Refining method of resorcinol

Abstract

The invention discloses a resorcinol refining method which comprises the following steps: O) mixing m-diisopropylbenzene dihydroperoxide with an acid catalyst, and carrying out cracking reaction and neutralization to obtain a reaction liquid oil phase; the method comprises the following steps: A) feeding a reaction liquid oil phase into a crude acetone tower for acetone separation, and further refining the separated acetone to obtain an acetone product; c) sending the acetone-removed component obtained in the step A) to a solvent removal tower, and removing the solvent to obtain a resorcinol crude stream; d) enabling the resorcinol crude stream to pass through a resorcinol resin bed, and removing aromatic olefin impurities; e) de-weighting the stream obtained in the step D) to obtain a resorcinol crude product, and passing the obtained resorcinol crude product through a refining tower to obtain a resorcinol product; and F) feeding the heavy components separated in the step E) into a reverse alkylation tower, decomposing part of the heavy components to generate resorcinol, and crystallizing to obtain a resorcinol product. According to the method, the loss of resorcinol can be reduced, the purity of resorcinol is improved, and the energy consumption in the refining process of resorcinol is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical raw material preparation, and particularly to a method for refining resorcinol. Background Art

[0002] Resorcinol is a colorless or off-white needle-like crystal or powder. As an important fine chemical, it has a wide range of applications in industries such as the rubber industry, low-temperature wood adhesives, dyes, and pharmaceuticals. There are three production processes for resorcinol in industry: the benzene sulfonation alkali fusion method, the m-phenylenediamine method, and the m-diisopropylbenzene oxidation method. The benzene sulfonation alkali fusion method is facing elimination; the m-phenylenediamine method is highly dangerous, and there have been many nitro compound explosion accidents. The Jiangsu Xiangshui explosion accident is the most typical accident of this process, with extremely high danger; the m-diisopropylbenzene oxidation method is only mastered by a few foreign enterprises in terms of production technology, and the process flow is as follows:

[0003]

[0004] In this process, m-diisopropylbenzene is air-oxidized to prepare 3-(1-hydroperoxy-1-methylethyl)-α,α-dimethylbenzyl alcohol HHP, DHP, peroxide MHP, etc. Subsequently, DHP goes to cracking to generate resorcinol, HHP can continue to react with hydrogen peroxide to generate DHP, and MHP returns to the raw material end to continue air-oxidation to generate DHP. The method for obtaining resorcinol by acid cracking of DHP can refer to US4339615A and US6350921B1. During the generation of resorcinol, isopropenylphenol-containing benzene series substances (abbreviated as ALK) such as m-isopropenylphenol, m-diisopropenylbenzene, and m-isopropenylcumene are generated. Removing these impurities is the key to the refinement of resorcinol products. In patent CN1390818A, the crude resorcinol containing impurities is mixed with water and then extracted with toluene to separate ALK from resorcinol. This scheme cannot recover the heavy components generated by resorcinol and ALK in the cracking reaction; after adding water, the water needs to be distilled out again, increasing the energy consumption of the device; in addition, this process route also needs to introduce the extraction agent toluene that has nothing to do with the system, increasing the solvent cost. Therefore, there is an urgent need in the art for an economical, efficient, and high-yield method for refining resorcinol. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for refining resorcinol, which can reduce the energy consumption of the device and improve the yield of the main product to produce resorcinol.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] A method for refining resorcinol, which comprises the following steps:

[0008] O) The meta - diisopropylbenzene dihydroperoxide (DHP) is mixed with an acid catalyst for cracking reaction and neutralization to obtain the oil phase of the reaction liquid;

[0009] A) The oil phase of the reaction liquid obtained in step O) is sent to a crude acetone tower for acetone separation to obtain the component after acetone removal;

[0010] Preferably, it further includes B): The crude acetone separated in step A) is rectified to obtain acetone products;

[0011] C) The component after acetone removal obtained in step A) is sent to a solvent removal tower to obtain a crude resorcinol stream;

[0012] D) The stream obtained in step C) passes through a resorcinol resin bed;

[0013] E) The stream obtained in step D) is de - heavied to obtain crude resorcinol;

[0014] F) The heavy components separated in step E) are sent to an anti - alkylation tower to obtain heavy components containing resorcinol;

[0015] G) The crude resorcinol separated in step E) is refined to obtain resorcinol products;

[0016] H) The heavy components containing resorcinol obtained in step F) are subjected to solution crystallization to obtain resorcinol products.

