CN113861017A - Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid - Google Patents

Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid Download PDF

Info

Publication number
CN113861017A
CN113861017A CN202111327589.2A CN202111327589A CN113861017A CN 113861017 A CN113861017 A CN 113861017A CN 202111327589 A CN202111327589 A CN 202111327589A CN 113861017 A CN113861017 A CN 113861017A
Authority
CN
China
Prior art keywords
calcium acetate
organic
acid
mpa
dry distillation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111327589.2A
Other languages
Chinese (zh)
Inventor
马梁惠东
马建义
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang A&F University ZAFU
Original Assignee
Zhejiang A&F University ZAFU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang A&F University ZAFU filed Critical Zhejiang A&F University ZAFU
Priority to CN202111327589.2A priority Critical patent/CN113861017A/en
Publication of CN113861017A publication Critical patent/CN113861017A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52—Adding ingredients
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16—Inorganic salts, minerals or trace elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Food Science & Technology (AREA)
  • Nutrition Science (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Mycology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)

Abstract

An organic product calcium acetate taking biomass dry distillation acid as a raw material, natural edible acetic acid prepared from the organic product calcium acetate and application of the natural edible acetic acid, and belongs to the technical field of organic food. Adopts biomass dry distillation acid as raw material, adopts a unique processing method to add CaCO after low-temperature vacuum distillation3Or Ca (OH)2Filtering after the reaction is finished, filteringThe liquid is vacuum distilled at high temperature to obtain solid matter organic calcium acetate, or added with water solution of hydrochloric acid/sulfuric acid for reaction, and then vacuum distilled at low temperature to obtain the organic edible vinegar. The liquid is organic edible vinegar, organic edible plant vinegar, acidity regulator and acidity regulator for organic food, and the solid is organic plant calcium health product, beverage additive and organic calcium supplement for cultured animals. The organic product calcium acetate taking the biomass dry distillation acid as the raw material, the natural edible acetic acid prepared from the organic product calcium acetate and the application of the organic product calcium acetate have the advantages of low waste utilization cost, simple preparation, good safety to people and livestock and good environmental compatibility, and can reach high organic food requirement value.

