CN106478575A - The method that corn cob furfuryl alcohol method prepares ethylmaltol - Google Patents
The method that corn cob furfuryl alcohol method prepares ethylmaltol Download PDFInfo
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- CN106478575A CN106478575A CN201610869069.7A CN201610869069A CN106478575A CN 106478575 A CN106478575 A CN 106478575A CN 201610869069 A CN201610869069 A CN 201610869069A CN 106478575 A CN106478575 A CN 106478575A
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- ethylmaltol
- furfuryl alcohol
- furfural
- chloroform
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
Abstract
This patent discloses the method that one of chemosynthesis technical field corn cob furfuryl alcohol method prepares ethylmaltol, corn cob two-step method prepares furfural；Furfural reaction generates furfuryl alcohol, and furfural is placed in reaction unit with the nitrogen-doped graphene material being loaded with platinum, adds distilled water, is passed through hydrogen, and at 90～160 DEG C, reaction 4～8h obtains furfuryl alcohol；Furfuryl alcohol chlorination isomerization reaction pyromeconic acid；It is condensed ethoxy maltol processed；Finally reduce ethylmaltol processed, continue heating after reaction and steam ethanol water, heat up and steam thick ethylmaltol, add chloroform dissolving into thick ethylmaltol, be cooled to 0 DEG C of recrystallization, crystallization air-dries as finished product maltol.High yield, pollution-free is prepared by the preparation method of the present invention, substantially the no pure food stage ethylmaltol of waste water, environmental friendliness, environmental protection, because the structure of maltol is similar to ethylmaltol, preparation method can be general, other raw materials of adjustment reaction.
Description
Technical field
The present invention relates to chemosynthesis technical field is and in particular to a kind of corn cob furfuryl alcohol method prepares the side of ethylmaltol
Method.
Background technology
Maltol, another name：Larch element, larixinic acid, 2- methyl pyromeconic acid, taste phenol etc., molecular formula, molecular weight：
C6H6O3、126.11；Ethylmaltol, calls 2- ethyl pyromeconic acid, molecular formula, molecular weight：C7H8O3、140.14；White or
Slightly yellow acicular crystal, meeting alkali is in yellow.89-92 DEG C of fusing point.It is soluble in hot water.Also it is dissolved in ethanol, chloroform.There is prominent Jiao
Sugared fragrance, chemical property is similar to maltol,
The structural formula of maltol is：The structural formula of ethylmaltol is：
Maltol is primarily present in bark of dahurian larch and Herba Cichorii.White or flavescent acicular crystal or crystalline powder,
There are special fragrance, 160-130 DEG C of fusing point.It is soluble in hot water, ethanol and chloroform, be slightly soluble in ether and benzene, insoluble in petroleum ether.
Reducible Fehling Regent and NH3·AgNO3Solution.It alkali is in yellow solution.It is sublimed into column when 93 DEG C.With ferrum oxide
Effect becomes reddish violet.Herba Cladoniae rangiferinae is reacted acid.
It is mainly used as foodstuff flavouring agent, article of everyday use and tobacco aromatics using, sensitive material, preservative and skin care drug.Add food
In product, make improving fragrance and enrichment, extend the food storage phase and not mouldy.For preparing skin protection cosmeticss, there is suppression melanin
Growth, the good performance of skin whitening.For various food, such as chocolate, confection, cake, fruit wine, fruit juice, the pouring of ice fine jade, cake
Dry, bread, canned food, coffee, soda pop and ice cream etc., general consumption is ten thousand/left and right.Improving fragrance to food and enhancing
There is remarkable result.Sweetened to sweet food.Portion can replace 4 parts of coumarins to use.Add 5 ~ 200g in feedstuff per ton, piglet can be promoted
F.F. grows.
Ethylmaltol, is widely used in food flavouring, fragrances, cigarette flavoring and preservative.Its flavouring effect is wheat
Six times of bud phenol, 1 part can replace 24 parts of coumarins to use, extensively welcome abroad and application.
