CN111689839B - Method for separating and refining phenol by leaching-phase separation-rectification coupling - Google Patents
Method for separating and refining phenol by leaching-phase separation-rectification coupling Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000008878 coupling Effects 0.000 title claims abstract description 16
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 16
- 238000007670 refining Methods 0.000 title claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 159
- 238000002386 leaching Methods 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 76
- 238000000926 separation method Methods 0.000 claims abstract description 71
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 239000012046 mixed solvent Substances 0.000 claims abstract description 21
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008247 solid mixture Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims description 53
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 50
- 239000012071 phase Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 238000001704 evaporation Methods 0.000 claims description 29
- 230000008020 evaporation Effects 0.000 claims description 26
- 239000007791 liquid phase Substances 0.000 claims description 25
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 238000005191 phase separation Methods 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004807 desolvation Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009270 solid waste treatment Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen Sodium oxide Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
本发明涉及一种以丙酮‑水混合溶剂为浸取剂浸取分离苯酚钠和氢氧化钠固态混合物，通过浸取‑相分离‑精馏耦合分离精制苯酚的方法，在分离精制得到苯酚的同时，使氢氧化钠及浸取剂得以循环利用。本发明的分离方法充分利用了被分离物系的特点以及分离过程的特性，不仅分离操作简单易行、操作费用低，而且有价成分利用率高，是符合绿色化工发展要求的清洁生产方法。
The invention relates to a method for leaching and separating a solid mixture of sodium phenate and sodium hydroxide by using an acetone-water mixed solvent as a leaching agent, and separating and purifying phenol through leaching-phase separation-rectification coupling. , so that sodium hydroxide and leaching agent can be recycled. The separation method of the present invention makes full use of the characteristics of the material to be separated and the characteristics of the separation process, not only the separation operation is simple and easy, the operation cost is low, but also the utilization rate of valuable components is high, and it is a clean production method that meets the development requirements of green chemical industry.
Description
技术领域technical field
本发明涉及一种浸取-相分离-精馏耦合分离精制苯酚的方法，特别是采用丙酮-水混合溶剂浸取分离苯酚钠和氢氧化钠固态混合物，然后经液-液相分离及精馏操作分离精制得到苯酚，同时使氢氧化钠及浸取剂得以循环利用的方法，属于化工分离技术领域。The invention relates to a method for leaching-phase separation-rectification coupling separation and purification of phenol, in particular using acetone-water mixed solvent to leaching and separating a solid mixture of sodium phenolate and sodium hydroxide, and then separating and rectifying a solid mixture of sodium phenolate and sodium hydroxide through liquid-liquid phase separation and distillation. The invention discloses a method for obtaining phenol through operation, separation and purification, and simultaneously recycling sodium hydroxide and a leaching agent, belonging to the technical field of chemical separation.
背景技术Background technique
通常含苯酚的物料进行蒸发脱水处理时，为了减少苯酚的挥发以及保护酚羟基使其不发生化学反应，在苯酚水溶液中加入氢氧化钠，使苯酚与氢氧化钠反应生成不易挥发且化学性质稳定的苯酚钠。同时，为了使该反应进行彻底，通常加入过量的氢氧化钠，因此在蒸发脱水及干燥处理后形成了苯酚钠和氢氧化钠固态混合物。Usually, when phenol-containing materials are subjected to evaporative dehydration treatment, in order to reduce the volatilization of phenol and protect the phenolic hydroxyl group from chemical reaction, sodium hydroxide is added to the phenol aqueous solution, so that the reaction between phenol and sodium hydroxide is non-volatile and chemically stable. of sodium phenolate. At the same time, in order to make the reaction complete, an excess of sodium hydroxide is usually added, so a solid mixture of sodium phenate and sodium hydroxide is formed after evaporative dehydration and drying treatment.