Description

Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid
Technical Field
The invention belongs to the technical field of organic food, and particularly relates to an organic product calcium acetate taking biomass dry distillation acid as a raw material, natural edible acetic acid prepared from the organic product calcium acetate and application of the natural edible acetic acid.
Background
At present, because of serious pollution to the environment such as soil, water, air and the like, public attention to food safety is more and more intense, organic foods and products are rapidly developed, but the region for producing the organic foods is smaller and smaller, so that strong market demands cannot be effectively met, and the variety of the organic foods can be supplied to a few. In the history of pollutant development in China, some environments without or with little manual intervention exist, such as bamboo forests and forests (non-economic forests), namely the regions have no history of using chemical fertilizers and pesticides, are generally in remote natural environments, manual intervention is little, even if bamboo and wood are cut down, the bamboo and wood are basically manually cut by a knife saw, transportation is also completed by manpower, the generated photosynthesis products belong to natural products, and the various harsh conditions of organic products are met.
The bamboo wood vinegar liquid is a liquid substance obtained by collecting gas generated in the decomposition of bamboo wood at the high temperature of 100 ℃ and 800 ℃ and cooling the gas at the normal temperature in the process of burning charcoal by using the bamboo wood. The bamboo vinegar liquid contains nearly 200 natural polymer organic compounds, although the functions are many, the marketized application is not wide or even limited, and the main reasons are as follows: 1) bamboo and wood vinegar contains obvious toxic and even carcinogenic substances, such as phenols, ketones, aldehydes, benzo (a) pyrene and the like, although the content is rarely in a trace level, various foods, food additives and medical and skin care products require trace levels on the content of the harmful substances, most of the foods, the food additives and the medical and skin care products require mg/kg or mug/kg or ng/kg levels, the bamboo and wood vinegar is in accordance with GB/T31734-2015 bamboo vinegar standard, the content of dissolved tar is 1.20-1.50% of refined bamboo vinegar and 0.08-0.10% of distilled bamboo vinegar, as is well known, various phenols account for more than 50% of tar, the content of the converted standard phenols is required to be 0.04-0.75% =400-7500mg/kg =400000- mg/kg =2 μ g/kg, and the integer exceeds 200000 times (20 ten thousand times), which is far from the edible standard. For example, according to the requirement of pollutant limit in GB 2762-; 2) Bamboo wood vinegar has unpleasant odor, which is easy to cause the dislike of consumers; in a word, the technology for removing harmful substances such as phenols and the like and benzopyrene carcinogenic substances from bamboo vinegar liquid determines whether the application of the bamboo vinegar liquid can be expanded and the bamboo vinegar liquid can be safely used.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide an organic product calcium acetate taking biomass dry distillation acid as a raw material, natural edible acetic acid prepared from the organic product calcium acetate and a technical scheme of application of the organic product calcium acetate, and the technical scheme has the advantages of low production cost, simple and environment-friendly processing method and realization of high-value utilization of waste.
The organic product calcium acetate taking biomass dry distillation acid as a raw material is characterized by comprising the following steps:
1) weighing biomass dry distillation acid, putting into a distillation device, performing primary distillation at the low temperature of 38-45 ℃ and the vacuum degree of-0.090 MPa to-0.097 MPa, and collecting distillate for later use, wherein the biomass dry distillation acid is at least one of bamboo vinegar, wood vinegar and straw vinegar;
2) transferring the distillate into a stirring kettle, and adding food grade CaCO with the mass of 0.02-0.18 part of biomass dry distillation acid3Stirring and reacting for 23-25 hours at the rotating speed of 25-35 r/min or food-grade Ca (OH)2Stirring and reacting for 1.5-2.5 hours at the rotating speed of 25-35 r/min;
3) filtering the reactant by a filter screen with the diameter of 0.4-0.5 mu m, and collecting filtrate;
4) performing secondary distillation at high temperature of 50-70 deg.C and vacuum degree of-0.090 MPa to-0.097 MPa until the distillation is complete, concentrating the dried substance to obtain final product calcium acetate, and collecting the distillate as waste liquid.
The organic product calcium acetate taking biomass dry distillation acid as a raw material is characterized in that in the step 1): the temperature is 40-43 ℃, and the vacuum degree is-0.093 MPa to-0.095 MPa.
The organic product calcium acetate taking biomass dry distillation acid as a raw material is characterized in that in the step 2): adding food grade CaCO with the mass of 0.05-0.15 part of biomass dry distillation acid3Or food grade Ca (OH)2Preferably 0.07 to 0.10 parts; food grade CaCO3Stirring and reacting for 24 hours at the rotating speed of 30-32 r/min, and food-grade Ca (OH)2Stirring and reacting for 2-2.2 hours at the rotating speed of 30-33 r/min.
The organic product calcium acetate taking biomass dry distillation acid as a raw material is characterized in that in the step 3): the filter screen is 0.45-0.48 mu m.
The organic product calcium acetate taking biomass dry distillation acid as a raw material is characterized in that in the step 4): the temperature is 55-64 ℃, and the vacuum degree is-0.093 MPa to-0.094 MPa.
The natural edible acetic acid prepared from the organic product calcium acetate by using the biomass dry distillation acid as the raw material is characterized by comprising the following components in parts by weight: slowly adding 60-70 parts by mass of the calcium acetate into 95-105 parts by mass of 30% hydrochloric acid, or slowly adding 75-85 parts by mass of the calcium acetate into 95-105 parts by mass of 49% sulfuric acid, stirring for dissolving, and performing third distillation at the low temperature of 38-45 ℃ and the vacuum degree of-0.090 MPa to-0.097 MPa, wherein the distillate is natural edible acetic acid.
The natural edible acetic acid prepared from the organic product calcium acetate by using the biomass dry distillation acid as the raw material is characterized by comprising the following components in parts by weight: 65-72 parts of calcium acetate and 102 parts of 30% hydrochloric acid; 79-81 parts of calcium acetate and 98-100 parts of 49% sulfuric acid; the temperature is 40-42 ℃, and the vacuum degree is-0.092 MPa to-0.095 MPa.