It is known that China is large agricultural country, Plant fiber's aboundresources, especially corn cob, corn cob is Semen Maydiss fruit
Fringe slough seed after fruit axle, the annual yield of Semen Maydiss, can be with the Semen Maydiss of more than 20,000,000 tons of by-product at 1.1 ~ 1.3 hundred million tons
Core, corn cob cannot utilize always well, or throwing away as agricultural wastes, or as fuel, bringing to resource
Great waste, is also in the primary stage around the deep processing of Semen Maydiss and comprehensive utilization at present both at home and abroad；Contain in corn cob
Substantial amounts of cellulose, can change into furfural, and furfural can be as the raw material producing maltol, therefore, prior art needs
Develop the technology that a corn cob produces maltol, solved prior art and only relied on industrial chemicals to produce the disadvantage of maltol
End.
Content of the invention
The invention is intended to providing a kind of technology turning waste into wealth using corn cob, solving prior art and having lacked a set of utilization
Semen Maydiss core raw material prepares maltol, is especially a lack of a set of problem preparing the ripe technique of ethylmaltol.
The method that corn cob furfuryl alcohol method in this programme prepares ethylmaltol, comprises the following steps and carries out：
Step one, corn cob two-step method prepare furfural：In the dilution heat of sulfuric acid of hydrolyst 5%, dissolve in sodium chloride, take jade
After rice core is pulverized, in the solution after 12h, flow control reaction temperature is 100 DEG C, during reaction next time to proceed to normal pressure in reactor for immersion
Between be 3.5h, obtain hydrolyzed solution, by hydrolyzed solution deliver to band distill reactor in, be warming up to constant temperature after 170 DEG C of assigned temperature, to
Persistently it is slowly dropped into toluene, blasting speed is 0.1 ~ 0.2dm in reactor3/ s nitrogen stream, reaction distillation 3h, organic faciess carbonic acid
Sodium solution neutralizes, then uses quick lime dehydrate, after through vacuum distillation, when being decompressed to 9.300～13.3kPa, collection evaporates
Journey is 90～100 DEG C of fraction, is furfural product, and toluene fraction can be recycled；
Step 2, furfural reaction generate furfuryl alcohol：The furfural that produce step one and the nitrogen-doped graphene material being loaded with platinum are put
In reaction unit, add distilled water, be passed through hydrogen, reaction 4～8h obtains furfuryl alcohol at 90～160 DEG C；
Step 3, furfuryl alcohol chlorination isomerization reaction pyromeconic acid：
A, charging：Add furfuryl alcohol, equivalent water and 10 ~ 15 times of methanol of furfuryl alcohol weight to enamel reaction still, open stirring, in chuck
Logical -5 DEG C are water-cooled to 0 DEG C；
B, chlorination：Reaction temperature is maintained at less than 0 DEG C, slowly leads to chlorine 3 ~ 4h, wherein furfuryl alcohol：The ratio of the amount of chlorine species is 1：
1.05, ventilation terminates, and the cooling water in chuck is drained, and changes logical steam of heating；
C, heating isomery：It is warmed up to 30 DEG C, the hydrogen chloride gas of effusion enter in water grain water shutoff, and wastewater disposal basin adds lime treatment；
D, steaming methanol：60 DEG C of intensification steams methanol and enters storage grain process use；
E, extraction：Add cold water, chloroform into enamel reaction still, wash extraction, release and filter waste, filtrate to separator stands divides
Layer, upper liquid decontamination pond；
F, crystallization：Lower floor's chloroform solution is cooled down 0 DEG C of crystallization, is pyromeconic acid after crystallization is air-dried；
Step 4, condensation ethoxy maltol processed：
A, charging：Add ethanol, pyromeconic acid, wherein, pyromeconic acid to stainless steel cauldron：The ratio of the amount of sodium hydroxide material
For：1：1.1, open stirring, in chuck, logical steam heating, is maintained at 55 ~ 60 DEG C and is passed through acetaldehyde vapour 3 ~ 4h, total reflux reaction,
Acetaldehyde：The ratio of the amount of pyromeconic acid material is more than 2, reacts and stops after terminating to flow back, and continuation heating steams acetaldehyde condensation and reclaims use,
After acetaldehyde steams completely, stop heating steam, change logical cold water and be down to room temperature；
