction on the carbonaceous precursor and the substance containing the sulfonate in the step (1) in a reaction kettle, and then grinding, washing, suction filtering and drying to synthesize the carbonaceous solid acid.
According to the invention, the inert atmosphere is a nitrogen atmosphere.
In some preferred embodiments of the present invention, the carbon source in step (1) is selected from at least one of glucose, fructose, sucrose, or naphthalene.
In some preferred embodiments of the present invention, the temperature of the carbonization reaction in step (1) is 150-200 ℃, preferably 170-190 ℃; the time is 20-30 hours;
in some preferred embodiments of the present invention, the washing in step (1) is preferably deionized water and ethanol, to ph=7, and the drying temperature is 80 to 120 ℃, preferably 80 to 90 ℃, and the drying time is 20 to 30 hours.
In some preferred embodiments of the present invention, the mass ratio of the carbonaceous precursor to the sulfonate-containing material in the step (2) is 1 (3-10), preferably 1 (5-8), and the sulfonate-containing material is selected from concentrated sulfuric acid, fuming sulfuric acid, or the like.
In some preferred embodiments of the present invention, the sulfonation reaction temperature in step (2) is 160-210 ℃, preferably 170-190 ℃; the time is 20-30 hours.
In some preferred embodiments of the invention, the sulphonated material is washed with ethanol and hot water, preferably hot water at 80 ℃ or higher. Washing until no sulfate ions exist in the filtrate, and then carrying out suction filtration and drying treatment, wherein the drying temperature is 80-120 ℃, preferably 80-90 ℃ and the drying time is 20-30 hours, thus obtaining the carbonaceous solid acid.
The invention has the beneficial effects that:
in the production process of preparing DAM, the generation mechanism of N-methyl impurities is that aniline and formaldehyde generate Schiff base with protons under the action of an acid catalyst, the Schiff base with protons generates N-methylaniline and N, N-dimethylaniline if reacting with formaldehyde, the N-methylaniline and the N, N-dimethylaniline are precursors of N-methyl compounds, and the N-methyl compounds are generated in the subsequent transposition process. Therefore, in order to achieve the objective of producing DAM with low content of N-methyl impurities, the production of N-methylaniline and N, N-dimethylaniline is suppressed. In the DAM generation process, the salifying and condensing processes are carried out simultaneously, and aniline reacts with formaldehyde and an acid catalyst respectively, so that the possibility of contact reaction of Schiff base with protons and formaldehyde is reduced, and the content of N-methyl impurities in the DAM can be obviously reduced.
Compared with the traditional liquid acid catalysts such as hydrochloric acid, the solid acid provided by the invention has stronger acidity, so that the reaction activity is higher and the selectivity is stronger. The binding force with aniline is strong in the salifying process, and the strong selectivity of the catalyst can enable proton-containing Schiff base to react with aniline more easily in the subsequent transposition process, so that the generation of N-methylaniline and N, N-dimethylaniline precursors is effectively avoided.
Detailed Description
So that the manner in which the features and aspects of the present invention can be understood in more detail, a more particular description of the invention, briefly summarized below, may be had by reference to embodiments. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
Example 1:
the solid acid catalyst of carbon is filled in the fixed bed reactor, and the catalyst is prepared by the following method. Adding 4g of glucose and 0.5g of benzyl chloride into a stainless steel high-pressure reaction kettle with the volume of 25ml, putting into a baking oven, carbonizing for 24 hours at the carbonizing temperature of 180 ℃, grinding into powder, washing with deionized water and ethanol until the pH value is=7, carrying out suction filtration, and drying in the baking oven at the temperature of 90 ℃ for 24 hours to obtain a carbon precursor with the surface rich in phenyl groups; then, 1g of the solid was taken and uniformly mixed with 6mL of concentrated sulfuric acid, and then placed in a reaction kettle, and treated in an oven at 180 ℃ for 24 hours, the obtained solid was ground, washed with ethanol and hot water at 85 ℃ until sulfate ions are not contained in the filtrate, and then suction-filtered, and then placed in an oven at 90 ℃ for drying for 24 hours, thus obtaining a carbonaceous solid acid.
