CN103408396B - Device and method for removing boron-containing impurities in polyalcohol - Google Patents
Device and method for removing boron-containing impurities in polyalcohol Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical engineering, and particularly relates to a device and method for removing boron-containing impurities in polyalcohol. The device uses two reactors as a combination, wherein a first reactor is provided with a first stirrer and a first condenser, and the second reactor is provided with a second stirrer, a second condenser and a packing tower; the first reactor is connected with the first condenser, the first condenser is connected with a first condensate pipeline, and the first condensate pipeline leads into the second reactor; and the second reactor is connected with the packing tower, the packing tower is connected with the second condenser, the second condenser is connected with a second condensate pipeline, the second condensate pipeline leads into the first reactor, the first stirrer is arranged in the first reactor, and the second stirrer is arranged in the second reactor. The use of the device can effectively remove multiple boron-containing impurities in the polyalcohol production process, thus obtaining high-purity polyalcohol.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of device and method removing boron-containing impurities in polyvalent alcohol.
Background technology
The present invention relates to boron-containing impurities device and method in a kind of removal chirality or achiral polyvalent alcohol (formula I).
?（Ⅰ）
Chirality or racemization polyvalent alcohol as the key intermediate in much medicine and pesticide synthesis process, important using value can be had.Such as, racemization BT is broad-spectrum solvent and synthetic intermediate, can be used for composite rocket propellant BT triol trinitrate.2-methylol-BDO is the important intermediate of synthetic pesticide MTI-446 (Dinotefuran).Use in the synthesis of anti-hiv drug An Ruinawei (Amprenavir) chirality (S)-BT (
org.Biomol.Chem. 2004, 2,2061-2070).Korean Patent (KR.008793,
2010) disclose in a kind of synthesis of important blood lipid-lowering medicine Rosuvastatin (Rosuvastatin) and also use (S)-BT as raw material.
Boric acid can and polyvalent alcohol in vicinal diamines and glycol formed complex compound (
natural Medicine Chemistry, P90, the second edition, People's Health Publisher), this kind of complex compound has good water-soluble usually, be difficult to by its with polyvalent alcohol simply to extract, to distill, the method such as crystallization is separated.
In the process of these polyvalent alcohols of synthesis, usually all use corresponding carboxylic acid or carboxylate methyl ester and ethyl ester for raw material.Use the borane reagent such as borine or sodium borohydride to be reductive agent, no matter use which kind of borane reagent, reduzate, after hydrolysis, all can not directly obtain corresponding polyvalent alcohol, but obtain the polyvalent alcohol of boron-containing impurities.These boron-containing impurities comprise, the complex compound (formula II) of boric acid and polyvalent alcohol and residual boric acid.The existence of these boron-containing impurities all can affect the distilation of polyvalent alcohol, distillment is dewatered, decompose, carbonizes, cause obtaining product or highly purified product.
?（Ⅱ）
For (S)-BT, Honda etc. (
org.Biomol.Chem. 2004, 2,2061-2070) and use sodium borohydride reduction L MALIC ACID dimethyl ester, after hydrolyzing, even the existence of very small amount of residual boric acid or boric acid complex all can cause the failure of distilation steps.
Therefore, use corresponding carboxylic acid or the carboxylicesters of borane reagent reduction polyvalent alcohol, the decisive step of its purifying how effectively to remove these boron-containing impurities.United States Patent (USP) (US6949684,
2005) and Korean Patent (KR.0092864,
2001) middle disclosure, the boron ion exchange resin Amberlite IRA-743 that removes being bonded with aminoglucose carbohydrate is used to remove residual boric acid and boric acid complex, the method needs to use a large amount of resins in industrialization, produce per kilogram (S)-1,2,4-trihydroxybutane needs the resin using more than 20 kilograms, and concentrate eluant needs to distill a large amount of water, with high costs, be unfavorable for plant-scale preparation.
The method Pawlak. etc. mentioned (
j.Org.Chem. 1987, 52,2896-2901) need to use purification by column chromatography in the process of synthesis (S)-BT, the method does not possess industrialized using value yet.
Therefore, be necessary to develop a kind of effective ways removing boron-containing impurities in polyvalent alcohol.
Summary of the invention
The object of the present invention is to provide that a kind of cost is lower, the device and method of boron-containing impurities in the removal polyvalent alcohol that is suitable for industrial applications.