B, neutralization：Add 10% hydrochloric acid and be neutralized to pH=7 into reactor；
C, extraction：After adding chloroform extraction, blowing liquid enters separator stratification, upper strata saline solution blowdown pond；
D, crystallization：Lower floor's chloroform solution is cooled to 0 DEG C of crystallization, leaches mother solution and returns chloroform solution and regular steaming recovery, leaching crystallize is
Ethoxy maltol；
Step 5, reduction ethylmaltol processed：
A, charging：Add ethoxy maltol, 50% ethanol and zinc powder to enamel reaction still, open stirring, lead to steam into chuck
Heating, is maintained at 55 ~ 60 DEG C, and under infinite reflux, Deca concentration is 37% hydrochloric acid 3 ~ 4h；Wherein, hydroxyethyl maltol：Zinc：Chlorination
The ratio of the amount of the material of sodium is 1:1.05:2.1；
B, steaming ethanol：Continue heating after reaction and steam ethanol water；
C, steaming：It is warming up to 100 DEG C and steams thick ethylmaltol, steam remaining saline solution and reclaim zinc；
D, recrystallization：Add chloroform dissolving into thick ethylmaltol, be cooled to 0 DEG C of recrystallization, crystallization air-dries as finished product ethyl wheat
Bud phenol.
The operation principle of the present invention and beneficial effect：The technique of the present invention adopts corn cob, is easy to get using Semen Maydiss core raw material
Easily purchase, inexpensive feature, turn waste into wealth, thicker processing and utilization is deep processing and utilization, improves the added value of agricultural byproducts, reduces life
Produce cost.The present invention passes through five step reaction and generates ethylmaltol, and the two-step method in step one prepares furfural, with existing skill
The one-step method preparation of art is compared, although one-step method flow process is relatively simple, the yield of furfural is not high, and furfural dregs are because showing strong acid
Property, the fuel of boiler can only be acted on, produce substantial amounts of sour gas during burning it is impossible to being used as fertilizer or making other application again, with
When one-step method also can produce substantial amounts of waste water, yield is also only 12%, carries out under different conditions because 2 steps reactions are controllable,
The yield of therefore furfural is more much higher than one-step method, can reach 20% about；Furfural hydrogenation to furfural alcohol technology in step 2 adopts
Be vapor phase method preparation, the catalyst of selection is the nitrogen-doped graphene material being loaded with platinum, with conventionally employed chromium-containing catalyst
Compare, will not be to environment, and reaction condition is gentle, uses water as solvent, environmental friendliness, and has higher bran
Alcohol yield；Step 3, step 4 are similar with the processing procedure of the reaction of step 5, furfuryl alcohol chlorination isomerization reaction pyromeconic acid,
It is condensed ethoxy maltol processed and reduces ethylmaltol processed, be all that filter wash obtains after extraction, crystallization, then pass through to control
Reaction temperature, time and proportioning are it is ensured that the yield of product.In sum, by the preparation method of the present invention prepare high yield,
Pollution-free, the no pure food stage ethylmaltol of waste water, environmental friendliness, environmental protection substantially, due to maltol structure with
Ethylmaltol similar, preparation method can be general, adjustment reaction other raw materials.
Further, the chloroform in described step 3, step 4 and step 5 is prepared using the following method：It is passed through into lime water
Chlorine, obtains calcium hypochlorite and calcium chloride, acetaldehyde or ethanol is passed through in time calcium chloride solution, obtains chloroform, calcium acetate and hydrogen
Calcium oxide, chloroform is steamed use.By homemade chloroform, compared with outsourcing, other raw materials in factory can be made full use of
Or during the recovery gas that produces, the chloroform that the method produces simultaneously do not contain other impurities composition, for example monochlor(in)ate carbon, two
Chlorination carbon or carbon tetrachloride, use as the new chloroform driven, and follow-up chloroform can be by recycling.