目前，处理苯酚钠和氢氧化钠固态混合物的方法是在该物料中加入硫酸或盐酸，与混合物中的氢氧化钠反应生成钠盐(硫酸钠、氯化钠)；同时苯酚钠与酸反应生成游离苯酚，利用游离苯酚易挥发的特性使苯酚得以回收。该方法主要存在以下问题：At present, the method for treating the solid mixture of sodium phenate and sodium hydroxide is to add sulfuric acid or hydrochloric acid to the material, and react with the sodium hydroxide in the mixture to generate sodium salt (sodium sulfate, sodium chloride); at the same time, sodium phenate reacts with acid to generate Free phenol can be recovered by utilizing the volatile property of free phenol. This method mainly has the following problems:
(1)分离过程中加入硫酸或盐酸作为中和剂，消耗了酸；(1) adding sulfuric acid or hydrochloric acid as neutralizing agent in separation process, consumed acid;
(2)加入的硫酸或盐酸与氢氧化钠反应，也消耗物料中的氢氧化钠；(2) the added sulfuric acid or hydrochloric acid react with sodium hydroxide, also consume the sodium hydroxide in the material;
(3)该处理方法还存在的一个突出问题是加入的酸与氢氧化钠反应产生了钠盐，该钠盐利用价值低，难以资源化利用，通常只能作为废物进行固废处理，而且该固废的处理难度也比较大。(3) an outstanding problem that this processing method also exists is that the acid that adds reacts with sodium hydroxide to produce sodium salt, and this sodium salt has low utilization value, is difficult to utilize as a resource, and usually can only be used as waste for solid waste treatment, and this Solid waste treatment is also more difficult.
因此，针对上述问题研发工艺合理、方法简单、成本低廉、有价成分利用率高的苯酚钠和氢氧化钠分离工艺，使苯酚及其他物料得以回收及资源化利用，不仅具有工业应用价值，而且具有显著的经济和社会效益。Therefore, in view of the above problems, the research and development of a sodium phenate and sodium hydroxide separation process with reasonable process, simple method, low cost and high utilization rate of valuable components, so that phenol and other materials can be recovered and utilized as resources, not only has industrial application value, but also It has significant economic and social benefits.
发明内容SUMMARY OF THE INVENTION
本发明的目的是针对现有技术的不足，研发工艺合理、方法简单、成本低廉、有价成分利用率高、清洁环保的浸取-相分离-精馏耦合分离精制苯酚的方法，在分离精制苯酚的同时，其他物料也得以资源化利用。The purpose of the present invention is to aim at the deficiencies of the prior art, develop a method for leaching-phase separation-rectification coupled separation and purification of phenol with reasonable process, simple method, low cost, high utilization rate of valuable components, clean and environmental protection, in the separation and purification At the same time as phenol, other materials can also be utilized as resources.
实现上述目的的技术方案是：The technical solution to achieve the above purpose is:
一种浸取-相分离-精馏耦合分离精制苯酚的方法，特别是采用丙酮-水混合溶剂浸取分离苯酚钠和氢氧化钠固态混合物，然后经液-液相分离及精馏操作分离精制得到苯酚，同时使氢氧化钠及浸取剂得以循环利用的方法，其特征在于所述方法步骤如下：A method for leaching-phase separation-rectification coupling separation and purification of phenol, particularly using acetone-water mixed solvent to leaching and separating a solid mixture of sodium phenolate and sodium hydroxide, and then separating and purifying through liquid-liquid phase separation and rectification operations Obtain phenol, make sodium hydroxide and the method for leaching agent to be recycled simultaneously, it is characterized in that described method steps are as follows:
(1)浸取剂配制：将丙酮和水混合，制得丙酮-水混合溶剂，此溶剂作为浸取剂进入下一步；(1) leaching agent preparation: acetone and water are mixed to obtain an acetone-water mixed solvent, and this solvent enters the next step as a leaching agent;
(2)浸取苯酚钠：采用上一步制得的浸取剂，在浸取设备中对苯酚钠和氢氧化钠固态混合物进行浸取分离操作，使固相物料中的苯酚钠溶解到液相中，经过浸取操作的物料进入下一步；(2) leaching sodium phenolate: using the leaching agent obtained in the previous step, the leaching and separation operation is performed on the solid mixture of sodium phenate and sodium hydroxide in the leaching equipment, so that the sodium phenolate in the solid phase material is dissolved into the liquid phase , the material that has undergone the leaching operation enters the next step;
(3)固-液分离：将上一步得到的物料在固-液分离设备中进行固-液分离，固相为氢氧化钠粗品，该物料可直接作为苯酚转化为苯酚钠过程中的反应物使用，也可以进一步处理后得到氢氧化钠产品，液相物料进入下一步；(3) solid-liquid separation: the material obtained in the previous step is subjected to solid-liquid separation in a solid-liquid separation device, and the solid phase is a crude sodium hydroxide product, which can be directly converted into a reactant in the process of sodium phenolate as phenol After use, the sodium hydroxide product can also be obtained after further processing, and the liquid phase material enters the next step;
