CN101486639B - Novel method for synthesizing mixed glucose derivative - Google Patents
Novel method for synthesizing mixed glucose derivative Download PDFInfo
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- CN101486639B CN101486639B CN2009100250557A CN200910025055A CN101486639B CN 101486639 B CN101486639 B CN 101486639B CN 2009100250557 A CN2009100250557 A CN 2009100250557A CN 200910025055 A CN200910025055 A CN 200910025055A CN 101486639 B CN101486639 B CN 101486639B
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Abstract
The invention relates to a synthetic method of mixed glucose derivatives. According to the weight proportion of glucose, solvent, weak acidic nitrate oxidant and catalyst of 0.1 percent to 98 percent : 0.1 percent to 98 percent : 0.1 percent to 98 percent : 0.001 percent to 60 percent, the glucose, solvent, weak acidic nitrate oxidant and catalyst are mixed, stirred and heated until the temperature rises to 40 DEG C to 100 DEG C; air (or oxygen) is filled into the reaction system at a speed of 0.001 percent to 100 percent of reaction solution volume per minute, reaction lasts for 0.1h to 20h and crude products are obtained; and mixed glucose derivatives composed of glucaric acid, glucaric acid-1,4-lactone and glucaric acid -1,4:3,6 dilactone are obtained through the separation and purification of the crude products. The products can be applied to the synthesis of polyester, polyamide and other high polymer materials and also can be taken as a medical intermediate and used for medicament synthesis.
Description
Technical field
The present invention relates to a kind of compound method of mixed glucose derivative, belong to the organic synthesis field.
Background technology
Along with the quickening of global process of industrialization, crisis of resource, oil crisis, ecocrisis and energy dilemma are deepened day by day, and the development and use renewable resources has become the research focus of countries in the world.Glucose is renewable resources starch and cellulosic hydrolysate, therefore, utilizes the hydrolysate of this renewable resources of glucose to carry out the synthetic of its verivate, and is significant undoubtedly to alleviating crisis of resource and ecocrisis.
Glucaric acid and single lactone thereof and dilactone are one type of important chemical material and medicine intermediate.At present, the home and abroad generally all is to adopt rare nitric acid oxidation glucose to come the synthesis of glucose diacid, again with synthetic its single lactone of glucaric acid and dilactone verivate.As everyone knows, rare nitric acid is a kind of volatile oxidisability strong acid, has extremely strong corrodibility, and nitric acid can cause environmental pollution because of volatilization, and is also very serious to the corrosion of production unit.In addition, the reduzate behind rare nitric acid oxidation glucose is an oxynitride, and the oxynitride strong toxicity is big to the harm of direct labor's physical and mental health, seriously polluted to ecotope.In a word, existing manufacturing technique requires high to production unit, and to the production unit seriously corroded, production unit is short work-ing life, and environmental pollution is serious.Therefore, the green production process of research and development glucaric acid and single lactone and dilactone is imperative.
Adopt green production process to substitute the existing production technique that falls behind; Help reducing the investment of production equipment of glucaric acid and single lactone and dilactone, enhance productivity, the environmental pollution in reduction and elimination glucaric acid and single lactone and the dilactone production process; Preserve the ecological environment; Safeguard the national sustainable development strategy, will produce remarkable economic efficiency, social benefit and ecological benefits, have important practical significance.At present, the report of the method for the invention synthesis of glucose diacid and single lactone and dilactone mixture is not seen in the home and abroad.
Summary of the invention
For fundamentally solving the serious and serious problem of environmental pollution of equipment corrosion in glucaric acid and single lactone thereof and the dilactone mixture production process; We are raw material with glucose, solvent, slightly acidic nitrate oxidizer, catalyzer, air (or oxygen); Adopt green synthesis process to replace traditional synthesis technique synthetic mixed glucose derivative, the i.e. mixture of glucaric acid and single lactone and dilactone.
The present invention provides a kind of compound method of mixed glucose derivative.It is little that this compound method has investment of production equipment, and reaction solution is little to corrosion on Equipment because of being slightly acidic, the high life of production unit, advantage such as production efficiency is high, and the environmental pollution in the production process is little.
