CN106957377B - Preparation method of inulin propionate - Google Patents
Preparation method of inulin propionate Download PDFInfo
- Publication number
- CN106957377B CN106957377B CN201710352475.0A CN201710352475A CN106957377B CN 106957377 B CN106957377 B CN 106957377B CN 201710352475 A CN201710352475 A CN 201710352475A CN 106957377 B CN106957377 B CN 106957377B
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- Prior art keywords
- inulin
- ethanol solution
- propionic anhydride
- stirring
- propionate
- Prior art date
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- 229920001202 Inulin Polymers 0.000 title claims abstract description 149
- 229940029339 inulin Drugs 0.000 title claims abstract description 149
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 title claims abstract description 147
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 238000005886 esterification reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- QKVOMHAOSPGHDT-UHFFFAOYSA-N ethanol;propanoyl propanoate Chemical compound CCO.CCC(=O)OC(=O)CC QKVOMHAOSPGHDT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 17
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- 230000032050 esterification Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 91
- 239000000243 solution Substances 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 56
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
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- 239000003960 organic solvent Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
- C08B37/0054—Inulin, i.e. beta-2,1-D-fructofuranan; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of additive preparation, and particularly relates to a preparation method of inulin propionate, wherein inulin, solid alkali and water are mixed under a stirring state, then propionic anhydride ethanol solution is added in batches for esterification, and alkali liquor is added during the esterification reaction, so that the pH value is controlled to be 9-11. The method for preparing the inulin propionate has the advantages of simple process, convenient operation, low energy consumption, less side reaction, low production cost, high product yield and little environmental pollution, is suitable for preparing the Ds inulin propionate with high substitution degree, and has good appearance and color, stable quality and obvious economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of additive preparation, and particularly relates to a preparation method of inulin propionate.
Background
Inulin propionate, also known as propionate inulin, is prepared by esterification of inulin monosaccharide hydroxyls with propionic anhydride. The inulin propionate has effects of lowering blood sugar, controlling blood lipid, promoting absorption of human body mineral substance, reducing intestinal pathogenic bacteria and putrefying bacteria, preventing constipation and treating obesity. Short-chain fatty acids such as propionate and propionic acid contained in inulin propionate may play an important role in appetite regulation, and can regulate intestinal flora and improve intestinal function; inhibiting toxic fermentation products, increasing defecation speed, and preventing colon cancer; it also can stimulate intestinal tract, promote secretion and release of hormone such as polypeptide YY and glucagon-like peptide-1, act on brain to reduce hunger sensation, help people with excessive weight eat less, and inhibit obesity. By taking the inulin propionate, more propionate can be released by intestinal tracts, the satiety of people is enhanced, the calorie intake is reduced, the inhibition effect on eating more foods is stronger, and the obesity chance is reduced.
Inulin propionate is also effective in pharmaceutical carriers, vaccine adjuvants, metal chelation, and detergency. Inulin propionate replaces organic phosphonate in the aspect of metal ion scale inhibition to be used for water body scale inhibition, can prevent water body eutrophication, and solves the problem of difficult degradation. The inulin propionate enables the surfaces of calcium carbonate crystals to be negatively charged and mutually repel and disperse through complexation with calcium ions, the calcium carbonate crystals are converted into more dispersible spheres from cubic shapes, and the scale inhibition effect of the inulin propionate is enhanced along with the increase of the degree of substitution Ds of the inulin propionate. Inulin propionate to divalent calcium ion Ca2+The scale inhibition rate reaches 99.6 percent, and the scale inhibitor is used for divalent copper ions Cu2+The removal rate reaches 92.5 percent.
