CN114685570B - Preparation method of green surfactant alkyl glycoside - Google Patents
Preparation method of green surfactant alkyl glycoside Download PDFInfo
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- CN114685570B CN114685570B CN202210310105.1A CN202210310105A CN114685570B CN 114685570 B CN114685570 B CN 114685570B CN 202210310105 A CN202210310105 A CN 202210310105A CN 114685570 B CN114685570 B CN 114685570B
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- 229930182470 glycoside Natural products 0.000 title claims abstract description 69
- -1 alkyl glycoside Chemical class 0.000 title claims abstract description 63
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 30
- 229920001685 Amylomaize Polymers 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006206 glycosylation reaction Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- 229920000856 Amylose Polymers 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 229920002472 Starch Polymers 0.000 claims description 19
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 235000019698 starch Nutrition 0.000 claims description 15
- 239000008107 starch Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 12
- 229920002261 Corn starch Polymers 0.000 claims description 10
- 239000008120 corn starch Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 240000004922 Vigna radiata Species 0.000 claims description 4
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 4
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 4
- 239000003622 immobilized catalyst Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229940100445 wheat starch Drugs 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 7
- 150000002338 glycosides Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 9
- 239000008103 glucose Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 230000013595 glycosylation Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005858 glycosidation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 230000006098 transglycosylation Effects 0.000 description 1
- 238000005918 transglycosylation reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B33/00—Preparation of derivatives of amylose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Materials Engineering (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a preparation method of novel green surfactant alkyl glycoside, and belongs to the technical field of surfactants. The preparation method comprises the following steps: s1, adding high amylose starch into mixed fatty alcohol, and stirring to uniformly disperse the high amylose starch; adding a mixed acid supported catalyst into the mixed solution, continuously stirring uniformly, slowly heating to raise the temperature, and vacuumizing and placing nitrogen for glycosylation reaction; s2, after the reaction is completed, cooling, regulating the pH value, and filtering to remove the mixed acid supported catalyst and byproducts, thereby obtaining the alkyl glycoside. The preparation method disclosed by the invention is simple in process, the high-amylose starch and the mixed fatty alcohol are used as raw materials, the mixed acid supported catalyst is adopted to synthesize the alkyl glycoside, the glycoside conversion rate is effectively improved, the side reaction is less, the prepared alkyl glycoside is light in color, and the catalyst is easy to separate and recycle.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a preparation method of a green surfactant alkyl glycoside.
Background
Alkyl glycoside (APG) is a nonionic surfactant with excellent performance, has many advantages of anionic surfactant, such as high surface activity, abundant, fine and stable foam, excellent detergency, excellent compatibility, good biodegradability, no irritation to skin, good compatibility with human body and the like, and is widely applied to many fields of washing industry, cosmetic industry, food processing industry, pesticide and the like. The alkyl glycoside is usually prepared from glucose or starch and fatty alcohol which are natural renewable resources, and toxicity test experiments show that the toxicity of APG is far lower than that of surfactants such as LAS, AEO and the like, and the APG belongs to a nontoxic product. The american society of soaps and detergents (Soap and Detergent Association, SDA for short) has experimentally demonstrated low irritation to skin and rapid and complete biodegradability of APG. Thus, alkyl glycosides are fully known as green surfactants.
The alkyl glycoside can be synthesized by a direct glycosidation method in one step or by a transglycosidation method in two steps, and the production process is mature. The direct glycosidation method (one-step method) is the most studied method at present, and particularly, glucose and fatty alcohol directly react to generate alkyl glycoside under the action of a catalyst, and compared with the transglycosidation method, the process of exchanging double alcohols and removing lower alcohols is omitted, so that the process is simpler, and the product quality is better. However, because of poor intersolubility of high-carbon alcohol and glucose, the reaction speed is low, so that strict control on reaction conditions is needed in the reaction process: for example, the water release rate is ensured to be higher than the water generation rate in the reaction process, otherwise problems such as caramel and glucose agglomeration are easy to generate. In the method, the quality of the alkyl glycoside product is greatly influenced by the kind of the catalyst, and acid substances such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, citric acid, inorganic acid and the like are often adopted as the catalyst. However, for some fatty alcohols branched at the beta-position, the steric hindrance of the hydroxyl group is large, so that the reactivity of the fatty alcohols with glucose to form glycoside is not high, and the reaction conversion rate is low or even not. The organic acid is fully contacted with the reactant, which is beneficial to accelerating the reaction speed and reducing the concentration of self-polymers of sugar, but also brings inconvenience to the subsequent separation and purification.