The present invention adopts following technical scheme:
Weight percent according to glucose, solvent, slightly acidic nitrate oxidizer and catalyzer is (0.1%～98%): (0.1%～98%): (0.1%～98%): the ratio of (0.001%～60%); With glucose, solvent, slightly acidic nitrate oxidizer and catalyst mix; Under agitation heat to 40 ℃～100 ℃; PM feeds reaction system with the speed of reaction solution volume 0.001%～100% with air (or oxygen), and reaction 0.1h～20h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the gac of its weight 0.001%～20%, be heated to 40 ℃～100 ℃ decoloring reaction 0.1h～5h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 20KHZ～1MHZ, power are under the ultrasonic dispersing of 30W～15KW, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting the zero(ppm) water of 1～10 times of three filter cake weight, add three times filter cake, is that 20KHZ～1MHZ, power are under the ultrasonic dispersing of 30W～15KW in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone;
A kind of mixed glucose derivative of the present invention is by glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1, and 4:3, the 6-dilactone is formed, and constitutional formula is distinguished as follows:
The constitutional formula of glucaric acid:
Glucaric acid-1, the constitutional formula of 4-lactone:
Glucaric acid-1; 4:3, the constitutional formula of 6-dilactone:
A kind of compound method that is used to prepare above-mentioned mixed glucose derivative; It synthesizes with the technology of separating the employing of purifying: the weight percent according to glucose, solvent, slightly acidic nitrate oxidizer and catalyzer is (0.1%～98%): (0.1%～98%): (0.1%～98%): the ratio of (0.001%～60%); With glucose, solvent, slightly acidic nitrate oxidizer and catalyst mix; Under agitation heat to 40 ℃～100 ℃; PM feeds reaction system with the speed of reaction solution volume 0.001%～100% with air (or oxygen), and reaction 0.1h～20h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the gac of its weight 0.001%～20%, be heated to 40 ℃～100 ℃ decoloring reaction 0.1h～5h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 20KHZ～1MHZ, power are under the ultrasonic dispersing of 30W～15KW, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting the zero(ppm) water of 1～10 times of three filter cake weight, add three times filter cake, is that 20KHZ～1MHZ, power are under the ultrasonic dispersing of 30W～15KW in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal again through 95% washing with alcohol, filter, be drying to obtain mixed glucose derivative, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone;
The used glucose of building-up reactions according to the invention is any one or more in anhydrous D-glucose, anhydrous alpha-D-glucose, anhydrous beta-D-glucose, a hydration D-glucose, a hydration alpha-D-glucose, the hydration β-D-glucose.
The used solvent of building-up reactions according to the invention is any in zero(ppm) water, tap water, the deionized water.
The used slightly acidic nitrate oxidizer of building-up reactions according to the invention is any one or more in an ammonium nitrate, urea nitrate, Monomethylamine nitrate salt, n n dimetylaniline nitrate salt, Trimethylamine 99 nitrate salt, monoethylamine nitrate salt, diethylamine nitrate salt and the triethylamine nitrate salt.
The used catalyzer of building-up reactions according to the invention is that particle diameter is that the 2nm～following pure metal powder of 10 μ m or the weight percent of metal are the metal load type powder of 0.025%-12%: the platinum powder end; The palladium powder; Nickel by powder; Copper powder; Platinum-active carbon powder; Palladium-active carbon powder; Nickel-active carbon powder; Copper-active carbon powder; Platinum-alumina powder; Palladium-alumina powder; The nickel-alumina powder; Copper-alumina powder; Platinum-silica gel powder; Palladium-silica gel powder; Nickel-silica gel powder; Copper-silica gel powder; Platinum-diatomite powder; Palladium-diatomite powder; Nickel-diatomite powder; Copper-diatomite powder; Platinum-titania powder; Palladium-titania powder; Nickel-titania powder; Copper-titania powder; Platinum-4A zeolite powder; Palladium-4A zeolite powder; Nickel-4A zeolite powder; Copper-4A zeolite powder; Platinum-4A type molecular sieve powder; Palladium-4A type molecular sieve powder; Nickel-4A type molecular sieve powder; In copper-4A type molecular sieve powder any one or more.
The used air of building-up reactions according to the invention is the air of handling through udst separation.
The used oxygen of building-up reactions according to the invention is air separation gained oxygen, brine electrolysis gained oxygen, heating ydrogen peroxide 50 gained oxygen and ydrogen peroxide 50 any in the catalytically decomposed gained oxygen under the Manganse Dioxide effect.
