Attapulgite-based mineralized water agent

Abstract

The application is a divisional application of 2022109403727. The application discloses a palygorskite-based mineralized water agent, which has a core-shell structure, and the content of the core is 75-90 wt%, wherein the core is a particle composed of the following components: palygorskite, lithia tourmaline, medical stone, serpentine, wood fish stone, hexacyclic stone and montmorillonite; the shell is composed of the following components: hydroxyapatite, tyrosine and methionine. Compared with the prior art, the mineralized water agent can not only increase beneficial substances such as strontium, selenium, zinc and lithium in drinking water, but also reduce fluorine, iron and manganese.

Description

[0001] This application is a divisional application of Chinese application No. 2022109403727, filed on August 5, 2022, entitled "A method for purifying attapulgite clay and an attapulgite-based mineralizing agent". Technical Field

[0002] This invention relates to an attapulgite-based mineralizing water agent. Background Technology

[0003] Attapulgite clay is a non-metallic clay mineral and a non-renewable resource. my country possesses over 70% of the world's attapulgite clay reserves, but most of these are low-grade attapulgite deposits. Further purification and dissociation are necessary before use to fully utilize the unique advantages of attapulgite. Currently reported purification methods for attapulgite clay include dry air classification and wet purification. Wet purification primarily utilizes flotation reagents and other agents, taking advantage of the differences in surface charge and density of various substances, to screen attapulgite using appropriate flotation agents. For example, Chinese patent CN 106904623 A (hereinafter referred to as background document 1) discloses a method for purifying and modifying attapulgite, which is carried out through the following steps: attapulgite ore is crushed and put into deionized water containing organic active agents such as silane coupling agent 550, silane coupling agent 570, aluminate coupling agent SG-A1821, and anti-settling aluminate ASA, and magnetically stirred. After soaking and standing, the solution is decanted to obtain an upper attapulgite suspension. An activating dispersant composed of sodium hexametaphosphate and carboxymethyl cellulose is added for synergistic ultrasonic hydrothermal treatment. After centrifugation, filtration, and drying, crude attapulgite powder is obtained. The powder is then transported to a rotary drying oven filled with inert argon gas for calcination. After calcination, the powder is cooled and allowed to stand at room temperature before being removed to obtain purified and modified attapulgite powder. This invention eliminates conventional acid washing wastewater discharge, is energy-saving and environmentally friendly, and uses argon as the calcination medium to improve the purity of attapulgite powder, further increasing its specific surface area, enhancing its adsorption capacity, and broadening its application fields. However, the invention does not mention the purity of the purified attapulgite clay. Chinese Patent CN 109809422 A (hereinafter referred to as Background Document 2) discloses a method for purifying attapulgite. The purification process includes the following steps: adding the ball-milled and sieved attapulgite raw clay to a dispersant solution, followed by centrifugation and washing, adding hydrochloric acid solution, mixing thoroughly in a colloid mill for 1 hour, centrifuging, adding ammonia solution, stirring in a magnetic stirrer, centrifuging, adding deionized water, mixing evenly, centrifuging again, and spray-drying the supernatant to obtain a specific surface area as high as 151.6 m². 2The process is simple, safe, low in raw material price, rich in reserves, easy to apply to industrial production, and has great application value. The dispersing agent used in the document is sodium hexametaphosphate and sodium pyrophosphate, and the purity of the purified palygorskite is close to 100%, but the content of palygorskite in the raw ore is not given. Chinese patent CN 110092386 A (hereinafter referred to as background document 3) discloses a purification method of palygorskite clay, which comprises: crushing the palygorskite clay to clay particles with a particle size of 10-20 mm; then adding water to prepare a mud slurry with a concentration of 35wt%; after ultrasonic and mechanical stirring, passing through a 200 mesh screen; then adjusting the concentration of the mud slurry to 15wt%, after ultrasonic and mechanical stirring, passing through a 2000 mesh screen; then adjusting the concentration of the mud slurry to 10wt%, adding sodium carboxymethyl starch, homogenizing, and centrifuging at 5500 rpm, then centrifuging the upper emulsion at 12000 rpm, washing, adding water to prepare a mud slurry with a concentration of 15%, adding phosphatidylcholine and pine oil for flotation, pressure filtration, Soxhlet extraction of the filter cake with ethanol, and drying to obtain purified palygorskite. Although the invention mentions that the final palygorskite clay purity is greater than 99.9%, the content of palygorskite in the raw ore is not mentioned.