The inulin propionate can also be used for inhibiting bacteria and sterilizing, absorbing moisture and keeping moisture, and has good antibacterial effect on gram-negative bacteria escherichia coli. The inulin propionate has good biocompatibility and no harm to human body, can replace biological glycerol and hyaluronic acid, and can be used for skin moisturizing of cosmetics and fresh keeping of various vegetables and fruits. The moisture absorption and moisture retention effects of the inulin propionate are superior to those of glycerol and hyaluronic acid, the moisture retention rate of the inulin propionate is about 2 times that of the glycerol and hyaluronic acid under the same humidity environment, and the higher the substitution degree Ds of the inulin propionate is, the better the moisture absorption and moisture retention effects are.
At present, the production method of inulin propionate is mainly a wet method, which is also called a slurry method, and water or inert organic solvent is usually used as a reaction medium for esterification reaction, and the method is generally divided into an aqueous solution method and an organic solvent method. The water solution method takes water as a reaction medium, the inulin is dissolved in the water, and the inulin and the propionic anhydride solution are subjected to homogeneous reaction under certain conditions. After the reaction is finished, the mixed solution of the crude inulin propionate is put into a cyclone scrubber and repeatedly washed by ethanol or pure water or evaporated and concentrated to remove unreacted substances and inorganic salts remained in the inulin propionate, and then the wet inulin propionate is subjected to reduced pressure filtration, vacuum drying and airflow pulverization. The aqueous solution method has the advantages of uniform reaction, simple process, less impurities, long reaction time, easy generation of inulin gel, large wastewater amount, more product loss, high energy consumption, more side reactions, low yield, high cost and poor product appearance and color, and only can prepare products with low degree of substitution Ds. The organic solvent method generally selects an organic solvent which can be mixed with water as a medium to carry out esterification reaction. The organic solvent can promote the reaction process to improve the substitution degree and the reaction efficiency of the product, and simultaneously keeps the original powder insoluble and undispersed, but has the disadvantages of multiple production links, complex process, solvent recovery, flammable and explosive production places and large investment. Therefore, methods and process conditions suitable for inulin propionate production are urgently needed to be sought, and the problems in the existing inulin propionate production are solved.
Disclosure of Invention
In view of the above, the invention provides a preparation method of inulin propionate.
The specific technical scheme of the invention is as follows:
under the stirring state, inulin, solid alkali and water are mixed, then propionic anhydride ethanol solution is added in batches for esterification, and alkali liquor is added during the esterification reaction to control the pH to be 9-11.
Preferably, the stirring is parallel biaxial stirring.
Preferably, the solid base is sodium hydroxide or potassium hydroxide; the weight ratio of the inulin to the water is 100: (8-16); the weight ratio of the inulin to the sodium hydroxide is 100: (2-5); the concentration of the propionic anhydride ethanol solution is 50 percent.
Preferably, the step of adding the ethanol solution of propionic anhydride in batches for esterification reaction specifically comprises the following steps:
A. adding propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 50-55 ℃ and the stirring speed of 20-25 rpm;
B. adding propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 60-65 ℃ and the stirring speed of 30-35 rpm;
C. adding propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 70-75 ℃ and the stirring speed of 40-45 rpm.
Preferably, the molar ratio of the propionic anhydride ethanol solution to the inulin in the step A is (1-1.2): 1; in the step B, the molar ratio of the propionic anhydride ethanol solution to the inulin is (0.8-1.6): 1; in the step C, the molar ratio of the propionic anhydride ethanol solution to the inulin is (0.8-1.6): 1.
preferably, the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; the vacuum pressure of the esterification reaction is 50-90 kPa.
Further, the esterification reaction also comprises a crystallization step.
The crystallization step specifically comprises the following steps: mixing the product after esterification with ethanol solution, neutralizing with acid, cooling and crystallizing.
Preferably, the concentration of the ethanol solution is 80-95%, and the acid is sulfuric acid.
The pH value after neutralization with acid is 7-8, and the crystallization temperature is 25-30 ℃.
Further, the method also comprises the step of filtering and washing the filter cake with ethanol after crystallization.
Further, the method also comprises a post-treatment step after the crystallization.