(4)蒸发脱丙酮：将上一步得到的液相物料在蒸发设备中经蒸发操作脱除丙酮，气相物料进入下一步，蒸发浓缩物进入第六步；(4) acetone removal by evaporation: the liquid phase material obtained in the previous step is removed acetone through evaporation operation in the evaporation equipment, the gas phase material enters the next step, and the evaporation concentrate enters the 6th step;
(5)气相冷凝：上一步得到的气相物料经冷凝器冷凝为液态，该物料可作为第一步浸取剂配制的原料使用；(5) gas phase condensation: the gas phase material obtained in the previous step is condensed into a liquid state through the condenser, and this material can be used as the raw material prepared by the first step leaching agent;
(6)硫酸中和：在中和设备中，第四步经蒸发脱溶剂后的苯酚钠与硫酸发生中和反应生成苯酚和硫酸钠，该物料进入下一步；(6) neutralization of sulfuric acid: in the neutralization equipment, the 4th step generates phenol and sodium sulfate through the neutralization reaction of the sodium phenate after the evaporative desolvation and sulfuric acid, and this material enters the next step;
(7)液-液分离：在液-液分离设备中，将上一步得到的物料进行油-水相分离，水相物料经进一步处理得到硫酸钠和水，油相物料为苯酚粗品，进入下一步进行精制；(7) Liquid-liquid separation: in the liquid-liquid separation equipment, the material obtained in the previous step is subjected to oil-water phase separation, the water-phase material is further processed to obtain sodium sulfate and water, and the oil-phase material is a crude phenol product, which enters the next step. One-step refining;
(8)精馏精制苯酚：上一步的物料进入精馏塔进行精馏，塔顶馏出液为苯酚，产生的极少量的釜液作为废液处理。(8) Refining phenol by rectification: the material of the previous step enters the rectifying tower for rectification, and the distillate at the top of the tower is phenol, and a very small amount of the still liquid produced is treated as a waste liquid.
进一步，在第一步浸取剂配制过程中，水与丙酮的体积比为1.0:100-10.0:100。Further, in the first step of preparing the leaching agent, the volume ratio of water to acetone is 1.0:100-10.0:100.
进一步，在第二步浸取过程中，苯酚钠和氢氧化钠混合物中苯酚钠质量与浸取剂体积的比为1.0kg:5.0 L-1.0kg:50L。Further, in the second step leaching process, the ratio of sodium phenolate mass and leaching agent volume in the sodium phenate and sodium hydroxide mixture is 1.0kg:5.0L-1.0kg:50L.
进一步，在第三步固-液分离过程中，所述的固-液分离设备可以是压滤设备、离心式过滤设备、叶片式过滤设备、管道式过滤设备及真空抽滤设备中的任意一种。Further, in the solid-liquid separation process of the third step, the solid-liquid separation equipment can be any one of filter press equipment, centrifugal filter equipment, blade filter equipment, pipeline filter equipment and vacuum filtration equipment. kind.
进一步，第四步的蒸发设备可以是常压蒸发设备或真空蒸发设备。Further, the evaporation equipment in the fourth step may be atmospheric pressure evaporation equipment or vacuum evaporation equipment.
进一步，在第六步硫酸中和操作过程中，将溶液的pH值中和至5-6。Further, in the sixth step sulfuric acid neutralization operation, the pH value of the solution is neutralized to 5-6.
进一步，第七步液-液分离过程的设备为沉降式、离心式或高效油-水分离器中的任意一种。Further, the equipment of the liquid-liquid separation process in the seventh step is any one of a sedimentation type, a centrifugal type or a high-efficiency oil-water separator.
进一步，第八步精馏分离过程可以是连续操作，也可以是间歇操作Further, the eighth step rectification separation process can be a continuous operation or a batch operation
本发明应用的主要原理和特点如下：The main principles and characteristics of the application of the present invention are as follows:
(1)利用了苯酚钠和氢氧化钠在丙酮及水中溶解性的差异。苯酚钠和氢氧化钠都易溶于水中，但氢氧化钠难溶于丙酮，而苯酚钠在丙酮中有一定的溶解度。随着温度的升高，苯酚钠在丙酮中的溶解度增大，在回流条件下，其溶解度约为22.0g/100ml。(1) The difference in solubility of sodium phenate and sodium hydroxide in acetone and water is utilized. Both sodium phenate and sodium hydroxide are easily soluble in water, but sodium hydroxide is insoluble in acetone, while sodium phenate has a certain solubility in acetone. With the increase of temperature, the solubility of sodium phenolate in acetone increases, and its solubility is about 22.0g/100ml under reflux conditions.