The molar ratio of formaldehyde solution to total aniline solution was 0.3:1, adding formaldehyde solution (the mass concentration is 35%) and aniline accounting for 70% of the total aniline molar quantity (the mass concentration is more than or equal to 99%) into a reactor, adding formaldehyde in a dropwise manner, reacting at 50 ℃ for 1.5h, and standing to separate out a water phase. The remaining 30% of aniline was fed to a fixed bed reactor loaded with carbonaceous solid acid at a molar ratio of solid acid loading to total aniline solution of 0.3:1. The reaction temperature of the aniline and the solid acid is 40 ℃ and the reaction time is 20min. And (3) adding a product obtained after the reaction of the aniline and the formaldehyde into a fixed bed reactor for reaction at the reaction temperature of 110 ℃ for 2 hours to generate a reaction mixture containing diamines and polyamines of diphenylmethane series, dehydrating and aniline by a rectifying tower, and finally obtaining the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Example 2:
the solid acid catalyst of carbon is filled in the fixed bed reactor, and the catalyst is prepared by the following method. Adding 4g of fructose into a stainless steel high-pressure reaction kettle with the volume of 25ml, putting into a baking oven for carbonization at the carbonization temperature of 170 ℃, grinding into powder, washing with deionized water and ethanol to the pH value of 7 for several times, performing suction filtration, and drying in the baking oven at the temperature of 90 ℃ for 30 hours to obtain a carbon precursor with the surface rich in phenyl groups; taking 1g of the solid, uniformly mixing with 8mL of fuming sulfuric acid, putting the mixture into a reaction kettle, sulfonating the mixture in a baking oven at 190 ℃ for 20 hours, grinding the obtained solid, washing the ground solid with ethanol and hot water at 90 ℃ until sulfate ions are not contained in the filtrate, carrying out suction filtration, and then drying the solid in the baking oven at 80 ℃ for 20 hours to obtain the carbonaceous solid acid catalyst.
The molar ratio of formaldehyde solution to total aniline solution was 0.5:1, adding formaldehyde solution (the mass concentration is 30%) and aniline accounting for 80% of the total aniline molar quantity (the mass concentration is more than or equal to 99%) into a reactor, adding formaldehyde in a dropwise manner, reacting at 60 ℃ for 1.5h, and standing to separate out a water phase. The remaining 20% of aniline was fed to a fixed bed reactor loaded with carbonaceous solid acid at a molar ratio of solid acid loading to total aniline solution of 0.35:1. The reaction temperature of the aniline and the solid acid is 35 ℃ and the reaction time is 10min. And (3) adding a product obtained after the reaction of the aniline and the formaldehyde into a fixed bed reactor for reaction at the reaction temperature of 115 ℃ for 3 hours to generate a reaction mixture containing diamines and polyamines of diphenylmethane series, dehydrating and aniline by a rectifying tower, and finally obtaining the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Example 3:
the solid acid catalyst of carbon is filled in the fixed bed reactor, and the catalyst is prepared by the following method. Adding 4g of sucrose into a stainless steel high-pressure reaction kettle with the volume of 25ml, putting into a baking oven, carbonizing for 30 hours at the carbonizing temperature of 200 ℃, grinding into powder, washing with deionized water and ethanol to the pH value of 7 for several times, filtering, and drying in the baking oven at the temperature of 80 ℃ for 20 hours to obtain a carbon precursor with the surface rich in phenyl groups; 1g of the solid is taken and evenly mixed with 10mL of concentrated sulfuric acid, then the mixture is put into a reaction kettle, the mixture is sulfonated for 30 hours in a baking oven at 200 ℃, the obtained solid is ground, and is washed with ethanol and hot water at 85 ℃ until no sulfate ions exist in the filtrate, and then the filtrate is filtered by suction, and then the filtrate is put into a baking oven at 100 ℃ for drying for 24 hours, thus obtaining the carbonaceous solid acid catalyst.
The molar ratio of formaldehyde solution to total aniline solution was 0.6:1, adding formaldehyde solution (the mass concentration is 40%) and aniline accounting for 50% of the total aniline molar quantity (the mass concentration is more than or equal to 99%) into a reactor, adding formaldehyde in a dropwise manner, reacting at 70 ℃ for 2 hours, and standing to separate out a water phase. The remaining 50% of aniline was fed to a fixed bed reactor loaded with carbonaceous solid acid at a molar ratio of solid acid loading to total aniline solution of 0.4:1. The reaction temperature of the aniline and the solid acid is 60 ℃ and the reaction time is 30min. And (3) adding a product obtained after the reaction of the aniline and the formaldehyde into a fixed bed reactor for reaction at the reaction temperature of 140 ℃ for 1h to generate a reaction mixture containing diamines and polyamines of diphenylmethane series, dehydrating and aniline by a rectifying tower, and finally obtaining the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Example 4:
the solid acid catalyst of carbon is filled in the fixed bed reactor, and the catalyst is prepared by the following method. Adding 4g of naphthalene into a stainless steel high-pressure reaction kettle with the volume of 25ml, putting into a baking oven, carbonizing for 28 hours at the carbonizing temperature of 150 ℃, grinding into powder, washing with deionized water and ethanol to the pH value of 7 for several times, performing suction filtration, and drying in the baking oven at the temperature of 120 ℃ for 26 hours to obtain a carbon precursor with the surface rich in phenyl groups; then, 1g of the solid was taken and uniformly mixed with 3mL of fuming sulfuric acid, and then placed in a reaction kettle, and treated in an oven at 160 ℃ for 20 hours, the obtained solid was ground, washed with ethanol and hot water at 85 ℃ until no sulfate ion exists in the filtrate, and then suction-filtered, and then placed in an oven at 120 ℃ for drying for 30 hours, thus obtaining the carbonaceous solid acid catalyst.