In the removal polyvalent alcohol that the present invention proposes, the device of boron-containing impurities, uses two reactors as a combination; First reactor 1 is furnished with the first agitator 3 and the first condenser 5, second reactor 2 and is furnished with the second agitator 4 and the second condenser 6 and packing tower 9; First reactor 1 is connected with the first condenser 5, and the first condenser 5 is connected with the first phlegma pipeline 7, and the first phlegma pipeline 7 passes in the second reactor 2; Second reactor 2 is connected with packing tower 9, and packing tower 9 is connected with the second condenser 6, and the second condenser 6 is connected with the second phlegma pipeline 8, and the second phlegma pipeline 8 passes in the first reactor 1; First agitator 3 is placed in the first reactor 1, second agitator 4 and is placed in the second reactor 2, and agitator is used for the reactant in stirred reactor.
In the first reactor 1, the polyvalent alcohol of boron-containing impurities and low-carbon alcohol are uniformly mixed heating, polyvalent alcohol and the low-carbon alcohol of boron-containing impurities react, dissociateing polyvalent alcohol stays in the first reactor 1, reaction produces the azeotrope of low-carbon alcohol boric acid ester and low-carbon alcohol formation simultaneously, this azeotrope cools through the first condenser 5, the second reactor 2 of the boronate reagent being added with the low-carbon alcohol identical with the first reactor 1 and being hydrolyzed low-carbon alcohol is flow into by the first pipeline 7, be hydrolyzed in the second reactor 2, generating borate stays in the second reactor 2, and low-carbon alcohol is regenerated, the second condenser 6 is entered into through packing tower 9 fractionation, low-carbon alcohol phlegma turns back to the first reactor 1 by second pipe 8.
The present invention can remove the boron-containing impurities in polyvalent alcohol effectively, obtains highly purified polyvalent alcohol, and low-carbon alcohol can reprocessing cycle, greatly reduces the usage quantity of low-carbon alcohol.This invention remove polyvalent alcohol boron-containing impurities side ratio juris and reaction formula as shown in the formula:
Described method concrete steps are as follows:
(1). add polyvalent alcohol and the low-carbon alcohol of boron-containing impurities in reactor 1;
(2). in reactor 2, add the aqueous solution of this low-carbon alcohol, hydrolysis low-carbon alcohol boronate reagent;
(3). reactor is heated to the boiling point under this working pressure, imported in reactor 2 by the phlegma in reactor 1, and the phlegma in reactor 2 imports in reactor 1, this process is for removing boron process;
(4). after boron terminates, by the reaction solution adjust pH in reactor 1 to 6-8; Filter, concentration of reaction solution, rectification under vacuum, obtains corresponding highly purified polyvalent alcohol.
In described method, use described except boron device (Figure of description), the polyvalent alcohol of boron-containing impurities and low-carbon alcohol are joined the first reactor 1 of device, the volume weight (kg/L) of low-carbon alcohol and boron-containing impurities polyvalent alcohol is than from 1:1 to 100:1, preferably 3:1 to 50:1, more preferably 4:1 to 20:1.Low-carbon alcohol comprises methyl alcohol, ethanol, propyl alcohol, Virahol etc., preferably methyl alcohol, ethanol, more preferably methyl alcohol.
Join in the second reactor 2 by the boronate reagent of low-carbon alcohol and hydrolysis low-carbon alcohol, the boronate reagent of hydrolysis low-carbon alcohol comprises the aqueous solution of the aqueous solution for the aqueous solution of the aqueous solution of alkali metal hydroxide, the oxyhydroxide of alkaline-earth metal, alkali-metal carbonate, alkali-metal supercarbonate.The wherein preferably aqueous solution of the aqueous solution of alkali metal hydroxide, the oxyhydroxide of alkaline-earth metal, the aqueous solution of alkali-metal carbonate.More preferably be the aqueous solution of the aqueous solution of alkali metal hydroxide, the oxyhydroxide of alkaline-earth metal.The most preferably aqueous solution of alkali metal hydroxide.In the second reactor 2, the massfraction (concentration) of the boronate reagent of hydrolysis low-carbon alcohol between 1% to 80%, preferably between 10% to 70%, more preferably between 30%-40%.