(2)利用了苯酚钠和氢氧化钠在丙酮-水混合溶剂中溶解性的差异。为了提高苯酚钠在浸取剂中的溶解度，创新性地研发了丙酮-水混合溶剂作为浸取剂，亦即在丙酮中添加少量的水，丙酮-水混合溶剂可以大幅度提高苯酚钠的溶解度。(2) The difference in solubility of sodium phenate and sodium hydroxide in acetone-water mixed solvent was utilized. In order to improve the solubility of sodium phenolate in leaching agent, acetone-water mixed solvent was innovatively developed as leaching agent, that is, adding a small amount of water to acetone, acetone-water mixed solvent can greatly improve the solubility of sodium phenolate .
(3)采用浸取法分离苯酚钠和氢氧化钠固态混合物。以丙酮-水混合溶剂为浸取剂，通过浸取操作将混合物中的苯酚钠浸取到液相中，从而实现苯酚钠与氢氧化钠的分离。(3) Use the leaching method to separate the solid mixture of sodium phenolate and sodium hydroxide. Using acetone-water mixed solvent as leaching agent, the sodium phenolate in the mixture is leached into the liquid phase through the leaching operation, so as to realize the separation of sodium phenolate and sodium hydroxide.
(4)利用丙酮易挥发的特点，蒸发脱除丙酮。因苯酚钠受热后不易发生化学变化，且苯酚钠作为盐也不易挥发，而丙酮易挥发，因此可采用蒸发的方法脱除丙酮，丙酮经冷凝器冷凝后可作为浸取剂原料循环使用。(4) Using the volatile characteristics of acetone, the acetone is removed by evaporation. Because sodium phenolate is not easy to undergo chemical changes after being heated, and sodium phenolate is not easily volatile as a salt, and acetone is volatile, so the acetone can be removed by evaporation, and the acetone can be recycled as a leaching agent raw material after being condensed by a condenser.
(5)利用苯酚与水在室温下不互溶的特性，可以通过液-液相分离的方法分离苯酚和水。由于苯酚在水中以及水在苯酚中的溶解度小，静置后苯酚与水易分层，因此通过液-液相分离的方法实现苯酚和水的分离。(5) Taking advantage of the immiscibility of phenol and water at room temperature, phenol and water can be separated by a liquid-liquid phase separation method. Since the solubility of phenol in water and water in phenol is small, phenol and water are easily separated after standing, so the separation of phenol and water is realized by the method of liquid-liquid phase separation.
(6)采用精馏的方法分离精制苯酚。苯酚沸点远低于300℃，可以采用常规精馏分离技术精制油-水分离得到的粗苯酚，从而得到符合标准(GB/T 339-2019工业用合成苯酚)要求的产品。(6) Adopt the method of rectification to separate and refine phenol. The boiling point of phenol is much lower than 300°C, and the crude phenol obtained by oil-water separation can be refined by conventional rectification separation technology to obtain products that meet the requirements of the standard (GB/T 339-2019 Synthetic Phenol for Industrial Use).
实现本发明的主要工艺设备为：浸取设备、固-液分离设备、液-液分离设备、精馏设备等。The main process equipments for realizing the present invention are: leaching equipment, solid-liquid separation equipment, liquid-liquid separation equipment, rectification equipment and the like.
上述技术方案的好处是：以丙酮-水混合溶剂为浸取剂浸取分离苯酚钠和氢氧化钠固态混合物，通过浸取-相分离-精馏耦合，在分离精制得到苯酚的同时，使氢氧化钠及浸取剂得以循环利用。具体表现在：The advantages of the above technical solutions are: using acetone-water mixed solvent as the leaching agent to leaching and separating the solid mixture of sodium phenate and sodium hydroxide, and coupling the leaching-phase separation-rectification, while separating and refining the phenol, the hydrogen Sodium oxide and leaching agent are recycled. Specifically in:
(1)采用含少量水的丙酮-水混合溶剂作为浸取剂。用含少量水的丙酮-水混合溶剂作为浸取剂，使苯酚钠在浸取剂中的溶解度明显增大，且分离过程仍具有较高的选择性。通过调整浸取剂中水的含量、浸取操作的固液比、浸取分离次数等可以分离得到所需纯度的苯酚钠。采用含少量水的丙酮-水混合溶剂作为浸取剂不仅使苯酚钠和氢氧化钠固态混合物的分离在技术上可行，而且也使该分离过程在经济上有利。(1) An acetone-water mixed solvent containing a small amount of water is used as the leaching agent. Using acetone-water mixed solvent containing a small amount of water as the leaching agent can significantly increase the solubility of sodium phenolate in the leaching agent, and the separation process still has high selectivity. The required purity of sodium phenolate can be obtained by adjusting the water content in the leaching agent, the solid-liquid ratio of the leaching operation, and the number of times of leaching and separation. The use of an acetone-water mixed solvent containing a small amount of water as the leaching agent not only makes the separation of the solid mixture of sodium phenate and sodium hydroxide technically feasible, but also makes the separation process economically advantageous.