The molar ratio of formaldehyde solution to total aniline solution was 0.8:1, adding formaldehyde solution (the mass concentration is 55%) and aniline accounting for 90% of the total aniline molar quantity (the mass concentration is more than or equal to 99%) into a reactor, adding formaldehyde in a dropwise manner, reacting at 80 ℃ for 1h, and standing to separate out a water phase. The remaining 10% of aniline was fed to a fixed bed reactor loaded with carbonaceous solid acid at a molar ratio of solid acid loading to total aniline solution of 0.2:1. The reaction temperature of the aniline and the solid acid is 20 ℃ and the reaction time is 20min. And (3) adding a product obtained after the reaction of the aniline and the formaldehyde into a fixed bed reactor for reaction at 90 ℃ for 5 hours to generate a reaction mixture containing diamines and polyamines of diphenylmethane series, dehydrating and aniline by a rectifying tower, and finally obtaining the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Example 5:
h beta-100 molecular sieve is filled in a fixed bed reactor as a solid acid catalyst, and H beta-100 molecular sieve (silicon-aluminum ratio 100) powder is pressed and sieved into 10-16 mesh particles.
The molar ratio of formaldehyde solution to total aniline solution was 0.4:1, adding formaldehyde solution (the mass concentration is 20%) and aniline accounting for 60% of the total aniline molar quantity (the mass concentration is more than or equal to 99%) into a reactor, adding formaldehyde in a dropwise manner, reacting for 2 hours at 40 ℃, and standing to separate out a water phase. The remaining 40% of aniline was charged to a fixed bed reactor loaded with H beta-100 molecular sieves, with a molar ratio of solid acid loading to total aniline solution of 0.5:1. The reaction temperature of the aniline and the solid acid is 30 ℃ and the reaction time is 15min. And (3) adding a product obtained after the reaction of the aniline and the formaldehyde into a fixed bed reactor for reaction at the reaction temperature of 108 ℃ for 2 hours to generate a reaction mixture containing diamines and polyamines of diphenylmethane series, dehydrating and aniline by a rectifying tower, and finally obtaining the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Example 6
The molar ratio of formaldehyde solution to total aniline solution was 0.2:1, adding formaldehyde solution (the mass concentration is 45%) and aniline accounting for 70% of the total aniline molar quantity (the mass concentration is more than or equal to 99%) into a reactor, adding formaldehyde in a dropwise manner, reacting for 1h at 40 ℃, and standing to separate out a water phase. The remaining 30% of aniline was mixed with hydrochloric acid at a molar ratio of hydrochloric acid to the total aniline solution of 0.35:1. The reaction temperature of the aniline and the hydrochloric acid is 40 ℃ and the reaction time is 20min. Adding the product obtained after the reaction of aniline and formaldehyde into a reactor filled with aniline hydrochloride, wherein the reaction temperature is 115 ℃, the reaction time is 3 hours, generating a reaction mixture containing diamine and polyamine of diphenylmethane series, neutralizing the obtained hydrochloride by using 50% sodium hydroxide solution, the neutralization reaction temperature is 90 ℃, taking an upper organic phase, washing by using pure water, removing water and aniline by a rectifying tower, and finally obtaining the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Comparative example 1
Hydrochloric acid solution (mass concentration is 33%) and aniline (mass concentration is more than or equal to 99%) are added into a reactor in a molar ratio of 0.3, and reacted for 5min at 50 ℃. Adding formaldehyde solution dropwise (the mass concentration is 37%), controlling the adding amount of formaldehyde to be 0.4 in the molar ratio of formaldehyde to aniline, reacting for 3 hours at 60 ℃ to obtain diamine and polyamine hydrochloride of diamino diphenyl series, neutralizing the obtained hydrochloride with 50% sodium hydroxide solution, washing an upper organic phase with pure water at the neutralization reaction temperature of 90 ℃, and removing water and aniline through a rectifying tower to obtain the refined DAM.