Further, when step 2 furfural reaction generates furfuryl alcohol, the pressure of hydrogen is 0.5～2MPa；Furfural and Supported Pt Nanoparticles
N doping nitrogen grapheme material mass ratio be 5～10：1.Strict control reaction condition, the yield making furfuryl alcohol is more than 98%.
Specific embodiment
Below by specific embodiment, the present invention is further detailed explanation：
Embodiment 1：
The method that corn cob furfuryl alcohol method prepares ethylmaltol, comprises the following steps and carries out：
Step one, corn cob two-step method prepare furfural：In the dilution heat of sulfuric acid of hydrolyst 5%, dissolve in sodium chloride, take jade
After rice core is pulverized, in the solution after 12h, flow control reaction temperature is 100 DEG C, during reaction next time to proceed to normal pressure in reactor for immersion
Between be 3.5h, obtain hydrolyzed solution, by hydrolyzed solution deliver to band distill reactor in, be warming up to constant temperature after 170 DEG C of assigned temperature, to
Persistently it is slowly dropped into toluene, blasting speed is 0.1dm in reactor3/ s nitrogen stream, reaction distillation 3h, organic faciess are molten with sodium carbonate
Liquid neutralizes, then use quick lime dehydrate, after through vacuum distillation, when being decompressed to 9.300～13.3kPa, collection boiling range is
90～100 DEG C of fraction, is furfural product, and toluene fraction can be recycled；
Step 2, furfural reaction generate furfuryl alcohol：The furfural that produce step one and the nitrogen-doped graphene material being loaded with platinum are put
In reaction unit, add distilled water, be passed through hydrogen, at 90 DEG C, the pressure of hydrogen is 2Mpa, the nitrogen of furfural and Supported Pt Nanoparticles is mixed
The mass ratio of miscellaneous nitrogen grapheme material is 10：1, reaction 8h obtains furfuryl alcohol；
Step 3, furfuryl alcohol chlorination isomerization reaction pyromeconic acid：
A, charging：Add the methanol of furfuryl alcohol, equivalent water and 10 times of furfuryl alcohol weight to enamel reaction still, open stirring, in chuck
Logical -5 DEG C are water-cooled to 0 DEG C；
B, chlorination：Reaction temperature is maintained at less than 0 DEG C, slowly leads to chlorine 3 ~ 4h, wherein furfuryl alcohol：The ratio of the amount of chlorine species is 1：
1.05, ventilation terminates, and the cooling water in chuck is drained, and changes logical steam of heating；
C, heating isomery：It is warmed up to 30 DEG C, the hydrogen chloride gas of effusion enter in water grain water shutoff, and wastewater disposal basin adds lime treatment；
D, steaming methanol：60 DEG C of intensification steams methanol and enters storage grain process use；
E, extraction：Add cold water, chloroform into enamel reaction still, wash extraction, release and filter waste, filtrate to separator stands divides
Layer, upper liquid decontamination pond；
F, crystallization：Lower floor's chloroform solution is cooled down 0 DEG C of crystallization, is pyromeconic acid after crystallization is air-dried；
Step 4, condensation ethoxy maltol processed：
A, charging：Add ethanol, pyromeconic acid, wherein, pyromeconic acid to stainless steel cauldron：The ratio of the amount of sodium hydroxide material
For：1：1.1, open stirring, in chuck, logical steam heating, is maintained at 55 DEG C and is passed through acetaldehyde vapour 3h, total reflux reaction, acetaldehyde：
The ratio of the amount of pyromeconic acid material is more than 2, reacts and stops after terminating to flow back, and continuation heating steams acetaldehyde condensation and reclaims use, treats second
After aldehyde steams completely, stop heating steam, change logical cold water and be down to room temperature；
B, neutralization：Add 10% hydrochloric acid and be neutralized to pH=7 into reactor；
C, extraction：After adding chloroform extraction, blowing liquid enters separator stratification, upper strata saline solution blowdown pond；
D, crystallization：Lower floor's chloroform solution is cooled to 0 DEG C of crystallization, leaches mother solution and returns chloroform solution and regular steaming recovery, leaching crystallize is
Ethoxy maltol；
Step 5, reduction ethylmaltol processed：
A, charging：Add ethoxy maltol, 50% ethanol and zinc powder to enamel reaction still, open stirring, lead to steam into chuck
Heating, is maintained at 55 DEG C, and under infinite reflux, Deca concentration is 37% hydrochloric acid 3h；Wherein, hydroxyethyl maltol：Zinc：The thing of sodium chloride
The ratio of the amount of matter is 1:1.05:2.1；
B, steaming ethanol：Continue heating after reaction and steam ethanol water；
C, steaming：It is warming up to 100 DEG C and steams thick ethylmaltol, steam remaining saline solution and reclaim zinc；
D, recrystallization：Add chloroform dissolving into thick ethylmaltol, be cooled to 0 DEG C of recrystallization, crystallization air-dries as finished product ethyl wheat
Bud phenol.