The present invention is used to prepare the method for said mixed glucose derivative, compares with the preparation method of existing mixed glucose derivative, and the present invention has following advantage:
1, the slightly acidic nitrate oxidizer of synthesis phase employing of the present invention: an ammonium nitrate, urea nitrate, Monomethylamine nitrate salt, n n dimetylaniline nitrate salt, Trimethylamine 99 nitrate salt, monoethylamine nitrate salt, diethylamine nitrate salt and triethylamine nitrate salt all are strong acid weak base salts; Its aqueous solution is slightly acidic; To the corrosion on Equipment ability very a little less than; Also do not have volatility, environmental pollution is little;
2, synthesis phase employing particle diameter of the present invention is that the 2nm～pure metal powder of 10 μ m or the weight percent of metal are the metal load type powder of 0.025%-12%: platinum powder end, palladium powder, nickel by powder, copper powder, platinum-active carbon powder, palladium-active carbon powder, nickel-active carbon powder, copper-active carbon powder, platinum-alumina powder, palladium-alumina powder, nickel-alumina powder, copper-alumina powder, platinum-silica gel powder, palladium-silica gel powder, nickel-silica gel powder, copper-silica gel powder, platinum-diatomite powder, palladium-diatomite powder, nickel-diatomite powder, copper-diatomite powder, platinum-titania powder, palladium-titania powder, nickel-titania powder, copper-titania powder, platinum-4A zeolite powder, palladium-4A zeolite powder, nickel-4A zeolite powder, copper-4A zeolite powder, platinum-4A type molecular sieve powder, palladium-4A type molecular sieve powder, nickel-4A type molecular sieve powder, copper-4A type molecular sieve powder are catalyzer; Effectively accelerated synthesising reacting speed; Synthesising reacting speed is 2～3 times of speed of response when not adding catalyzer, has improved production efficiency.
3, synthesis phase of the present invention has adopted the method to reaction system bubbling air (or oxygen), makes reaction system have reaction of the systemic circulation shown in (1) formula～(5) formula as follows and the partial circulating reaction shown in (3) formula～(4) formula:
The hydrolysis in water of slightly acidic nitrate oxidizer forms following running balance, generates weak base MOH and nitric acid:
Nitric acid oxidation glucose produces nitrogen protoxide, and the balanced reaction shown in (1) formula is moved right:
HNO
3+HOH
2C(CHOH)
4CHO→HOOC(CHOH)
4COOH+NO+H
2O (2)
Oxygen that nitrogen protoxide is passed into or airborne dioxygen oxidation generate nitrogen peroxide:
2NO+O
2→2NO
2(3)
Nitrogen peroxide is absorbed by water and generates nitric acid and nitrogen protoxide:
3NO
2+H
2O→2HNO
3+NO (4)
Nitric acid and weak base MOH reaction generate slightly acidic nitrate oxidizer MNO
3:
HNO
3+MOH→MNO
3+H
2O (5)
Wherein, in (1) formula and (5) formula:
M is NH
4, H
2NCONH
3, CH
3NH
3, (CH
3)
2NH
2, (CH
3)
3NH, CH
3CH
2NH
3, (CH
3CH
2)
2NH
2(CH
3CH
2)
3NH;
Adopt building-up reactions of the present invention; Owing to have systemic circulation reaction shown in (1) formula～(5) formula and the partial circulating reaction shown in (3) formula～(4) formula; Significantly reduced the consumption of slightly acidic nitrate oxidizer; Improve economic benefit, also effectively stoped nitrogen protoxide and nitrogen peroxide toxic gas to enter atmosphere, eliminated environmental pollution;
4, to separate the method that purification phase adopts different with traditional separating and purifying method in the present invention; At first; In secondary mother liquid, drip and adopt ultrasonic scattering method when the lime acetate saturated aqueous solution is transformed into the glucaric acid calcium deposit with glucaric acid; Make the antacidine deposit seeds particle diameter of generation as far as possible little, the impurity that is mingled with in the solid particulate significantly reduces, and the purity of intermediates antacidine significantly improves; Secondly; In the zero(ppm) water of 1～10 times of three filter cake weight, add three filter cakes, adopt ultrasonic scattering method when dripping concentrated hydrochloric acid again, significantly accelerated the solubilizing reaction that the glucaric acid calcium deposit is converted into glucaric acid; Accelerate production rate, improved production efficiency; The 3rd, in the solution of three filter cake CL gained clears, drip 95% ethanol and adopt ultrasonic scattering method when no longer including crystallization and separate out; Make the crystalline particle particle diameter of generation as far as possible little, the impurity that is mingled with in the crystalline particle significantly reduces, the finished product mixed glucose derivative; Be glucaric acid, glucaric acid-1; 4-lactone and glucaric acid-1,4:3, the purity of the mixture of 6-dilactone significantly improves; The method of the invention can make mixed glucose derivative content reach more than 99.5%, for preparing highly purified mixed glucose derivative a kind of new separating and purifying method is provided.
