A method for purifying resorcinol
By optimizing the resorcinol purification method, including pyrolysis, acetone separation, resin bed adsorption, and crystallization steps, the problems of high energy consumption and low yield in the existing technology have been solved, and efficient and economical resorcinol production has been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2025-03-03
- Publication Date
- 2026-07-10
AI Technical Summary
Existing resorcinol production processes suffer from high energy consumption, incomplete impurity removal, and high solvent costs. In particular, the heavy components generated by resorcinol and ALK during the cracking reaction cannot be recovered, resulting in low yield.
The resorcinol yield was improved by using a mixture of m-diisopropylbenzene dihydroperoxide and an acid catalyst for pyrolysis, followed by acetone separation, resin bed adsorption, deweighting, dealkylation, and solution crystallization. The operating conditions were optimized by combining a weakly polar solvent and a specific catalyst.
The separation process was simplified, energy consumption was reduced, the yield of resorcinol was increased, and solvent use and wastewater generation were reduced, thus achieving economical and efficient resorcinol production.
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Figure CN120058486B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of chemical raw material preparation technology, and in particular to a method for purifying resorcinol. Background Technology
[0002] Resorcinol is a colorless or off-white needle-like crystal or powder. As an important fine chemical, it has wide applications in the rubber industry, low-temperature wood adhesives, dyes, and pharmaceuticals. There are three industrial processes for producing resorcinol: benzene sulfonation alkali fusion method, m-phenylenediamine method, and m-diisopropylbenzene oxidation method. The benzene sulfonation alkali fusion method is facing elimination; the m-phenylenediamine method is highly dangerous, with numerous explosions involving nitro compounds occurring; the Xiangshui explosion in Jiangsu is a prime example of this process's extreme danger; the m-diisopropylbenzene oxidation method is only mastered by a few foreign companies, and its process flow is as follows:
[0003]
[0004] In this process, m-diisopropylbenzene is oxidized in air to prepare 3-(1-hydroperoxy-1-methylethyl)-α,α-dimethylbenzyl alcohol (HHP), DHP, and peroxide (MHP). DHP is then decomposed to generate resorcinol, HHP can react with hydrogen peroxide to generate more DHP, and MHP returns to the feedstock for further air oxidation to generate more DHP. Methods for obtaining resorcinol through acidic pyrolysis of DHP can be found in US4339615A and US6350921B1. During resorcinol formation, isopropenylphenol, m-diisopropenylbenzene, and m-isopropenyl cumene, which contain isopropenyl groups (ALK), are also generated. Removing these impurities is crucial for resorcinol product purification. Patent CN1390818A describes a method of separating ALK from resorcinol by mixing crude resorcinol containing impurities with water and then extracting with toluene. This method cannot recover the heavy components generated by resorcinol and ALK during the pyrolysis reaction; it requires the water to be distilled off again after addition, increasing energy consumption; furthermore, the process route introduces toluene, an extractant independent of the system, increasing solvent costs. Therefore, there is an urgent need in the field for an economical, efficient, and high-yield method for resorcinol purification. Summary of the Invention
[0005] The purpose of this invention is to provide a method for purifying resorcinol, which can reduce equipment energy consumption and increase the yield of the main product to produce resorcinol.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0007] A method for purifying resorcinol, comprising the following steps:
[0008] O) diisopropylbenzene dihydroperoxide (DHP) is mixed with an acid catalyst for cracking and neutralization to obtain the reaction liquid oil phase;
[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 acetone-free component;
[0010] Preferably, it also includes B): distilling the crude acetone separated in step A) to obtain the acetone product;
[0011] C) The acetone-free component obtained in step A) is sent to a solvent removal tower to obtain a resorcinol coarse stream.
[0012] D) Pass the stream obtained in step C) through a bed of resorcinol resin;
[0013] E) Remove the heavy weight from the stream obtained in step D) to obtain crude resorcinol;
[0014] F) The heavy fraction separated in E) is fed into the anti-alkylation tower to obtain the heavy fraction containing resorcinol;
[0015] G) The crude resorcinol obtained from E) is purified to obtain the resorcinol product;
[0016] H) The resorcinol-containing heavy component obtained in F) is subjected to solution crystallization to obtain the resorcinol product.