The organic product calcium acetate taking the biomass dry distillation acid as the raw material is applied to the preparation of organic plant calcium health products, beverage additives and organic cultured animal calcium supplements.
The natural edible acetic acid of the natural edible acetic acid prepared from the organic product calcium acetate taking the biomass dry distillation acid as the raw material is applied to preparing organic edible vinegar, organic edible plant vinegar and acidity regulator of organic food.
The biomass dry distillation acid comprises at least one of bamboo vinegar, wood vinegar and straw vinegar, and the condition of meeting organic input products means that bamboo, wood and crop straws used as raw materials for burning the biochar are non-transgenic biomass and are not applied with chemical fertilizers or chemical pesticide management, namely the biochar raw materials belong to organic raw materials.
The organic product calcium acetate taking the biomass dry distillation acid as the raw material, the natural edible acetic acid prepared from the organic product calcium acetate and the application of the organic product calcium acetate have the following innovation points:
1) in the aspect of application, at present, all edible vinegar is a grain fermentation product, and the definition of GB2719-2018 national food safety standard vinegar is referred to: the liquid acidic condiment is prepared by singly or mixedly using various materials containing starch and sugar and edible alcohol and brewing by microbial fermentation, and at present, no standard and product for edible plant vinegar and organic calcium acetate exist. The invention firstly gives the biomass dry distillation acid a novel purpose after unique processing;
2) the prepared product is used for organic food and additives thereof, and the whole processing process is that the physical process traceability conforms to the organic product specification;
3) the invention not only realizes the utilization of the waste, but also realizes the price 5-15 times higher than that of the traditional edible vinegar, realizes the aim of high-value utilization, and has the environmental benefits, the ecological benefits and the social benefits of waste utilization, saving pollution-free grains and organic and green grains compared with the edible vinegar brewed by using organic foods;
4) the unique processing method comprises the steps of carrying out primary low-temperature distillation, removing phenolic harmful substances, unpleasant odor and carcinogenic benzopyrene in the biomass dry distillation acid, wherein a small amount of volatile harmful substances such as phenol, benzoquinone, hydroquinone, guaiacol and the like enter the product, reacting with calcium salt, further heating and carrying out secondary distillation to obtain calcium acetate, and volatilizing the harmful substances (the phenols and the benzopyrene volatilized in the primary distillation) remained in the product into distillate wastewater of the secondary distillation to further reduce the content of the harmful substances in the final product, so that the product meeting the national standard is obtained, and simultaneously ensuring that the carbon source of the final product is from natural substances of the biomass dry distillation acid, wherein the natural degree is more than 95%;
5) after the qualified calcium acetate product reacts with the aqueous solution of sulfuric acid or hydrochloric acid, the method of tertiary distillation at medium and low temperature is used, so that harmful substances are further reduced to enter the final product of plant vinegar through volatilization, the content of the harmful substances is reduced to reach the national standard, and meanwhile, the carbon source of the final product is ensured to come from natural substances of biomass dry distillation acid to reach the standard of organic products;
6) the invention adopts a reverse process to firstly generate calcium acetate and then reversely produce acetic acid by utilizing the calcium acetate, and the process can greatly reduce the content of harmful substances in the final product and meet the edible requirement.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings and detailed description, in which it is to be understood that the embodiments described are merely illustrative of some, but not all embodiments of the invention. 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.
Example 1
Weighing 100kg bamboo vinegar, loading into distillation equipment, performing first distillation at vacuum degree of-0.090 MPa and low temperature of 45 deg.C, collecting distillate, and transferring into stirring kettle; adding 18kg of food grade CaCO3Stirring and reacting for 24 hours at the rotating speed of 30 r/min, transferring the mixture into a filtering device, filtering the mixture by a filter screen of 0.45 mu m, transferring the filtrate into a distilling device, carrying out secondary distillation at the vacuum degree of-0.090 MPa and the high temperature of 70 ℃ until the distillation is complete, concentrating and drying the product, namely the final product calcium acetate, slowly adding 67kg of the calcium acetate into 100kg of 30% hydrochloric acid according to the mass fraction, stirring and dissolving the calcium acetateThen, the third distillation is carried out at the low temperature of 45 ℃ and the vacuum degree of-0.097 MPa, and the distillate is the final product of the natural edible acetic acid.
Example 2
Weighing 100kg of pyroligneous liquor, loading into a distillation device, carrying out first distillation at a vacuum degree of-0.097 MPa and a low temperature of 38 ℃, collecting distillate, and transferring into a stirring kettle; adding 10kg of food grade Ca (OH)2Stirring and reacting for 2 hours at the rotating speed of 30 r/min, transferring the mixture into a filtering device, filtering the mixture by a 0.45 mu m filter screen, transferring the filtrate into a distilling device, carrying out secondary distillation at the vacuum degree of-0.090 MPa and the high temperature of 60 ℃ until the distillation is complete, obtaining a concentrated and dried substance, namely a final product of calcium acetate, slowly adding 79kg of the calcium acetate into 100kg of 49% sulfuric acid by mass fraction, stirring and dissolving, carrying out tertiary distillation at the low temperature of 38 ℃ and the vacuum degree of-0.097 MPa, and obtaining a distillate which is the final product of natural edible acetic acid.
Example 3