[0017] In one embodiment of the present invention, in step O), the meta - diisopropylbenzene dihydroperoxide often participates in the cracking reaction in the form of a solution, and the solvent used is a weakly polar and water - insoluble solvent, such as methyl isobutyl ketone (MIBK); the meta - diisopropylbenzene dihydroperoxide solution comes from steps such as the oxidation and extraction of meta - diisopropylbenzene, and specifically, reference can be made to CN117843457A, etc. Preferably, the concentration of the meta - diisopropylbenzene dihydroperoxide is 10 - 30 wt%.

[0018] Preferably, in step O), the acid catalyst is sulfuric acid, and the dosage of the acid catalyst is 0.05 - 0.5 wt% of the meta - diisopropylbenzene dihydroperoxide solution, preferably 0.05 - 0.2 wt%.

[0019] Preferably, in step O), acetone is also added to facilitate the control of the reaction temperature.

[0020] Preferably, in step O), the cracking reaction temperature is 40 - 90 °C, preferably 50 - 80 °C, and the reaction time is 5 - 30 min, preferably 10 - 20 min.

[0021] The neutralization in step O) of the present invention can refer to the prior art, such as CN118666650A, etc.

[0022] Preferably, in step O), the temperature for neutralization is 40 - 60°C, and neutralization is carried out by mixing an alkaline solution with the oil phase; preferably, after neutralization, the oil phase is washed with water, and the washed oil phase is then subjected to step A).

[0023] Preferably, the alkaline solution for neutralization can be an aqueous sodium hydroxide solution, with a preferred concentration of 1 - 10 wt%, and the amount of sodium hydroxide used is 1 - 1.1 times the molar amount of the acid catalyst; after neutralization, 1 - 5 wt% of the mass of the oil phase of water is added to wash the oil phase, and the obtained oil phase goes to step A), and the aqueous phase goes to wastewater treatment.

[0024] In one embodiment of the present invention, in step A), the operating temperature of the crude acetone tower is 50 - 65°C, and the operating pressure is 50 - 75 kPaA.

[0025] In one embodiment of the present invention, in step A), the light components drawn from the top of the crude acetone tower are mainly acetone, which go to step B) for rectification to obtain acetone products; the heavy components obtained at the bottom of the crude acetone tower go to step C) and are sent to the solvent removal tower.

[0026] In one embodiment of the present invention, in step B), acetone rectification is carried out using a rectification tower, and the operating temperature of the tower is 55 - 60°C; the operating pressure is 40 - 60 kPaA.

[0027] In one embodiment of the present invention, in step C), the operating temperature of the solvent removal tower is 65 - 75°C, and the operating pressure is 3 - 6 kPaA.

[0028] In one embodiment of the present invention, in step D), the operating temperature of the resorcinol resin bed is 120 - 180°C, and the mass space velocity of the reaction liquid is 1.0 h -1 ~4.0 h -1 ; the catalyst in the resin bed is a resin catalyst, preferably an acidic resin catalyst, and more preferably a T311 resin catalyst.

[0029] In one embodiment of the present invention, in step D), the impurities removed by the resorcinol resin bed are isopropenylphenol, diisopropenylbenzene, isopropenylcumene and other isopropenyl-containing benzene substances (i.e., ALK impurities). The content of ALK impurities in the stream before entering the resin bed is about 1 - 10 wt%, and the content of ALK impurities at the outlet of the resin bed is about 0.01 - 0.5 wt%.

[0030] In one embodiment of the present invention, in step E), heavy component removal is carried out using a heavy component removal tower, and the operating temperature of the heavy component removal tower is 180 - 240°C, and the operating pressure is 80 - 200 PaA.

[0031] In one embodiment of the present invention, in step G), the crude resorcinol obtained by separation in step E) is rectified in a rectification column to obtain a resorcinol product. The rectification can adopt the existing technologies in the field, such as normal pressure, the number of trays is 10 - 30, and the reflux ratio is 0.5 - 3.