[0017] In one embodiment of the present invention, in step O), m-diisopropylbenzene dihydroperoxide often participates in the cracking reaction in the form of a solution, and the solvent used is a weakly polar solvent that is insoluble in water, such as methyl isobutyl ketone (MIBK); the m-diisopropylbenzene dihydroperoxide solution comes from steps such as m-diisopropylbenzene oxidation and extraction, as can be specifically referred to CN117843457A, etc., and preferably, the concentration of m-diisopropylbenzene dihydroperoxide is 10-30 wt%.
[0018] Preferably, in step O), the acid catalyst is sulfuric acid, and the amount of acid catalyst used is 0.05-0.5 wt% of the m-diisopropylbenzene dihydroperoxide solution, preferably 0.05-0.2 wt%.
[0019] Preferably, acetone is added in step O) to help control the reaction temperature.
[0020] Preferably, in step O), the pyrolysis reaction temperature is 40–90°C, more preferably 50–80°C, and the reaction time is 5–30 min, more preferably 10–20 min.
[0021] The neutralization in step O) of this invention can be referenced from existing technologies, such as CN118666650A.
[0022] Preferably, in step O), the neutralization temperature is 40-60°C, and neutralization is performed by mixing 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 neutralizing alkaline solution can be an aqueous sodium hydroxide solution with a concentration of 1-10 wt%, and the amount of sodium hydroxide is 1-1.1 times the molar amount of the acid catalyst. After neutralization, 1-5 wt% water of the oil phase mass is added to wash the oil phase, and the resulting oil phase is sent to step A), while the aqueous phase is sent to wastewater treatment.
[0024] In one embodiment of the present invention, the operating temperature of the crude acetone tower in step A) is 50-65°C and the operating pressure is 50-75 kPa.
[0025] In one embodiment of the present invention, the light component collected from the top of the crude acetone column in step A) is mainly acetone, which is then distilled in step B) to obtain acetone product; the heavy component obtained from the bottom of the crude acetone column is sent to the solvent removal column in step C).
[0026] In one embodiment of the present invention, in step B), acetone distillation is carried out using a distillation column with an operating temperature of 55-60°C and an operating pressure of 40-60 kPa.
[0027] In one embodiment of the present invention, the operating temperature of the solvent removal tower in step C) 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 hourly space velocity of the reaction solution is 1.0 h⁻¹. -1 ~4.0h -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, m-diisopropenylbenzene, m-isopropenyl cumene, and other isopropenylbenzene-containing benzene compounds (i.e., ALK-type impurities). The ALK-type impurity content in the stream before entering the resin bed is approximately 1-10 wt%, and the ALK-type impurity content at the resin bed outlet is approximately 0.01-0.5 wt%.
[0030] In one embodiment of the present invention, step E) involves deweighting using a deweighting tower, the operating temperature of which 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 from separation in E) is distilled in a refining column to obtain the resorcinol product. The distillation can be carried out using existing technologies in the field, such as atmospheric pressure, 10-30 trays, and a reflux ratio of 0.5-3.
[0032] To further recover resorcinol consumed as a byproduct during resorcinol generation, this invention provides a recovery method, namely step F) as described in this invention. The heavy component separated from E) contains PLK, a tandem byproduct of resorcinol, and the content of PLK-like substances in the heavy component is approximately 10-60 wt%. In step F), the aforementioned heavy component decomposes to regenerate resorcinol, and the content of PLK-like substances in the obtained resorcinol-containing heavy component is reduced to 0-0.1 wt%, thereby recovering the resorcinol lost during the reaction process and improving the final yield of resorcinol.
[0033] In one embodiment of the present invention, the operating temperature of the anti-alkylation tower in step F) is 220–300°C, and the mass hourly space velocity (WHSV) of the reaction liquid is 0.1 h⁻¹. -1 ~2.0h -1 The anti-alkylation tower is filled with a catalyst, which is a metal sulfate, including ferric sulfate, zinc sulfate, magnesium sulfate, etc., with magnesium sulfate being preferred.