Embodiment 2：The method that corn cob furfuryl alcohol method prepares ethylmaltol, comprises the following steps and carries out：
Step one, corn cob two-step method prepare furfural：In the dilution heat of sulfuric acid of hydrolyst 5%, dissolve in sodium chloride, take jade
After rice core is pulverized, in the solution after 12h, flow control reaction temperature is 100 DEG C, during reaction next time to proceed to normal pressure in reactor for immersion
Between be 3.5h, obtain hydrolyzed solution, by hydrolyzed solution deliver to band distill reactor in, be warming up to constant temperature after 170 DEG C of assigned temperature, to
Persistently it is slowly dropped into toluene, blasting speed is 0.2dm in reactor3/ s nitrogen stream, reaction distillation 3h, organic faciess are molten with sodium carbonate
Liquid neutralizes, then use quick lime dehydrate, after through vacuum distillation, when being decompressed to 9.300～13.3kPa, collection boiling range is
90～100 DEG C of fraction, is furfural product, and toluene fraction can be recycled；
Step 2, furfural reaction generate furfuryl alcohol：The furfural that produce step one and the nitrogen-doped graphene material being loaded with platinum are put
In reaction unit, add distilled water, be passed through hydrogen, at 120 DEG C, the pressure of hydrogen is 1Mpa, the nitrogen of furfural and Supported Pt Nanoparticles
The mass ratio of doping nitrogen grapheme material is 8：1, reaction 6h obtains furfuryl alcohol；
Step 3, furfuryl alcohol chlorination isomerization reaction pyromeconic acid：
A, charging：Add the methanol of furfuryl alcohol, equivalent water and 12 times of furfuryl alcohol weight to enamel reaction still, open stirring, in chuck
Logical -5 DEG C are water-cooled to 0 DEG C；
B, chlorination：Reaction temperature is maintained at less than 0 DEG C, slowly leads to chlorine 3 ~ 4h, wherein furfuryl alcohol：The ratio of the amount of chlorine species is 1：
1.05, ventilation terminates, and the cooling water in chuck is drained, and changes logical steam of heating；
C, heating isomery：It is warmed up to 30 DEG C, the hydrogen chloride gas of effusion enter in water grain water shutoff, and wastewater disposal basin adds lime treatment；
D, steaming methanol：60 DEG C of intensification steams methanol and enters storage grain process use；
E, extraction：Add cold water, chloroform into enamel reaction still, wash extraction, release and filter waste, filtrate to separator stands divides
Layer, upper liquid decontamination pond；
F, crystallization：Lower floor's chloroform solution is cooled down 0 DEG C of crystallization, is pyromeconic acid after crystallization is air-dried；
Step 4, condensation ethoxy maltol processed：
A, charging：Add ethanol, pyromeconic acid, wherein, pyromeconic acid to stainless steel cauldron：The ratio of the amount of sodium hydroxide material
For：1：1.1, open stirring, in chuck, logical steam heating, is maintained at 60 DEG C and is passed through acetaldehyde vapour 4h, total reflux reaction, acetaldehyde：
The ratio of the amount of pyromeconic acid material is more than 2, reacts and stops after terminating to flow back, and continuation heating steams acetaldehyde condensation and reclaims use, treats second
After aldehyde steams completely, stop heating steam, change logical cold water and be down to room temperature；
B, neutralization：Add 10% hydrochloric acid and be neutralized to pH=7 into reactor；
C, extraction：After adding chloroform extraction, blowing liquid enters separator stratification, upper strata saline solution blowdown pond；
D, crystallization：Lower floor's chloroform solution is cooled to 0 DEG C of crystallization, leaches mother solution and returns chloroform solution and regular steaming recovery, leaching crystallize is
Ethoxy maltol；
Step 5, reduction ethylmaltol processed：
