CN112144075A - Method for continuously synthesizing potassium tert-butoxide by membrane electrolysis - Google Patents
Method for continuously synthesizing potassium tert-butoxide by membrane electrolysis Download PDFInfo
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Abstract
A process for continuously synthesizing potassium tert-butoxide by membrane electrolysis features that the saturated solution mixture of tert-butanol and potassium hydroxide is continuously dewatered on cathode and anode after the membrane electrolyzer is powered on, and the potassium tert-butoxide is continuously synthesized in cathode chamber. The advantages of good quality and low content of free KOH of the metallic potassium method and the advantages of safety and low cost of the KOH azeotropic dehydration method are integrated, the defects of danger, easy explosion and high cost of the metallic potassium method are overcome, and the defects of high heating energy consumption, low efficiency, incomplete reaction/high content of free KOH and poor quality of the KOH azeotropic dehydration method are overcome.
Description
Technical Field
The invention relates to a synthesis method of organic strong base, belonging to the technical field of organic synthetic chemistry.
Background
Potassium tert-butoxide is an organic superbase and has many uses; widely used for the alkali-catalyzed synthesis of ketone group by trifluoromethane, the alkali-catalyzed synthesis of 2, 2-bipyridine and the like. Refer to the production method of potassium tert-butoxide of the Budweiser et al, chemical intermediate 2012 (07): 31-35, the public production method of potassium tert-butoxide is mainly classified into a potassium metal method and a potassium hydroxide method according to the raw material classification, namely 2 types:
the first metal potassium method is to adopt a highly flammable, explosive and dangerous metal potassium block to react with anhydrous tertiary butanol in a reaction kettle to synthesize potassium tert-butoxide, and CN2010105105675, CN2017108806310 and CN 107664506 all introduce a method for synthesizing potassium tert-butoxide by using metal potassium, although the synthesized potassium tert-butoxide has high purity and good quality and the content of free KOH is less than or equal to 2 percent, the metal potassium is too dangerous and very expensive, so the method is forbidden to be used by safety production departments and is eliminated at present. The potassium metallate method for synthesizing potassium tert-butoxide is a reaction chemical formula of a formula C:
the second method is a KOH azeotropic distillation dehydration method, which adopts cheap solid potassium hydroxide and a large excess of tert-butyl alcohol as raw materials, and adds cyclohexane for azeotropic distillation dehydration to synthesize potassium tert-butoxide, because the potassium tert-butoxide is alkali stronger than potassium hydroxide KOH, the potassium tert-butoxide can not be completely converted into potassium tert-butoxide after the reaction reaches balance, and the tert-butyl alcohol and water are azeotropic, and cyclohexane, toluene and other third nonpolar solvents are added as water-carrying agents to carry out azeotropic distillation dehydration; this equilibrium reaction is the chemical reaction of formula D:
application numbers CN2016100057225, CN2019113211893 and the like disclose that KOH and tert-butyl alcohol are subjected to azeotropic rectification dehydration after cyclohexane is added, and potassium tert-butoxide with higher purity is obtained; although the production and synthesis process is safer than the potassium metal method, and the cost of raw materials of the KOH azeotropic distillation dehydration method is much lower than that of the potassium metal method, the synthesis method for synthesizing the potassium tert-butoxide by the KOH method has many defects, and the main problems are that the azeotropic heating energy consumption is very large, the pollution is heavy, the quality is poor, and the production efficiency is extremely low. Because large reflux ratio azeotropic distillation is needed, the steam heating energy consumption is very large and can reach more than or equal to 20000 yuan/ton; the waste water containing tert-butyl alcohol is removed by azeotropy, and the COD is high; the equilibrium reaction of potassium tert-butoxide is not complete, the free KOH is difficult to reach the standard, and the quality of potassium tert-butoxide is poor. Because the boiling point of the tertiary butanol and the cyclohexane is lower than 90 ℃, the tertiary butanol and the cyclohexane are difficult to be completely condensed in summer, a large amount of the tertiary butanol and the cyclohexane are volatilized into the air, and the pollution is serious.
The invention provides a low-energy-consumption cleaning process for continuously synthesizing potassium tert-butoxide by membrane electrolysis, which does not need to be heated to more than or equal to 80 ℃ for azeotropic rectification, and can overcome the defects of high energy consumption, incomplete equilibrium conversion and the like of a KOH azeotropic rectification method.