[0004] Although natural mineral water has many advantages, the nutritional elements of mineral water from different producing areas are not uniform, or some trace elements exceed the standard, which needs to be further prepared. Artificial mineral water production has great flexibility, which can be directly produced in the consumption area, and various types of artificial mineral water can be produced according to needs. However, consumers do not agree with the practice of adding food additives to increase trace elements, and through market research, it is found that the method of treating drinking water with natural minerals can be accepted by consumers. The drinking water prepared by this process is safer and more nutritious than single natural mineral water.

[0005] Palygorskite is a natural clay mineral. In the paper "Study on Palygorskite Purification and Mineralization of Drinking Water" by Zhang Guosheng, published in Water Treatment Technology, 1997, Vol. 23, No. 1 (background document 4), palygorskite clay is used as the main raw material to add various minerals to prepare an artificial mineralizer. The water quality test results show that palygorskite is very suitable for making mineral water agent, especially the good sterilization effect of palygorskite, which reduces the total bacterial count from 5500 / mL to 10 / mL, and the total number of coliform bacteria from more than 230 / mL to less than 3 / mL, but the mineralization of water changes little. SUMMARY

[0006] The purpose of the present application is to provide a method for purifying high-purity palygorskite directly from low-grade palygorskite clay ore.

[0007] The present application adopts the following technical solutions to achieve the above-mentioned purpose.

[0008] A purification method of attapulgite clay, the attapulgite clay is purified by a flotation method, comprising: adding a flotation agent and a foam stabilizer to the attapulgite clay slurry, collecting the above-mentioned suspension, and then the suspension is subjected to demulsification, separation and washing to obtain attapulgite, wherein the flotation agent is composed of at least 10-20 wt% of white deto ester, 5-15 wt% of benzoin ester, 40-60 wt% of sodium hexametaphosphate and 5-35 wt% of clove bud oil.

[0009] Preferably, the amount of the flotation agent is 3-10 wt% of the attapulgite clay.

[0010] Preferably, the flotation agent further contains not more than 30 wt% of one or more selected from the group consisting of oxidized starch, locust bean gum, flaxseed gum, sesbania gum, curdlan, soluble soybean polysaccharide, phosphated distarch phosphate, tamarind gum, hydroxypropyl distarch phosphate, safflower gum and sorbitan monooleate.

[0011] Most preferably, the flotation agent is composed of 20 wt% of white deto ester, 10 wt% of benzoin ester, 50 wt% of sodium hexametaphosphate and 20 wt% of clove bud oil.

[0012] Preferably, the foam stabilizer is composed of components including 30-50 wt% of sodium carboxymethyl cellulose, 10-20 wt% of microcrystalline cellulose and 30-60 wt% of gamma-cyclodextrin.

[0013] Preferably, the amount of the foam stabilizer is 1-3 wt% of the attapulgite clay.

[0014] Most preferably, the foam stabilizer is composed of 50 wt% of sodium carboxymethyl cellulose, 10 wt% of microcrystalline cellulose and 40 wt% of gamma-cyclodextrin.

[0015] Preferably, after the suspension is subjected to demulsification, centrifugal separation is performed at a speed of 2000-4000 rpm.

[0016] Another object of the present application is to provide an improved attapulgite-based mineralized water agent using the purified attapulgite as a raw material.

[0017] The present application adopts the following technical solutions to achieve the above-mentioned purpose.

[0018] An attapulgite-based mineralized water agent, the attapulgite-based mineralized water agent has a core-shell structure, the content of the core is 75-90 wt%, wherein,

[0019] The core is a particle composed of the following components: attapulgite, lithia tourmaline, medical stone, serpentine, hexagonal stone and montmorillonite.

[0020] The shell is composed of components including hydroxyapatite, tyrosine and methionine.

[0021] Preferably, the composition of the core is: 30-70wt% of palygorskite, 5-10wt% of lepidolite, 10-20wt% of zeolite, 5-10wt% of serpentine, 5-20wt% of hexacyclite and 5-10wt% of montmorillonite.