[0034] In one embodiment of the present invention, the solvent used for the resorcinol crystallization in step H) is an alkylbenzene compound such as toluene, ethylbenzene, or cumene, preferably toluene, and the amount added is 2 to 5 times the mass of resorcinol in the resorcinol-containing heavy component 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℃; during crystallization, segmented crystallization is preferred; specifically, the segmented crystallization includes a first-stage crystallization and a second-stage crystallization. During the first-stage crystallization, the temperature is lowered to 60-70℃ and held for 2-4 hours at a cooling rate of 1-2℃ / min; during the second-stage crystallization, the temperature is lowered to 20-30℃ and held for 2-4 hours at a cooling rate of 0.2-0.5℃ / min, thereby obtaining the resorcinol product.
[0036] Compared with the prior art, the present invention has the following advantages:
[0037] (1) The separation process is simple, saving on equipment and land investment;
[0038] (2) In the preferred embodiment, the loss of resorcinol during the reaction process can be recovered, thereby increasing the final yield of resorcinol;
[0039] (3) Reduce the use of extractants, eliminate the need for water distillation, and reduce energy consumption;
[0040] (4) The separation process generates little wastewater and is environmentally friendly. Attached Figure Description
[0041] Figure 1 This is a schematic diagram of the resorcinol purification process in Example 1 of the present invention. Detailed Implementation
[0042] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.
[0043] Unless otherwise specified, the raw materials and reagents used in the embodiments and comparative examples of this invention were all purchased from commercially available sources.
[0044] Detection methods
[0045] This invention uses high-performance liquid chromatography (HPLC) to analyze the components of a stream. The chromatographic analysis conditions are as follows:
[0046] Instrument Model: LC-6A High Performance Liquid Chromatograph (Shimadzu)
[0047] Analytical column: CLC-SIL 150*6.0mm (Shimadzu)
[0048] Preparation column: Zorbax SIL 250*9.4mm (column bonding)
[0049] Mobile phase: Water: Methanol: Isopropanol: Isopropylcyclohexane (60-90℃) = 15:3:3:60 (v / v)
[0050] Flow rate: 0.7 ml / min
[0051] Column temperature: room temperature
[0052] Ultraviolet detector (Shimadzu SPD-6AV UV-Vis spectrophotometer) wavelength: 235nm.
[0053] The total yield of resorcinol = actual mass / theoretical mass × 100%, where theoretical mass = resorcinol molecular weight × (mass of raw material DHP / molecular weight of DHP).
[0054] Example 1
[0055] As attached Figure 1As shown, 100 kg of a 20 wt% MIBK solution of cumene dihydroperoxide (DHP), 0.1 kg of sulfuric acid, and 100 kg of acetone were introduced into a pyrolysis reactor and reacted at 60°C for 20 min. The reaction was then neutralized with alkali and washed with water. Neutralization was carried out at 50°C by mixing the oil phase with a 3 wt% sodium hydroxide aqueous solution for 1.5 min. The molar amount of sodium hydroxide was 1.01 times that of sulfuric acid in the pyrolysis reaction. After neutralization, 2 wt% water was added to the oil phase of the reaction solution for washing.