Disclosure of Invention
The invention relates to a low-cost method for continuously synthesizing potassium tert-butoxide by membrane electrolysis, which adopts solid potassium hydroxide KOH and tert-butyl alcohol as raw materials, and after a membrane electrolysis device is electrified, a saturated mixed solution of the solid potassium hydroxide and the tert-butyl alcohol is kept at 30-60 ℃ for membrane electrolysis continuous dehydration, and high-purity potassium tert-butoxide is synthesized in a cathode chamber.
At the anode of an E-membrane electrolyzer, a large number of HO from the cathode compartment—The anion penetrates through the compact cross-linked anion membrane and migrates to the anode chamber, and the mixed solution of potassium hydroxide and tertiary butanol in the anode chamber continuously generates the dehydration electrochemical reaction of the formula A:
HO of the cathode Chamber—Under the drive of electric field, the anions continuously pass through the compact cross-linked anion membrane and enter the anode chamber for 4 HO—The anion loses 4 electrons at the anode to generate 2 molecules of water and one part of O2So that water is continuously enriched at the anode.
At the cathode of the membrane electrolyzer, the mixture of potassium hydroxide and tert-butanol continuously undergoes a dehydrating electrochemical reaction of formula B:
in the Membrane Electrolysis device of the formula E, 2 molecules of K+Cation, 2 electrons are obtained on a cathode, active 2 molecules of metal potassium are generated on the cathode in situ, and the metal potassium reacts with tert-butyl alcohol instantly to generate 2 molecules of potassium tert-butoxide; since the metal potassium is very active, the metal potassium reacts with the tertiary butanol rapidly on the cathodeAnd dangerous metal potassium cannot be accumulated. Because the reaction between metal potassium with high activity and tert-butyl alcohol is continuously generated at the cathode, the equilibrium effect of an azeotropic distillation method does not exist, and KOH at the cathode can be completely reacted into potassium tert-butoxide.
The method is essentially an improved version of a potassium metal method, integrates the advantages of good quality and low free KOH of the potassium metal method and the advantages of low cost and safety of a KOH azeotropic distillation method, and overcomes the respective process defects of high risk and high cost of the potassium metal method, high energy consumption, low efficiency and poor quality of the free KOH of the KOH azeotropic distillation method; high-activity metal potassium is continuously generated on the electrified cathode and is also continuously and rapidly consumed with the tert-butyl alcohol of the cathode, so that dangerous metal potassium cannot be accumulated on the cathode; however, the raw materials are solid KOH and tert-butyl alcohol which are safe and cheap, and equilibrium dehydration reaction does not exist.
Wherein: membrane a is a dense cross-linked anionic membrane.
The E-membrane electrolyzer of the invention must adopt a compact cross-linked anion membrane, and can only permeate HO with small ion size in the cathode chamber under the drive of an electric field—The anions to the anode can completely prevent the tertiary butyl oxygen anions with large ionic size from permeating into the anode chamber, thereby ensuring HO of the cathode—Anions can completely permeate and migrate to the anode, the reaction of the potassium tert-butoxide of the cathode is complete, the generated water of the anode and the potassium tert-butoxide of the cathode chamber are prevented from being contacted and hydrolyzed, and the tert-butyl oxyanion of the cathode is prevented from permeating to the anode to generate dangerous di-tert-butyl peroxide;
in the E-film electrolyzer of the invention, the distance between the cathode and the anode is less than or equal to 1mm, HO—The moving distance of the anions is very short, thereby ensuring the electrolysis of a large current membrane.
The membrane electrolysis temperature is controlled to be 30-60 ℃, and the reflux is not required to be heated to be more than or equal to 80 ℃, so that the heating steam energy consumption is greatly saved compared with a KOH azeotropic distillation dehydration method.
Description of the drawings:
FIG. 1: a membrane electrolysis unit device for continuously synthesizing potassium tert-butoxide:
1: a cathode chamber;
2: stainless steel cathode mesh plate: 78mm wide by 142mm long;
3: dense cross-linked anionic membrane: the thickness is 0.3 mm;
4: plating a platinum-gold titanium mesh anode: 78mm wide by 142mm long;
5: an anode chamber;
abbreviated terms:
t-BuOH is tert-butyl alcohol;
KOH: potassium hydroxide;
for a better understanding of the continuous synthesis of potassium tert-butoxide by electromembrane synthesis according to the invention, the following series of examples are given, without the invention being restricted to these examples.