The post-treatment step comprises one or more of drying, crushing and sieving.
Preferably, the drying is vacuum rake stirring drying.
The pulverization is air flow pulverization.
The sieving is to sieve inulin propionate with the granularity of less than or equal to 100 meshes.
In conclusion, the invention provides a method for preparing alaninate, which comprises the steps of mixing inulin, solid alkali and water under the stirring state, then adding an ethanol solution of propionic anhydride in batches for esterification, and adding alkali liquor during the esterification reaction to control the pH to be 9-11. Compared with the prior art, the method has the advantages of simple process, convenient operation, low energy consumption, less side reaction, low production cost, high product yield and little environmental pollution, is suitable for preparing high-substitution Ds inulin propionate products, and the inulin propionate prepared by the method has good appearance and color, stable quality and obvious economic and social benefits.
Detailed Description
The invention discloses a preparation method of inulin propionate. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods described herein, as well as appropriate variations and combinations of the methods described herein, may be made to implement and use the techniques of the present invention without departing from the spirit and scope of the invention.
The invention provides a preparation method of inulin propionate, which comprises the steps of mixing inulin, solid alkali and water under the stirring state, then adding propionic anhydride ethanol solution in batches for esterification reaction, and adding alkali liquor during the esterification reaction to control the pH value to be 9-11.
Hydroxyl in the inulin and propionic anhydride are subjected to chemical reaction to generate inulin propionate and water, and the reaction formula is as follows:
the number of active hydroxyl groups on each D-glucose unit in inulin, which are substituted by propionic anhydride, is called the degree of substitution, and is given in English by the term of severity of failure, Ds for short.
Inulin (Inulin) also known as chrysanthemumSugar, white odorless powder, slightly sweet, odorless, slightly soluble in cold water, soluble in hot water, and widely present in plant tissues such as Jerusalem artichoke (Helianthus, Tuberosus) or herba Cichorii (Chicoriy). Inulin of the general molecular formula (C)6H10O5) n, average molecular weight 5400, polymerization degree DP of 2-60 usually, average polymerization degree 9, it is produced by connecting D-fructose molecules with β - (2, 1) glycosidic bond, inulin molecule is polymerized from about 31 β -D-fructose and 1-2 pyranose residues, most of the chain is fructose, the chain end often has a glucose, propionate inulin is prepared by acylation reaction of propionic anhydride with terminal hydroxyl group at one end, pure inulin is odorless, white amorphous powder, slightly soluble in cold water and easily soluble in hot water, short chain inulin is usually more soluble in water than long chain inulin, solubility of long chain inulin is relatively small, and solubility of inulin increases significantly with temperature increase.
TABLE 1 inulin raw material specifications
TABLE 2 inulin solubility
Propionic anhydride, also known as primary oleic anhydride, Propionic anhydride, and methylacetic anhydride, is a colorless transparent liquid with a molecular formula of (CH)3CH2CO)2O, molecular weight 130.14, relative density 1.0125(20/4 ℃), Refractive index 1.4038, flash point 73 ℃, propionic anhydride melting point-45 ℃, boiling point 167 ℃, Refractive index n20/D is 1.4020-1.4050, the propionic anhydride is dissolved in methanol, ethanol, ether, chloroform and alkali and decomposed in water to form propionic acid, and the Purity of the propionic anhydride is more than or equal to 98% (GC).
In the present invention, the stirring is parallel biaxial stirring. The method can be carried out by adopting a conical ribbon mixer, a rubber internal mixer or a flour-mixing machine, and a parallel double-shaft spiral turbine stirring paddle is arranged in an equipment mixer, so that parallel double-shaft stirring can be carried out, and multi-dimensional mixing, stirring, shearing, conveying and reacting of materials are realized. Meanwhile, the mixing chamber of the device is communicated with an exhaust pipe hole and provided with a thermocouple, and a casting jacket cavity is welded outside the shell of the mixing chamber.