[0032] In order to further recover the resorcinol consumed by by-products during the production process of resorcinol, the present invention provides a recovery method, that is, step F) of the present invention. The heavy components separated in step E) contain the tandem by-product PLK of resorcinol, and the content of PLK substances in the heavy components is approximately 10 - 60 wt%. In step F), a part of the above heavy components will decompose and regenerate resorcinol, and the content of PLK substances in the obtained resorcinol-containing heavy components is reduced to 0 - 0.1 wt%, so that the loss of resorcinol during the reaction process can be recovered, and the final yield of resorcinol can be improved.

[0033] In one embodiment of the present invention, the operating temperature of the transalkylation column in step F) is 220 - 300 °C, and the mass space velocity of the reaction liquid is 0.1h -1 ~2.0h -1 ; The transalkylation column is filled with a catalyst, and the catalyst is a metal sulfate, including iron sulfate, zinc sulfate, magnesium sulfate, etc., and magnesium sulfate is preferred.

[0034] In one embodiment of the present invention, the solvent used for resorcinol crystallization in step H) is an alkylbenzene compound such as toluene, ethylbenzene, isopropylbenzene, etc., preferably toluene, and the addition amount is 2 - 5 times the mass of resorcinol in the resorcinol-containing heavy components obtained in step F).

[0035] Preferably, in step H), the specific steps of crystallization are as follows: Before the start of solution crystallization, the solution temperature is preferably adjusted to 100 - 120 °C. During crystallization, preferably, fractional crystallization is adopted; specifically, the fractional crystallization includes the first-stage crystallization and the second-stage crystallization. During the first-stage crystallization, the temperature is lowered to 60 - 70 °C, held for 2 - 4 h, and the cooling rate is 1 - 2 °C / min; during the second-stage crystallization, the temperature is lowered to 20 - 30 °C, held for 2 - 4 h, and the cooling rate is 0.2 - 0.5 °C / min, thereby obtaining a resorcinol product.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The separation process is simple, saving equipment and land investment;

[0038] (2) In the preferred scheme, the loss of resorcinol during the reaction process can be recovered, and the final yield of resorcinol is improved;

[0039] (3) The use of extractant is reduced, and there is no need to evaporate water, reducing energy consumption;

[0040] (4) The separation process produces less wastewater and is environmentally friendly. Description of the Drawings

[0041] Figure 1 It is a schematic diagram of the resorcinol refining process of Embodiment 1 of the present invention. Detailed Embodiments

[0042] The present invention will be further described below through specific embodiments. The embodiments described in the present invention are only for the purpose of illustrating the present invention and do not limit the scope of the present invention.

[0043] The raw materials and reagents used in the examples and comparative examples of the present invention are all obtained through commercial channels on the market, unless otherwise specified.

[0044] Detection Method

[0045] The present invention uses high performance liquid chromatography to analyze the composition of the stream. The chromatographic analysis conditions are as follows:

[0046] Instrument model: LC-6A high performance liquid chromatograph (Shimadzu)

[0047] Analysis column: CLC-SIL 150*6.0mm (Shimadzu)

[0048] Preparation column: Zorbax SIL 250*9.4mm (Columnbond)

[0049] Mobile phase: water: methanol: isopropanol: isopropylcyclohexane (60-90 °C) = 15:3:3:60 (v / v)

[0050] Flow rate: 0.7 ml / min

[0051] Column temperature: room temperature

[0052] Wavelength of the ultraviolet detector (Shimadzu SPD-6AV ultraviolet-visible spectrophotometric detector): 235 nm.

[0053] The total yield of resorcinol = actual mass / theoretical mass × 100%, where the theoretical mass = resorcinol molecular weight × (mass of raw material DHP / DHP molecular weight).

[0054] Example 1

[0055] As shown in the appendix Figure 1As shown in the figure, a MIBK solution of 100 kg of 20 wt% diisopropylbenzene dihydroperoxide (DHP), 0.1 kg of sulfuric acid, and 100 kg of acetone enter the cracking reactor and react at 60°C for 20 minutes, followed by alkali neutralization and water washing. Among them, the neutralization is carried out at 50°C, and a 3 wt% aqueous sodium hydroxide solution is mixed with the oil phase for 1.5 minutes. The molar amount of sodium hydroxide is 1.01 times that of sulfuric acid in the cracking reaction. After neutralization, 2 wt% of water based on the oil phase of the reaction solution is added for water washing.