Weighing 100kg of straw vinegar, loading into a distillation device, carrying out first distillation at a vacuum degree of-0.095 MPa and a low temperature of 40 ℃, collecting distillate, and transferring into a stirring kettle; 2kg of food grade Ca (OH) were added2Stirring and reacting for 1.5 hours at the rotating speed of 30 r/min, transferring the mixture into a filtering device, filtering the mixture by a 0.45 mu m filter screen, transferring the filtrate into a distilling device, carrying out secondary distillation at the vacuum degree of-0.094 MPa and the high temperature of 50 ℃ until the distillation is complete, wherein the concentrated and dried substance is the final product calcium acetate, slowly adding 79kg of the calcium acetate into 100kg of 49% sulfuric acid by mass fraction, stirring and dissolving, carrying out third distillation at the low temperature of 41 ℃ and the vacuum degree of-0.095 MPa, and obtaining the distillate which is the final product of the natural edible acetic acid.
Example 4
Weighing 50kg bamboo vinegar and 50kg wood vinegar, placing into distillation equipment, performing first distillation at vacuum degree of-0.094 MPa and low temperature of 42 deg.C, collecting distillate, and transferring into stirring kettle; adding 8kg of food grade CaCO3Stirring and reacting for 1.5 hours at the rotating speed of 25 r/min, transferring into a filtering device, filtering by a 0.40 mu m filter screen, transferring the filtrate into a distilling device, carrying out secondary distillation at the high temperature of 50 ℃ and the vacuum degree of-0.096 MPa until the distillation is complete, concentrating and drying the substance, namely the final product calcium acetate, slowly adding 62kg of the calcium acetate into 95kg of 30% hydrochloric acid,stirring for dissolving, distilling at 45 deg.C and-0.097 MPa for the third time to obtain final product natural edible acetic acid.
Example 5
Weighing 40kg of bamboo vinegar liquid and 60kg of straw vinegar liquid, loading into a distillation device, carrying out first distillation at a vacuum degree of-0.096 MPa and a low temperature of 39 ℃, collecting distillate, and transferring into a stirring kettle; adding 4kg of food grade Ca (OH)2Stirring and reacting for 2.5 hours at the rotating speed of 35 r/min, transferring the mixture into a filtering device, filtering the mixture by a 0.50 mu m filter screen, transferring the filtrate into a distilling device, carrying out secondary distillation at the vacuum degree of-0.095 MPa and the high temperature of 55 ℃ until the distillation is complete, wherein the concentrated and dried substance is the final product calcium acetate, slowly adding 82kg of the calcium acetate into 102kg of 49% sulfuric acid by mass fraction, stirring and dissolving, then carrying out third distillation at the low temperature of 42 ℃ and the vacuum degree of-0.094 MPa, and obtaining the distillate which is the final product of the natural edible acetic acid.
Example 6
Weighing 60kg of wood vinegar and 40kg of straw vinegar, loading into a distillation device, carrying out first distillation at a vacuum degree of-0.094 MPa and a low temperature of 41 ℃, collecting distillate, and transferring into a stirring kettle; adding 12kg of food grade CaCO3Stirring and reacting for 25 hours at the rotating speed of 30 r/min, transferring the mixture into a filtering device, filtering the mixture by a 0.45 mu m filter screen, transferring the filtrate into a distilling device, carrying out secondary distillation at the vacuum degree of-0.092 MPa and the high temperature of 60 ℃ until the distillation is complete, wherein the concentrated and dried substance is the final product calcium acetate, slowly adding 75kg of calcium acetate into 95kg of 49% sulfuric acid by mass fraction, stirring and dissolving, carrying out tertiary distillation at the low temperature of 41 ℃ and the vacuum degree of-0.095 MPa, and obtaining the distillate which is the final product of the natural edible acetic acid.
Example 7
Weighing 30kg bamboo vinegar, 40kg wood vinegar and 30kg straw vinegar, placing into a distillation device, performing primary distillation at vacuum degree of-0.096 MPa and low temperature of 42 deg.C, collecting distillate, and transferring into a stirring kettle; adding 5kg of food grade Ca (OH)2Stirring at 30 r/min for 2 hr, filtering with 0.45 μm filter screen, distilling at-0.091 MPa and 65 deg.C until the filtrate is completely distilled, concentrating to obtain final product calcium acetate, and collecting the filtrateAdding 80kg of calcium acetate into 100kg of 49% sulfuric acid, stirring for dissolving, distilling at 40 deg.C and-0.097 MPa for the third time to obtain distillate as final product.
Example 8
Weighing 10kg bamboo vinegar, 20kg wood vinegar and 70kg straw vinegar, placing into a distillation device, performing first distillation at-0.095 MPa vacuum degree and 44 deg.C low temperature, collecting distillate, and transferring into a stirring kettle; adding 12kg of food grade CaCO3Stirring and reacting for 24 hours at the rotating speed of 30 r/min, transferring the mixture into a filtering device, filtering the mixture by a 0.45 mu m filter screen, transferring the filtrate into a distilling device, carrying out secondary distillation at the vacuum degree of-0.092 MPa and the high temperature of 68 ℃ until the distillation is complete, concentrating and drying the substance to obtain the final product calcium acetate, slowly adding 67kg of the calcium acetate into 105kg of 30% hydrochloric acid by mass fraction, stirring and dissolving, carrying out third distillation at the low temperature of 43 ℃ and the vacuum degree of-0.094 MPa, and obtaining the distillate which is the final product of the natural edible acetic acid.
The content change of the effective components and the harmful components of the calcium acetate and the acetic acid is illustrated by the following experiments, and the experiments refer to a plurality of national standards, and are specifically designed as follows: all assays were repeated 3 times for analysis of variance.
1. Method for measuring content of total organic acid (calculated by acetic acid)
According to the GB2719 and 2018 food safety national standard vinegar and the GB/T5009.41-2003 vinegar sanitary standard analysis method, the vinegar mainly comprises acetic acid and a small amount of other organic acids, the acetic acid is titrated by a sodium hydroxide standard solution, the PH8.2 endpoint is measured by an acidimeter, and the result is expressed by acetic acid.
10.0mL of sample is taken and placed in a 100mL volumetric flask, water is added to the scale, and the mixture is mixed uniformly. 20.0mL of the solution was aspirated, placed in a 200 mL beaker, and 60 mL of water were added, following the protocol of GB/T5009.39-2003, 4.2.1.4, starting from "start magnetic stirrer … …". And simultaneously, carrying out a reagent blank test. The total acid content (in acetic acid) in the sample was calculated as follows. X = (V1-V2) × c × 0.060/(V × 10/100) × 100, wherein: x: the total acid content (in terms of acetic acid) in the sample is grams per hundred milliliters (g/100 mL); v1: measuring the volume of sodium hydroxide standard titration consumed with sample dilution in milliliters (mL); v2: reagent blank the volume of sodium hydroxide standard titration solution in milliliters (mL) was consumed; c: the concentration of the sodium hydroxide standard titration solution is expressed in units of mol per liter (mol/L); 0.060-the mass of acetic acid in grams (g) corresponding to 1.OO mL of sodium hydroxide standard solution [ c (NaOH) = 1.000 mol/L ]; v: sample volume in milliliters (mL).