In the present invention, the solid base is preferably sodium hydroxide or potassium hydroxide.
In the invention, the weight ratio of the inulin to the water is 100 (8-16); the weight ratio of the inulin to the sodium hydroxide is 100 (2-5); the concentration of the propionic anhydride ethanol solution is 50 percent.
In some specific embodiments, the weight ratio of the inulin to the water is 100: 10; the weight ratio of the inulin to the sodium hydroxide is 100: 5; the concentration of the propionic anhydride ethanol solution is 50 percent.
In the invention, the step of adding the propionic anhydride ethanol solution in batches for esterification reaction specifically comprises the following steps:
A. adding propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 50-55 ℃ and the stirring speed of 20-25 rpm;
B. adding propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 60-65 ℃ and the stirring speed of 30-35 rpm;
C. adding propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 70-75 ℃ and the stirring speed of 40-45 rpm.
In the invention, before the step A, the temperature of the inulin is increased to 40 ℃, and the temperature increasing speed is 2 ℃/min.
In the invention, the molar ratio of the propionic anhydride ethanol solution to the inulin in the step A is preferably (1-1.2): 1; the molar ratio of the propionic anhydride ethanol solution to the inulin in the step B is preferably (0.8-1.6): 1; the molar ratio of the propionic anhydride ethanol solution to the inulin in the step C is preferably (0.8-1.6): 1.
in some embodiments, the molar ratio of the ethanol solution of propionic anhydride to inulin in step a is 1: 1; the molar ratio of the propionic anhydride ethanol solution to the inulin in the step B is 0.8: 1; the molar ratio of the propionic anhydride ethanol solution to inulin in step C is 0.8: 1.
in the invention, the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution; the vacuum pressure of the esterification reaction is 50-90 kPa.
The amount of the added water in the inulin is suitable for ensuring that the inulin raw material is just soaked and coated by the water, so that water molecules can penetrate into inulin raw material particles, the inulin particles expand by heating after absorbing the water, and the inulin hydroxyl groups are activated. Meanwhile, propionic anhydride is hydrolyzed into propionic acid, and then esterification reaction with inulin is easier to occur. A small amount of water can promote the esterification reaction process of inulin and propionic anhydride materials, so that the materials are prevented from agglomerating into blocks after being mixed, the mutual reaction is not uniform, and the yield of inulin propionate is reduced. On the contrary, if the amount of water added into the inulin raw material is too much, the mixed material flows, so that more side reactions are generated, the esterification reaction is incomplete, and the reaction efficiency is reduced. Therefore, the esterification reaction is firstly carried out under a certain moisture, and then the moisture of the materials is slowly reduced along with the progress of the reaction until the reaction is finished.
Factors affecting the production of inulin propionate according to the invention are also many, such as the amount of base used, the speed of stirring the materials, the esterification temperature, the pressure and the reaction time. The esterification reaction is reversible. Under the catalysis of alkali, inulin hydroxyl OH-The inulin is easy to be changed into oxygen anions, the nucleophilic ability of the inulin is greatly enhanced, the inulin directly generates liquid-solid reaction with a propionic anhydride solution, the esterification reaction is rapidly performed, however, the use amount of alkali is too large, the side reaction is accelerated, and the yield of the inulin propionic anhydride is reduced. Therefore, sodium hydroxide must be continuously added as the esterification reaction proceeds. Firstly, grinding solid sodium hydroxide or potassium hydroxide into powder, mixing the powder with inulin powder, and then spraying 40% sodium hydroxide aqueous solution at any time according to the pH value of reaction materials.