[0056] The oil phase obtained by phase separation during water washing enters the crude acetone column, and the water phase goes to wastewater treatment. The light components at the top of the crude acetone column enter the acetone purification column to obtain acetone products, and the heavy components at the bottom enter the solvent removal column to separate MIBK. Then, the main material is discharged from the bottom of the solvent removal column and enters the resorcinol resin bed to remove ALK impurities. Subsequently, the main material enters the resorcinol heavy component removal column. The heavy components at the bottom enter the transalkylation column to remove the heavy components. The crude resorcinol product without heavy components enters the resorcinol purification column to further obtain resorcinol products. The transalkylation column decomposes the heavy components to obtain heavy components containing resorcinol, and this part of the material enters the crystallizer for crystallization to obtain resorcinol products. The process parameters are as follows: the operating temperature of the crude acetone column is 50°C, and the operating pressure is 50 kPaA. The operating temperature of the acetone purification column is 60°C; the operating pressure is 60 kPaA. The operating temperature of the solvent removal column is 75°C, and the operating pressure is 3 kPaA. The content of ALK impurities in the stream before entering the resin bed is about 10 wt%. The operating temperature of the resorcinol resin bed is 120°C, and the mass space velocity of the reaction solution is 4.0 h -1 , the catalyst is T311 resin catalyst, and the content of ALK impurities at the outlet of the resin bed is 0.5 wt%. The operating temperature of the resorcinol heavy component removal column is 180°C, and the operating pressure is 80 PaA. The content of PLK substances in the heavy components is 30 wt%. The number of plates in the resorcinol purification column is 15, and the reflux ratio is 1; the operating temperature of the transalkylation column is 220°C, and the mass space velocity of the reaction solution is 0.1 h -1 , the catalyst is magnesium sulfate, and the content of PLK at the outlet of the transalkylation column is reduced to 0.1 wt%. The solvent used for resorcinol crystallization is toluene. The addition amount of toluene is 5 times the mass of resorcinol in the resorcinol-containing heavy components. Before the start of solution crystallization, the temperature is raised to 100°C. During crystallization, staged crystallization is adopted. During the first stage of crystallization, the temperature is lowered to 70°C and kept for 4 hours, and the cooling rate is 1°C / min. During the second stage of crystallization, the temperature is lowered to 30°C and kept for 4 hours, and the cooling rate is 0.2°C / min.

[0057] After detection and calculation, the total yield of resorcinol is 98.1%, the separation energy consumption is 100 parts (calculated based on 100 parts of the example, the same below), the number of equipment is 28 sets, the toluene solvent consumption is 3 kg, and the wastewater treatment is 6.6 kg.

[0058] Example 2

[0059] React and separate according to the same process as in Example 1. The process parameters are as follows: A solution of 100 kg of 20 wt% diisopropylbenzene dihydroperoxide (DHP) in MIBK, 0.1 kg of sulfuric acid, and 100 kg of acetone enter the cracking reactor and react at 60°C for 20 min. After alkali neutralization and water washing, the neutralization is carried out at 40°C. A 5 wt% aqueous sodium hydroxide solution is mixed with the oil phase for 1 min, and the molar amount of sodium hydroxide is 1.01 times that of sulfuric acid. After neutralization, 3 wt% of water based on the oil phase of the reaction solution is added for water washing, and the remaining operations are the same as in Example 1. Among them, the operating temperature of the crude acetone column is 50°C, and the operating pressure is 65 kPaA. The operating temperature of the acetone refining column is 60°C, and the operating pressure is 60 kPaA. The operating temperature of the solvent removal column is 65°C, and the operating pressure is 3 kPaA. The operating temperature of the resorcinol resin bed is 180°C, and the mass space velocity of the reaction solution is 4.0 h -1 , the catalyst is T311 resin catalyst. The content of ALK impurities in the stream before entering the resin bed is about 8 wt%, and the content of ALK impurities at the outlet of the resin bed is approximately 0.1 wt%. The operating temperature of the resorcinol heavy component removal column is 240°C, and the operating pressure is 200 PaA. The content of PLK substances in the heavy components accounts for 50 wt%. The number of trays in the resorcinol refining column is 10, and the reflux ratio is 2; the operating temperature of the transalkylation column is 300°C, and the mass space velocity of the reaction solution is 2.0 h -1 , the catalyst is iron sulfate, and the content of PLK heavy components at the outlet of the transalkylation column is reduced to 0.03 wt%. The solvent used for resorcinol crystallization is isopropylbenzene, and the addition amount of isopropylbenzene is 2 times that of resorcinol. Before the start of solution crystallization, the temperature is raised to 120°C. During crystallization, staged crystallization is adopted. During the first stage of crystallization, the temperature is lowered to 70°C and held for 4 h, and the cooling rate is 2°C / min; during the second stage of crystallization, the temperature is lowered to 30°C and held for 4 h, and the cooling rate is 0.5°C / min.