After first reactor 1 and the second reactor 2 add reagent, open heating and stir, set certain pressure, its pressure between 5atm to 0.09atm, preferably between 1.5atm to 0.05atm.Heating makes the first reactor 1 and the second reactor 2 all seethe with excitement, and the phlegma in the first reactor 1 to be imported in the second reactor 2 the second, the phlegma of reactor 2 imports in the first reactor 1.Like this, boric acid ester with low-carbon alcohol reaction generation low-carbon alcohol is directed in the second reactor 2 by the boron-containing impurities in the first reactor 1, react with the boric acid ester reaction reagent in the second reactor 2, and low-carbon alcohol is able to regeneration turns back in the first reactor 1, through repeatedly such circulation, use the low-carbon alcohol of small amount just the boron in the boron-containing impurities in the first reactor 1 can be eliminated.
After boron end of processing, between the reaction solution adjust pH in the first reactor 1 to 6-8.Concentrated, rectification under vacuum can obtain highly purified corresponding polyvalent alcohol.
In the present invention, the structural formula of described polyvalent alcohol is for shown in formula I
（Ⅰ）
Wherein, R
1for hydrogen, methylol, C
1-C
3alkyl; R
2for hydrogen, hydroxyl, C
1-C
3alkyl; N is 0-1 carbon atom; Described polyvalent alcohol is chirality or achiral.
In the present invention, described boron-containing impurities is the complex compound of free boric acid, boric acid and polyvalent alcohol.
In the present invention, described low-carbon alcohol is C
1-C
5straight chain and branched-chain alcoho and their mixture.
In the present invention, the boiling of low-carbon alcohol is carried out under middle pressure, normal pressure or decompression, and pressure is from 5atm to 0.09atm.
The advantage of the inventive method is that cheaper starting materials is easy to get, easy and simple to handle, and low-carbon alcohol can recycle, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is production equipment structural representation of the present invention.
Number in the figure: 1-first reactor 1,2 second-reactor 2,3-first agitator 3,4-second agitator 4,5-first condenser 5,6-second condenser 6,7-first phlegma pipeline 7,8-second phlegma pipeline 8,9-packing tower.
Embodiment
The following example for a kind of polyvalent alcohol BT except boron process, be to further illustrate the present invention, the scope that these embodiments do not limit the present invention in any way.
Embodiment 1
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add 7.2kg sodium borohydride, under stirring, be cooled to-5 DEG C, be progressively added dropwise in reactor by 24.8kg oxysuccinic acid dimethyl ester, control temperature is between-5 DEG C to 0 DEG C.After adding oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 18 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 24.5kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 3000L glassed steel reaction vessels 1 of boron device, then add 2000L methyl alcohol.400L methyl alcohol is added, 120L water and 6 kilograms of sodium hydroxide in 1000L stainless steel cauldron 2 as shown in the figure.Under 4.5atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 10 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 12.6kg, yield 78%.
1H-NMR(D
2O):1.57(1H,m),1.66(1H,m),3.40(1H,m),3.51(1H,m),3.63(2H,m),3.73(1H,m)ppm。
13C-NMR?(D
2O):?34.74,?58.29,?65.54,?68.85?ppm。
Embodiment 2
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add 7.2kg sodium borohydride, under stirring, be cooled to-5 DEG C, be progressively added dropwise in reactor by 24.8kg oxysuccinic acid dimethyl ester, control temperature is between-5 DEG C to 0 DEG C.After adding oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 18 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 25.8kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 500L glassed steel reaction vessels 1 of boron device, then add 200L methyl alcohol.200L methyl alcohol is added, 60L water and 20 kilograms of sodium hydroxide in 500L stainless steel cauldron 2 as shown in the figure.Under 2.5atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 12 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 12.9kg, yield 80%.
1h-NMR (D
2o): consistent with embodiment 1.
13c-NMR (D
2o): consistent with embodiment 1.
Embodiment 3
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add 7.2kg sodium borohydride, under stirring, be cooled to-5 DEG C, be progressively added dropwise in reactor by 24.8kg oxysuccinic acid dimethyl ester, control temperature is between-5 DEG C to 0 DEG C.After adding oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 18 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 25.3kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.48L methyl alcohol is added, 30L water and 30 kilograms of sodium hydroxide in 200L stainless steel cauldron 2 as shown in the figure.Under 1.5atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 13 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 12.2kg, yield 75%.
1h-NMR (D
2o): consistent with embodiment 1.
13c-NMR (D
2o): consistent with embodiment 1.