A, charging：Add ethoxy maltol, 50% ethanol and zinc powder to enamel reaction still, open stirring, lead to steam into chuck
Heating, is maintained at 60 DEG C, and under infinite reflux, Deca concentration is 37% hydrochloric acid 4h；Wherein, hydroxyethyl maltol：Zinc：The thing of sodium chloride
The ratio of the amount of matter is 1:1.05:2.1；
B, steaming ethanol：Continue heating after reaction and steam ethanol water；
C, steaming：It is warming up to 100 DEG C and steams thick ethylmaltol, steam remaining saline solution and reclaim zinc；
D, recrystallization：Add chloroform dissolving into thick ethylmaltol, be cooled to 0 DEG C of recrystallization, crystallization air-dries as finished product ethyl wheat
Bud phenol.
Embodiment 3：The method that corn cob furfuryl alcohol method prepares ethylmaltol, comprises the following steps and carries out：
Step one, corn cob two-step method prepare furfural：In the dilution heat of sulfuric acid of hydrolyst 5%, dissolve in sodium chloride, take jade
After rice core is pulverized, in the solution after 12h, flow control reaction temperature is 100 DEG C, during reaction next time to proceed to normal pressure in reactor for immersion
Between be 3.5h, obtain hydrolyzed solution, by hydrolyzed solution deliver to band distill reactor in, be warming up to constant temperature after 170 DEG C of assigned temperature, to
Persistently it is slowly dropped into toluene, blasting speed is 0.2dm in reactor3/ s nitrogen stream, reaction distillation 3h, organic faciess are molten with sodium carbonate
Liquid neutralizes, then use quick lime dehydrate, after through vacuum distillation, when being decompressed to 9.300～13.3kPa, collection boiling range is
90～100 DEG C of fraction, is furfural product, and toluene fraction can be recycled；
Step 2, furfural reaction generate furfuryl alcohol：The furfural that produce step one and the nitrogen-doped graphene material being loaded with platinum are put
In reaction unit, add distilled water, be passed through hydrogen, at 120 DEG C, the pressure of hydrogen is 1Mpa, the nitrogen of furfural and Supported Pt Nanoparticles
The mass ratio of doping nitrogen grapheme material is 8：1, reaction 6h obtains furfuryl alcohol；
Step 3, furfuryl alcohol chlorination isomerization reaction pyromeconic acid：
A, charging：Add the methanol of furfuryl alcohol, equivalent water and 12 times of furfuryl alcohol weight to enamel reaction still, open stirring, in chuck
Logical -5 DEG C are water-cooled to 0 DEG C；
B, chlorination：Reaction temperature is maintained at less than 0 DEG C, slowly leads to chlorine 3 ~ 4h, wherein furfuryl alcohol：The ratio of the amount of chlorine species is 1：
1.05, ventilation terminates, and the cooling water in chuck is drained, and changes logical steam of heating；
C, heating isomery：It is warmed up to 30 DEG C, the hydrogen chloride gas of effusion enter in water grain water shutoff, and wastewater disposal basin adds lime treatment；
D, steaming methanol：60 DEG C of intensification steams methanol and enters storage grain process use；
E, extraction：Add cold water, chloroform into enamel reaction still, wash extraction, release and filter waste, filtrate to separator stands divides
Layer, upper liquid decontamination pond；
F, crystallization：Lower floor's chloroform solution is cooled down 0 DEG C of crystallization, is pyromeconic acid after crystallization is air-dried；
Step 4, condensation ethoxy maltol processed：
A, charging：Add ethanol, pyromeconic acid, wherein, pyromeconic acid to stainless steel cauldron：The ratio of the amount of sodium hydroxide material
For：1：1.1, open stirring, in chuck, logical steam heating, is maintained at 60 DEG C and is passed through acetaldehyde vapour 4h, total reflux reaction, acetaldehyde：
The ratio of the amount of pyromeconic acid material is more than 2, reacts and stops after terminating to flow back, and continuation heating steams acetaldehyde condensation and reclaims use, treats second