[0056] The oil phase obtained from water washing and phase separation enters the crude acetone tower, while the aqueous phase is sent to wastewater treatment. The light component from the top of the crude acetone tower enters the acetone refining tower to obtain acetone product, while the heavy component from the bottom enters the solvent removal tower to separate MIBK. Next, the main material, after exiting the bottom of the solvent removal tower, enters the resorcinol resin bed to remove ALK-type impurities. Subsequently, the main material enters the resorcinol de-heavy component tower, while the heavy component from the bottom enters the de-alkylation tower. The crude resorcinol product, after the heavy component has been removed, enters the resorcinol refining tower to further obtain the resorcinol product. The de-alkylation tower decomposes the heavy component to obtain a heavy component containing resorcinol, which enters the crystallizer for crystallization to obtain the resorcinol product. The process parameters are: the operating temperature of the crude acetone tower is 50℃, and the operating pressure is 50 kPaA. The operating temperature of the acetone refining tower is 60℃, and the operating pressure is 60 kPaA. The operating temperature of the solvent removal tower is 75℃, and the operating pressure is 3 kPaA. The ALK-type impurities in the pre-resin bed stream were approximately 10 wt%. The operating temperature of the resorcinol resin bed was 120 °C, and the mass hourly space velocity (WHSV) of the reaction solution was 4.0 h⁻¹. -1 The catalyst was T311 resin catalyst, and the ALK impurity content at the resin bed outlet was 0.5 wt%. The resorcinol de-heavy component tower operated at a temperature of 180℃ and a pressure of 80 PaA, with the PLK content in the heavy component being 30 wt%. The resorcinol purification tower had 15 trays and a reflux ratio of 1; the de-alkylation tower operated at a temperature of 220℃ and a reaction liquid mass hourly space velocity (MSV) of 0.1 h⁻¹. -1 The catalyst was magnesium sulfate, and the PLK content at the outlet of the anti-alkylation tower was reduced to 0.1 wt%. Toluene was used as the solvent for resorcinol crystallization, with the amount of toluene added being five times the mass of resorcinol in the resorcinol-containing heavy component. Before crystallization began, the temperature was raised to 100℃. Crystallization was carried out in stages: in the first stage, the temperature was lowered to 70℃ and held for 4 hours at a rate of 1℃ / min; in the second stage, the temperature was lowered to 30℃ and held for 4 hours at a rate of 0.2℃ / min.
[0057] After testing and calculation, the total yield of resorcinol was 98.1%, the separation energy consumption was 100 samples (calculated based on 100 samples of the example, the same below), the number of equipment was 28, the toluene solvent consumption was 3 kg, and the wastewater treatment was 6.6 kg.
[0058] Example 2
[0059] The reaction and separation were carried out according to the same process as in Example 1. The process parameters were as follows: 100 kg of a 20 wt% MIBK solution of cumene dihydroperoxide (DHP), 0.1 kg of sulfuric acid, and 100 kg of acetone were introduced into the cracking reactor and reacted at 60°C for 20 min. After alkali neutralization and water washing, the neutralization was carried out at 40°C, using a 5 wt% sodium hydroxide aqueous solution mixed with the oil phase for 1 min. The molar amount of sodium hydroxide was 1.01 times that of sulfuric acid. After neutralization, 3 wt% water was added to the oil phase of the reaction solution for washing. The remaining operations were the same as in Example 1. The operating temperature of the crude acetone tower was 50°C, and the operating pressure was 65 kPaA. The operating temperature of the acetone purification tower was 60°C, and the operating pressure was 60 kPaA. The operating temperature of the solvent removal tower was 65°C, and the operating pressure was 3 kPaA. The operating temperature of the resorcinol resin bed was 180°C, and the mass hourly space velocity (HHSV) of the reaction solution was 4.0 h⁻¹. -1 The catalyst is a T311 resin catalyst. The ALK-like impurities in the inlet stream are approximately 8 wt%, and the ALK-like impurities at the outlet stream are approximately 0.1 wt%. The resorcinol de-heavy component operates at a temperature of 240℃ and a pressure of 200 PaA, with PLK-like substances accounting for 50 wt% of the heavy component. The resorcinol purification column has 10 trays and a reflux ratio of 2; the de-alkylation column operates at a temperature of 300℃ and a reaction time of 2.0 h⁻¹. -1 The catalyst was ferric sulfate, and the content of PLK-type heavy components at the outlet of the dealkylation tower was reduced to 0.03 wt%. The solvent used for resorcinol crystallization was cumene, with the amount of cumene added being twice that of resorcinol. Before crystallization began, the temperature was raised to 120℃. During crystallization, a staged crystallization process was adopted. In the first stage, the temperature was lowered to 70℃ and held for 4 hours at a cooling rate of 2℃ / min. In the second stage, the temperature was lowered to 30℃ and held for 4 hours at a cooling rate of 0.5℃ / min.