In addition, the alkyl glycoside is required to be prepared under the high-temperature and acid catalysis conditions, and the starch or glucose can easily generate side reactions of generating colored impurities such as ether, levulinic acid, furfural or hydroxymethylfurfural in the environment, so that the product is dark and has darker color, the burden of a decoloring step is increased, and the production cost is increased.
The long carbon chain alkyl glycoside has the defects of poor water solubility and the like, and at present, fatty alcohol polyoxyethylene ether with low EO addition number is mostly adopted to replace fatty alcohol for glycosylation to prepare an alcohol ether glycoside product, so that the excellent performance of the alkyl glycoside can be maintained, and the water solubility of the alkyl glycoside can be improved. But simultaneously has the problems of liquid acid corrosion equipment, complex process, low catalytic activity, impure products and the like.
Therefore, it is necessary to develop a preparation method of alkyl glycoside with simple process, high catalytic activity, high glycoside conversion rate, less side reaction and light color.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a green surfactant alkyl glycoside, which has simple process, and the prepared alkyl glycoside has light color and luster by taking high amylose starch and mixed fatty alcohol as raw materials and adopting a mixed acid supported catalyst to synthesize the alkyl glycoside, thereby effectively improving the glycoside conversion rate and having less side reaction.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing a green surfactant alkyl glycoside, which comprises the following steps:
s1, adding high amylose starch into mixed fatty alcohol, and stirring to uniformly disperse the high amylose starch; adding a mixed acid supported catalyst into the mixed solution, continuously stirring uniformly, slowly heating to raise the temperature, and vacuumizing and placing nitrogen for glycosylation reaction; detecting or observing the color of the mixture by using a Filin reagent in the reaction process to judge the reaction end point;
s2, after the reaction is completed, cooling, regulating the pH value, and filtering to remove the mixed acid supported catalyst and byproducts, thus obtaining the crude product of the alkyl glycoside.
In the preparation method, the glycosylation reaction formula of the high amylose starch and the mixed fatty alcohol is as follows:
wherein R1 independently represents a straight-chain or isomeric alkyl group having 2 to 16 carbon atoms; n is the degree of polymerization of glucose, n=1 to 10.
In the mixed system obtained by the above method, the average polymerization degree of glucose is 1.5 to 2.6, preferably 1.5 to 1.8.
As a preferred embodiment of the present invention, the mass ratio of the high amylose starch to the mixed fatty alcohol is 1:3-5.
As a preferred embodiment of the present invention, the mixed acid supported catalyst is prepared by supporting p-toluenesulfonic acid and citric acid on activated alumina. Further preferably, the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1:3-1:8, preferably 1:6.
As a preferred embodiment of the invention, the preparation method of the mixed acid supported catalyst comprises the following steps: roasting active alumina at 350-450 deg.c for 4-6 hr, water washing for 2-3 times and drying at 100-120 deg.c for 2-4 hr; adding the treated active alumina carrier into a mixed solution of p-toluenesulfonic acid and citric acid, continuously stirring in a water bath at 75-95 ℃ until moisture is evaporated to dryness, drying at 125-145 ℃ until the weight is constant, and calculating the load quantity to obtain the catalyst.
As a preferred embodiment of the present invention, the amount of the mixed acid supported catalyst added is 0.2 to 3%, preferably 1.5% of the total mass of the high amylose starch and the mixed fatty alcohol.
In a preferred embodiment of the present invention, the mixed fatty alcohol is a mixture of dodecanol and tetradecanol mixed in a mass ratio of 2:1 to 4:1.