[0060] After detection and calculation, the total yield of resorcinol is 97.5%. The separation energy consumption is 96 parts, the number of equipment is 28 sets, the consumption of isopropylbenzene solvent is 1.2 kg, and the wastewater treatment is 6.9 kg.

[0061] Example 3

[0062] React and separate according to the same process as in Example 1. The process parameters are as follows: 100 kg of a MIBK solution containing 20 wt% of diisopropylbenzene dihydroperoxide (DHP), 0.15 kg of sulfuric acid, and 100 kg of acetone enter the cracking reactor and react at 70 °C for 25 min. After alkali neutralization and water washing, the neutralization is carried out at 50 °C. A 3 wt% aqueous sodium hydroxide solution is mixed with the oil phase for 1 min, and the molar amount of sodium hydroxide is 1.01 times that of sulfuric acid. After neutralization, 2 wt% of water based on the oil phase of the reaction solution is added for water washing, and the remaining operations are the same as in Example 1. Among them, the operating temperature of the crude acetone column is 55 °C, and the operating pressure is 70 kPaA. The operating temperature of the acetone purification column is 55 °C; the operating pressure is 40 kPaA. The operating temperature of the solvent removal column is 75 °C, and the operating pressure is 3 kPaA. The operating temperature of the resorcinol resin bed is 150 °C, and the mass space velocity of the reaction solution is 2.5 h -1 ; The catalyst is T311 resin catalyst. The content of ALK impurities in the stream before entering the resin bed is about 1 wt%, and the content of ALK impurities at the outlet of the resin bed is approximately 0.01 wt%. The operating temperature of the resorcinol heavy component removal column is 220 °C, the operating pressure is 160 PaA, and the content of PLK substances in the heavy components accounts for 40 wt%. The number of plates of the resorcinol purification column is 20, and the reflux ratio is 3; the operating temperature of the transalkylation column is 280 °C, and the mass space velocity of the reaction solution is 1.3 h -1 , The catalyst is zinc sulfate, and the content of PLK heavy components at the outlet of the transalkylation column is reduced to 0.01 wt%. The solvent used for resorcinol crystallization is isopropylbenzene, and the addition amount of isopropylbenzene is 3 times that of resorcinol. Before the start of solution crystallization, the temperature is raised to 120 °C. During crystallization, staged crystallization is adopted. During the first stage of crystallization, the temperature is lowered to 65 °C and kept for 3 h, and the cooling rate is 1 °C / min; during the second stage of crystallization, the temperature is lowered to 30 °C and kept for 3 h, and the cooling rate is 0.4 °C / min.

[0063] After detection and calculation, the total yield of resorcinol is 98.8%. The separation energy consumption is 101 parts, the number of equipment is 28 units, the consumption of isopropylbenzene solvent is 1.8 kg, and the wastewater treatment is 5.9 kg.