In the invention, along with the increase of the concentration of the propionic anhydride reagent in the reaction system, the substitution degree and the reaction efficiency of the inulin propionic anhydride are rapidly increased; after the concentration of the inulin propionic anhydride reaches a certain value, the substitution degree of the inulin propionic anhydride and the rising range of the concentration of the inulin propionic anhydride become small, and the reaction efficiency is reduced. This is because the available reactive hydroxyl groups in the inulin are constant, and the available substituted hydroxyl groups are relatively reduced as the esterification proceeds; on the other hand, the steric hindrance of the inulin product is increased, the reaction is difficult to perform, the reaction efficiency is gradually reduced, and the whole reaction tends to be balanced. In addition, the reaction process of inulin molecules also undergoes changes in physical and chemical properties. Besides the above influence factors, stirring is also an important influence factor, after all, the mixing of inulin and propionic anhydride solution is an organic reaction with extremely high solid content, and the quality and reaction efficiency of the product are directly influenced by the good or bad stirring effect. The materials are mixed and stirred, at the moment, the concentration of the materials is high, the reaction speed is high, and the stirring speed is not suitable to be too fast; as the reaction proceeds, the stirring speed is increased slowly. The reaction temperature is also the same, the reaction materials are easily evaporated to dryness by rapidly heating the inulin, the reaction chance of the materials is lost, and simultaneously, the burning gelatinization and the decomposition of esterification products of the inulin are caused. Along with the reaction, the heating temperature is slowly increased, the reaction process of the propionate inulin product is improved, and the esterification of the inulin is promoted. In addition, in order to promote the esterification reaction, water and other organic volatile gases generated in the reaction need to be continuously pumped out, so that the reaction is always in a micro-negative pressure condition, and the pressure rise is avoided. To ensure the completion of the esterification reaction, the dry reaction time should not be too short, but the reaction time should not be too long to avoid decomposition of the product.
Further, a crystallization step is also included after the esterification reaction; the crystallization step specifically comprises the following steps: mixing the product after esterification with ethanol solution, neutralizing with acid, cooling and crystallizing.
In the invention, the product after the esterification reaction is mixed with unreacted inulin, inorganic salt and other impurities, and water is added into the crude product for humidifying and balancing water, and impurity removal and purification are carried out. Since inulin is easily gelled with water and inulin propionate is easily hydrolyzed, an organic solvent miscible with water should be selected as a reaction and purification solvent. Commonly used organic solvents are methanol, ethanol, acetone or isopropanol, etc. Wherein, the methanol can avoid the side reaction of hydrolysis, but the methanol is toxic; acetone and isopropanol have the best effect, but acetone has a low boiling point and is volatile; isopropanol is used as a solvent, inulin propionate has high substitution degree and good purity, but isopropanol has high boiling point, solvent recovery energy consumption is high, and hydrous isopropanol has strong corrosivity; ethanol is low in price and non-toxic, but ethanol is used as a reagent, and the substitution degree of inulin propionate products is slightly low. Since ethanol denatures proteins, it is desirable that the protein content of the inulin raw material should be less than 5%.
In the invention, the concentration of the ethanol solution is 80-95%, and the acid is sulfuric acid; the pH value after neutralization with acid is 7-8, and the crystallization temperature is 25-30 ℃.
Further, the method also comprises the step of filtering and washing the filter cake with ethanol after crystallization.
Filtering the inulin propionate, continuously spraying ethanol to wash and leach the inulin propionate filter cake until indexes of inorganic salt and unreacted monomer residues in the washed inulin propionate are qualified.
Further, the method also comprises a post-treatment step after the crystallization; the post-treatment step comprises one or more of drying, crushing and sieving.
The drying is vacuum rake stirring drying; the crushing is air flow crushing; the sieving is to sieve inulin propionate with the granularity of less than or equal to 100 meshes.