(2)该分离工艺彻底克服了加酸中和分离苯酚钠与氢氧化钠工艺的缺点，不仅不需要消耗酸，而且不会损失物料中的氢氧化钠，同时也不再产生钠盐固体废物。(2) This separation process completely overcomes the shortcoming of acid addition and neutralization and separation of sodium phenolate and sodium hydroxide process, not only does not need to consume acid, but also does not lose the sodium hydroxide in the material, and also no longer produces sodium salt solid waste at the same time .
(3)采用蒸发脱丙酮技术，不仅操作简单，而且回收得到的丙酮还可作为浸取剂的原料循环使用，节约了资源，同时也大幅度减少了废物的排放量。(3) The evaporative deacetone technology is adopted, which is not only easy to operate, but also the recovered acetone can be recycled as the raw material of the leaching agent, which saves resources and greatly reduces the amount of waste discharged.
(4)利用苯酚与水在室温下不互溶的特性通过液-液相分离苯酚和水，不仅分离操作简单易行，而且过程的能耗也低。(4) The liquid-liquid phase separation of phenol and water by utilizing the immiscibility of phenol and water at room temperature is not only simple and easy to operate, but also the energy consumption of the process is low.
(5)采用常规精馏的方法精制苯酚可以分离得到符合标准(GB/T 339-2019工业用合成苯酚)要求的产品，精馏分离也容易实现连续规模化生产。(5) Refining phenol by conventional rectification method can separate and obtain products that meet the requirements of the standard (GB/T 339-2019 Synthetic Phenol for Industrial Use), and rectification separation is also easy to achieve continuous large-scale production.
本发明的方法特别适用于从苯酚钠和氢氧化钠混合物中分离回收苯酚。该方法充分利用了被分离物系的特点以及分离过程的特性，不仅分离操作简单易行，而且有价成分利用率高，是符合绿色化工发展要求的清洁生产方法。The method of the present invention is particularly suitable for separating and recovering phenol from a mixture of sodium phenate and sodium hydroxide. The method makes full use of the characteristics of the system to be separated and the characteristics of the separation process, not only the separation operation is simple and feasible, but also the utilization rate of valuable components is high, and it is a clean production method that meets the requirements of green chemical development.
附图说明Description of drawings
附图1为本发明的工艺流程图。Accompanying drawing 1 is the process flow diagram of the present invention.
具体实施方式Detailed ways
下面结合附图和实施例对本发明作进一步详细的说明。The present invention will be described in further detail below with reference to the accompanying drawings and embodiments.
实施例一Example 1
主要工艺设备为浸取设备、固-液分离设备、液-液分离设备、精馏设备等。The main process equipment is leaching equipment, solid-liquid separation equipment, liquid-liquid separation equipment, rectification equipment, etc.