[0064] Example 4

[0065] React and separate according to the same process as in Example 1. The process parameters are as follows: The conditions of cracking reaction, alkali neutralization and water washing are the same as in Example 1. The operating temperature of the crude acetone column is 60 °C, and the operating pressure is 75 kPaA. The operating temperature of the acetone purification column is 58 °C; the operating pressure is 51 kPaA. The operating temperature of the solvent removal column is 70 °C, and the operating pressure is 4 kPaA. The operating temperature of the resorcinol resin bed is 160 °C, and the mass space velocity of the reaction solution is 2.8 h -1; The catalyst is T311 resin catalyst. The content of ALK impurities in the stream before entering the resin bed is about 5 wt%, and the content of ALK impurities at the outlet of the resin bed is approximately 0.05 wt%. The operating temperature of the resorcinol heavy component removal tower is 240 °C, the operating pressure is 130 PaA, and the content of PLK in the heavy components accounts for 60 wt%. The number of trays in the resorcinol refining tower is 15, and the reflux ratio is 1; the operating temperature of the transalkylation tower is 285 °C, and the mass hourly space velocity of the reaction liquid is 1.4 h -1 , the catalyst is zinc sulfate, and the content of PLK heavy components at the outlet of the transalkylation tower is reduced to 0.1 wt%. The solvent used for resorcinol crystallization is cumene, and the addition amount of cumene is 3 times that of resorcinol. The temperature is raised to 110 °C before the solution crystallization starts. During crystallization, staged crystallization is adopted. During the first stage of crystallization, the temperature is lowered to 70 °C, held for 3 h, and the cooling rate is 1.6 °C / min; during the second stage of crystallization, the temperature is lowered to 30 °C, held for 3 h, and the cooling rate is 0.4 °C / min.

[0066] After detection and calculation, the total yield of resorcinol is 98.3%. The separation energy consumption is 111 parts, the number of equipment is 28 sets, the consumption of cumene solvent is 1.8 kg, and the wastewater treatment is 6.1 kg.

[0067] Example 5

[0068] React and separate according to the same process as in Example 1. The process parameters are as follows: the pyrolysis reaction, alkali neutralization and water washing conditions are the same as in Example 1. The operating temperature of the crude acetone tower is 60 °C, and the operating pressure is 75 kPaA. The operating temperature of the acetone refining tower is 60 °C, and the operating pressure is 60 kPaA. The operating temperature of the solvent removal tower is 73 °C, and the operating pressure is 5 kPaA. The operating temperature of the resorcinol resin bed is 160 °C, and the mass hourly space velocity of the reaction liquid is 2.8 h -1 ; The catalyst is T311 resin catalyst. The content of ALK impurities in the stream before entering the resin bed is about 10 wt%, and the content of ALK impurities at the outlet of the resin bed is approximately 0.4 wt%. The operating temperature of the resorcinol heavy component removal tower is 240 °C, the operating pressure is 130 PaA, and the content of PLK in the heavy components accounts for 10 wt%. The number of trays in the resorcinol refining tower is 15, and the reflux ratio is 2; the operating temperature of the transalkylation tower is 290 °C, and the mass hourly space velocity of the reaction liquid is 1.8 h -1 , the catalyst is zinc sulfate, and the content of PLK heavy components at the outlet of the transalkylation tower is reduced to 0.02 wt%. The solvent used for resorcinol crystallization is cumene, and the addition amount of cumene is 2.5 times that of resorcinol. The temperature is raised to 110 °C before the solution crystallization starts. During crystallization, staged crystallization is adopted. During the first stage of crystallization, the temperature is lowered to 70 °C, held for 2 h, and the cooling rate is 1.8 °C / min; during the second stage of crystallization, the temperature is lowered to 20 °C, held for 4 h, and the cooling rate is 0.5 °C / min.

[0069] After detection and calculation, the total yield of resorcinol is 98.3%. The separation energy consumption is 108 parts, the number of equipment is 28 sets, the consumption of cumene solvent is 1.5 kg, and the wastewater treatment is 6.3 kg.

[0070] Comparative Example 1

[0071] Compared with Example 1, the difference in this comparative example is that after the material is stripped of MIBK through the solvent stripping column, it directly enters the resorcinol heavy component removal column, and the crude resorcinol is taken out from the top of the column. The conditions of the heavy component removal column are the same as those in Example 1. Subsequently, the crude product is dissolved in water, and the mass of the added water is 3 times that of the crude product. Toluene with a double amount of the aqueous phase is used to extract ALK impurities, the number of extraction tower stages is 3, and the temperature is normal temperature. The raffinate phase (ALK impurity content is about 3 wt%) is separated from water through a distillation column. The operating temperature of the distillation column is 150 °C, and the pressure is 150 PaA. Finally, the total yield of the resorcinol product obtained is 90.3%, the separation energy consumption is 115 parts, the number of equipment is 31 sets, the consumption of toluene solvent is 30 kg, and the wastewater treatment is 66.6 kg.