As a preferred embodiment of the present invention, the high amylose starch means a starch having an amylose content of 50% or more, preferably 50% of the amylose content of the starch granule. Further preferably, the high amylose starch is one of corn starch, wheat starch, tapioca starch, potato starch or mung bean starch; corn starch is preferred.
As a preferred embodiment of the invention, the reaction temperature of the glycosylation reaction in the step S1 is 90-140 ℃, and the vacuum pumping is carried out until the residual pressure is less than 60mmHg; the reaction time is 130 to 210min, preferably 180min.
In the preferred embodiment of the present invention, in the step S2, the pH of the mixed solution is adjusted to be greater than 7 by NaOH solution or KOH solution, and the pH is preferably 7 to 8. Further preferably, the mass concentration of the NaOH solution or KOH solution is 30 to 50%, preferably 35 to 40%.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the alkyl glycoside provided by the invention takes high amylose starch and mixed fatty alcohol as raw materials, adopts a mixed acid supported catalyst and prepares the alkyl glycoside by a direct glycosylation method (one-step method), and has the following advantages:
1. compared with the conventional alkyl glycoside product synthesized by using common starch as a raw material, the high-amylose starch can avoid side reaction, so that the raw material utilization rate is higher, the surface tension of the product is low, and the surface activity is higher.
2. The supported solid mixed acid catalyst is adopted for catalytic reaction, so that the catalyst has the advantages of light color and luster of a product, high catalytic activity, small environmental pollution, no corrosion to a device, easiness in separation, repeated utilization and the like in the synthesis of the alkyl glycoside, can alleviate the defects of troublesome subsequent separation, impure product, environmental pollution, equipment corrosion and the like caused by taking liquid acid as the catalyst, and has good economic benefit and environmental benefit.
3. The direct glycosidation method (one-step method) is adopted, starch and mixed alcohol directly react under the action of a catalyst to generate alkyl glycoside, and compared with the transglycosylation method, the process of exchanging double alcohols and removing lower alcohols is omitted, so that the process is simpler, and the product quality is better.
In conclusion, the preparation method provided by the invention effectively improves the reactivity of the fatty alcohol and high-amylose glycosylation, and has the advantages of simple process flow, high glycoside conversion rate, less side reaction, light color and no need of additional decolorization.
Drawings
FIG. 1 is a diagram of the product of the alkyl glycoside synthesized in example 1 of the present invention;
FIG. 2 is a product diagram of the alkyl glycoside synthesized in example 2 of the present invention;
FIG. 3 is a product diagram of the alkyl glycoside synthesized in example 3 of the present invention;
FIG. 4 is a product diagram of the alkyl glycoside synthesized in example 4 of the present invention;
FIG. 5 is a product diagram of the alkyl glycoside synthesized in comparative example 1 of the present invention;
FIG. 6 is a product diagram of the alkyl glycoside synthesized in comparative example 2 of the present invention;
FIG. 7 is a diagram showing the product of the alkyl glycoside synthesized in comparative example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the detailed description, but the embodiments of the present invention are not limited thereto. The reagents used in the examples are commercially available as usual unless otherwise specified.
A method for preparing a green surfactant alkyl glycoside, which comprises the following steps:
s1, adding high-amylose starch into mixed fatty alcohol according to the mass ratio of the high-amylose starch to the mixed fatty alcohol of 1:3-5, and stirring to uniformly disperse the high-amylose starch; adding a mixed acid immobilized catalyst into the mixed solution according to 0.2-3% of the total mass of high amylose starch and mixed fatty alcohol, continuously stirring uniformly, slowly heating to 90-140 ℃, vacuumizing to residual pressure less than 60mmHg, and placing nitrogen for glycosylation reaction for 130-210 min; in the reaction process, a Filin reagent or observing the color of the mixture is adopted to judge the reaction end point; wherein the mixed fatty alcohol is a mixture formed by mixing dodecanol and tetradecanol according to the mass ratio of 2:1-4:1;
s2, after the reaction is completed, cooling, adjusting the pH to be more than 7 by adopting a NaOH solution or a KOH solution with the mass concentration of 30-50%, and filtering to remove the mixed acid supported catalyst and byproducts, thereby obtaining the crude product of the alkyl glycoside.