[0022] Preferably, the content of hydroxyapatite in the palygorskite-based mineralized water agent is 9-20wt%, and the total content of tyrosine and methionine is 1-5wt%.

[0023] More preferably, the mass ratio of tyrosine to methionine is 1:1-1:4.

[0024] The preparation method of the above-mentioned palygorskite-based mineralized water agent comprises:

[0025] (1) uniformly mixing palygorskite and potassium bicarbonate and then heating and activating to obtain activated palygorskite;

[0026] (2) uniformly mixing the activated palygorskite with palygorskite, lepidolite, zeolite, serpentine, hexacyclite and montmorillonite and then granulating;

[0027] (3) sequentially spraying the granules obtained in step (2) with hydroxyapatite emulsion, mixed aqueous solution of tyrosine and methionine, and drying to obtain the palygorskite-based mineralized water agent.

[0028] Preferably, the amount of potassium bicarbonate is 10%-20% of the mass of palygorskite, and the activation temperature is 250-300℃.

[0029] The application of the above-mentioned palygorskite-based mineralized water agent in the production of drinking water.

[0030] Beneficial effects:

[0031] Compared with the existing purification technology, the application has wider applicability, can directly obtain high-purity palygorskite from low-grade palygorskite clay ore with a content of less than 40%, and thus can fully utilize the abundant low-grade palygorskite ore.

[0032] The palygorskite-based mineralized water agent of the application is based on high-purity palygorskite obtained by purification, and is compounded with various minerals, hydroxyapatite, tyrosine and methionine, which can increase the content of beneficial substances such as zinc and lithium elements in drinking water, obtain nutritionally balanced selenium and strontium-rich type water, and reduce the excessive fluorine, iron and manganese elements in water. DETAILED DESCRIPTION

[0033] The technical solutions of the application are further described below in combination with examples.

[0034] Example 1

[0035] Select attapulgite ore, detect no harmful heavy metal ions to the human body, after drying, then crushed into 100-120 mesh particles, add pure water to 10-30% slurry.

[0036] Select composite floatation agent (see Table 1), ball mill uniformly, add pure water, ultrasonic stirring, add the above attapulgite slurry, continue ultrasonic stirring for 10-50 minutes, then add 2wt% of attapulgite ore by sodium carboxymethyl cellulose 50wt%, microcrystalline cellulose 10wt%, γ-cyclodextrin 40wt% mixed foam stabilizer, stirring uniformly. After 24-48 hours, the upper suspension and the bottom precipitate are separated, the upper suspension is added with citric acid solution, and then centrifuged at 2000-4000 rpm, the paste obtained by centrifugation is washed with pure water 3-5 times, and then washed with edible alcohol 2-3 times, and then prepared into 10-20% slurry, spray dried to obtain superfine attapulgite powder (hereinafter referred to as ATP-0), particle size not less than 2500 mesh. The obtained superfine attapulgite powder is analyzed by whole rock clay mineral, the content of attapulgite is greater than 99.9%, the content of attapulgite in the ore is 35.4%, and the purification effect of the ore in this embodiment by the method described in the background documents 1-3 is compared, the specific results are shown in Table 2.

[0037] Table 1: Compound floatation agent ratio (by weight)

[0038] raw ore butter ester benzoin ester sodium hexametaphosphate clove bud oil comparative experiment 1 100 10 \ \ \ comparative experiment 2 100 \ 10 \ \ comparative experiment 3 100 \ \ 10 \ comparative experiment 4 100 \ \ \ 10 comparative experiment 5 100 2 3 5 \ comparative experiment 6 100 \ 3 5 2 comparative experiment 7 100 3 \ 5 2 comparative experiment 8 100 3 5 \ 2 comparative experiment 9 100 5 5 \ \ comparative experiment 10 100 5 \ 5 \ comparative experiment 11 100 5 \ \ 5 comparative experiment 12 100 \ 5 5 \ comparative experiment 13 100 \ 5 \ 5 comparative experiment 14 100 \ \ 5 5 example 1 100 2 1 5 2

[0039] In the table, "\" means not added.