一种浸取-相分离-精馏耦合分离精制苯酚的方法，特别是采用丙酮-水混合溶剂浸取分离苯酚钠和氢氧化钠固态混合物，然后经液-液相分离及精馏操作分离精制得到苯酚，同时使氢氧化钠及浸取剂得以循环利用的方法，其特征在于所述方法步骤如下：A method for leaching-phase separation-rectification coupling separation and purification of phenol, particularly using acetone-water mixed solvent to leaching and separating a solid mixture of sodium phenolate and sodium hydroxide, and then separating and purifying through liquid-liquid phase separation and rectification operations Obtain phenol, make sodium hydroxide and the method for leaching agent to be recycled simultaneously, it is characterized in that described method steps are as follows:
(1)浸取剂配制：将丙酮和水混合，制得的浸取剂中水与丙酮的体积比为5.0:100，此溶剂作为浸取剂进入下一步；(1) leaching agent preparation: acetone and water are mixed, the volume ratio of water and acetone in the obtained leaching agent is 5.0:100, and this solvent enters the next step as the leaching agent;
(2)浸取苯酚钠：在浸取设备中，以上一步制得的丙酮-水混合溶剂作为浸取剂对苯酚钠和氢氧化钠固态混合物进行浸取分离操作，混合物中苯酚钠质量与浸取剂体积的比为1.0kg:20L，操作温度为56℃，固相物料中的苯酚钠溶解到液相中，经过浸取操作的物料进入下一步；(2) leaching sodium phenolate: in the leaching equipment, the acetone-water mixed solvent obtained in the previous step is used as the leaching agent to carry out the leaching and separation operation on the solid mixture of sodium phenolate and sodium hydroxide. The ratio of the volume of the extracting agent is 1.0kg: 20L, the operating temperature is 56 ° C, the sodium phenolate in the solid phase material is dissolved in the liquid phase, and the material through the leaching operation enters the next step;
(3)固-液分离：在叶片式过滤设备中，将上一步得到的物料进行固-液分离，得到的固相物料为氢氧化钠粗品，该物料可直接作为苯酚转化为苯酚钠过程中的反应物使用，也可以进一步处理后得到氢氧化钠产品，液相物料进入下一步；(3) solid-liquid separation: in the blade filter equipment, the material obtained in the previous step is subjected to solid-liquid separation, and the obtained solid phase material is a crude sodium hydroxide product, which can be directly converted into sodium phenolate as phenol in the process The reactant is used, and the sodium hydroxide product can also be obtained after further processing, and the liquid phase material enters the next step;
(4)蒸发脱溶剂：将上一步得到的液相物料在蒸发设备中经蒸发操作脱除溶剂，气相物料进入下一步，蒸发浓缩物进入第六步；(4) desolvation by evaporation: the liquid phase material obtained in the previous step is removed from the solvent through evaporation operation in the evaporation equipment, the gas phase material enters the next step, and the evaporation concentrate enters the sixth step;
(5)气相冷凝：上一步得到的气相物料经冷凝器冷凝为液态，该物料可作为第一步浸取剂配制的原料使用；(5) gas phase condensation: the gas phase material obtained in the previous step is condensed into a liquid state through the condenser, and this material can be used as the raw material prepared by the first step leaching agent;
(6)硫酸中和：第四步经蒸发脱溶剂的蒸发浓缩物在中和设备中与硫酸中和至溶液的pH为6.0，硫酸与苯酚钠反应生成苯酚和硫酸钠，该物料进入下一步；(6) neutralization of sulfuric acid: the 4th step is 6.0 through the evaporating concentrate of evaporating desolventizing and neutralizing to the pH of solution with sulfuric acid in neutralization equipment, and sulfuric acid reacts with sodium phenate to generate phenol and sodium sulfate, and this material enters the next step ;
(7)液-液分离：在液-液分离设备中，将上一步得到的物料进行油-水相分离，水相物料经进一步处理得到硫酸钠和水，油相物料为苯酚粗品，进入下一步进行精制；(7) Liquid-liquid separation: in the liquid-liquid separation equipment, the material obtained in the previous step is subjected to oil-water phase separation, the water-phase material is further processed to obtain sodium sulfate and water, and the oil-phase material is a crude phenol product, which enters the next step. One-step refining;
(8)精馏精制苯酚：上一步的物料进入精馏塔进行精馏，塔顶馏出液为苯酚，产生的极少量的釜液作为废液处理。(8) Refining phenol by rectification: the material of the previous step enters the rectifying tower for rectification, and the distillate at the top of the tower is phenol, and a very small amount of the still liquid produced is treated as a waste liquid.
实施例二Embodiment 2
主要工艺设备为浸取设备、固-液分离设备、液-液分离设备、精馏设备等。The main process equipment is leaching equipment, solid-liquid separation equipment, liquid-liquid separation equipment, rectification equipment, etc.