In the method, the mixed acid supported catalyst is prepared by supporting p-toluenesulfonic acid and citric acid on activated alumina. Further preferably, the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1:3-1:8, preferably 1:6. The preparation method of the mixed acid supported catalyst comprises the following steps: roasting active alumina at 350-450 deg.c for 4-6 hr, water washing for 2-3 times and drying at 100-120 deg.c for 2-4 hr; adding the treated active alumina carrier into a mixed solution of p-toluenesulfonic acid and citric acid, continuously stirring in a water bath at 75-95 ℃ until moisture is evaporated to dryness, drying at 125-145 ℃ until the weight is constant, and calculating the load quantity to obtain the catalyst.
Example 1
A method for preparing a green surfactant alkyl glycoside, which comprises the following steps:
s1, weighing 32g of high-amylose corn starch with the amylose content of 50%, adding the high-amylose corn starch into a 500ml four-necked flask with a stirrer, a thermometer and a water diversion device, wherein the 500ml four-necked flask is provided with 160g of mixed fatty alcohol consisting of dodecanol and tetradecanol according to the mass ratio of 2:1, and stirring the mixture to uniformly disperse the high-amylose corn starch; adding 2.9g of mixed acid immobilized catalyst (the mixed mass ratio of p-toluenesulfonic acid to citric acid is 1:5) into the mixed solution according to 1.5% of the total mass of high amylose starch and mixed fatty alcohol, continuously stirring uniformly, slowly heating to 120 ℃ for glycosylation reaction after a condensing reflux pipe is arranged, reacting for 180min, vacuumizing by a diaphragm pump until the residual pressure is less than 60mmHg, and adding nitrogen; taking 1ml of reaction system mixture every 30min in the reaction process, adding 1ml of Filin reagent, heating in boiling water for 2min, and considering the reaction to the end point if only a small amount of brick red precipitate appears at the phase interface or the organic phase; if a large amount of brick red precipitate appears, the system is provided with a large amount of unreacted high-amylose corn starch, and the reaction is continued to the end point.
S2, after the reaction is completed, cooling to 70 ℃, regulating the pH to about 8 by adopting a NaOH solution with the mass concentration of 35%, filtering and removing a mixed acid supported catalyst and other solid byproducts to obtain an alkyl glycoside crude product with the polymerization degree of 1.6, wherein the appearance is shown in a figure 1, the obtained alkyl glycoside crude product is light in color, and the content of residual alcohol is measured to be 0.31%.
Example 2
A method for preparing a green surfactant alkyl glycoside, which comprises the following steps:
s1, weighing 32g of high-amylose mung bean starch with the amylose content of 60%, adding the high-amylose mung bean starch into a 500ml four-necked flask with a stirrer, a thermometer and a water diversion device, wherein the 500ml four-necked flask is provided with 160g of mixed fatty alcohol consisting of dodecanol and tetradecanol according to the mass ratio of 2:1, and stirring the mixture to enable the mixed fatty alcohol to be uniformly dispersed; adding 2.9g of mixed acid immobilized catalyst (the mixed mass ratio of p-toluenesulfonic acid to citric acid is 1:5) into the mixed solution according to 1.5% of the total mass of high amylose starch and mixed fatty alcohol, continuously stirring uniformly, slowly heating to 130 ℃ for glycosylation reaction after a condensing reflux pipe is arranged, reacting for 120min, vacuumizing until the residual pressure is 60mmHg, and placing nitrogen; in the reaction process, using a KI-I reagent to detect whether starch is completely hydrolyzed, taking 1ml of reaction system mixture every 30min, adding 1ml of Filin reagent, heating in boiling water for 2min, and considering the reaction to the end point if only a small amount of brick red precipitation appears at a phase interface or an organic phase; if a large amount of brick red precipitate appears, the system is provided with a large amount of unreacted high-amylose corn starch, and the reaction is continued to the end point.
S2, after the reaction is completed, cooling to 80 ℃, regulating the pH to about 8 by adopting a NaOH solution with the mass concentration of 30%, filtering and removing a mixed acid supported catalyst and other solid byproducts to obtain an alkyl glycoside crude product with the polymerization degree of 1.4, wherein the appearance is shown in a figure 2, the obtained alkyl glycoside crude product is light in color, and the content of residual alcohol is measured to be 0.34%.