After DAM was prepared by the method of the present invention, the N-methyl compound content was measured, and the results are shown in Table 1.
Table 1 effect data of examples and comparative examples
| N-methyl compound content in DAM% | |
| Example 1 | 0.02 |
| Example 2 | 0.03 |
| Example 3 | 0.05 |
| Example 4 | 0.09 |
| Example 5 | 0.14 |
| Example 6 | 0.18 |
| Comparative example 1 | 1.08 |
Claims (12)
1. A preparation method of di-amine and polyamine of diphenyl methane series comprises the following steps:
a) Dividing aniline into two parts, mixing part of aniline with formaldehyde to perform condensation reaction to obtain a mixture containing Schiff base, and removing water in the mixture;
b) Reacting another part of aniline with solid acid to obtain aniline salts;
c) Adding the mixture dehydrated in the step a) into the aniline salt obtained in the step b) in a reactor, fully stirring and mixing, and further carrying out transposition reaction to obtain a mixture containing di-amine and polyamine of diphenylmethane series;
d) Post-treating the mixture obtained in step c) to obtain a refined DAM;
the synthesis process of the solid acid comprises the following steps: (1) Under the protection of inert atmosphere, biomass, natural raw materials or a polycyclic aromatic hydrocarbon carbon source are carbonized in a reaction kettle by adopting water as a solvent, and grinding, washing, suction filtration and drying are carried out to obtain a carbonaceous precursor;
(2) And (3) continuously carrying out sulfonation reaction on the carbonaceous precursor and the substance containing the sulfonate in the step (1) in a reaction kettle, and then grinding, washing, suction filtering and drying to synthesize the carbonaceous solid acid.
2. The process according to claim 1, wherein the molar ratio of formaldehyde to aniline in step a) is from 0.2 to 0.8, aniline being the total aniline amount mixed with formaldehyde and with solid acid; and/or the molar ratio of aniline mixed with formaldehyde to total aniline is 0.5-0.9; and/or the condensation reaction temperature of aniline and formaldehyde is 40-80 ℃ and the reaction time is 1-2 hours.
3. The process according to claim 2, wherein the molar ratio of formaldehyde to aniline in step a) is from 0.3 to 0.6; the molar ratio of aniline mixed with formaldehyde to total aniline is 0.7-0.8, and the condensation reaction temperature of aniline and formaldehyde is 50-70 ℃.
4. A process according to any one of claims 1 to 3, wherein the molar ratio of solid acid to aniline in step b) is from 0.2 to 0.5, aniline being the total aniline amount mixed with formaldehyde and solid acid; and/or the reaction temperature of the aniline and the solid acid is 20-60 ℃ and the reaction time is 10-30min.
5. The method of claim 4, wherein the molar ratio of the solid acid to the aniline in step b) is 0.3 to 0.4, and aniline refers to the total aniline amount mixed with formaldehyde and the solid acid; and/or the reaction temperature of the aniline and the solid acid is 30-40 ℃.
6. A process according to any one of claims 1 to 3, wherein the reactor for the mixing and metathesis of the products of the condensation reaction and the salt formation reaction in step c) is a fixed bed reactor, the metathesis temperature being from 90 to 140 ℃ and the reaction time being from 1 to 5 hours.
7. A process according to any one of claims 1 to 3, wherein in step d) the post-treatment step comprises a step of removing water and organic phase, including resin adsorption, distillation.
8. The method according to any one of claims 1 to 3, wherein the carbon source in step (1) is at least one selected from glucose, fructose, sucrose, or naphthalene; and/or, the temperature of the carbonization reaction in the step (1) is 150-200 ℃; the time is 20-30 hours.
9. A method according to any one of claims 1 to 3, wherein the mass ratio of the carbonaceous precursor to the sulfonate-containing material in step (2) is 1 (3 to 10), and the sulfonate-containing material is selected from concentrated sulfuric acid or fuming sulfuric acid.
10. The method according to claim 9, wherein the mass ratio of the carbonaceous precursor to the sulfonate group-containing material in the step (2) is 1 (5-8).
11. A process according to any one of claims 1 to 3, wherein the sulphonation reaction temperature in step (2) is 160 to 210 ℃; the time is 20-30 hours.
12. The process according to claim 11, wherein the sulfonation reaction temperature in step (2) is 170 to 190 ℃.
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