一种浸取-相分离-精馏耦合分离精制苯酚的方法，特别是采用丙酮-水混合溶剂浸取分离苯酚钠和氢氧化钠固态混合物，然后经液-液相分离及精馏操作分离精制得到苯酚，同时使氢氧化钠及浸取剂得以循环利用的方法，其特征在于所述方法步骤如下：A method for leaching-phase separation-rectification coupling separation and purification of phenol, particularly using acetone-water mixed solvent to leaching and separating a solid mixture of sodium phenolate and sodium hydroxide, and then separating and purifying through liquid-liquid phase separation and rectification operations Obtain phenol, make sodium hydroxide and the method for leaching agent to be recycled simultaneously, it is characterized in that described method steps are as follows:
(1)浸取剂配制：将丙酮和水混合，制得的浸取剂中水与丙酮的体积比为1.0:100，此溶剂作为浸取剂进入下一步；(1) leaching agent preparation: acetone and water are mixed, the volume ratio of water and acetone in the obtained leaching agent is 1.0:100, and this solvent enters the next step as the leaching agent;
(2)浸取苯酚钠：在浸取设备中，以上一步制得的丙酮-水混合溶剂作为浸取剂对苯酚钠和氢氧化钠固态混合物进行浸取分离操作，混合物中苯酚钠质量与浸取剂体积的比为1.0kg:50L，操作温度为60℃，固相物料中的苯酚钠溶解到液相中，经过浸取操作的物料进入下一步；(2) leaching sodium phenolate: in the leaching equipment, the acetone-water mixed solvent obtained in the previous step is used as the leaching agent to carry out the leaching and separation operation on the solid mixture of sodium phenolate and sodium hydroxide. The ratio of the volume of the extracting agent is 1.0kg:50L, the operating temperature is 60 ° C, the sodium phenolate in the solid phase material is dissolved in the liquid phase, and the material that has undergone the leaching operation enters the next step;
(3)固-液分离：在压滤式固-液分离设备中，将上一步得到的物料进行固-液分离，得到的固相物料为氢氧化钠粗品，该物料可直接作为苯酚转化为苯酚钠过程中的反应物使用，也可以进一步处理后得到氢氧化钠产品，液相物料进入下一步；(3) solid-liquid separation: in the filter press type solid-liquid separation equipment, the material obtained in the previous step is subjected to solid-liquid separation, and the obtained solid phase material is a crude sodium hydroxide product, which can be directly converted into phenol as The reactant in the sodium phenolate process is used, and the sodium hydroxide product can also be obtained after further processing, and the liquid phase material enters the next step;
(4)蒸发脱溶剂：将上一步得到的液相物料在蒸发设备中经蒸发操作脱除溶剂，气相物料进入下一步，蒸发浓缩物进入第六步；(4) desolvation by evaporation: the liquid phase material obtained in the previous step is removed from the solvent through evaporation operation in the evaporation equipment, the gas phase material enters the next step, and the evaporation concentrate enters the sixth step;
(5)气相冷凝：上一步得到的气相物料经冷凝器冷凝为液态，该物料可作为第一步浸取剂配制的原料使用；(5) gas phase condensation: the gas phase material obtained in the previous step is condensed into a liquid state through the condenser, and this material can be used as the raw material prepared by the first step leaching agent;
(6)硫酸中和：第四步经蒸发脱溶剂的蒸发浓缩物在中和设备中与硫酸中和至溶液的pH为5.6，硫酸与苯酚钠反应生成苯酚和硫酸钠，该物料进入下一步；(6) neutralization of sulfuric acid: the 4th step is 5.6 through the evaporative concentrate of evaporative desolvation in the neutralization equipment and the pH of the solution is neutralized with sulfuric acid, and sulfuric acid reacts with sodium phenate to generate phenol and sodium sulfate, and this material enters the next step ;
(7)液-液分离：在液-液分离设备中，将上一步得到的物料进行油-水相分离，水相物料经进一步处理得到硫酸钠和水，油相物料为苯酚粗品，进入下一步进行精制；(7) Liquid-liquid separation: in the liquid-liquid separation equipment, the material obtained in the previous step is subjected to oil-water phase separation, the water-phase material is further processed to obtain sodium sulfate and water, and the oil-phase material is a crude phenol product, which enters the next step. One-step refining;
(8)精馏精制苯酚：上一步的物料进入精馏塔进行精馏，塔顶馏出液为苯酚，产生的极少量的釜液作为废液处理。(8) Refining phenol by rectification: the material of the previous step enters the rectifying tower for rectification, and the distillate at the top of the tower is phenol, and a very small amount of the still liquid produced is treated as a waste liquid.
实施例三Embodiment 3
主要工艺设备为浸取设备、固-液分离设备、液-液分离设备、精馏设备等。The main process equipment is leaching equipment, solid-liquid separation equipment, liquid-liquid separation equipment, rectification equipment, etc.