Example 3
A method for preparing a green surfactant alkyl glycoside, which comprises the following steps:
s1, weighing 32g of high-amylose wheat starch with 50% of amylose content, adding the high-amylose wheat starch into a 500ml four-necked flask with a stirrer, a thermometer and a water diversion device, wherein 160g of mixed fatty alcohol consisting of dodecanol and tetradecanol according to the mass ratio of 2:1 is filled in the four-necked flask, and stirring the mixture to enable the mixture to be uniformly dispersed; adding 2g of mixed acid supported catalyst (the mixing mass ratio of p-toluenesulfonic acid to citric acid is 1:5) into the mixed solution, continuously stirring uniformly, arranging a condensing reflux pipe, slowly heating to 120 ℃ for glycosylation reaction, wherein the reaction time is 180min, vacuumizing to residual pressure of 30mmHg, and placing nitrogen; when the mixture changed from white emulsion to translucent paste, the reaction was detected by using the kit until the residual starch content was 0.21%.
S2, after the reaction is completed, cooling to 70 ℃, regulating the pH to 7.5 by adopting a NaOH solution with the mass concentration of 40%, filtering to remove a mixed acid supported catalyst and other solid byproducts, and obtaining an alkyl glycoside crude product with the polymerization degree of 1.3, wherein the appearance is shown in a figure 3, the obtained alkyl glycoside crude product is lighter in color, and the content of residual alcohol is measured to be 0.35%.
Example 4
A method for preparing a green surfactant alkyl glycoside, which comprises the following steps:
s1, weighing 200kg of high-amylose tapioca starch with 50% of amylose content and 830kg of mixed fatty alcohol consisting of dodecanol and tetradecanol according to the mass ratio of 2:1 into a reaction kettle, and stirring to uniformly disperse the mixed fatty alcohol; adding 3.9kg of mixed acid supported catalyst (the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1:5) into a reaction kettle, continuously stirring uniformly, slowly heating to 125 ℃ for glycosylation reaction, vacuumizing to residual pressure of 30mmHg, and placing nitrogen for 3 hours; when the reaction liquid becomes transparent, the reaction is considered to reach the end point.
S2, after the reaction is completed, cooling to 70 ℃, regulating the pH to 7.5 by adopting a NaOH solution with the mass concentration of 45%, filtering to remove a mixed acid supported catalyst and byproducts, and obtaining an alkyl glycoside crude product with the polymerization degree of 1.5, wherein the appearance is shown in figure 4, the obtained alkyl glycoside crude product is light in color, and the content of residual alcohol is measured to be 0.32%.
Comparative example 1:
60.7g of high-amylose corn starch (the molecular content of the amylose is 50%) is weighed and added into 139.3g of ethylene glycol, and the mixture is stirred uniformly; then adding 1.6g of p-toluenesulfonic acid and 0.4g of phosphoric acid into the mixed solution, and uniformly stirring; heating the mixed solution to 105 ℃, stirring, and reacting for 60min to obtain a clear and transparent solution; maintaining the temperature at 105 ℃, and finally adding 69.7g of dodecanol into the clear and transparent solution, and uniformly stirring; the mixed solution was kept at 105℃for 180min. As shown in FIG. 5, the alkyl glycoside obtained by the above steps has a residual alcohol content of 0.62% and a deep color.
Comparative example 2:
60.7g of high-amylose corn starch (the molecular content of the amylose is 80%) is weighed and added into 139.3g of ethylene glycol, and the mixture is stirred uniformly; then adding 1.6g of p-toluenesulfonic acid and 0.4g of phosphoric acid into the mixed solution, and uniformly stirring; heating the mixed solution to 120 ℃, stirring, and reacting for 60min to obtain a clear and transparent solution; maintaining the temperature at 120 ℃, and finally adding 48.7g of octanol into the clear and transparent solution, and uniformly stirring; the mixed solution was kept at 120℃for 180min. The alkyl glycoside product obtained by the above procedure is shown in FIG. 6, and gives a transparent liquid with a residual alcohol content of 0.66% which is almost colorless.