[0040] Table 2: Purification effect of different floatation agents and methods

[0041]

[0042]

[0043] Examples 2-7

[0044] The purification process of attapulgite ore is the same as that of Example 1, and the material ratio is shown in Table 3:

[0045] Table 3: Raw material ratio of Examples 2-7 (by weight)

[0046] example 2 example 3 example 4 example 5 example 6 example 7 raw ore 100 100 100 100 100 100 butter ester 0.6 0.6 0.5 0.6 0.9 1.6 benzoin ester 0.15 0.45 0.25 0.4 0.3 0.8 sodium hexametaphosphate 1.8 1.8 2.5 2.2 3.6 4.4 clove bud oil 0.45 0.15 1.75 0.8 1.2 1.2 oxidized starch 0.5 / / / 0.1 0.3 locust bean gum / 1 0.1 / 0.1 0.1 flaxseed gum / / 0.2 / 0.1 0.2 curdlan / / 0.2 / 0.1 0.1 soluble soybean polysaccharide 0.5 / 0.5 / 0.1 0.2 phosphated distarch phosphate / / / 0.2 0.1 0.1 artemisia gum / / / 0.8 0.1 / sodium carboxymethyl cellulose 0.9 0.5 0.8 1.5 0.6 0.4 microcrystalline cellulose 0.3 0.2 0.3 0.6 0.4 0.15 γ-cyclodextrin 1.8 0.3 0.9 0.9 1.0 0.45

[0047] The whole rock clay mineral analysis results of the purified products of each example are shown in Table 4:

[0048] Table 4. Whole-rock clay mineral analysis of attapulgite obtained in Examples 2-7

[0049]

[0050]

[0051] Example 8

[0052] 1. ATP-0 from Example 1 was mixed with food-grade anhydrous potassium bicarbonate and ball-milled at high speed at 25–35 degrees Celsius. The anhydrous potassium bicarbonate was loaded onto the surface of attapulgite rod crystals, with the amount of anhydrous potassium bicarbonate added being 10%–20% of the attapulgite powder. The composite was then placed in a microwave sintering furnace and rapidly heated to 250–300 degrees Celsius, followed by activation at this temperature for 10 minutes. This is designated as ATP-1.

[0053] After microwave sintering and activation, the specific surface area of ​​ATP-1 is 3.5 times that of ATP-0, the bulk density is reduced by 34.2%, and the powder has a meat floss-like appearance.

[0054] 2. Lithium tourmaline, maifanite, serpentine, hexagonal stone and montmorillonite are blended in a certain proportion and pulverized into ultrafine powder with D100 less than 5 micrometers. Then, they are blended with ATP-0 in a high-speed ball mill and denoted as ATP-MO.

[0055] 3. First, ATP-MO is granulated into small particles with a particle size of 2 to 4 mm using a disc granulator. Then, hydroxyapatite emulsion (hydroxyapatite content of 20% to 30%) is sprayed onto the surface of the ATP-MO small particles, which is designated as ATP-MO-1.

[0056] 4. Mix tyrosine and methionine in a certain proportion and dissolve them in pure water. This mixture is called AA aqueous solution.

[0057] 5. Spray a 2-5% (by mass) aqueous solution of AA (dry basis) onto the surface of ATP-MO-1 and dry it under vacuum at low temperature to obtain the attapulgite-based mineralizing agent, denoted as ATP-MO-AA (see Table 5 for specific raw material ratios).

[0058] Mineralized water experiment

[0059] Using a certain natural mineral water as the base water source, all indicators of the mineral water were tested according to GB 5749-2022 and GB8537-2018. The mineral water was found to be rich in strontium (content not less than 0.765 mg / L), but other beneficial substances such as selenium, zinc, and lithium were almost undetectable. More concerningly, the mineral water was found to contain fluoride exceeding the standard by 1.8 times (2.7 mg / L), manganese exceeding the standard by 1.3 times (0.514 mg / L), and iron exceeding the standard by 1.25 times (1.375 mg / L).