Embodiment 4
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add 7.2kg sodium borohydride, under stirring, be cooled to-5 DEG C, be progressively added dropwise in reactor by 24.8kg oxysuccinic acid dimethyl ester, control temperature is between-5 DEG C to 0 DEG C.After adding oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 18 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 25.5kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.48L methyl alcohol is added, 30L water and 150 kilograms of sodium hydroxide in 200L stainless steel cauldron 2 as shown in the figure.Under 1.0atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 9 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 14.3kg, yield 89%.
1h-NMR (D
2o): consistent with embodiment 1.
13c-NMR (D
2o): consistent with embodiment 1.
Embodiment 5
In the enamel reaction still of a 200L, add 21kg oxysuccinic acid, add the tetrahydrofuran (THF) of 40L; under stirring, be cooled to-10 DEG C, under nitrogen protection; progressively drip 50L (4M) borine tetrahydrofuran (THF) in reactor, control temperature is between-5 DEG C to 0 DEG C.After adding, temperature control stirring reaction 12 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 22 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 35.6kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.48L methyl alcohol is added, 40L water and 80 kilograms of potassium hydroxide in 200L stainless steel cauldron 2 as shown in the figure.Under 0.6atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 10 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 15.1kg, yield 94%.
1h-NMR (D
2o): consistent with embodiment 1.
13c-NMR (D
2o): consistent with embodiment 1.
Embodiment 6
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add 7.2kg sodium borohydride, under stirring, be cooled to-5 DEG C, be progressively added dropwise in reactor by 24.8kg oxysuccinic acid dimethyl ester, control temperature is between-5 DEG C to 0 DEG C.After adding oxysuccinic acid dimethyl ester, temperature control stirring reaction 12 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 18 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 29.8kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 200L glassed steel reaction vessels 1 in boron device, then add 80L methyl alcohol.48L methyl alcohol is added, 25L water and 8 kilograms of sodium carbonate in 200L stainless steel cauldron 2 as shown in the figure.Under 0.3atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 16 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 11.0kg, yield 67%.
1h-NMR (D
2o): consistent with embodiment 1.
13c-NMR (D
2o): consistent with embodiment 1.
Embodiment 7
In the enamel reaction still of a 200L, add 21kg oxysuccinic acid, add the tetrahydrofuran (THF) of 40L; under stirring, be cooled to-10 DEG C, under nitrogen protection; progressively drip 50L (4M) borine tetrahydrofuran (THF) in reactor, control temperature is between-5 DEG C to 0 DEG C.After adding, temperature control stirring reaction 12 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 22 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 37.2kg of boron-containing impurities.The mixture of this boron-containing impurities is joined as shown in drawings except in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.48L methyl alcohol is added, 20L water and 10 kilograms of salt of wormwood in 200L stainless steel cauldron 2 as shown in the figure.Under 0.1atm pressure, setting stirring velocity 80 revs/min, reacting by heating still 1 and reactor 2 to boiling, make the phlegma of reactor 1 enter reactor 2, and the phlegma of reactor 2 enters reactor 1.React 14 hours, except boron terminates.Reaction solution in reactor 1 is derived, reclaims methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtains BT fine work 13.6kg, yield 84%.
1h-NMR (D
2o): consistent with embodiment 1.
13c-NMR (D
2o): consistent with enforcement 1.
Comparative example
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add 7.2kg sodium borohydride, under stirring, be cooled to-5 DEG C, be progressively added dropwise in reactor by 24.8kg oxysuccinic acid dimethyl ester, control temperature is between-5 DEG C to 0 DEG C.After adding oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 DEG C to 0 DEG C.Reaction terminates, and slowly adds the concentrated hydrochloric acid 18 kilograms of 36%, has gas to release, and separates out white precipitate.Stirring is continued 1 hour after adding concentrated hydrochloric acid.Filter, filter cake tetrahydrofuran (THF) (5L × 3) washing, merging filtrate, reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 24.5kg of boron-containing impurities.By direct for this liquid rectifying, obtain the carbonized product of coking, do not obtain BT.
Claims (8)
1. remove a device for boron-containing impurities in polyvalent alcohol, it is characterized in that use two reactors are as a combination; First reactor is furnished with the first agitator and the first condenser, and the second reactor is furnished with the second agitator and the second condenser and packing tower; First reactor is connected with the first condenser, and the first condenser is connected with the first phlegma pipeline, and the first phlegma pipeline passes in the second reactor; Second reactor is connected with packing tower, packing tower is connected with the second condenser, and the second condenser is connected with the second phlegma pipeline, and the second phlegma pipeline passes in the first reactor, first agitator is placed in the first reactor, and the second agitator is placed in the second reactor.