Comparative example 3:
s1, adding 1128kg of fatty alcohol (C18-20) and 198kg of glucose into a reaction kettle, adding 4.5kg of acid catalyst, heating to 110-120 ℃, carrying out acetalation reaction under vacuum condition of 0.09MPa, reacting for 8-10 hours, adding potassium hydroxide to adjust pH value to 6-7 after the reaction liquid is transparent, and transferring the reaction liquid into a distillation kettle.
S2, performing secondary evaporation in a distillation kettle by using a thin film evaporator to remove excessive C18-20 alcohol, wherein the alkyl glycoside product obtained by the steps is shown in figure 7, and the alkyl glycoside crude product with the polymerization degree of 1.4 and the residual C18-20 alcohol content of 0.87% is obtained.
As can be seen from FIGS. 1 to 7, the alkyl glycoside products prepared in examples 1 to 4 are lighter in color and have a residual alcohol content of 0.31 to 0.35%, wherein the color and the residual alcohol content of FIG. 1 are the best, and thus the product performance of example 1 is the best; the residual alcohol content was higher in each of comparative examples 1 to 3. The preparation method provided by the invention has the advantages that the reactivity of the fatty alcohol and high-amylose glycosylation is effectively improved, the process flow is simple, the glycoside conversion rate is high, the side reaction is less, the color is light, and no additional decolorization is needed.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (7)
1. A preparation method of a green surfactant alkyl glycoside is characterized by comprising the following steps: the method comprises the following steps:
s1, adding high amylose starch into mixed fatty alcohol, and stirring to uniformly disperse the high amylose starch; adding a mixed acid supported catalyst into the mixed solution, continuously stirring uniformly, slowly heating, vacuumizing, placing nitrogen, and carrying out glycosylation reaction at the reaction temperature of 90-140 ℃ for 130-210 min; wherein the mixed acid supported catalyst is prepared by loading p-toluenesulfonic acid and citric acid on active alumina, and the mixing mass ratio of the p-toluenesulfonic acid to the citric acid is 1:3-1:8; the mixed fatty alcohol is a mixture formed by mixing dodecanol and tetradecanol according to the mass ratio of 2:1-4:1;
s2, after the reaction is completed, cooling to 70-80 ℃, regulating the pH value, and filtering to remove the mixed acid supported catalyst and byproducts, thus obtaining the crude product of the alkyl glycoside.
2. The method for preparing the green surfactant alkyl glycoside according to claim 1, wherein: the mass ratio of the high amylose starch to the mixed fatty alcohol is 1:3-5.
3. The method for preparing the green surfactant alkyl glycoside according to claim 1, wherein: the preparation method of the mixed acid supported catalyst comprises the following steps: roasting active alumina at 350-450 deg.c for 4-6 hr, water washing for 2-3 times and drying at 100-120 deg.c for 2-4 hr; adding the treated active alumina carrier into a mixed solution of p-toluenesulfonic acid and citric acid, continuously stirring in a water bath at 75-95 ℃ until moisture is evaporated to dryness, drying at 125-145 ℃ until the weight is constant, and calculating the load quantity to obtain the catalyst.
4. The method for preparing the green surfactant alkyl glycoside according to claim 1 or 2, characterized in that: the addition amount of the mixed acid immobilized catalyst is 0.2-3% of the total mass of the high amylose starch and the mixed fatty alcohol.
5. The method for preparing the green surfactant alkyl glycoside according to claim 1 or 2, characterized in that: the content of the amylose in the high amylose starch is more than or equal to 50 percent.
6. The method for preparing the green surfactant alkyl glycoside according to claim 1 or 2, characterized in that: the high amylose starch is one of corn starch, wheat starch, tapioca starch, potato starch or mung bean starch.
7. The method for preparing the green surfactant alkyl glycoside according to claim 1 or 2, characterized in that: in the step S2, naOH solution or KOH solution with the mass concentration of 30-50% is adopted to adjust the pH value of the mixed solution to be more than 7.
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