After aldehyde steams completely, stop heating steam, change logical cold water and be down to room temperature；
B, neutralization：Add 10% hydrochloric acid and be neutralized to pH=7 into reactor；
C, extraction：After adding chloroform extraction, blowing liquid enters separator stratification, upper strata saline solution blowdown pond；
D, crystallization：Lower floor's chloroform solution is cooled to 0 DEG C of crystallization, leaches mother solution and returns chloroform solution and regular steaming recovery, leaching crystallize is
Ethoxy maltol；
Step 5, reduction ethylmaltol processed：
A, charging：Add ethoxy maltol, 50% ethanol and zinc powder to enamel reaction still, open stirring, lead to steam into chuck
Heating, is maintained at 60 DEG C, and under infinite reflux, Deca concentration is 37% hydrochloric acid 4h；Wherein, hydroxyethyl maltol：Zinc：The thing of sodium chloride
The ratio of the amount of matter is 1:1.05:2.1；
B, steaming ethanol：Continue heating after reaction and steam ethanol water；
C, steaming：It is warming up to 100 DEG C and steams thick ethylmaltol, steam remaining saline solution and reclaim zinc；
D, recrystallization：Add chloroform dissolving into thick ethylmaltol, be cooled to 0 DEG C of recrystallization, crystallization air-dries as finished product ethyl wheat
Bud phenol.
Above-described is only embodiments of the invention, and in scheme, the general knowledge here such as known concrete structure and characteristic is not made
Excessive description.It should be pointed out that for a person skilled in the art, on the premise of without departing from present configuration, acceptable
Make some deformation and improve, these also should be considered as protection scope of the present invention, these are implemented all without the impact present invention
Effect and practical applicability.This application claims protection domain should be defined by the content of its claim, in description
Specific embodiment etc. records the content that can be used for explaining claim.
Claims (3)
1. corn cob furfuryl alcohol method is prepared the method for ethylmaltol and is carried out it is characterised in that comprising the following steps：
Step one, corn cob two-step method prepare furfural：In the dilution heat of sulfuric acid of hydrolyst 5%, dissolve in sodium chloride, take jade
After rice core is pulverized, in the solution after 12h, flow control reaction temperature is 100 DEG C, during reaction next time to proceed to normal pressure in reactor for immersion
Between be 3.5h, obtain hydrolyzed solution, by hydrolyzed solution deliver to band distill reactor in, be warming up to constant temperature after 170 DEG C of assigned temperature, to
Persistently it is slowly dropped into toluene, blasting speed is 0.1 ~ 0.2dm in reactor3/ s nitrogen stream, reaction distillation 3h, organic faciess carbonic acid
Sodium solution neutralizes, then uses quick lime dehydrate, after through vacuum distillation, when being decompressed to 9.300～13.3kPa, collection evaporates
Journey is 90～100 DEG C of fraction, is furfural product, and toluene fraction can be recycled；
Step 2, furfural reaction generate furfuryl alcohol：The furfural that produce step one and the nitrogen-doped graphene material being loaded with platinum are put
In reaction unit, add distilled water, be passed through hydrogen, reaction 4～8h obtains furfuryl alcohol at 90～160 DEG C；
Step 3, furfuryl alcohol chlorination isomerization reaction pyromeconic acid：
A, charging：Add furfuryl alcohol, equivalent water and 10 ~ 15 times of methanol of furfuryl alcohol weight to enamel reaction still, open stirring, in chuck
Logical -5 DEG C are water-cooled to 0 DEG C；
B, chlorination：Reaction temperature is maintained at less than 0 DEG C, slowly leads to chlorine 3 ~ 4h, wherein furfuryl alcohol：The ratio of the amount of chlorine species is 1：
1.05, ventilation terminates, and the cooling water in chuck is drained, and changes logical steam of heating；
C, heating isomery：It is warmed up to 30 DEG C, the hydrogen chloride gas of effusion enter in water grain water shutoff, and wastewater disposal basin adds lime treatment；
D, steaming methanol：60 DEG C of intensification steams methanol and enters storage grain process use；
E, extraction：Add cold water, chloroform into enamel reaction still, wash extraction, release and filter waste, filtrate to separator stands divides
Layer, upper liquid decontamination pond；
F, crystallization：Lower floor's chloroform solution is cooled down 0 DEG C of crystallization, is pyromeconic acid after crystallization is air-dried；
Step 4, condensation ethoxy maltol processed：
A, charging：Add ethanol, pyromeconic acid, wherein, pyromeconic acid to stainless steel cauldron：The ratio of the amount of sodium hydroxide material
For：1：1.1, open stirring, in chuck, logical steam heating, is maintained at 55 ~ 60 DEG C and is passed through acetaldehyde vapour 3 ~ 4h, total reflux reaction,
Acetaldehyde：The ratio of the amount of pyromeconic acid material is more than 2, reacts and stops after terminating to flow back, and continuation heating steams acetaldehyde condensation and reclaims use,
After acetaldehyde steams completely, stop heating steam, change logical cold water and be down to room temperature；
B, neutralization：Add 10% hydrochloric acid and be neutralized to pH=7 into reactor；
C, extraction：After adding chloroform extraction, blowing liquid enters separator stratification, upper strata saline solution blowdown pond；
D, crystallization：Lower floor's chloroform solution is cooled to 0 DEG C of crystallization, leaches mother solution and returns chloroform solution and regular steaming recovery, leaching crystallize is
Ethoxy maltol；
Step 5, reduction ethylmaltol processed：
A, charging：Add ethoxy maltol, 50% ethanol and zinc powder to enamel reaction still, open stirring, lead to steam into chuck
Heating, is maintained at 55 ~ 60 DEG C, and under infinite reflux, Deca concentration is 37% hydrochloric acid 3 ~ 4h；Wherein, hydroxyethyl maltol：Zinc：Chlorination
The ratio of the amount of the material of sodium is 1:1.05:2.1；
B, steaming ethanol：Continue heating after reaction and steam ethanol water；
C, steaming：It is warming up to 100 DEG C and steams thick ethylmaltol, steam remaining saline solution and reclaim zinc；
D, recrystallization：Add chloroform dissolving into thick ethylmaltol, be cooled to 0 DEG C of recrystallization, crystallization air-dries as finished product ethyl wheat
Bud phenol.
2. corn cob furfuryl alcohol method according to claim 1 prepare ethylmaltol method it is characterised in that：Described step
3rd, the chloroform in step 4 and step 5 is prepared using the following method：It is passed through chlorine into lime water, obtain calcium hypochlorite and chlorination
Calcium, acetaldehyde or ethanol is passed through in time calcium chloride solution, obtains chloroform, calcium acetate and calcium hydroxide, chloroform is steamed use.
3. corn cob furfuryl alcohol method according to claim 2 prepare ethylmaltol method it is characterised in that：In step 2
When furfural reaction generates furfuryl alcohol, the pressure of hydrogen is 0.5～2MPa；The matter of the N doping nitrogen grapheme material of furfural and Supported Pt Nanoparticles
Amount ratio is 5～10：1.
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| CN111533719A (en) * | 2020-04-29 | 2020-08-14 | 广东省肇庆华格生物科技有限公司 | Synthesis process of ethyl maltol |
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| CN111533719A (en) * | 2020-04-29 | 2020-08-14 | 广东省肇庆华格生物科技有限公司 | Synthesis process of ethyl maltol |
| CN111533719B (en) * | 2020-04-29 | 2022-04-01 | 广东省肇庆华格生物科技有限公司 | Synthesis process of ethyl maltol |
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