Synthetic of the present invention is by glucaric acid, glucaric acid-1; 4-lactone and glucaric acid-1,4:3, the mixed glucose derivative that the 6-dilactone is formed; It all is bifunctional compound; Have carboxyl and lactone group, can be used for the synthetic of macromolecular materials such as polyester and polymeric amide, also can be used as medicine intermediate and be used for synthetic drugs.
Embodiment
Embodiment 1
Anhydrous D-glucose: 200g
Deionized water: 600g
An ammonium nitrate: 190g
0.05% platinum-active carbon powder (≤50nm): 10g
With the anhydrous D-glucose of 200g, 600g deionized water, 190g an ammonium nitrate and 10g 0.05% platinum-active carbon powder (≤50nm) add in the reactor drum, under agitation heat to 100 ℃, with 60ml.min
-1Speed will feed reaction system through the air of udst separation, reaction 8h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the 5g gac, be heated to 80 ℃ of decoloring reaction 0.5h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 40KHZ, power are under the ultrasonic dispersing of 600W, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting 600g zero(ppm) water, add three times filter cake, is that 40KHZ, power are under the ultrasonic dispersing of 600W in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
Embodiment 2
One hydration D-glucose: 300g
Zero(ppm) water: 400g
Urea nitrate: 280g
0.1% nickel-diatomite powder (≤50nm): 20g
With 300g one hydration D-glucose, 400g zero(ppm) water, 280g urea nitrate and 20g 0.1% nickel-diatomite powder (≤50nm) add in the reactor drum, under agitation heat to 95 ℃, with 30ml.min
-1Speed will feed reaction system through the air of udst separation, reaction 10h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the 4g gac, be heated to 70 ℃ of decoloring reaction 1h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 40KHZ, power are under the ultrasonic dispersing of 1KW, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting the 400g deionized water, add three times filter cake, is that 40KHZ, power are under the ultrasonic dispersing of 1KW in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
Embodiment 3
One hydration alpha-D-glucose: 220g
Tap water: 565g
Monomethylamine nitrate salt: 210g
0.04% palladium-4A zeolite powder (≤50nm): 5g
With 220g one hydration alpha-D-glucose, 565g tap water, 210g monomethylamine nitrate salt and 5g 0.04% palladium-4A zeolite powder (≤50nm) add in the reactor drum, under agitation heat to 90 ℃, with 80ml.min
-1Speed oxygen is fed reaction system, the reaction 11h obtain crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the 6g gac, be heated to 90 ℃ of decoloring reaction 0.5h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 40KHZ, power are under the ultrasonic dispersing of 800W, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting 350g zero(ppm) water, add three times filter cake, is that 40KHZ, power are under the ultrasonic dispersing of 800W in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
Embodiment 4
One hydration β-D-glucose: 200g
Tap water: 600g
N n dimetylaniline nitrate salt: 192g
0.03% platinum-4A type molecular sieve powder (≤50nm): 8g
With 200g one hydration β-D-glucose, 600g tap water, 192g n n dimetylaniline nitrate salt and 8g 0.03% platinum-4A type molecular sieve powder (≤50nm) add in the reactor drum, under agitation heat to 85 ℃, with 50ml.min
-1Speed will feed reaction system through the air of udst separation, reaction 12h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the 10g gac, be heated to 80 ℃ of decoloring reaction 1h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 40KHZ, power are under the ultrasonic dispersing of 800W, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting 700g zero(ppm) water, add three times filter cake, is that 40KHZ, power are under the ultrasonic dispersing of 800W in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
Embodiment 5
Anhydrous beta-D-glucose: 280g
Tap water: 400g
Monoethylamine nitrate salt: 300g
0.1% nickel-4A type molecular sieve powder (≤50nm): 20g
With 280g anhydrous beta-D-glucose, 400g tap water, 300g monoethylamine nitrate salt and 20g 0.1% nickel-4A type molecular sieve powder (≤50nm) add in the reactor drum, under agitation heat to 100 ℃, with 55ml.min
