CN103408396A - 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 of 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).
Chirality or racemization polyvalent alcohol can be used as the key intermediate in much medicine and agricultural chemicals building-up process, have important using value.For example, the 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).In anti-hiv drug An Ruinawei (Amprenavir) synthetic, use chirality (S)-BT (
Org.Biomol.Chem. 2004, 2,2061-2070).Korean Patent (KR.008793,
2010) disclose in a kind of important blood lipid-lowering medicine Rosuvastatin (Rosuvastatin) synthetic and also use (S)-BT as raw material.
Boric acid can and polyvalent alcohol in adjacent glycol and between glycol form complex compound (
Natural Medicine Chemistry, P90, second edition, People's Health Publisher), this class complex compound has good water-soluble usually, be difficult to by its with polyvalent alcohol simply extracting, the method such as distillation, crystallization separates.
In the process of synthetic these polyvalent alcohols, usually all use corresponding carboxylic acid or carboxylate methyl ester and ethyl ester to be raw material.Use the borane reagents 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 of boric acid and polyvalent alcohol (formula II) and residual boric acid.The existence of these boron-containing impurities all can affect the distilation of polyvalent alcohol, makes distillment dehydration, decomposition, charing, causes obtaining product or highly purified product.
(the S)-BT of take is example, Honda etc. (
Org.Biomol.Chem. 2004, 2,2061-2070) use sodium borohydride reduction L MALIC ACID dimethyl ester, after hydrolysis, 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 is how effectively to remove these boron-containing impurities.United States Patent (USP) (US6949684,
2005) and Korean Patent (KR.0092864,
2001) the middle disclosure, use bonding to have the boron ion exchange resin Amberlite IRA-743 that removes of glucosamine class 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 need to be used the resin more than 20 kilograms, and concentrate eluant need to distill a large amount of water, with high costs, be unfavorable for plant-scale preparation.
Pawlak. wait the method mentioned (
J.Org.Chem. 1987, 52,2896-2901) in the process of synthetic (S)-BT, need to use the column chromatography purifying, the method does not possess industrialized using value yet.
Therefore, be necessary to develop a kind of effective ways of 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, used two reactors as a combination; The first reactor 1 is furnished with the first agitator 3 and the first condenser 5, the second reactors 2 are furnished with the second agitator 4 and the second condenser 6 and packing tower 9; The 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; The 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; The first agitator 3 is placed in the first reactor 1, the second agitator 4 and is placed in the second reactor 2, and agitator is for the reactant of stirred reactor.
In the first reactor 1, the polyvalent alcohol of boron-containing impurities and low-carbon alcohol are uniformly mixed to 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 is cooling through the first condenser 5, by the first pipeline 7 flow into be added with the first reactor 1 in second reactor 2 of boric acid ester reagent of identical low-carbon alcohol and hydrolysis low-carbon alcohol, hydrolysis in the second reactor 2, generating borate stays in the second reactor 2, and low-carbon alcohol is regenerated, through packing tower 9 fractionation, enter into the second condenser 6, the 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 the principle of polyvalent alcohol boron-containing impurities method and reaction formula as shown in the formula:
Described method concrete steps are as follows:
(1). in reactor 1, add polyvalent alcohol and the low-carbon alcohol of boron-containing impurities;
(2). in reactor 2, add the aqueous solution of this low-carbon alcohol, hydrolysis low-carbon alcohol boric acid ester reagent;
(3). reactor is heated to the boiling point under this working pressure, the phlegma in reactor 1 is imported in reactor 2, and the phlegma in reactor 2 imports in reactor 1, this process is for removing the boron process;
(4). except after boron finishes, by the reaction solution adjust pH in reactor 1 to 6-8; Filter, concentration of reaction solution, rectification under vacuum, obtain 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 to the first reactor 1 of device, the volume weight of low-carbon alcohol and boron-containing impurities polyvalent alcohol (kg/L) is than from 1:1 to 100:1, preferably 3:1 is to 50:1, and more preferably 4:1 is to 20:1.Low-carbon alcohol comprises methyl alcohol, ethanol, propyl alcohol, Virahol etc., preferably methyl alcohol, ethanol, more preferably methyl alcohol.
The boric acid ester reagent of low-carbon alcohol and hydrolysis low-carbon alcohol is joined in the second reactor 2, and the boric acid ester reagent of hydrolysis low-carbon alcohol is included as the aqueous solution of the oxyhydroxide of the aqueous solution of alkali metal hydroxide, alkaline-earth metal, the aqueous solution of alkali-metal carbonate, the aqueous solution of alkali-metal supercarbonate.The aqueous solution of the aqueous solution of the oxyhydroxide of the aqueous solution of alkali metal hydroxide, alkaline-earth metal, alkali-metal carbonate preferably wherein.More preferably be the aqueous solution of oxyhydroxide of the aqueous solution, the alkaline-earth metal of alkali metal hydroxide.The aqueous solution of alkali metal hydroxide most preferably.In the second reactor 2, the massfraction (concentration) from 1% to 80% of the boric acid ester reagent of hydrolysis low-carbon alcohol, preferably from 10% to 70%, more preferably between 30%-40%.
After the first reactor 1 and the second reactor 2 add reagent, open heating and stir, setting certain pressure, its pressure is at 5atm between 0.09atm, and preferably 1.5atm is between 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 is imported in the second reactor 2 to the second, and the phlegma of reactor 2 imports in the first reactor 1.Like this, boron-containing impurities in the first reactor 1 will be directed in the second reactor 2 with the boric acid ester of low-carbon alcohol reaction generation low-carbon alcohol, with the boric acid ester reaction reagent in the second reactor 2, react, and low-carbon alcohol is regenerated and is turned 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.
Except after the boron end of processing, by the reaction solution adjust pH in the first reactor 1 between 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 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 the boric acid, boric acid and the polyvalent alcohol that dissociate.
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 raw material is cheap and easy to get, easy and simple to handle, and low-carbon alcohol can recycle, and is suitable for suitability for industrialized production.
The 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-the first agitator 3,4-the second agitator 4,5-the first condenser 5,6-the second condenser 6,7-the first phlegma pipeline 7,8-the second phlegma pipeline 8,9-packing tower.
Embodiment
What the following example be take a kind of polyvalent alcohol BT is example except the boron process, is in order to further illustrate the present invention, the scope that these embodiment 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 the 7.2kg sodium borohydride, under stirring, be cooled to-5 ℃, 24.8kg oxysuccinic acid dimethyl ester progressively is added dropwise in reactor, control temperature between-5 ℃ to 0 ℃.After adding the oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 18 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 3000L glassed steel reaction vessels 1 of boron device, then add 2000L methyl alcohol.In 1000L stainless steel cauldron 2 as shown in the figure, add 400L methyl alcohol, 120L water and 6 kilograms of sodium hydroxide.Under 4.5atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted 10 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 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。
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add the 7.2kg sodium borohydride, under stirring, be cooled to-5 ℃, 24.8kg oxysuccinic acid dimethyl ester progressively is added dropwise in reactor, control temperature between-5 ℃ to 0 ℃.After adding the oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 18 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 500L glassed steel reaction vessels 1 of boron device, then add 200L methyl alcohol.In 500L stainless steel cauldron 2 as shown in the figure, add 200L methyl alcohol, 60L water and 20 kilograms of sodium hydroxide.Under 2.5atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted 12 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 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 the 7.2kg sodium borohydride, under stirring, be cooled to-5 ℃, 24.8kg oxysuccinic acid dimethyl ester progressively is added dropwise in reactor, control temperature between-5 ℃ to 0 ℃.After adding the oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 18 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.In 200L stainless steel cauldron 2 as shown in the figure, add 48L methyl alcohol, 30L water and 30 kilograms of sodium hydroxide.Under 1.5atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted 13 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 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 the 7.2kg sodium borohydride, under stirring, be cooled to-5 ℃, 24.8kg oxysuccinic acid dimethyl ester progressively is added dropwise in reactor, control temperature between-5 ℃ to 0 ℃.After adding the oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 18 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.In 200L stainless steel cauldron 2 as shown in the figure, add 48L methyl alcohol, 30L water and 150 kilograms of sodium hydroxide.Under 1.0atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted 9 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 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 the 21kg oxysuccinic acid, add the tetrahydrofuran (THF) of 40L, under stirring, be cooled to-10 ℃, under nitrogen protection, progressively drip 50L (4M) borine tetrahydrofuran (THF) in reactor, control temperature between-5 ℃ to 0 ℃.After adding, temperature control stirring reaction 12 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 22 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.In 200L stainless steel cauldron 2 as shown in the figure, add 48L methyl alcohol, 40L water and 80 kilograms of potassium hydroxide.Under 0.6atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted about 10 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 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 the 7.2kg sodium borohydride, under stirring, be cooled to-5 ℃, 24.8kg oxysuccinic acid dimethyl ester progressively is added dropwise in reactor, control temperature between-5 ℃ to 0 ℃.After adding the oxysuccinic acid dimethyl ester, temperature control stirring reaction 12 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 18 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 200L glassed steel reaction vessels 1 in the boron device, then add 80L methyl alcohol.In 200L stainless steel cauldron 2 as shown in the figure, add 48L methyl alcohol, 25L water and 8 kilograms of sodium carbonate.Under 0.3atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted about 16 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 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 the 21kg oxysuccinic acid, add the tetrahydrofuran (THF) of 40L, under stirring, be cooled to-10 ℃, under nitrogen protection, progressively drip 50L (4M) borine tetrahydrofuran (THF) in reactor, control temperature between-5 ℃ to 0 ℃.After adding, temperature control stirring reaction 12 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 22 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the 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 and removes in the 200L glassed steel reaction vessels 1 of boron device, then add 80L methyl alcohol.In 200L stainless steel cauldron 2 as shown in the figure, add 48L methyl alcohol, 20L water and 10 kilograms of salt of wormwood.Under 0.1atm pressure, set 80 rev/mins of stirring velocitys, 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 enter reactor 1.Reacted about 14 hours, except boron finishes.Reaction solution in reactor 1 is derived, reclaim methyl alcohol.Concentrated solution is the crude product of BT.Crude product rectifying, obtain BT elaboration 13.6kg, yield 84%.
1H-NMR (D
2O): consistent with embodiment 1.
13C-NMR (D
2O): consistent with enforcement 1.
The comparative example
In the enamel reaction still of a 200L, add the tetrahydrofuran (THF) of 80L, then add the 7.2kg sodium borohydride, under stirring, be cooled to-5 ℃, 24.8kg oxysuccinic acid dimethyl ester progressively is added dropwise in reactor, control temperature between-5 ℃ to 0 ℃.After adding the oxysuccinic acid dimethyl ester, temperature control stirring reaction 10 hours between-5 ℃ to 0 ℃.Reaction finishes, and slowly adds 18 kilograms of 36% concentrated hydrochloric acids, has gas to emit, and separates out white precipitate.After adding concentrated hydrochloric acid, continue to stir 1 hour.Filter, filter cake washs with tetrahydrofuran (THF) (5L * 3), merging filtrate, and the reclaim under reduced pressure tetrahydrofuran (THF), filtrate is concentrated into viscous liquid, obtains the BT 24.5kg of boron-containing impurities.By the direct rectifying of this liquid, obtain the carbonized product of coking, do not obtain BT.
Claims (9)
1. a device of removing boron-containing impurities in polyvalent alcohol, is characterized in that using two reactors as a combination; The 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; The 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; The 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, the first agitator is placed in the first reactor, and the second agitator is placed in the second reactor.
2. a right to use requires 1 described device to remove the method for 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 heating, 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 is cooling through the first condenser, by the first phlegma pipeline flow into be added with the first reactor in second reactor of boric acid ester reagent of identical low-carbon alcohol and hydrolysis low-carbon alcohol, in the second reactor, be hydrolyzed, generate borate, stay in the second reactor, and low-carbon alcohol is regenerated, through the packing tower fractionation, enter into the second condenser, the low-carbon alcohol phlegma turns back to the first reactor by the second phlegma pipeline.
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 boric acid ester reagent;
(3). two reactors are heated to the boiling point under this working pressure, the phlegma in the first reactor is imported in the second reactor, and the phlegma in the second reactor import in the first reactor, this process is for removing the boron process;
(4). except after boron finishes, by the reaction solution adjust pH in the first reactor (1) to 6-8; Filter, concentration of reaction solution, rectification under vacuum, obtain corresponding highly purified polyvalent alcohol.
4. method according to claim 2, it is characterized in that: in the polyvalent alcohol and low-carbon alcohol of the described boron-containing impurities that joins the first reactor, the envelope-bulk to weight ratio of low-carbon alcohol and boron-containing impurities polyvalent alcohol is that 1:1 is 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: the reagent of the boric acid ester of the described hydrolysis low-carbon alcohol that joins the second reactor 2 is the aqueous solution, the aqueous solution of alkali-metal carbonate or the aqueous solution of alkali-metal supercarbonate of the oxyhydroxide of the aqueous solution of alkali metal hydroxide, alkaline-earth metal; The massfraction of the boric acid ester 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 that 5atm is to 0.09atm; Heating makes the first reactor and the second reactor all seethe with excitement, and the phlegma in the first reactor is imported in the second reactor, and the phlegma of the second reactor imports in the first reactor; Like this, boron-containing impurities in the first reactor will be directed in the second reactor with the boric acid ester of low-carbon alcohol reaction generation low-carbon alcohol, with the boric acid ester reaction reagent in the second reactor, react, and low-carbon alcohol is regenerated and is turned back in the first reactor, through repeatedly such circulation, low-carbon alcohol eliminates the boron in the boron-containing impurities in the first reactor.
7. method according to claim 2, it is characterized in that: the structural formula of described polyvalent alcohol is 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 the boric acid, boric acid and the polyvalent alcohol that dissociate.
9. method according to claim 2, it is characterized in that: described low-carbon alcohol is C
1-C
5Straight chain and branched-chain alcoho and their mixture.
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| CN103638887A (en) * | 2013-12-09 | 2014-03-19 | 福建华天裕科学技术发展有限公司 | Phthalocyanine compound synthesizer |
| CN107098328A (en) * | 2017-05-05 | 2017-08-29 | 石兵兵 | A kind of low boron carbonaceous reducing agent and preparation method thereof |
| CN111377889A (en) * | 2018-12-27 | 2020-07-07 | 江苏联昇化学有限公司 | Production process of 3-hydroxytetrahydrofuran by combining pipeline reaction |
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2013
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638887A (en) * | 2013-12-09 | 2014-03-19 | 福建华天裕科学技术发展有限公司 | Phthalocyanine compound synthesizer |
| CN107098328A (en) * | 2017-05-05 | 2017-08-29 | 石兵兵 | A kind of low boron carbonaceous reducing agent and preparation method thereof |
| CN111377889A (en) * | 2018-12-27 | 2020-07-07 | 江苏联昇化学有限公司 | Production process of 3-hydroxytetrahydrofuran by combining pipeline reaction |
| 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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| CN103408396B (en) | 2015-01-07 |
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