2. the method using device described in claim 1 to remove boron-containing impurities in polyvalent alcohol, it is characterized in that concrete steps are: the polyvalent alcohol of boron-containing impurities and low-carbon alcohol are added in the first reactor, be uniformly mixed, and heat, polyvalent alcohol and the low-carbon alcohol of boron-containing impurities react, dissociateing polyvalent alcohol stays in the first reactor, reaction produces the azeotrope of low-carbon alcohol boric acid ester and low-carbon alcohol formation simultaneously, this azeotrope cools through the first condenser, the second reactor of the boronate reagent being added with the low-carbon alcohol identical with the first reactor and being hydrolyzed low-carbon alcohol is flow into by the first phlegma pipeline, be hydrolyzed in the second reactor, generate borate, stay in the second reactor, and low-carbon alcohol is regenerated, the second condenser is entered into through packing tower fractionation, low-carbon alcohol phlegma turns back to the first reactor by the second phlegma pipeline,
Described low-carbon alcohol is C
1-C
5straight chain and branched-chain alcoho and their mixture.
3. method according to claim 2, is characterized in that concrete operation step is as follows:
(1). in the first reactor, add polyvalent alcohol and the low-carbon alcohol of boron-containing impurities;
(2). in the second reactor, add the aqueous solution of this low-carbon alcohol, hydrolysis low-carbon alcohol boronate reagent;
(3). two reactors are heated to the boiling point under this working pressure, imported in the second reactor by the phlegma in the first reactor, and the phlegma in the second reactor import in the first reactor, this process is for removing boron process;
(4). after boron terminates, by the reaction solution adjust pH in the first reactor to 6-8; Filter, concentration of reaction solution, rectification under vacuum, obtains corresponding highly purified polyvalent alcohol.
4. method according to claim 2, it is characterized in that: described in join the boron-containing impurities of the first reactor polyvalent alcohol and low-carbon alcohol in, the envelope-bulk to weight ratio of low-carbon alcohol and boron-containing impurities polyvalent alcohol is 1:1 to 100:1(kg/L), described low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol or Virahol.
5. method according to claim 2, is characterized in that: described in join the boric acid ester of the hydrolysis low-carbon alcohol of the second reactor reagent be the aqueous solution of the aqueous solution of alkali metal hydroxide, the aqueous solution of the oxyhydroxide of alkaline-earth metal, the aqueous solution of alkali-metal carbonate or alkali-metal supercarbonate; The massfraction of the boronate reagent of hydrolysis low-carbon alcohol is 1% to 80%.
6. method according to claim 2, is characterized in that: after the first reactor and the second reactor add reactant, start heating and stir, and setting pressure is 5atm to 0.09atm; Heating makes the first reactor and the second reactor all seethe with excitement, and imported to by the phlegma in the first reactor in the second reactor, the phlegma of the second reactor imports in the first reactor; Like this, boric acid ester with low-carbon alcohol reaction generation low-carbon alcohol is directed in the second reactor by the boron-containing impurities in the first reactor, react with the boric acid ester reaction reagent in the second reactor, and low-carbon alcohol is able to regeneration turns back in the first reactor, through repeatedly such circulation, the boron in the boron-containing impurities in the first reactor eliminates by low-carbon alcohol.
7. method according to claim 2, is characterized in that: the structural formula of described polyvalent alcohol is for shown in formula I
（Ⅰ）
Wherein, R
1for hydrogen, methylol, C
1-C
3alkyl; R
2for hydrogen, hydroxyl, C
1-C
3alkyl; N is 0-1 carbon atom; Described polyvalent alcohol is chirality or achiral.
8. method according to claim 2, is characterized in that: described boron-containing impurities is the complex compound of free boric acid, boric acid and polyvalent alcohol.
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| CN107098328A (en) * | 2017-05-05 | 2017-08-29 | 石兵兵 | A kind of low boron carbonaceous reducing agent and preparation method thereof |
| CN111377889B (en) * | 2018-12-27 | 2023-07-18 | 江苏联昇化学有限公司 | Production process of 3-hydroxytetrahydrofuran combined with pipeline reaction |
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| 水中硼的去除方法研究进展;侯若昕等;《工业水处理》;20120331;第32卷(第3期);14-18 * |
| 沉淀法提取卤水中硼的研究进展;张珍等;《内蒙古石油化工》;20081231(第1期);7-9 * |
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