The product after crystallization is paste-like, has high moisture content, is inflammable and explosive, is decomposed by oxidation, and needs to select proper dehumidifying and drying equipment. In the invention, the dryer is a vacuum rake stirring dryer. The vacuum rake dryer consists of a shell, a rotating shaft and rake teeth, and can enable materials to be operated in a closed mode, and the rake teeth of the dryer rotate forward and backward to enable inulin propionate to be continuously pushed towards the middle and two ends; and a plurality of stainless steel bars among the rake teeth continuously move up and down in the rotation process of the rake shaft to vibrate, crush and dry the inulin propionate adhered on the wall of the rake shaft and the agglomerated materials, steam is indirectly heated, the heat transfer surface is large, the heat efficiency is high, the vacuum drying vacuum degree is 50kPa, 0.3Mpa water vapor is introduced into a jacket for heating, the whole drying time is 45min, and the discharged tail gas can be recycled after water condensation and can be returned to a system for recycling.
The pulverizer is a jet mill, and the sieving is to sieve out inulin propionate with the granularity less than or equal to 100 meshes. And introducing water vapor into the jacket of the dryer for heating, starting the vacuum pump, and recovering the ethanol solvent after water condensation of the exhausted tail gas. The jet milling has no temperature rise, no pollution, small abrasion, less dust and low noise, and is particularly suitable for milling heat-sensitive, low-melting-point, sugar-containing and volatile inulin propionate. Recovering the mother liquid, washing liquid and filtrate, dewatering and removing impurities in alcohol distilling tower, and recovering ethanol for next production.
In order to further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available.
Example 1
Weighing 40kg of sodium hydroxide flaky solid (the content is more than or equal to 98 percent), and crushing and grinding the flaky solid into powder with the number of 100 meshes; 800kg of inulin (100 meshes, the content of which is more than or equal to 96%) is weighed, the sodium hydroxide powder and the inulin are respectively added into a reaction device (the volume is 1500L) through a screw conveyer hopper, and the stirring revolution of the reaction device is 25 rpm. 20kg of deionized water is added into the reaction device by a metering pump, steam is arranged on a jacket of the reaction device, and heating is carried out at the temperature rising speed of 2 ℃/min. Starting the vacuum pump and opening the exhaust valve of the reaction device. Measuring deionized water, placing the deionized water in a lye tank to prepare 100kg of 40% sodium hydroxide aqueous solution, measuring 95% ethanol, placing the ethanol in a liquid medicine tank to prepare 100kg of 50% propionic anhydride ethanol solution. When the temperature of the inulin in the reaction device rises to 40 ℃, 10kg of 40 percent sodium hydroxide aqueous solution and 40kg of 50 percent propionic anhydride ethanol solution are respectively sprayed. Alternatively introducing steam or water into the jacket of the reaction device to ensure that the temperature of the materials in the reaction device is 50-55 ℃, and stirring and reacting for 60min at the temperature. And heating the reaction device material, increasing the stirring speed of the reaction device to 35rpm, and slowly spraying a small amount of 40% sodium hydroxide aqueous solution into the reaction device to ensure that the pH value of the reaction material is between 9 and 11. Then 30kg of 50% propionic anhydride ethanol solution is pumped from a medicine tank through a metering pump and slowly sprayed into the reaction device. Alternatively introducing steam or water into the jacket of the reaction device to ensure that the temperature of the materials in the reaction device is 60-65 ℃, and stirring and reacting for 60min at the temperature. And finally, heating the material of the reaction device again, increasing the temperature, adjusting the stirring revolution of the reaction device to 45rpm, and slowly spraying a small amount of 40% sodium hydroxide aqueous solution to the reaction device to ensure that the pH value of the reaction material is 9-11. 30kg of 50 percent propionic anhydride ethanol solution is pumped from a medicine tank through a metering pump and slowly sprayed into the reaction device. Alternatively introducing steam or water into the jacket of the reaction device to ensure that the temperature of the materials in the reaction device is 70-75 ℃, and stirring and reacting for 60min at the temperature. The whole dry esterification reaction time is 3h, and the crude product of the inulin propionate is obtained.