[0060] The mineral water is rich in strontium element required by human body, but needs to be further processed to reduce the content of fluorine element, manganese element and iron element and increase other beneficial nutrient elements before entering the drinking stage. The specific process is as follows:

[0061] 1. 5% to 20% mass fraction of ATP-MO-AA is added to 1 ton of the mineral water raw water, slowly stirred for 1 to 2 hours, and then filtered by using 0.2 to 0.25 micropore filter membrane to obtain water marked as NMW-1.

[0062] 2. The NMW-1 is subjected to ultrasonic treatment by using high-energy direct insertion type ultrasonic wave, the ultrasonic frequency is 20 KHz, the ultrasonic time is 8 to 12 minutes, and then the water body is subjected to microwave treatment, the microwave frequency is 2.45 GHz, and the microwave treatment time is 3 to 5 minutes to obtain water marked as NMW-2.

[0063] 3. The NMW-2 is filtered by using ultra-micro filter membrane, and the water quality detection data of the obtained drinking water are shown in Table 6. The water quality detection is all carried out according to the national standard, and only the changed data and the key attention data are listed in Table 6, and the data not listed all meet the national drinking water standard.

[0064] Table 5 Raw material ratio (by weight fraction) of different mineralized water agents and treatment of mineralized water

[0065]

[0066] "\ " in the table represents no addition or no treatment.

[0067] In addition, the same amount of palygorskite clay ore, ATP-1 and the mineralized agent of background literature 4 are subjected to comparative experiments according to the above mineralized water experimental steps.

[0068] Table 6 Water quality index test after natural mineral water treated by different mineralized agents

[0069]

[0070] Table 6 (continued)

[0071]

[0072] Cluster number characterization method of small molecule group water: high-resolution superconducting nuclear magnetic resonance spectrometer is used to characterize the cluster structure of water molecules, and the cluster number is measured 17 O nuclear magnetic resonance half-peak width, the lower the half-peak width value, the smaller the cluster number.

[0073] Examples 9 to 16

[0074] The palygorskite-based mineralized water agents of examples 9 to 16 are prepared in the same manner as example 8, and the specific raw material ratio is shown in Table 7:

[0075] Table 7 Raw material ratio of examples 9-16 (in parts by weight)

[0076]

[0077] After the raw water is mineralized by the mineralizer of the present application, the selenium and strontium rich mineral spring water with balanced nutrition can be obtained, and the excessive fluorine, iron and manganese in the raw water can be adsorbed and treated, and the beneficial substances such as zinc and lithium are increased. After the ultrasonic and microwave treatment, the cluster degree of the final water body is greatly reduced and is close to the best natural mineral spring water on the market.

[0078] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An attapulgite-based mineralizing agent, characterized in that: The attapulgite-based mineralizing agent has a core-shell structure, with the core content ranging from 75% to 90 wt%. The core is a particle composed of the following components: attapulgite, lithium tourmaline, maifanite, serpentine, hexagonalite, and montmorillonite; The shell is composed of the following components: hydroxyapatite, tyrosine, and methionine; The core is composed of: attapulgite 30-70 wt%, lithium tourmaline 5-10 wt%, maifanite 10-20 wt%, serpentine 5-10 wt%, hexagonalite 5-20 wt%, and montmorillonite 5-10 wt%. The attapulgite-based mineralizing agent contains 9-20 wt% hydroxyapatite and 1-5 wt% tyrosine and methionine.

2. The attapulgite-based mineralizing agent according to claim 1, characterized in that: The mass ratio of tyrosine to methionine is 1:1 to 1:

4.

3. The preparation method of the attapulgite-based mineralizing agent according to claim 1, comprising: (1) After mixing attapulgite and potassium bicarbonate, heat and activate to obtain activated attapulgite. (2) After the activated attapulgite is mixed with lithium tourmaline, maifanite, serpentine, hexagonalite and montmorillonite, it is granulated. (3) The particles obtained in step (2) are sequentially sprayed with hydroxyapatite emulsion and a mixed aqueous solution of tyrosine and methionine, and then dried to obtain the attapulgite-based mineralizing agent.

4. The preparation method according to claim 3, characterized in that: The amount of potassium bicarbonate used is 10% to 20% of the mass of attapulgite, and the activation temperature is 250 to 300℃.

5. The application of the attapulgite-based mineralizing agent according to claim 1 in the production of drinking water.

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