[0072] Comparative Example 2

[0073] Compared with Example 1, the difference in this comparative example is that the heavy components separated by the resorcinol heavy component removal column do not pass through the transalkylation column and are directly sent to an environmental protection company for incineration, and the other conditions are the same as those in Example 1. Finally, the total yield of the resorcinol product obtained is 86.5%, the separation energy consumption is 91 parts, the number of equipment is 26 sets, the solvent consumption is 0 kg, and the wastewater treatment is 7.1 kg.

[0074] It can be seen from the above results that the refining scheme of resorcinol provided by the present invention has a high yield and better economy. The above is only a preferred embodiment of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the method of the present invention, several improvements and supplements can be made, and these improvements and supplements should also be regarded as the protection scope of the present invention.

Claims

1. A method for purifying resorcinol, characterized in that: The method comprises: (2) m-diisopropylbenzene dihydroperoxide is mixed with an acid catalyst to perform a cracking reaction, and neutralize to obtain a reaction liquid oil phase; A) sending the oil phase of the reaction liquid obtained in step (2) into a crude acetone tower to separate acetone to obtain a component after deacetone; C) sending the components after deacetone removal obtained in step A) to a solvent removal tower to obtain a crude resorcinol stream; D) passing the crude resorcinol stream obtained in step C) through a resorcinol resin bed; E) de-weighting the stream obtained in step D) to obtain crude resorcinol, which is then refined to obtain a resorcinol product.

2. The method according to claim 1, characterized in that O) in step A, the acid catalyst is sulfuric acid, preferably, the amount of the acid catalyst is 0.05-0.5wt% of the m-diisopropylbenzene dihydroperoxide solution; and / or: the cleavage reaction temperature is 40-90° C., preferably 50-80° C., and the reaction time is 5-30 min, preferably 10-20 min.

3. The method according to claim 1, characterized in that: The operating temperature of the crude acetone tower in step A) is 50-65° C., and the operating pressure is 50-75 kPaA; preferably, the resorcinol purification method further comprises step B) of distilling the crude acetone removed in step A) to obtain an acetone product.

4. The method according to claim 3, characterized in that In step B), the acetone is distilled using a distillation tower with an operating temperature of 55-60° C. and an operating pressure of 40-60 kPaA.

5. The method according to claim 1, characterized in that The operating temperature of the solvent removal tower in step C) is 65-75° C., and the operating pressure is 3-6 kPaA.

6. The method according to claim 1, characterized in that The operating temperature of the resorcinol resin bed in step D) is 120-180°C, and the mass space velocity of the reaction liquid is 1.0h -1 ~4.0h -1 ; Preferably, the catalyst in the resin bed is an acidic resin catalyst, more preferably a T311 resin catalyst.

7. The method according to claim 1, characterized in that In step E), the deweighting is performed by using a deweighting tower, the operating temperature of the deweighting tower is 180-240° C., and the operating pressure is 80-200 PaA.

8. The method according to claim 1, characterized in that The resorcinol purification method further comprises the step F) of sending the heavy components separated by weight removal in the step E) into a reverse alkylation tower to obtain a heavy component containing resorcinol, and obtaining a resorcinol product by crystallization; preferably, the operating temperature of the reverse alkylation tower in the step F) is 220-300° C., and the mass space velocity of the reaction liquid is 0.1 h -1 ~2.0h -1 Preferably, the reverse alkylation tower is filled with a catalyst, and the catalyst is a metal sulfate, preferably one or more of iron sulfate, zinc sulfate, and magnesium sulfate.

9. The method according to claim 1, characterized in that: In step H), the resorcinol crystallization is solution crystallization, and the solvent used is one or more of toluene, ethylbenzene and isopropylbenzene, preferably toluene; the amount of the solvent added is 2 to 5 times the mass of the resorcinol in the resorcinol-containing heavy component.

10. The method according to claim 9, characterized in that In step H), the crystallization is staged crystallization. In the first stage of crystallization, the temperature is lowered to 60-70° C. and kept warm for 2-4 hours at a cooling rate of 1-2° C. / min. In the second stage of crystallization, the temperature is lowered to 20-30° C. and kept warm for 2-4 hours at a cooling rate of 0.2-0.5° C. / min to obtain a resorcinol product. Preferably, the solution temperature is adjusted to 100-120° C. before the start of crystallization.

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