2. A method for measuring the content of calcium acetate is based on GB1903.15-2016 calcium acetate (calcium acetate) as food nutrition enhancer
Identification of calcium: weighing about 0.1g of sample, accurately obtaining 0.01g of sample, placing the sample in a 10 mL beaker, and adding 20mL of water to dissolve the sample to obtain a sample solution. The platinum wire is wetted by hydrochloric acid, is firstly burnt on a colorless flame until the platinum wire is colorless, and then the platinum wire is dipped in the sample solution and burnt on the colorless flame, and the flame is brick red. 2 drops of methyl red indicator liquid are added into the sample solution, the sample solution is neutralized by ammonia solution, and then the solution of hydrochloric acid is gradually dropped until the solution is acidic. Addition of ammonium oxalate solution resulted in a white precipitate of calcium oxalate that was insoluble in acetic acid but soluble in hydrochloric acid. Identification of acetate: when the sample was co-heated with sulfuric acid and ethanol, a special fragrance of ethyl acetate was generated. The neutral aqueous solution of the sample added with ferric chloride solution generates deep red, and the red color disappears after the addition of inorganic acid.
Calcium acetate (C)4H6O4Determination of Ca) content: weighing about 0.2g of sample, accurately measuring to 0.002g, adding 10 mL of water for dissolving, adding 5mL of triethanolamine solution, 15mL of sodium hydroxide solution and about 0.1g of chrome blue black R indicator, and titrating by using an ethylene diamine tetraacetic acid standard titration solution until the solution is changed from red to pure blue. Meanwhile, a blank test is carried out, and the types and the amounts of other reagents (except for standard titration solution) added in the blank test solution are the same as those of the test solution except that no sample is added in the blank test solution. Calcium acetate (C)4H6O4Ca) content, w1, calculated according to the formula:
w1 = (V1-V0). times.c.times.M/[ M × (1 w of water). times.1000 ]. times.100%
Wherein: v1: the volume of disodium ethylenediaminetetraacetate standard titration solution consumed by the test solution in milliliters (mL); v2: the volume of disodium ethylenediaminetetraacetate standard titration solution consumed by the blank test solution in milliliters (mL); c: the concentration of the standard titration solution of the disodium ethylene diamine tetraacetate is expressed in units of mol per liter (mo 1/L); m: molar mass of calcium acetate in grams per mole (g/mo 1) [ M (C4H6O4 Ca) =158.17 ]; m: the mass of the sample in grams (g); 1000: a scaling factor.
3. The method for measuring the content of total phenols comprises the following steps:
according to GB/T7490-1987 determination of water quality volatile phenol and HJ 503-2009 determination of water quality volatile phenol 4-aminoantipyrine spectrophotometry, samples with mass concentration higher than the upper limit of standard determination of 0.04mg/L are appropriately diluted and then determined. The solid was dissolved in distilled water and then measured. The pH of the liquid sample is adjusted by sodium carbonate, the liquid is distilled along with water vapor and can react with 4-aminoantipyrine to generate volatile phenolic compounds of colored compounds, and the result is calculated by phenol. The volatile phenolic compounds are distilled off by distillation and separated from interfering substances and fixing agents. Since the volatilization rate of the phenolic compound varies depending on the volume of the distillate, the volume of the distillate must be equal to the volume of the sample. The distilled phenolic compound; reacting with 4-aminoantipyrine in the presence of potassium iron Yin in a pH (10.0 + -0.2) medium to give orange-red antipyrine dye, extracting with chloroform, and measuring the absorbance at 460 nm.
The specific analysis steps are as follows: 1) pre-distillation: and (3) transferring 250 ml of sample into a 500 ml full glass distiller, adding 25ml of water, adding a plurality of glass beads to prevent bumping, adding a plurality of drops of methyl orange indicating liquid, and continuously adding phosphoric acid solution if the sample does not show orange red. Connecting with a condenser, heating and distilling, and collecting 250 ml of stuffing liquid into a volumetric flask. During the distillation, if the methyl orange red color is faded, the solution should be cooled after the distillation is finished, and then 1 drop of methyl orange indicator solution is added. If the residual liquid after distillation is not acidic, sampling again, increasing the adding amount of the phosphoric acid solution, and distilling. Transferring 250 ml of stuffing liquid into a separating funnel, adding 2.0 ml of buffer solution, mixing uniformly until the pH value is 10.0 +/-0.2, adding 1.5ml of 4-aminoantipyrine solution, mixing uniformly, adding 1.5ml of iron Yin potassium solution, mixing uniformly, sealing, and standing for 10 min.
2) And (3) extraction: accurately adding 10.0ml of chloroform into the color separation funnel, sealing, shaking vigorously for 2 min, inverting to release gas, and standing for layering. Wiping the inner wall of the neck pipe of the separating funnel with dry absorbent cotton or filter paper, plugging a small group of dry absorbent cotton or filter paper in the neck pipe, leading the chloroform layer to pass through the dry absorbent cotton group or filter paper, discarding a plurality of drops of initially filtered extract liquor, and directly putting the rest chloroform into a cuvette with the optical path of 30 mm.
3) And (3) measuring absorbance: and measuring the absorbance value of the trichloromethane layer at the wavelength of 460nm by taking trichloromethane as a reference.
4) Blank test: the sample was replaced with water and the absorbance was measured. The blank should be measured simultaneously with the sample.
Subtracting the absorbance value of a zero concentration tube from the absorbance value measured by the calibration series, drawing a curve of the absorbance value to the phenol content, and enabling the correlation coefficient of a regression equation of the calibration curve to reach more than 0.999;
mass concentration of volatile phenol in the sample (in terms of phenol) according to the formulapCalculation of = (As-Ab-a)/(bV) × 1000: in the formula: p mass concentration of volatile phenol in the sample, mg/L; as: absorbance value of the sample; ab: absorbance values for the blank test; a: calibrating the intercept value of the curve; b-the slope of the calibration curve; volume of V sample, mL.
4. The method for measuring the content of benzo (a) pyrene in calcium carbonate solid and acetic acid liquid comprises the following steps:
the determination of benzo (a) pyrene in food according to the national standard for food safety of GB 5009.27-2016 is summarized as follows:
calcium acetate solid assay: pretreatment: removing impurities, grinding into uniform sample, storing in clean sample bottle, marking, and storing at room temperature or according to the storage condition required by product packaging. Extraction: weighing 1g (accurate to 0.001g) of sample, adding 5mL of n-hexane, vortex mixing for 0.5min, ultrasonic extracting at 40 ℃ for 10min, centrifuging at 4000r/min for 5min, and transferring the supernatant. The extraction was repeated once with the addition of 5mL of n-hexane. And combining the supernatants, adopting a neutral alumina column for purification, activating the column by using 30mL of normal hexane, and closing a cock at the bottom when the liquid level is reduced to a column bed. Transferring the solution to be purified into the column, opening the cock, collecting the purified solution to the eggplant-shaped bottle at a speed of 1 mL/min, transferring into 50 mL of n-hexane for elution, and continuously collecting the purified solution. The purified solution was rotary evaporated to about 1mL at 40 ℃, transferred to a chromatograph injection vial, and concentrated to near dryness under a 40 ℃ nitrogen stream. The eggplant-shaped bottle was washed with 1mL of n-hexane, and the washing solution was transferred again to a sample injection vial of a chromatograph and concentrated to dryness. Accurately sucking 1mL of acetonitrile into a sample injection vial of a chromatograph, carrying out vortex redissolution for 0.5min, and carrying out liquid chromatography determination after passing through a microporous filter membrane.
And (3) liquid acetic acid determination: extraction: 0.4g (exactly to 0.001g) of sample is weighed, 5mL of n-hexane is added, vortex mixed for 0.5min, and the mixture is purified. The purification process in the solid was followed except that the sample was finally vortexed with 0.4mL of acetonitrile.
When samples are prepared, pretreatment of different samples needs to be carried out simultaneously to carry out a sample blank test. Chromatographic conditions are as follows: a) a chromatographic column: c18, column length 250mm, inner diameter 4.6mm, particle size 5 μm, or equivalent performance; b) Mobile phase: acetonitrile + water =88+ 12; c) Flow rate: 1.0 mL/min; d) A fluorescence detector: excitation wavelength 384nm, emission wavelength 406 nm; e) Column temperature: 35 ℃; f) Sample introduction amount: 20 μ L. And (3) preparing a standard curve: and respectively injecting the standard series working solutions into the liquid chromatogram, determining corresponding chromatographic peaks, and taking the concentration of the standard series working solutions as a horizontal coordinate and the peak area as a vertical coordinate to obtain a standard curve regression equation. Measurement of sample solution: and (4) sampling and measuring the liquid to be measured to obtain the chromatographic peak area of benzo (a) pyrene. And calculating the concentration of benzo (a) pyrene in the sample solution according to a standard curve regression equation. The content of benzo (a) pyrene in the sample is calculated according to the formula:
x = (ρ × V)/m × 1000/1000 formula:
benzo (a) pyrene content in X-samples in micrograms per kilogram (μ g/kg);
ρ -sample purified solution concentration in nanograms per milliliter (ng/mL) from the standard curve;
v-final volumetric volume of sample in milliliters (mL);
m-sample mass in grams (g);
1000-conversion factor from ng/g to μ g/kg.
5. Naturalness detection
According to the following: ASTM D6866-2016, the sample is fully combusted in pure oxygen to carbon dioxide, purified to remove nitrogen oxides and sulfur oxides, converted to sodium carbonate aqueous solution, after purging the instrument with pure nitrogen, 40-50% phosphoric acid is added, the generated carbon dioxide is absorbed to the prepared solution by freezing to remove water: in a quantitative mixture of ethylenediamine and scintillation liquid, carbon dioxide and ethylenediamine generate a stable cyclic compound; and weighing to calculate the net weight of the carbon dioxide. The carbon 14 atoms in the sample completely enter carbon dioxide, when the test bottle enters an ultralow background liquid scintillation meter, the carbon 14 atoms decay once, the emitted BETA rays activate the scintillator to emit light once, and the meter records the number of light emission times in unit time. The unit of measurement is DPM/g.C (average: 1 minute per gram of carbon, how many decays); coal is taken as 0, fresh plants (the current standard value of 13.6DPM/g.C according to ASTM D6866-2016) are taken as 100%, and 95-105% are taken as qualified plants (12.92-14.28 DPM/g.C).
Figure DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE004
As shown in Table 1, the total organic acid (calculated by acetic acid) content in the final product liquid of examples 1-8 is 4.6-9.4%, which all reach the organic acid (calculated by acetic acid) content of not less than 3.5 g/100mL in the edible vinegar of GB2719-2018 national food safety standard, wherein example 1 also meets the organic acid content requirement of common 9-degree white vinegar in the market. The total phenol content (mg/L) is less than 0.002mg/L, and the total phenol content (mg/L) also reaches the safety standard of drinking water (refer to GB/T7490-1987). The content of benzo (a) pyrene is less than 3.0 mug/kg, and the limit of pollutants in food is 5.0-10.0 mug/kg according to GB 2762-2017 national standard of food safety, so that the requirement of the national standard is met. The natural degree of the natural fiber is 96.0-99.6%, and the natural degree is more than or equal to 95%, and the natural fiber also reaches the international ASTM D6866-2016 standard.
Table 1 the solid products of examples 1-8 contained 98.6-99.4% calcium acetate, which was over 98.0%, and met the content requirements of calcium acetate (calcium acetate) as a food nutrition enhancer for food safety national standard according to GB 1903.15-2016. The total phenol content (mg/L) is less than 0.002mg/L, and the reference GB/T7490-1987 also reaches the safety standard of drinking water. The content of benzo (a) pyrene is less than 3.0 mug/kg, and the limit of pollutants in food is 5.0-10.0 mug/kg according to GB 2762-2017 national standard of food safety, so that the requirement of the national standard is met. The natural degree of the natural fiber is 96.0-99.6%, and the natural degree is more than or equal to 95%, and the natural fiber also reaches the international ASTM D6866-2016 standard.
The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the examples, but rather as being defined by the claims and the equivalents thereof which can occur to those skilled in the art upon consideration of the present inventive concept.