-1Speed will feed reaction system through the air of udst separation, reaction 8h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the 10g gac, be heated to 85 ℃ of decoloring reaction 0.5h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 40KHZ, power are under the ultrasonic dispersing of 800KW, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting the 500g deionized water, add three times filter cake, is that 40KHZ, power are under the ultrasonic dispersing of 800KW in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
Embodiment 6
Anhydrous alpha-D-glucose: 180g
Tap water: 600g
Diethylamine nitrate salt: 210g
0.02% palladium-alumina powder (≤50nm): 10g
With the anhydrous alpha-D-glucose of 180g, 600g tap water, 210g diethylamine nitrate salt and 10g 0.02% palladium-alumina powder (≤50nm) add in the reactor drum, under agitation heat to 100 ℃, with 40ml.min
-1Speed oxygen is fed reaction system, the reaction 9h obtain crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the 9g gac, be heated to 80 ℃ of decoloring reaction 1h, filter and obtain secondary filter cake (discarding) and secondary mother liquid; In frequency is that 40KHZ, power are under the ultrasonic dispersing of 600W, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters to obtain three filter cakes and three mother liquors (discarding); Getting 450g zero(ppm) water, add three times filter cake, is that 40KHZ, power are under the ultrasonic dispersing of 600W in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
Claims (6)
1. the compound method of a mixed glucose derivative; It is characterized in that the weight percent according to glucose, solvent, slightly acidic nitrate oxidizer and catalyzer is 0.1%～98%: 0.1%～98%: 0.1%～98%: 0.001%～60% ratio; Wherein, Catalyst system therefor is that particle diameter is that the 2nm～following pure metal powder of 10 μ m or the weight percent of metal are the metal load type powder of 0.025%-12%: any one or more in platinum powder end, palladium powder, nickel by powder, platinum-active carbon powder, palladium-active carbon powder, nickel-active carbon powder, platinum-alumina powder, palladium-alumina powder, nickel-alumina powder, platinum-silica gel powder, palladium-silica gel powder, nickel-silica gel powder, platinum-diatomite powder, palladium-diatomite powder, nickel-diatomite powder, platinum-titania powder, palladium-titania powder, nickel-titania powder, platinum-4A type molecular sieve powder, palladium-4A type molecular sieve powder, the nickel-4A type molecular sieve powder; With glucose, solvent, slightly acidic nitrate oxidizer and catalyst mix; Under agitation heat to 40 ℃～100 ℃; PM feeds reaction system with the speed of reaction solution volume 0.001%～100% with air or oxygen, and reaction 0.1h～20h obtains crude product; Filtration of crude product is obtained a filter cake and a mother liquor, and a filter cake is a catalyzer, after washing, filtration and oven dry are handled, recycles; In a mother liquor, add the gac of its weight 0.001%～20%, be heated to 40 ℃～100 ℃ decoloring reaction 0.1h～5h, filter and obtain secondary filter cake and secondary mother liquid; In frequency is that 20KHz～1MHz, power are under the ultrasonic dispersing of 30W～15KW, in secondary mother liquid, drips the lime acetate saturated aqueous solution and produces to no longer including the glucaric acid calcium deposit, filters and obtains three filter cakes and three mother liquors; Getting the zero(ppm) water of 1～10 times of three filter cake weight, add three times filter cake, is that 20KHz～1MHz, power are under the ultrasonic dispersing of 30W～15KW in frequency; Drip concentrated hydrochloric acid to three time filter cake CL and obtain clear solution, drip 95% ethanol again and separate out, filter and obtain crystal and mother liquor to no longer including crystallization; Mother liquor reclaims ethanol through fractionation; Crystal promptly obtains mixed glucose derivative through 95% washing with alcohol, filtration and oven dry again, i.e. glucaric acid, glucaric acid-1,4-lactone and glucaric acid-1; 4:3, the mixture of 6-dilactone.