[0060] After testing and calculation, the total yield of resorcinol was 97.5%. The separation energy consumption was 96 parts, the number of equipment was 28, the consumption of cumene solvent was 1.2 kg, and the wastewater treatment was 6.9 kg.
[0061] Example 3
[0062] The reaction and separation were carried out according to the same process as in Example 1. The process parameters were as follows: 100 kg of a 20 wt% MIBK solution of cumene dihydroperoxide (DHP), 0.15 kg of sulfuric acid, and 100 kg of acetone were introduced into the cracking reactor and reacted at 70°C for 25 min. After alkali neutralization and water washing, the neutralization was carried out at 50°C, using a 3 wt% sodium hydroxide aqueous solution mixed with the oil phase for 1 min. The molar amount of sodium hydroxide was 1.01 times that of sulfuric acid. After neutralization, 2 wt% water was added to the oil phase of the reaction solution for washing. The remaining operations were the same as in Example 1. The operating temperature of the crude acetone tower was 55°C, and the operating pressure was 70 kPaA. The operating temperature of the acetone purification tower was 55°C, and the operating pressure was 40 kPaA. The operating temperature of the solvent removal tower was 75°C, and the operating pressure was 3 kPaA. The operating temperature of the resorcinol resin bed was 150°C, and the mass hourly space velocity (HHSV) of the reaction solution was 2.5 h⁻¹. -1 The catalyst was T311 resin catalyst. The ALK-like impurities in the inlet stream were approximately 1 wt%, and the ALK-like impurities at the outlet stream were approximately 0.01 wt%. The resorcinol de-heavy component tower operated at 220℃ and 160 PaA, with PLK-like substances accounting for 40 wt% of the heavy component. The resorcinol purification tower had 20 trays and a reflux ratio of 3; the de-alkylation tower operated at 280℃ with a reaction time of 1.3 h⁻¹. -1 The catalyst was zinc sulfate, and the content of PLK-type heavy components at the outlet of the dealkylation tower was reduced to 0.01 wt%. The solvent used for resorcinol crystallization was cumene, with the amount of cumene added being three times that of resorcinol. Before crystallization began, the temperature was raised to 120℃. During crystallization, segmented crystallization was adopted. In the first stage of crystallization, the temperature was lowered to 65℃ and held for 3 hours at a rate of 1℃ / min. In the second stage of crystallization, the temperature was lowered to 30℃ and held for 3 hours at a rate of 0.4℃ / min.
[0063] After testing and calculation, the total yield of resorcinol was 98.8%. The separation energy consumption was 101 parts, the number of equipment was 28, the consumption of cumene solvent was 1.8 kg, and the wastewater treatment was 5.9 kg.
[0064] Example 4
[0065] The reaction and separation were carried out according to the same process as in Example 1. The process parameters were as follows: the pyrolysis reaction, alkali neutralization, and water washing conditions were the same as in Example 1; the operating temperature of the crude acetone tower was 60°C, and the operating pressure was 75 kPaA; the operating temperature of the acetone purification tower was 58°C, and the operating pressure was 51 kPaA; the operating temperature of the solvent removal tower was 70°C, and the operating pressure was 4 kPaA; the operating temperature of the resorcinol resin bed was 160°C, and the mass hourly space velocity (HHSV) of the reaction solution was 2.8 h⁻¹. -1The catalyst was T311 resin catalyst. The ALK-like impurities in the inlet stream were approximately 5 wt%, and the ALK-like impurities at the outlet stream were approximately 0.05 wt%. The resorcinol de-heavy component tower operated at 240℃ and 130 PaA, with PLK content in the heavy component being 60 wt%. The resorcinol purification tower had 15 trays and a reflux ratio of 1; the de-alkylation tower operated at 285℃ with a reaction time of 1.4 h⁻¹. -1 The catalyst was zinc sulfate, and the content of PLK-type heavy components at the outlet of the dealkylation tower was reduced to 0.1 wt%. The solvent used for resorcinol crystallization was cumene, with the amount of cumene added being three times that of resorcinol. The temperature was raised to 110℃ before crystallization began. Crystallization was carried out in stages: in the first stage, the temperature was lowered to 70℃ and held for 3 hours at a cooling rate of 1.6℃ / min; in the second stage, the temperature was lowered to 30℃ and held for 3 hours at a cooling rate of 0.4℃ / min.