Example 1:
electrolyzing at 7V by adopting a single-group membrane electrolysis device with a structure of formula E, and controlling the temperature of the electrolysis materials to be 45-50 ℃;
3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat A of 5000ml, and the saturated solution is pumped to the anode for circulation by a circulating pump A; 3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat B of 5000ml, and the saturated solution is pumped to a cathode for circulation by a circulating pump B; and (3) switching on an electrolysis power supply 7V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 18A, the temperature of the material slowly rises to 46 ℃ along with continuous electrolysis, the current does not rise any more, reaches 28A with the maximum current, the electrolysis is continued for 4h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 11.2%, and the KOH residue is 0.6%.
Example 2:
electrolyzing at 8V by adopting a single-group membrane electrolysis device with a structure of formula E, and controlling the temperature of the electrolysis materials to be 45-50 ℃;
3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat A of 5000ml, and the saturated solution is pumped to the anode for circulation by a circulating pump A; 3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat B of 5000ml, and the saturated solution is pumped to a cathode for circulation by a circulating pump B; and (3) switching on an electrolysis power supply of 8V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 22A, the temperature of the material slowly rises to 48 ℃ along with the continuous electrolysis, the temperature of the material does not rise, the current reaches 34A at the maximum, the electrolysis is continued for 3.6h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a material storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 11.4%, and the KOH residue is 0.4%.
Example 3:
electrolyzing at 9V by adopting a single-group membrane electrolysis device with a structure of formula E, and controlling the temperature of the electrolysis materials to be 45-55 ℃;
3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat A of 5000ml, and the saturated solution is pumped to the anode for circulation by a circulating pump A; 3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat B of 5000ml, and the saturated solution is pumped to a cathode for circulation by a circulating pump B; and (3) switching on an electrolysis power supply 9V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 25A, the temperature of the material slowly rises to 50 ℃ along with continuous electrolysis, the current does not rise any more, reaches 39A with the maximum current, the electrolysis is continued for 3h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 11.8%, and the KOH residue is 0.3%.
Example 4:
electrolyzing at an electrolytic voltage of 10V by adopting a single-group membrane electrolysis device with a structure of formula E, and controlling the temperature of an electrolysis material to be 45-55 ℃;
3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat A of 5000ml, and the saturated solution is pumped to the anode for circulation by a circulating pump A; 3500g (35 ℃) of saturated solution of anhydrous tert-butyl alcohol and solid KOH is added into a storage vat B of 5000ml, and the saturated solution is pumped to a cathode for circulation by a circulating pump B; and (2) switching on an electrolysis power supply 10V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 28A, the temperature of the material slowly rises to 52 ℃ along with continuous electrolysis, the current does not rise any more, reaches 45A with the maximum current, the electrolysis is continued for 2.5h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 12.2 percent, and KOH remains 0.1 percent.
Example 5:
electrolyzing at an electrolytic voltage of 14V by using a double-group series-connection feeding and discharging membrane electrolysis device with a structure shown as a formula E, and controlling the temperature of an electrolysis material to be 45-50 ℃;
adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butyl alcohol and solid KOH into a 10000ml storage barrel A, and pumping the saturated solution to an anode by using a circulating pump A for circulation; adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butanol and solid KOH into a 10000ml storage barrel B, and pumping to a cathode for circulation by using a circulating pump B; switching on an electrolysis power supply 14V to perform constant voltage membrane electrolysis, wherein the initial current reaches 22A, the temperature of the material slowly rises to 52 ℃ along with continuous electrolysis, the current does not rise any more, reaches 34A with the maximum current, the electrolysis is continued for 3.2h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a material storage barrel B obtains a tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is 10.8 percent and percent, and KOH residue is 0.3 percent through titration detection.
Example 6:
electrolyzing at 16V by adopting a membrane electrolysis device with double groups of series-connected feeding and discharging materials and a structure shown as a formula E, and controlling the temperature of the electrolyzed materials to be 50-55 ℃;
adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butyl alcohol and solid KOH into a 10000ml storage barrel A, and pumping the saturated solution to an anode by using a circulating pump A for circulation; adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butanol and solid KOH into a 10000ml storage barrel B, and pumping to a cathode for circulation by using a circulating pump B; and (3) switching on an electrolysis power supply 16V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 28A, the temperature of the material slowly rises to 54 ℃ along with continuous electrolysis, the current does not rise any more, reaches 46A with the maximum current, the electrolysis is continued for 2.8h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a material storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. Titration detection shows that the content of potassium tert-butoxide is 11.3 percent, and the KOH residue is 0.2 percent.