一种浸取-相分离-精馏耦合分离精制苯酚的方法，特别是采用丙酮-水混合溶剂浸取分离苯酚钠和氢氧化钠固态混合物，然后经液-液相分离及精馏操作分离精制得到苯酚，同时使氢氧化钠及浸取剂得以循环利用的方法，其特征在于所述方法步骤如下：A method for leaching-phase separation-rectification coupling separation and purification of phenol, particularly using acetone-water mixed solvent to leaching and separating a solid mixture of sodium phenolate and sodium hydroxide, and then separating and purifying through liquid-liquid phase separation and rectification operations Obtain phenol, make sodium hydroxide and the method for leaching agent to be recycled simultaneously, it is characterized in that described method steps are as follows:
(1)浸取剂配制：将丙酮和水混合，制得的浸取剂中水与丙酮的体积比为10.0:100，此溶剂作为浸取剂进入下一步；(1) leaching agent preparation: acetone and water are mixed, the volume ratio of water and acetone in the obtained leaching agent is 10.0:100, and this solvent enters the next step as the leaching agent;
(2)浸取苯酚钠：在浸取设备中，以上一步制得的丙酮-水混合溶剂作为浸取剂对苯酚钠和氢氧化钠固态混合物进行浸取分离操作，混合物中苯酚钠质量与浸取剂体积的比为1.0kg:5.0L，操作温度为40℃，固相物料中的苯酚钠溶解到液相中，经过浸取操作的物料进入下一步；(2) leaching sodium phenolate: in the leaching equipment, the acetone-water mixed solvent obtained in the previous step is used as the leaching agent to carry out the leaching and separation operation on the solid mixture of sodium phenolate and sodium hydroxide. The ratio of the volume of the extract is 1.0kg:5.0L, the operating temperature is 40 ° C, the sodium phenolate in the solid phase material is dissolved in the liquid phase, and the material that has undergone the leaching operation enters the next step;
(3)固-液分离：在真空抽滤设备中，将上一步得到的物料进行固-液分离，得到的固相物料为氢氧化钠粗品，该物料可直接作为苯酚转化为苯酚钠过程中的反应物使用，也可以进一步处理后得到氢氧化钠产品，液相物料进入下一步；(3) solid-liquid separation: in the vacuum filtration equipment, the material obtained in the previous step is subjected to solid-liquid separation, and the obtained solid phase material is a crude sodium hydroxide product, which can be directly converted into sodium phenolate as phenol in the process The reactant is used, and the sodium hydroxide product can also be obtained after further processing, and the liquid phase material enters the next step;
(4)蒸发脱溶剂：将上一步得到的液相物料在蒸发设备中经蒸发操作脱除溶剂，气相物料进入下一步，蒸发浓缩物进入第六步；(4) desolvation by evaporation: the liquid phase material obtained in the previous step is removed from the solvent through evaporation operation in the evaporation equipment, the gas phase material enters the next step, and the evaporation concentrate enters the sixth step;
(5)气相冷凝：上一步得到的气相物料经冷凝器冷凝为液态，该物料可作为第一步浸取剂配制的原料使用；(5) gas phase condensation: the gas phase material obtained in the previous step is condensed into a liquid state through the condenser, and this material can be used as the raw material prepared by the first step leaching agent;
(6)硫酸中和：第四步经蒸发脱溶剂的蒸发浓缩物在中和设备中与硫酸中和至溶液的pH为5.0，硫酸与苯酚钠反应生成苯酚和硫酸钠，该物料进入下一步；(6) neutralization of sulfuric acid: the 4th step is 5.0 through the evaporative concentrate of evaporative desolvation and neutralization to the pH of solution with sulfuric acid in the neutralization equipment, and the reaction of sulfuric acid and sodium phenate generates phenol and sodium sulfate, and this material enters the next step ;
(7)液-液分离：在液-液分离设备中，将上一步得到的物料进行油-水相分离，水相物料经进一步处理得到硫酸钠和水，油相物料为苯酚粗品，进入下一步进行精制；(7) Liquid-liquid separation: in the liquid-liquid separation equipment, the material obtained in the previous step is subjected to oil-water phase separation, the water-phase material is further processed to obtain sodium sulfate and water, and the oil-phase material is a crude phenol product, which enters the next step. One-step refining;
(8)精馏精制苯酚：上一步的物料进入精馏塔进行精馏，塔顶馏出液为苯酚，产生的极少量的釜液作为废液处理。(8) Refining phenol by rectification: the material of the previous step enters the rectifying tower for rectification, and the distillate at the top of the tower is phenol, and a very small amount of the still liquid produced is treated as a waste liquid.
除上述各实施例，本发明的实施方案还有很多，凡采用等同或等效替换的技术方案，均在本发明的保护范围之内。In addition to the above-mentioned embodiments, there are still many embodiments of the present invention, and any technical solutions that are equivalent or equivalently replaced are all within the protection scope of the present invention.
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