[0066] After testing and calculation, the total yield of resorcinol was 98.3%. The separation energy consumption was 111 units, the number of equipment was 28, the consumption of cumene solvent was 1.8 kg, and the wastewater treatment was 6.1 kg.
[0067] Example 5
[0068] The reaction and separation were carried out according to the same process as in Example 1. The process parameters were as follows: the pyrolysis reaction, alkali neutralization, and water washing conditions were the same as in Example 1; the operating temperature of the crude acetone tower was 60°C, and the operating pressure was 75 kPaA; the operating temperature of the acetone purification tower was 60°C, and the operating pressure was 60 kPaA; the operating temperature of the solvent removal tower was 73°C, and the operating pressure was 5 kPaA; the operating temperature of the resorcinol resin bed was 160°C, and the mass hourly space velocity (HHSV) of the reaction solution was 2.8 h⁻¹. -1 The catalyst was T311 resin catalyst. The ALK-like impurities in the inlet stream were approximately 10 wt%, and the ALK-like impurities at the resin bed outlet were approximately 0.4 wt%. The resorcinol de-heavy component tower operated at 240℃ and 130 PaA, with PLK content in the heavy component being 10 wt%. The resorcinol purification tower had 15 trays and a reflux ratio of 2; the de-alkylation tower operated at 290℃ with a reaction time of 1.8 h⁻¹. -1 The catalyst was zinc sulfate, and the content of PLK-type heavy components at the outlet of the dealkylation tower was reduced to 0.02 wt%. The solvent used for resorcinol crystallization was cumene, with the amount of cumene added being 2.5 times that of resorcinol. The temperature was raised to 110℃ before crystallization began. Crystallization was carried out in stages: in the first stage, the temperature was lowered to 70℃ and held for 2 hours at a cooling rate of 1.8℃ / min; in the second stage, the temperature was lowered to 20℃ and held for 4 hours at a cooling rate of 0.5℃ / min.
[0069] After testing and calculation, the total yield of resorcinol was 98.3%. The separation energy consumption was 108 samples, the number of equipment was 28, the consumption of cumene solvent was 1.5 kg, and the wastewater treatment was 6.3 kg.
[0070] Comparative Example 1
[0071] The difference between this comparative example and Example 1 is that after the material passes through a solvent removal tower to remove MIBK, it directly enters a resorcinol de-heavy product tower, and crude resorcinol is collected from the top of the tower. The conditions of the de-heavy product tower are the same as in Example 1. Subsequently, the crude product is dissolved in water, with the mass of water added being three times that of the crude product. An equivalent amount of toluene is used to extract ALK-type impurities using this aqueous phase. The extraction tower has three stages and is set at room temperature. The raffinate phase (containing approximately 3 wt% ALK-type impurities) is separated from the water in a distillation column. The distillation column operates at 150°C and 150 PaA. Finally, the total yield of resorcinol is 90.3%, the separation energy consumption is 115 parts, the number of equipment used is 31 units, the toluene solvent consumption is 30 kg, and 66.6 kg of wastewater is treated.
[0072] Comparative Example 2
[0073] The difference between this comparative example and Example 1 is that the heavy components separated by the resorcinol de-heavy tower are not passed through the anti-alkylation tower but are directly sent to the environmental protection company for incineration. All other conditions are the same as in Example 1. Finally, the total yield of resorcinol product was 86.5%, the separation energy consumption was 91 parts, the number of equipment used was 26 units, the solvent consumption was 0 kg, and the wastewater treatment was 7.1 kg.
[0074] The above results demonstrate that the resorcinol purification method provided by this invention achieves high yield and better economic efficiency. The above description is merely a preferred embodiment of this invention. It should be noted that those skilled in the art can make various improvements and additions without departing from the method of this invention, and these improvements and additions should also be considered within the scope of protection of this invention.