Example 7:
electrolyzing at 18V by adopting a membrane electrolysis device with double groups of series-connected feeding and discharging materials and a structure shown as a formula E, and controlling the temperature of the electrolyzed materials to be 50-60 ℃;
adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butyl alcohol and solid KOH into a 10000ml storage barrel A, and pumping the saturated solution to an anode by using a circulating pump A for circulation; adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butanol and solid KOH into a 10000ml storage barrel B, and pumping to a cathode for circulation by using a circulating pump B; and (3) switching on an electrolysis power supply 18V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 32A, the temperature of the material slowly rises to 56 ℃ along with continuous electrolysis, the current does not rise any more, reaches the maximum 51A, the electrolysis is continued for 2.4h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a material storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 11.6 percent, and the KOH residue is 0.1 percent.
Example 8:
electrolyzing at an electrolytic voltage of 20V by adopting a membrane electrolysis device with a structure of formula E and two groups of series-connected feeding and discharging materials, and controlling the temperature of the electrolyzed materials to be 50-60 ℃;
adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butyl alcohol and solid KOH into a 10000ml storage barrel A, and pumping the saturated solution to an anode by using a circulating pump A for circulation; adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butanol and solid KOH into a 10000ml storage barrel B, and pumping to a cathode for circulation by using a circulating pump B; and (3) switching on an electrolysis power supply of 20V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 34A, the temperature of the material slowly rises to 58 ℃ along with continuous electrolysis, the current does not rise any more, reaches 56A with the maximum current, the electrolysis is continued for 2 hours, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 12.1 percent, and the KOH residue is 0.1 percent.
Example 9:
electrolyzing at 7V by adopting a membrane electrolysis device with double groups of parallel material inlet and outlet structures in a formula E, and controlling the temperature of the electrolyzed materials to be 45-50 ℃;
adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butyl alcohol and solid KOH into a 10000ml storage barrel A, and pumping the saturated solution to an anode by using a circulating pump A for circulation; adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butanol and solid KOH into a 10000ml storage barrel B, and pumping to a cathode for circulation by using a circulating pump B; and (3) switching on an electrolysis power supply 7V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 38A, the temperature of the material slowly rises to 50 ℃ along with continuous electrolysis, the current does not rise any more, reaches the maximum 59A, the electrolysis is continued for 3h, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and the storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 11.3 percent, and the KOH residue is 0.3 percent.
Example 10:
electrolyzing at 8V by adopting a double-group parallel connection feeding and discharging membrane electrolysis device with a structure shown as a formula E, and controlling the temperature of an electrolysis material to be 50-60 ℃;
adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butyl alcohol and solid KOH into a 10000ml storage barrel A, and pumping the saturated solution to an anode by using a circulating pump A for circulation; adding 7000g (35 ℃) of saturated solution of anhydrous tertiary butanol and solid KOH into a 10000ml storage barrel B, and pumping to a cathode for circulation by using a circulating pump B; and (3) switching on an electrolysis power supply 8V to perform constant-voltage membrane electrolysis, wherein the initial current reaches 42A, the temperature of the material slowly rises to 58 ℃ along with continuous electrolysis, the current does not rise any more, reaches 65A with the maximum current, the electrolysis is continued for 2 hours, the current is gradually reduced to 5-6A, when the current is reduced to be less than or equal to 3A, the membrane electrolysis is finished, and a storage barrel B obtains the tert-butyl alcohol solution of potassium tert-butoxide. The content of potassium tert-butoxide is detected by titration to be 11.6 percent, and the KOH residue is 0.1 percent.
Claims (6)
1. A process for continuously synthesizing potassium tert-butoxide by membrane electrolysis features that the saturated solution mixture of tert-butanol and potassium hydroxide is continuously dewatered on cathode and anode after the membrane electrolyzer is powered on, and the potassium tert-butoxide is continuously synthesized in cathode chamber.
2. The membrane electrolysis device according to claim 1, characterized in that the electrochemical reaction of formula a occurs by circulating a saturated mixed solution of solid KOH and t-butanol in the anode compartment:
3. the membrane electrolyzer of claim 1 characterized in that the electrochemical reaction of formula B occurs by circulating a saturated mixed solution of solid KOH and t-butanol in the cathode compartment:
4. the membrane electrolysis device according to claim 1, characterized essentially by the necessity of using dense cross-linked anionic membranes.
5. The membrane electrolysis device according to claim 1, characterized in that the distance between the cathode and the anode is ≤ 1 mm.
6. The method for continuously synthesizing potassium tert-butoxide by membrane electrolysis according to claim 1, which is mainly characterized in that the temperature of the membrane electrolysis material is controlled at 30-60 ℃.
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