Claims (9)

1. An organic product calcium acetate taking biomass dry distillation acid as a raw material is characterized by comprising the following steps:
1) weighing biomass dry distillation acid, putting into a distillation device, performing primary distillation at the low temperature of 38-45 ℃ and the vacuum degree of-0.090 MPa to-0.097 MPa, and collecting distillate for later use, wherein the biomass dry distillation acid is at least one of bamboo vinegar, wood vinegar and straw vinegar;
2) transferring the distillate into a stirring kettle, and adding food grade CaCO with the mass of 0.02-0.18 part of biomass dry distillation acid3Stirring and reacting for 23-25 hours at the rotating speed of 25-35 r/min or food-grade Ca (OH)2Stirring and reacting for 1.5-2.5 hours at the rotating speed of 25-35 r/min;
3) filtering the reactant by a filter screen with the diameter of 0.4-0.5 mu m, and collecting filtrate;
4) performing secondary distillation at high temperature of 50-70 deg.C and vacuum degree of-0.090 MPa to-0.097 MPa until the distillation is complete, concentrating the dried substance to obtain final product calcium acetate, and collecting the distillate as waste liquid.
2. The organic product calcium acetate with biomass dry distillation acid as raw material according to claim 1, characterized in that in step 1): the temperature is 40-43 ℃, and the vacuum degree is-0.093 MPa to-0.095 MPa.
3. The organic product calcium acetate using biomass dry distillation acid as raw material according to claim 1, wherein in step 2): adding food grade CaCO with the mass of 0.05-0.15 part of biomass dry distillation acid3Or food grade Ca (OH)2Preferably 0.07 to 0.10 parts; food grade CaCO3Stirring and reacting for 24 hours at the rotating speed of 30-32 r/min, and food-grade Ca (OH)2Stirring and reacting for 2-2.2 hours at the rotating speed of 30-33 r/min.
4. The organic product calcium acetate using biomass dry distillation acid as raw material according to claim 1, wherein in step 3): the filter screen is 0.45-0.48 mu m.
5. The organic product calcium acetate with biomass dry distillation acid as raw material according to claim 1, characterized in that in step 4): the temperature is 55-64 ℃, and the vacuum degree is-0.093 MPa to-0.094 MPa.
6. The natural edible acetic acid prepared from the organic product calcium acetate taking the biomass dry distillation acid as the raw material as claimed in claim 1 is characterized in that: slowly adding 60-70 parts by mass of the calcium acetate into 95-105 parts by mass of 30% hydrochloric acid, or slowly adding 75-85 parts by mass of the calcium acetate into 95-105 parts by mass of 49% sulfuric acid, stirring for dissolving, and performing third distillation at the low temperature of 38-45 ℃ and the vacuum degree of-0.090 MPa to-0.097 MPa, wherein the distillate is natural edible acetic acid.
7. The natural edible acetic acid prepared from the organic product calcium acetate taking the biomass dry distillation acid as the raw material as claimed in claim 6 is characterized in that: 65-72 parts of calcium acetate and 102 parts of 30% hydrochloric acid; 79-81 parts of calcium acetate and 98-100 parts of 49% sulfuric acid; the temperature is 40-42 ℃, and the vacuum degree is-0.092 MPa to-0.095 MPa.
8. The use of the organic product calcium acetate of claim 1 in the preparation of organic plant calcium health products, beverage additives, and organic calcium supplements for animals.
9. The use of the natural edible acetic acid produced from the organic product calcium acetate as the raw material according to claim 6 in the preparation of organic edible vinegar, organic edible plant vinegar, sour agent for organic food, and acidity regulator.
CN202111327589.2A 2021-11-10 2021-11-10 Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid Pending CN113861017A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111327589.2A CN113861017A (en) 2021-11-10 2021-11-10 Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111327589.2A CN113861017A (en) 2021-11-10 2021-11-10 Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid

Publications (1)

Publication Number Publication Date
CN113861017A true CN113861017A (en) 2021-12-31

Family

ID=78987617

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111327589.2A Pending CN113861017A (en) 2021-11-10 2021-11-10 Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid

Country Status (1)

Country Link
CN (1) CN113861017A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1094909A (en) * 1993-05-13 1994-11-16 雷传喜 A kind of calcium additive and production method thereof with the preparation of birds, beasts and eggs shell
CN1094919A (en) * 1993-05-13 1994-11-16 雷传喜 A kind of calcium-enriching drink additive and preparation method thereof
JP2985003B1 (en) * 1998-11-25 1999-11-29 俊則 國府 Production method of bamboo vinegar liquid
CN101396161A (en) * 2007-09-28 2009-04-01 山东龙力生物科技有限公司 Xylitol corn-silk vinegar beverage and production method thereof
CN102106403A (en) * 2009-12-25 2011-06-29 光明乳业股份有限公司 Acid processed cheese and production method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1094909A (en) * 1993-05-13 1994-11-16 雷传喜 A kind of calcium additive and production method thereof with the preparation of birds, beasts and eggs shell
CN1094919A (en) * 1993-05-13 1994-11-16 雷传喜 A kind of calcium-enriching drink additive and preparation method thereof
JP2985003B1 (en) * 1998-11-25 1999-11-29 俊則 國府 Production method of bamboo vinegar liquid
CN101396161A (en) * 2007-09-28 2009-04-01 山东龙力生物科技有限公司 Xylitol corn-silk vinegar beverage and production method thereof
CN102106403A (en) * 2009-12-25 2011-06-29 光明乳业股份有限公司 Acid processed cheese and production method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
国家林业局职业技能鉴定指导中心: "木材热解与活性炭生产", 中国物资出版社, pages: 64 - 70 *
高子亭等: "一种木醋液制备环保型融雪剂的方法", 应用化学, vol. 38, no. 8, pages 1022 - 1024 *

Similar Documents

Publication Publication Date Title
Gusain et al. Vermicomposting of duckweed (Spirodela polyrhiza) by employing Eisenia fetida: Changes in nutrient contents, microbial enzyme activities and earthworm biodynamics
CN103553746B (en) Selenium-rich nutrient and application thereof
CN100368509C (en) Process for producing vinegar liquid for plant
Karinen et al. Marine decomposition persistence of carbaryl in the marine estuarine environment. Chemical and biological stability in aquarium systems
CN106495770A (en) A kind of efficient high-rate composting fermentation process of utilization agriculture and forestry organic waste material
James et al. General food studies
Paradelo et al. Plant tests for determining the suitability of grape marc composts as components of plant growth media
Moldes et al. Negative effect of discharging vinification lees on soils
Aranganathan et al. Spectral and microscopic analysis of fulvic acids isolated from marine fish waste and sugarcane bagasse co-compost
CN113996078B (en) Simple processing method for concentrated natural organic acid by using biomass dry distillation acid as raw material
CN113861017A (en) Organic product calcium acetate with biomass dry distillation acid as raw material, natural edible acetic acid prepared from organic product calcium acetate and application of natural edible acetic acid
CN109738610A (en) A kind of method of Fast Evaluation lignocellulose castoff compost rotten degree
CN101914586B (en) Method for preparing and purifying DON toxin
CN109406427A (en) The detection method of enzyme activity in a kind of tobacco
CN114032159A (en) Processing method for producing organic plant edible vinegar by using plant vinegar liquid and application thereof
CN113975212B (en) Processing method for removing harmful substances in bamboo-wood vinegar, wet tissue liquid and mouthwash prepared by processing method
CN102818801A (en) Method for determining ATP
CN101618974B (en) Method for preparing triple superphosphate fertilizer by using waste water generated in synthetic process of 2, 4, 6-trichloropyrimidine
Mattos et al. Influence of sugarcane variety and management on the mineral composition of vinasse from alembic cachaça
Beshgetoor et al. Determining Phenols in Dilute Solutions. Notes on the Gibbs Method
Levy et al. Pyrethrum Analysis, Rapid Colorimetric Determination of Total Pyrethrins by Reaction with Sulfur
Klapa Bioenergy and industrial applications of grape pomace from" Vinho Verde"
CN109520947B (en) Method for quantitatively determining 3-hydroxy butanone in fermentation liquor
TREET et al. Society of Public Anadysts.
Pecegueiro do Amaral Evaluation of algae concentration in manure based media

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination