CN1055274C

CN1055274C - Method for producing hard mineral water by carbonic anhydrase catalysis

Info

Publication number: CN1055274C
Application number: CN 93118281
Authority: CN
Inventors: 邵靖宇; 胡元强
Original assignee: Individual
Current assignee: Individual
Priority date: 1993-10-09
Filing date: 1993-10-09
Publication date: 2000-08-09
Anticipated expiration: 2013-10-09
Also published as: CN1101626A

Abstract

The present invention relates to a method for producing hard mineral water by carbonic anhydrase catalysis, which has the characteristic that in the process of corroding calcium carbonate (magnesium) into hard water in pressurized carbon dioxide water, small amount of carbonic anhydrase is added in raw material water, a water flow filled with carbon dioxide is firstly converted into carbonic acid by a fixed carbonic anhydrase post (bed), or granular carbonic anhydrase with a solid phase is put in a reactor. Consequently, the generation of the carbonic acid is accelerated thousandfold so that the reaction time of dissolving the calcium carbonate (magnesium) for generating calcium bicarbonate (magnesium) is largely shortened; the carbonic anhydrase is protein with zinc; the dissolved carbonic anhydrase can also provide a small amount of zinc easily absorbed.

Description

Method for producing hard mineral water by carbonic anhydrase catalysis method

The present invention belongs to the field of producing artificial mineral water by carbon dioxide corrosion method.

Hard water means that calcium and magnesium are dissolved in waterWater of the main alkaline earth metal salt, usually as its bicarbonate, Ca (Hco)₃)₂And Mg (Hco)₃)₂Mainly comprises the following steps. The hardness of the part is lost due to the deposition of the boiled carbon dioxide, which is called temporary hard water; calcium and magnesium sulfates dissolve in water to form part of the hardness, but do not precipitate on boiling, and are called permanent hard water. Calcium and magnesium can be absorbed and utilized by human bodies in dissolved state no matter temporary hard water or permanent hard water.

The function of hard water in nutrition and health care is increasingly known, especially the health care function for heart and cerebral vessels has a lot of evidence abroad, and in addition, the hard water is greatly beneficial to the development of children skeletons, the supplement of calcium for women in lactation period and the prevention and treatment of senile osteoporosis. Nutrition studies show that the intake of calcium and magnesium in the daily diet of ordinary people is often low or even insufficient, and besides unreasonable dietary structure (such as more oxalate in food), the daily drinking water is mostly boiled first, and the loss of calcium and magnesium bicarbonate is also one of the reasons for the precipitation of scale. Therefore, hard water that can be drunk directly without boiling is considered to be the best choice for daily calcium and magnesium supplementation.

Natural mineral waters are ubiquitous and their composition is not necessarily ideal. The artificial mineral water with hardness higher than that of natural mineral water can be obtained by using high-quality spring water or underground water for artificial mineralization. There are roughly two methods for producing hard artificial mineral water: 1. direct melting method. That is, sodium bicarbonate, calcium chloride, magnesium chloride, etc. are directly added to natural water, and carbon dioxide is charged. The mineral water produced by this method has low alkalinity, and is difficult to increase the content of calcium and magnesium in mineral water, and contains excessive sodium chloride. 2. Carbon dioxide etching method. With the method, all types of mineral water can be prepared.

The basic principle is to make the raw material water of carbon dioxide act on powdered carbonate alkaline earth metal salt under pressure to convert it into bicarbonate which is dissolved in water. Another modified carbon dioxide etching method is to install an ultrasonic wave on one side of the reaction tankA generator for promoting mineral dissolution by using ultrasonic waves. (Soft drink technologics, 1993, 1 month, Shao Chang Fu, Zhao jin Fu main edition, China light industry Press). The main chemical reactions that take place during mineralization are:

among the above reactions, the first step is a rate-limiting slow reaction, which is the key point. The water pressure must be higher than the carbon dioxide gas pressure to mineralize smoothly, which is difficult to achieve in practice, and the small difference of the pressure may affect the mineralization speed and the solubility of minerals.

The invention aims to overcome the defects of the prior art and provide a method for producing hard mineral water by a carbonic anhydrase catalysis method, which shortens the reaction time, reduces the equipment occupation time and improves the economic benefit.

Due to Ca (Hco)₃)₂And Mg (Hco)₃)₂Is dependent on H₂co₃The amount of production and stability of the compound. The present invention adopts carbonic anhydrase with very high catalytic efficiency, carbonic anhydrase is used to catalyze carbonic acid to generate in raw material water filled with carbon dioxide, and calcium carbonate (magnesium) is dissolved in carbonic acid water solution to generate hard water containing calcium (magnesium) carbonate. The reaction is as follows:

the molecular weight of carbonic anhydrase (EC421.1) is 29000, the highest efficiency of all known enzymes is achieved, and the conversion rate (turu over sulfate) reaches 3.6 × 10⁷Substrate molecules/enzyme molecules/minute, which is more than a thousand times higher than most enzymes. The calculation shows that 1 mg of carbonic anhydrase can catalyze 1.24 mol/min under the optimum conditionThe generation of carbonic acid in mole number can be almost instantly dissolved under the condition that the adopted calcium carbonate (magnesium) has enough fine granularity, thereby greatly shortening the reaction time and improving the utilization rate of equipment.

There are several indications of water hardness, often referred to as "degree". The unit of water hardness of different countries can be converted, at present, in America, calcium and magnesium ions in each million parts of water are converted into parts of calcium carbonate, one magnesium ion is alsoconverted into one calcium ion, and the molecular weight of CaCo3 is just 100, so that the molar concentration can be conveniently converted into the percentage concentration, namely the ppm value of the calcium carbonate. As the hardness, the hardness is less than 55ppm, the hardness is micro-hard water 55-100ppm, the hardness is medium hard water 200ppm, and the hardness is very hard water 200ppm or more (scientific Press scientific dictionary). The water sources in various places are quite different, the very hard water with more than 200ppm is not common, the hardness of boiled water (cold boiled water) which is actually drunk is very low, because most of calcium and magnesium are precipitated, the hardness of the hard artificial mineral water produced by the technology can be between 200ppm and 1000ppm according to market requirements, the chemical components are the same as those of natural hard mineral water, the hardness can reach or exceed the natural hard water, the added carbonic anhydrase can also provide trace zinc, and because the carbon dioxide water has cool feeling and slight stimulation to taste buds, and calcium ions have slight sweet taste, the hard artificial mineral water produced by the technology is quite delicious, sweet and appetizing, is beneficial to heart and brain health, and is suitable for people of all ages.

The first embodiment is as follows: examples of addition of dissolved carbonic anhydrase

1. The raw material water is selected. The water source without industrial and agricultural pollution and resident living pollution is selected as the production key, mountain spring water, mineral water or deep well water which accord with the sanitary standard and have pure taste is an ideal water source, and the uncontaminated ground water can also be used as raw material water;

2. and (4) pretreating raw material water. The method mainly comprises filtering and sterilizing, wherein the raw material water is sterilized after solid suspended matters are filtered, and a working procedure of adsorbing by using active pottery clay can be added according to needs to improve the quality of the water. Ultraviolet lamp irradiation or ozone sterilization is adopted for sterilization treatment, and no odor is generated; the boiling or steam introduction has high energy consumption and can lose part of the original hardness, but the equipment is simple and easy to operate:

3. and (6) hardening treatment.

(1) The hardness of raw water is measured, and the addition amount of calcium carbonate and magnesium carbonate is calculated according to the hardness required by the product. Assuming that the hardness of raw material water is 50ppm, hard artificial mineral water having a hardness of 300ppm is to be produced, and the hardness should be increased to 250 ppm. The hardness of the steel is designed to be increased by 85 percent of calcium carbonate and 15 percent of magnesium carbonate (the proportion basically meets the requirement of human bodies on calcium and magnesium), and then the steel is dissolved into water per ton, wherein the calcium carbonate is 250 multiplied by 0.85 to 212.5 (grams), the magnesium carbonate is 250 multiplied by 0.15 multiplied by 0.84 to 31.5 (grams), and the 0.84 is a coefficient which is multiplied by the magnesium carbonate (molecular weight 84) to replace the calcium carbonate.

(2) Carbonic anhydrase is added in solution. The enzyme product with specific activity of 2500W-A unit per milligram is used as raw material, and is added into 250W-A unit per liter, 100 milligram of the enzyme is needed to be added into each ton of hard artificial mineral water, and the enzyme can be dissolved in dozens of milliliters of sterile water and then injected into a reaction tank. Since carbonic anhydrase is a zinc-containing enzyme, trace zinc sulfate (ZnSo) can be added into water to ensure its catalytic activity₄·7H₂O), a concentration of 1ppm can be achieved by adding 4.5 g per ton of water.

The purity of carbonic anhydrase in the method is more than 2000W-A units of specific activity per milligram of enzyme preparation, and the carbonic acid can be accelerated hundreds of times by adding 200-1000-W-A units of enzyme into each liter of raw material.

(3) Stirred and charged with high pressure carbon dioxide. The pressure reactor for producing hard artificial mineral water is similar to common fermentation tank or sealed reaction tank, has stirrer inside, and can bear 10kg/cm²The above pressure is preferably stainless steel, and the reaction can be carried out at room temperature by selecting an appropriate volume depending on the scale of production. Pretreating raw material water, injecting into a reactor, weighing light calcium carbonate and magnesium carbonate, adding dissolved carbonic anhydrase, stirring at high speed until solid material is stirred and no bubble is generated on liquid surface, introducing high-pressure carbon dioxide, and maintaining pressure at the same3-5Kg/cm²Continuously stirring, changing the turbid reaction solution from transparent to clear as the reaction end point, and determining the required time according to the granularity, solubility and feeding amount of the raw materials (the required hardness of the product)Degree) and the number of units of enzyme activity per liter of water. The product flows through the pipeline filter under the pressure of the carbon dioxide and is directly bottled, the pressure of the carbon dioxide is adjusted to be in a safe range during bottling, and the product is an aerated beverage.

Example two: an example of immobilized carbonic anhydrase is used.

In principle, any solid phase method (such as covalent cross-linking method, charge cross-linking method, adsorption method, coating method and the like), any kind of support (cellulose and derivatives thereof, polysaccharide derivatives, polyamide resin, polysulfone resin, porous glass and the like) can be used for immobilizing carbonic anhydrase, the related technology is open technology, reference can be made to books related to solid phase enzyme technology, solid phase carbonic anhydrase can be repeatedly used for many times until the enzyme activity is gradually reduced to be unsatisfactory, so the investment is high, but the total production cost is low, and in addition, the purity requirement of raw material enzyme for producing the solid phase enzyme is relatively low, and the cost is saved.

The immobilized carbonic anhydrase can be used in one of two ways for the production of hard mineral water.

1. Raw material water is filtered, sterilized and measured for hardness, the addition amount of calcium carbonate and magnesium carbonate is calculated, carbon dioxide is filled, the carbon dioxide filled water flows through an immobilized carbonic anhydrase column (or bed) before entering a reaction tank, and carbon dioxide dissolved under high pressure is converted into carbonic acid. The size of the column and the activity of immobilized total enzyme are in a certain proportion to the volume of the reaction tank, 10-100 ten thousand W-A unit activity of a catalytic column matched with a 1-10 ton reaction tank is sufficient, the carbonic acid generated by catalysis enters the reaction tank and reacts with calculated amount of calcium carbonate and magnesium carbonate preset in the tank to be dissolved, a stirrer is started when the carbonic water reaches a certain volume in the tank during production, a source of the carbonic water is provided, the volume of the water in the tank is gradually increased to finally reach the designed volume, and the reaction liquid is the endpoint when the reaction liquid is changed from turbid to clear and transparent.

2. The immobilized carbonic anhydrase is made into particles, such as the immobilized carbonic anhydrase is fixed on the surfaces of ion exchange resin particles or embedded in polyamide gel blocks, and the like, and the immobilized carbonic anhydrase particles are filtered and recovered after the reaction is finished so as to be prepared for the next batch production and reuse.

The two embodiments introduce three methods for producing artificial hard mineral water by introducing carbonic anhydrase, which can effectively accelerate the dissolution of calcium carbonate and magnesium carbonate, achieve the hardness required by design, greatly shorten the equipment occupation time and improve the economic benefit. The hard mineral water produced by the process is quite delicious, sweet and delicious, is beneficial to heart and brain health, and is suitable for people of all ages.

Claims

1. A method for producing hard mineral water is characterized in that: adding carbonic anhydrase into raw water containing calcium carbonate, magnesium carbonate and carbonated water to catalyze the generation of carbonic acid, wherein the addition amount of the carbonic anhydrase is as follows: each liter of raw material water contains 200-1000-W-A units, and calcium carbonate and magnesium carbonate are dissolved in carbonic acid water solution to prepare hard water containing calcium bicarbonate and magnesium bicarbonate.

2. Process for producing hard mineral water according to claim 1, characterized in that: the carbonated raw water is passed through immobilized carbonic anhydrase column or bed to convert it into carbonic acid-containing raw water, which is then reacted with calcium carbonate and magnesium carbonate in reactor to dissolve it and generate hard water containing calcium bicarbonate and magnesium bicarbonate.

3. Process for producing hard mineral water according to claim 1, characterized in that: granular immobilized carbonic anhydrase is added into raw material water for carbon dioxide charging, and filtration and recovery are carried out after the catalytic reaction is finished.