2. compound method according to claim 1 is characterized in that the glucose that reacts used is any one or more in anhydrous D-glucose, anhydrous alpha-D-glucose, anhydrous beta-D-glucose, a hydration D-glucose, a hydration alpha-D-glucose, the hydration β-D-glucose.
3. compound method according to claim 1 is characterized in that the solvent that reacts used is any in zero(ppm) water, tap water, the deionized water.
4. compound method according to claim 1 is characterized in that the slightly acidic nitrate oxidizer of reacting used is any one or more in an ammonium nitrate, urea nitrate, Monomethylamine nitrate salt, n n dimetylaniline nitrate salt, Trimethylamine 99 nitrate salt, monoethylamine nitrate salt, diethylamine nitrate salt and the triethylamine nitrate salt.
5. compound method according to claim 1 is characterized in that the air that reacts used is the air of handling through udst separation.
6. compound method according to claim 1 is characterized in that the oxygen that reacts used is air separation gained oxygen, brine electrolysis gained oxygen, thermal degradation ydrogen peroxide 50 gained oxygen and ydrogen peroxide 50 any in the catalytically decomposed gained oxygen under the Manganse Dioxide effect.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501989B2 (en) | 2009-06-13 | 2013-08-06 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US8669397B2 (en) | 2009-06-13 | 2014-03-11 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US8669393B2 (en) | 2010-03-05 | 2014-03-11 | Rennovia, Inc. | Adipic acid compositions |
| US8785683B2 (en) | 2009-06-13 | 2014-07-22 | Rennovia, Inc. | Production of glutaric acid and derivatives from carbohydrate-containing materials |
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| US9770705B2 (en) | 2010-06-11 | 2017-09-26 | Rennovia Inc. | Oxidation catalysts |
| KR101679914B1 (en) * | 2014-08-18 | 2016-11-25 | 현대자동차주식회사 | Synthesis method of glucaric acid |
| JP6290756B2 (en) * | 2014-09-17 | 2018-03-07 | 旭化成株式会社 | Method for producing compound having two or more carboxyl groups from primary alcohol, and catalyst used therefor |
| RU2017109722A (en) * | 2014-09-29 | 2018-11-07 | Арчер-Дэниелс-Мидлэнд Компани | PRODUCTION AND SEPARATION OF A MIXTURE CONTAINING DICARBOXYLIC ACID USING THE DICARBOXYLATE FORM OF ANION EXCHANGE RESIN FOR CHROMATOGRAPHY |
| CN107188795A (en) * | 2017-06-05 | 2017-09-22 | 中国石油大学(华东) | A kind of method that low-temperature catalytic oxidation method prepares saccharic acid |
| CN108117782A (en) * | 2017-12-25 | 2018-06-05 | 金华联创塑粉科技有限公司 | A kind of glucose modified environment-friendly type coating and preparation method thereof |
| KR102598533B1 (en) * | 2018-08-24 | 2023-11-03 | 현대자동차주식회사 | Method for manufacturing the d-glucaro-1,4:6,3-dilactone |
| CN109678695B (en) * | 2019-01-21 | 2021-05-04 | 江苏东南纳米材料有限公司 | Preparation method of calcium glucarate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501989B2 (en) | 2009-06-13 | 2013-08-06 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US8669397B2 (en) | 2009-06-13 | 2014-03-11 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US8785683B2 (en) | 2009-06-13 | 2014-07-22 | Rennovia, Inc. | Production of glutaric acid and derivatives from carbohydrate-containing materials |
| US8927768B2 (en) | 2009-06-13 | 2015-01-06 | Rennovia, Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US9156766B2 (en) | 2009-06-13 | 2015-10-13 | Rennovia Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US9174911B2 (en) | 2009-06-13 | 2015-11-03 | Rennovia Inc. | Production of glutaric acid and derivatives from carbohydrate-containing materials |
| US9434709B2 (en) | 2009-06-13 | 2016-09-06 | Rennovia Inc. | Production of adipic acid and derivatives from carbohydrate-containing materials |
| US8669393B2 (en) | 2010-03-05 | 2014-03-11 | Rennovia, Inc. | Adipic acid compositions |
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