Example 2
The crude inulin propionate obtained in example 1 was introduced into an enamel elution tank having a volume of 3000L, and dissolved and stirred for the first time with 2000L of 80% ethanol solution. And (3) cooling the jacket of the enamel elution kettle by introducing water, and slowly dropwise adding 93% sulfuric acid into the solution in the kettle to neutralize the solution until the pH value is 7-8. And stopping stirring when the temperature of the solution in the kettle is reduced to 25-30 ℃, and precipitating a large amount of white precipitate which is crude inulin propionate after the solution in the kettle is static. Discharging the supernatant in the kettle, and adding 2000L of 95% ethanol into the crude product precipitate at the bottom of the kettle again for soaking and dissolving. And (3) introducing water into a jacket of the enamel elution kettle for cooling, stopping stirring when the temperature of the solution in the kettle is reduced to 25-30 ℃, and precipitating a crude inulin propionate product after the solution in the kettle is static. Similarly, the supernatant in the kettle is discharged, and the crude precipitate at the bottom of the kettle is soaked and dissolved in 2000L of 95% ethanol for the third time. And (3) introducing water into a jacket of the enamel elution kettle for cooling, stopping stirring when the temperature of the solution in the kettle is reduced to 25-30 ℃, and precipitating crude inulin propionate after the solution in the kettle is static. Discharging supernatant in the kettle, introducing coarse precipitate at the bottom of the kettle into a horizontal centrifugal filter for filtering, and continuously spraying 95% ethanol to wash and leach the inner cavity propionate inulin filter cake, wherein the pasty filter cake is the purified inulin propionate wet product.
Example 3
850kg of inulin propionate wet product with 20% moisture content obtained in example 2 is placed in a WHD-1200 rake type vacuum drier, 0.3Mpa of water vapor is introduced into a jacket of the drier for heating, a 2X-8 rotary vane vacuum pump is started, a vacuum exhaust valve of the drier is opened, after the vacuum degree of the drier is 5000Kpa, the drier is started for stirring, the propionate wet product is continuously turned over along with the forward and reverse rotation of rake teeth, and meanwhile, a plurality of stainless steel rods between the rake teeth continuously move up and down in the rotation of a rake shaft, and the wall of the machine cavity and agglomerated materials are crushed, beaten, vibrated and dried. The whole drying time is 45min, about 80kg of alcohol solution can be recovered after tail gas is condensed by water, and the alcohol solution can be returned to the system for recycling.
Turning off the vacuum pump, opening the blow valve of the rake vacuum drier, and feeding the inulin propionate of the vacuum drier to the feeder of the jet mill YQS-1400. The compressed gas passes through the feeding ejector and a plurality of crushing nozzles at the periphery of the crushing chamber to eject supersonic airflow so as to lead the materials to impact, collide and rub and crush each other. The pulverizer classifier tube then separates the fine particles and the coarse particles return to the pulverizing chamber for continued recycle. And (3) separating fine micro powder particles, sieving the fine micro powder particles by a phi 600X1600 cylindrical rotary sieve, and collecting white powder below 100 meshes to obtain the inulin propionate product.
And (3) recovering the elution mother liquor, the washing liquor and the filtrate, then sending the recovered mother liquor, the washing liquor and the filtrate into a phi 800 alcohol recovery tower for normal pressure alcohol distillation, collecting a 95% ethanol solution of 75-80 ℃ fraction at the tower top, wherein the ethanol solution can be recycled, and sending the water and the residue in the tower bottom to a sewage plant for further treatment.
Example 4
The propionate inulin is produced by using imported Belgian national inulin, Shaanxi inulin and Hebei inulin as raw materials and adopting the dry method described in the embodiments 1 to 3 and the existing organic solvent wet method respectively. The results are as follows:
TABLE 3 comparison of two production methods for inulin propionate
The reaction rate of propionate inulin produced by the dry method is 53-82%, the product yield is 46-76%, and the substitution degree Ds0.35-0.86. Compared with an organic solvent method and a water solvent method, the method for producing the inulin propionate by the dry method has the advantages of simple process, convenient operation, low energy consumption, less side reaction, low production cost, high product yield and small environmental pollution, is suitable for preparing the high-substitution Ds inulin propionate product, and has obvious economic benefit and social benefit.
