CN100465157C - Preparation process for synthesizing AGA using loop reactor - Google Patents
Preparation process for synthesizing AGA using loop reactor Download PDFInfo
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- CN100465157C CN100465157C CNB2006101021496A CN200610102149A CN100465157C CN 100465157 C CN100465157 C CN 100465157C CN B2006101021496 A CNB2006101021496 A CN B2006101021496A CN 200610102149 A CN200610102149 A CN 200610102149A CN 100465157 C CN100465157 C CN 100465157C
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Abstract
The invention discloses a preparing method of glucose amide through circuit reactor, which is characterized by the following: adding anhydrous glucose in the solvent; aerating methylamine gas to react until transparent solution; adding catalyst in the transparent solution; entering in the circuit reactor to hydrogenate; crystallizing under 0-10 deg.c to obtain the glucosamine; adding glucosamine and fatty acid methyl ester in the solvent; heating to 60-70 deg.c under catalytic condition; amidating under normal pressure for 2-6h; heating; extracting into vacuum; evaporating solvent; heating to 160 deg.c at the most; obtaining the product.
Description
Technical field
The invention belongs to class nonionogenic tenside and preparation method thereof, the preparation method of specifically relevant glucamide, at first react generation glucose methylamine with dextrose anhydrous and Monomethylamine in loop reactor, the reaction of glucose methylamine and fatty acid methyl ester generates glucamide then.
Background technology
Glucamide is a kind of glycosyl surfactant active of nontoxic non-stimulated, readily biodegradable, the raw materials used renewable resources that comes from, to environment and biological safety height, has good surfactivity, the performance gentleness, be nonionogenic tenside, and can adjust every performance of product by fatty acid carbons chain length, substituting group and glycosyl with certain anionic nature.Have been widely used as cosurfactant, be applied in washing powder, liquid washing agent, detergent for washing dishware with hand, multi-usage clean-out system and the individual's protection articles for use.
At first use reducing sugar such as glucose and C
1-4Alkylamine or hydroxyalkyl amine are reacted in solvent or water and are generated adducts, and hydrogenation reaction generates the glucose methylamine then, and the hydrogenation catalyst that can be used for this reaction is more, as Ni, Pt, Pd, Fe, Cu etc., catalyzer commonly used is a nickel, and nickel both can be particle nickel, also can be nickel-loaded or Raney's nickel.Use such as US5334764, WO9208687 be nickel-loaded, in organic alcohol solvent and aqueous systems, reaction is carried out under 50 ℃～120 ℃, 0.7MPa～8MPa usually in the high pressure stirring tank.
The synthetic of glucamide is an amidate action, fatty acid ester commonly used and the reaction of glucose methylamine, and catalysis is carried out under basic catalyst, and basic catalyst commonly used is sodium methylate, yellow soda ash or salt of wormwood.Be reflected under two kinds of systems and carry out: (1) US5194639, US5652098, WO9633967 etc. are solvent-laden reaction system, because the fusing point of glucose methylamine is higher, for the dissolving that helps the glucose methylamine and with the mixing of fatty acid ester, in reaction system, add hydroxyl organic solvent usually, as methyl alcohol, ethanol, propyl alcohol and propylene glycol etc., the most frequently used is the mixture of methyl alcohol and propylene glycol or methyl alcohol and propylene glycol.When using methyl alcohol, reaction is easy to reclaim methyl alcohol from reaction product after finishing, and propylene glycol is stayed in the reaction product, can not produce any negative impact to product as washing composition.(2) WO9507256, US5380891 are solvent-free system: under solvent-free condition, be warmed up to 130 ℃～140 ℃ usually and make the fusing of glucose methylamine, form liquid/liquid mixture with fatty acid ester.But because the polarity difference of glucose methylamine and fatty acid ester is bigger, both do not dissolve each other, and need to add consisting of phase-transferring agent or emulsifying agent, to promote the mixing of two kinds of liquid, the consisting of phase-transferring agent or the emulsifying agent that use are nonionogenic tensides, as fatty alcohol-polyoxyethylene ether, and APG and glucamide.
Summary of the invention
The preparation method who the purpose of this invention is to provide glucamide at first reacts generation glucose methylamine with dextrose anhydrous and Monomethylamine in loop reactor, the reaction of glucose methylamine and fatty acid methyl ester generates glucamide then.
The present invention uses loop reactor to prepare the glucose methylamine first, and the preparation of glucose methylamine is typical gas-liquid-solid phase reaction.The reaction of this class relates to the mass transfer process between the gas-liquid-solid three-phase, for the mass-transfer efficiency of reactor higher requirement is arranged.The loop reactor of being made up of reaction kettle body, venturi-type eductors, external heat exchanger and recycle pump has tangible mass transfer advantage than traditional stirred-tank reactor, can make liquid mist change into micron order or nano level small droplets via venturi-type eductors, the contact area of increase and gas and solid catalyst, thereby compare with stirring tank and can increase mass-transfer efficiency greatly.
The structural formula of glucamide of the present invention is as follows:
N=8-22 wherein
Synthetic method can be divided into three the step carry out the following expression of reaction equation:
The first step: the aldehyde radical of methylamine and glucose carries out addition reaction and generates the glucose imines:
Second step: the glucose imines carries out hydrogenation reaction and generates the glucose methylamine:
The 3rd step: glucose methylamine and fatty acid methyl ester carry out amidate action and generate glucamide:
The concrete preparation process of the present invention comprises the steps:
(1) at first dextrose anhydrous is under agitation added in the solvent, making the weight concentration of glucose in solvent is 10～80%, is preferably 40～50% (wt), feed Monomethylamine gas, temperature of reaction is at 20-50 ℃, and normal pressure is reaction 1-3h down, transparent until solution, charge into N during reaction in the reactor
2, the mol ratio of glucose and Monomethylamine is 1.0:1.0～3.0, preferably 1.0:1.2-1.5;
Aforesaid solvent is the solvent that contains hydroxyl, as: methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, ethylene glycol, propylene glycol etc. are preferably methyl alcohol and ethanol.
(2) clear solution that makes in (1) step is added catalyzer, the catalyzer add-on is 2～20% (wt) of glucose quality, enters then in the loop reactor, uses N
2H is used in displacement again
2After the displacement, there is hydrogen to exist down, react 1-2h down at 50 ℃～60 ℃, 70 ℃-80 ℃ are reacted 1-3h down, and reaction pressure 0.3MPa～6.0MPa is preferably in and carries out hydrogenation reaction under 0.6MPa～1.0MPa, filter out catalyzer, carry out crystallization under 0-10 ℃ then, obtain glucose methylamine white crystals, carry out drying;
What aforesaid catalyzer was commonly used is Raney's nickel or nickel-loaded;
(3) glucose methylamine that (2) step is made and fatty acid methyl ester are that 1.0:1.0～1.10 add in the solvent by the mol ratio of glucose methylamine and fatty acid methyl ester, and the amount of solvent is 20～60wt% of glucose methylamine and fatty acid methyl ester weight sum, feeds N
2With the protection color and luster, under the catalyzer condition, the add-on of catalyzer is 1-5wt% of glucose methylamine; rise to 60-70 ℃, normal pressure carries out amidate action, behind 2-6h; intensification vacuumizes and steams solvent, and top temperature rises to 160 ℃, obtains purpose product glucamide.
Aforesaid solvent is generally the solvent that contains hydroxyl, as: methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, ethylene glycol or propylene glycol etc., be preferably methyl alcohol or propylene glycol,
Aforesaid catalyzer is a basic catalyst, as: sodium methylate, potassium methylate or yellow soda ash etc.
Aforesaid fatty acid methyl ester is coconut oil methyl ester or Laurate methyl.
Glucamide have to the skin surface action temperature and; biological degradation rapidly and safety; nontoxic non-stimulated; strong detergency; foam enriches fine and smooth and stablizes; premium properties that can be unique with various surfactant compounds and good synergistic function etc.; have been widely used as cosurfactant; can be used for washing composition and cosmetic industry; foodstuffs industry; fields such as agricultural and textile industry; now be widely used in washing powder; liquid washing agent; detergent for washing dishware with hand; in multi-usage clean-out system and the individual's protection articles for use, become the product that a class has development potentiality.
The present invention compared with prior art has following advantage:
1. preparation glucose methylamine uses loop reactor, can improve the mass-transfer efficiency of phase reaction, shortens the reaction times, reduces reaction pressure.The present invention uses loop reactor, compares mass-transfer efficiency with stirred-tank reactor and obviously improves, and the reaction times can foreshorten to 3-5h, and reaction pressure can be reduced to below the 1.0MPa.
2. raw materials of glucose and fatty acid methyl ester meet the requirement of green, environmental protection and Sustainable development from renewable resources.
3. glucamide has good performance and purposes widely.
Embodiment:
Embodiment 1:
In tank reactor, add the 60kg alcohol solvent, under agitation add the 25kg dextrose anhydrous, feed 5.8kg Monomethylamine gas, 30 ℃ of reaction 2h are transparent to solution.
Above-mentioned clear solution is added the 2.5kg Raney's nickel catalyst, enter then in the 200L loop reactor, use N
2H is used in displacement again
2Displacement has hydrogen to exist down, and pressure remains on 0.9MPa, and the ON cycle pump is warming up to 55 ℃ of reaction 2h down, continues to be warming up to 75 ℃ of reaction 1h.Filter out catalyzer, carry out crystallization under 0 ℃ then, filter out solvent, obtain glucose methylamine white crystals, carry out drying.
In tank reactor, add methyl alcohol 60kg, open and stir, add above-mentioned glucose methylamine 19kg that obtains and Laurate methyl 21kg, add 50% sodium methylate 0.5kg, rise to 60 ℃, after normal pressure carries out amidate action 6h, feed N
2With the protection color and luster, heating up to vacuumize steams solvent, and top temperature rises to 160 ℃.Cooling obtains glucamide.
Embodiment 2:
In tank reactor, add the 58kg methanol solvate, under agitation add the 25kg dextrose anhydrous, feed 6kg Monomethylamine gas, feed N
2With the protection color and luster, 50 ℃ of certain 1.5h of reaction are transparent to solution.
Above-mentioned clear solution is added the 1kg Raney's nickel catalyst, enter then in the 200L loop reactor, use N
2H is used in displacement again
2Displacement has hydrogen to exist down, and pressure remains on 0.6MPa, and the ON cycle pump is warming up to 50 ℃ of reaction 2h down, continues to be warming up to 80 ℃ of reaction 2h.Cooling filters out catalyzer, carries out crystallization under 5 ℃ then, filters out solvent, obtains glucose methylamine white crystals, carries out drying.
In tank reactor, add methyl alcohol 50kg, open and stir, add above-mentioned glucose methylamine 19kg that obtains and coconut oil methyl ester 21kg, add 5% potassium methylate 8kg, rise to 65 ℃, after normal pressure carries out amidate action 2h, feed N
2With the protection color and luster, heating up to vacuumize steams solvent, and top temperature rises to 140 ℃.The cooling blowing obtains glucamide.
Embodiment 3:
In tank reactor, add the 50kg alcohol solvent, under agitation add the 25kg dextrose anhydrous, feed 4.5kg Monomethylamine gas, 25 ℃ of reaction 3h are transparent to solution.
Above-mentioned clear solution is added the 1.5kg Raney's nickel catalyst, enter then in the 200L loop reactor, use N
2H is used in displacement again
2Displacement has hydrogen to exist down, and pressure remains on 1.0MPa, and the ON cycle pump is warming up to 55 ℃ of reaction 1h down, continues to be warming up to 70 ℃ of reaction 2h.Filter out catalyzer, carry out crystallization under 10 ℃ then, filter out solvent, obtain glucose methylamine white crystals, carry out drying.
Add methyl alcohol 50kg in tank reactor, propylene glycol 5kg opens and stirs, and adds above-mentioned glucose methylamine 19kg that obtains and Laurate methyl 21kg, adds yellow soda ash 1kg, rises to 70 ℃, after normal pressure carries out amidate action 6h, feeds N
2With the protection color and luster, heating up to vacuumize steams solvent, and top temperature rises to 160 ℃.Cooling obtains glucamide.
Embodiment 4:
In tank reactor, add the 40kg alcohol solvent, under agitation add the 25kg dextrose anhydrous, feed 5kg Monomethylamine gas, 35 ℃ of reaction 2h are transparent to solution.
Above-mentioned clear solution is added the 2kg Raney's nickel catalyst, enter then in the 200L loop reactor, use N
2H is used in displacement again
2Displacement has hydrogen to exist down, and pressure remains on 0.8MPa, and the ON cycle pump is warming up to 60 ℃ of reaction 2h down, continues to be warming up to 75 ℃ of reaction 1h.Cooling filters out catalyzer, carries out crystallization under 0 ℃ then, filters out solvent, obtains glucose methylamine white crystals, carries out drying.
In tank reactor, add methyl alcohol 60kg, open and stir, add above-mentioned glucose methylamine 19kg that obtains and Laurate methyl 21kg, add 50% sodium methylate 1kg, rise to 63 ℃, after normal pressure carries out amidate action 4h, feed N
2With the protection color and luster, heating up to vacuumize steams solvent, and top temperature rises to 150 ℃.Cooling obtains glucamide.
Claims (9)
1, a kind of preparation technology who adopts the synthetic glucamide of loop reactor is characterized in that comprising the steps:
(1) at first dextrose anhydrous is under agitation added in the solvent, making the weight concentration of glucose in solvent is 10～80wt%, feeds Monomethylamine gas, and temperature of reaction is at 20-50 ℃, and normal pressure is reaction 1-3h down, and is transparent until solution, charges into N during reaction in the reactor
2, the mol ratio of glucose and Monomethylamine is 1.0:1.0～3.0;
(2) clear solution that makes in (1) step is added catalyzer, the catalyzer add-on is 2～20wt% of glucose quality, enters then in the loop reactor, uses N
2H is used in displacement again
2After the displacement, there is hydrogen to exist down, reacts 1-2h down at 50 ℃～60 ℃, 70 ℃-80 ℃ are reacted 1-3h down, carry out hydrogenation reaction under reaction pressure 0.3MPa～6.0MPa, filter out catalyzer, carry out crystallization under 0-10 ℃ then, obtain glucose methylamine white crystals, carry out drying;
(3) glucose methylamine that (2) step is made and fatty acid methyl ester are that 1.0:1.0～1.10 add in the solvent by the mol ratio of glucose methylamine and fatty acid methyl ester, and the amount of solvent is 20～60wt% of glucose methylamine and fatty acid methyl ester weight sum, feeds N
2With the protection color and luster, under the catalyzer condition, the add-on of catalyzer is 1-5wt% of glucose methylamine; rise to 60-70 ℃, normal pressure carries out amidate action, behind 2-6h; intensification vacuumizes and steams solvent, and top temperature rises to 160 ℃, obtains purpose product glucamide.
2, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1 is characterized in that the weight concentration of described glucose in solvent is 40～50wt%.
3, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1, the mol ratio that it is characterized in that described glucose and Monomethylamine is 1.0:1.2-1.5.
4, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1 is characterized in that described solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, ethylene glycol or propylene glycol.
5, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 4 is characterized in that described solvent is methyl alcohol or ethanol.
6, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1 is characterized in that described step (2) reaction pressure is at 0.6MPa～1.0MPa.
7, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1, the catalyzer that it is characterized in that described step (2) is Raney's nickel or nickel-loaded.
8, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1, the catalyzer that it is characterized in that described step (3) is sodium methylate, potassium methylate or yellow soda ash.
9, a kind of preparation technology who adopts the synthetic glucamide of loop reactor as claimed in claim 1 is characterized in that described fatty acid methyl ester is coconut oil methyl ester or Laurate methyl.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863793A (en) * | 2010-06-25 | 2010-10-20 | 凤台精兴生物科技有限公司 | Synthesizing method of N-methyl glucamine |
| CN102875410B (en) * | 2012-09-17 | 2014-11-26 | 中国日用化学工业研究院 | N, N-dimethyl-N [3-(carbohydrate amide group)] propyl group-N-alkyl ammonium bromide and synthetic method thereof |
| CN105601150B (en) * | 2015-12-17 | 2017-10-27 | 江苏苏博特新材料股份有限公司 | A kind of reinforcing steel bar corrosion inhibitor and its application |
| CN112457206A (en) * | 2020-12-12 | 2021-03-09 | 弘健制药(上海)有限公司 | Refining process of meglumine |
| CN112479906B (en) * | 2020-12-12 | 2022-11-22 | 弘健制药(上海)有限公司 | Production process of meglumine |
| CN114315597B (en) * | 2022-01-21 | 2022-10-28 | 海南卓科制药有限公司 | Preparation method of meglumine |
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Patent Citations (2)
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| WO1992006984A1 (en) * | 1990-10-12 | 1992-04-30 | The Procter & Gamble Company | Process for preparing n-alkyl polyhydroxy amines and fatty acid amides therefrom in hydroxy solvents |
| WO1992008687A1 (en) * | 1990-11-09 | 1992-05-29 | The Procter & Gamble Company | Process for preparing n-alkyl polyhydroxy amines in amine and amine/water solvents and fatty acid amides therefrom |
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