Claims
1. A method for purifying resorcinol, characterized in that, The method includes: O) diisopropylbenzene dihydroperoxide was mixed with an acid catalyst and subjected to a cracking reaction, followed by neutralization to obtain the reaction liquid oil phase; 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 acetone-free component; C) The acetone-free component obtained in step A) is sent to a solvent removal tower to obtain a resorcinol coarse stream. D) Pass the resorcinol coarse stream obtained in step C) through a resorcinol resin bed; E) Remove the heavy weight from the stream obtained in step D) to obtain crude resorcinol, and then refine it to obtain the resorcinol product. F) The heavy component separated in step E) is fed into the anti-alkylation tower to obtain the heavy component containing resorcinol, which is then crystallized to obtain the resorcinol product.
2. The method according to claim 1, characterized in that, In step O), the acid catalyst is sulfuric acid; and / or the pyrolysis reaction temperature is 40–90°C, and the reaction time is 5–30 min.
3. The method according to claim 2, characterized in that, In step O), the amount of acid catalyst used is 0.05 to 0.5 wt% of the m-diisopropylbenzene dihydroperoxide solution.
4. The method according to claim 2, characterized in that, In step O), the pyrolysis reaction temperature is 50–80℃ and the reaction time is 10–20 min.
5. The method according to claim 1, characterized in that, A) The operating temperature of the crude acetone tower in step A is 50-65℃ and the operating pressure is 50-75kPa.
6. The method according to claim 1, characterized in that, The resorcinol purification method further includes step B): distilling the crude acetone obtained in step A) to obtain the acetone product.
7. The method according to claim 6, characterized in that, B) In step B, acetone distillation is carried out using a distillation column with an operating temperature of 55-60℃ and an operating pressure of 40-60kPa.
8. The method according to claim 1, characterized in that, In step C), the operating temperature of the solvent removal tower is 65–75°C, and the operating pressure is 3–6 kPaA.
9. The method according to claim 1, characterized in that, In step D), the operating temperature of the hydroquinone resin bed is 120–180°C, and the mass hourly space velocity of the reaction solution is 1.0 h⁻¹–4.0 h⁻¹.
10. The method according to claim 9, characterized in that, In step D), the catalyst in the hydroquinone resin bed is an acidic resin catalyst.
11. The method according to claim 10, characterized in that, In step D), the catalyst in the hydroquinone resin bed is a T311 resin catalyst.
12. The method according to claim 1, characterized in that, In step E), a deweighting tower is used for deweighting. The operating temperature of the deweighting tower is 180-240℃ and the operating pressure is 80-200PaA.
13. The method according to claim 1, characterized in that, In step F), the operating temperature of the anti-alkylation tower is 220–300 °C, and the mass hourly space velocity of the reaction liquid is 0.1 h⁻¹–2.0 h⁻¹.
14. The method according to claim 13, characterized in that, In step F), the anti-alkylation tower is filled with a catalyst, which is a metal sulfate.
15. The method according to claim 14, characterized in that, In step F), the catalyst packed in the anti-alkylation tower is one or more of ferric sulfate, zinc sulfate, and magnesium sulfate.
16. The method according to claim 1, characterized in that, H) The resorcinol crystallization in step H is a solution crystallization, and the solvent used is one or more of toluene, ethylbenzene, and cumene; the amount of solvent added is 2 to 5 times the mass of the resorcinol-containing heavy component resorcinol.
17. The method according to claim 16, characterized in that, In step H), the crystallization is segmented. During the first stage of crystallization, the temperature is lowered to 60-70℃ and held for 2-4 hours at a cooling rate of 1-2℃ / min. During the second stage of crystallization, the temperature is lowered to 20-30℃ and held for 2-4 hours at a cooling rate of 0.2-0.5℃ / min to obtain the resorcinol product.
18. The method according to claim 17, characterized in that, In step H), the solution temperature is adjusted to 100-120℃ before crystallization begins.