Example 5
The structure, morphology, melting temperature, decomposition temperature and thermal stability of the inulin propionate product prepared in example 1 were characterized and analyzed by using an infrared (FTIR) spectrophotometer, a GC gas chromatograph, a GPC gel permeameter, an ICP ion chromatograph, a Differential Scanning Calorimetry (DSC), an X-ray diffraction analyzer (XRD), a thermal weight loss (TGA), an X-ray diffraction (XRD), a Scanning Electron Microscope (SEM) and other detection instruments, and the results are shown in table 4.
TABLE 4 Inulin Propionate (IPE) product characterization results
As can be seen from the results in Table 4, the degree of substitution Ds 0.54 of the Inulin Propionate (IPE) produced is a moderate value. The high and low degree of substitution Ds is mainly related to the molar ratio of the ethanol solution of propionic anhydride to the inulin, and the higher the molar ratio, the larger the degree of substitution Ds. The prepared inulin propionate has low fat and protein content, is beneficial to obese people to use, has less microbial toxic bacteria than common food, has extremely low heavy metal content, meets the requirements of food, and is one of ideal food additives.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A dry preparation method of inulin propionate is characterized in that,
under the stirring state, mixing inulin, solid alkali and water, heating the inulin to 40 ℃, then spraying propionic anhydride ethanol solution in batches for esterification reaction, and adding alkali liquor to control the pH to be 9-11; the weight ratio of the inulin to the water is 100 (8-16); the method for carrying out the esterification reaction by spraying the propionic anhydride ethanol solution in batches comprises the following steps:
A. spraying propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 50-55 ℃ and the stirring speed of 20-25 rpm;
B. spraying propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 60-65 ℃ and the stirring speed of 30-35 rpm;
C. spraying propionic anhydride ethanol solution, and stirring for 50-60min at the temperature range of 70-75 ℃ and the stirring speed of 40-45 rpm.
2. The dry production method according to claim 1, wherein the stirring is a parallel biaxial stirring.
3. The dry-process preparation method according to claim 1, wherein the solid base is sodium hydroxide or potassium hydroxide; the weight ratio of the inulin to the solid alkali is 100: (2-5); the concentration of the propionic anhydride ethanol solution is 50 percent.
4. The dry preparation method according to claim 1, wherein the molar ratio of the ethanol solution of propionic anhydride to inulin in step A is (1-1.2): 1; in the step B, the molar ratio of the propionic anhydride ethanol solution to the inulin is (0.8-1.6): 1; in the step C, the molar ratio of the propionic anhydride ethanol solution to the inulin is (0.8-1.6): 1.
5. the dry preparation method according to claim 1, wherein the alkali solution is an aqueous solution of sodium hydroxide or potassium hydroxide; the vacuum pressure of the esterification reaction is 50-90 kPa.
6. The dry-process preparation method according to claim 1, further comprising a crystallization step after the esterification reaction;
the crystallization step specifically comprises the following steps: mixing the product after esterification with ethanol solution, neutralizing with acid, cooling and crystallizing.
7. The dry-process preparation method according to claim 6, wherein the concentration of the ethanol solution is 80% to 95%, and the acid is sulfuric acid;
the pH value after neutralization with acid is 7-8, and the crystallization temperature is 25-30 ℃.
8. The dry preparation method according to claim 6, further comprising a step of filtering while ethanol washing the cake after the crystallization.
9. The dry-process production method according to claim 6, further comprising a post-treatment step after the crystallization;
the post-treatment step comprises one or more of drying, crushing and sieving.
10. The dry production method according to claim 9, wherein the drying is vacuum rake stirring drying;
the crushing is air flow crushing;
the sieving is to sieve inulin propionate with the granularity of less than or equal to 100 meshes.
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