Preparation method of natural hot spring carbon nanobubbles and stabilized product and application thereof

Abstract

The application discloses a preparation method of natural hot spring carbon nanobubbles, and a stabilized product and application thereof, relates to the technical field of deep processing of natural products and high-end personal care raw materials, and comprises a specific preparation method, a stabilized product obtained by using the preparation method, and application of the stabilized product in the preparation of daily chemical products. Through ultrahigh-speed rotary cutting dispersion and interface modification technology, free carbon dioxide (CO2) and bicarbonate (HCO3 ‑ ) systems in hot spring water are efficiently converted into nanobubble dispersion with super-long stability and a stabilized product with characteristic mineral ions, which can be directly used as a core raw material of high-end bubble bath and skin care products.

Description

Technical Field

[0001] This invention relates to the field of deep processing of natural products and high-end personal care raw materials, and more specifically to a method for preparing carbonated nanobubbles based on natural hot springs, its stabilized products, and their applications. Background Technology

[0002] The core health value of carbonated hot springs (also known as "bubble hot springs") lies in their high content of free CO2. During bathing, CO2 is absorbed transdermally through the skin, causing capillary dilation and significantly improving local blood circulation; this effect is medically known as "carbonated spring therapy." However, transforming this therapy into a standardized, commercially viable home product faces three major industry-level bottlenecks:

[0003] 1. The non-concentrability of active substances (CO2): Traditional processes such as evaporation and membrane concentration, while enriching minerals, cause 100% of free CO2 gas to escape, resulting in the final product losing its core activity.

[0004] 2. The fundamental contradiction between storage stability and the timeliness of experience: Existing technologies (such as pressurized dissolution) cannot preserve CO2 for a long time in normal pressure packaging; while effervescent tablets and other dosage forms can only provide a brief (<5 minutes) burst of intense bubbles, which cannot simulate the gentle and delicate stimulation of natural hot springs that lasts for 20-40 minutes.

[0005] 3. Disruption of the synergistic system of mineral ions and gaseous activity: Natural carbonic acid springs are characterized by a "CO2-HCO3" reaction. - -Ca² + / Mg² + This is a dynamic equilibrium system. Simply adding exogenous CO2 or mineral salts cannot reproduce the unique biological effects and skin feel of this complex system.

[0006] Therefore, whether a method for preparing carbonated nanobubbles based on natural hot springs, as well as its stabilized products and applications, can be developed to simultaneously achieve CO2 nano-sizing, long-term stabilization, and in-situ composite with the mineral ion spectrum of the original spring water is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0007] In view of this, the present invention provides a method for preparing carbonated nanobubbles based on natural hot spring water, its stabilized products, and their applications. It involves a three-step synergistic process of "physical trapping-nano-reconstruction-interface locking".

[0008] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing carbonated nanobubbles based on natural hot spring water includes the following steps: (1) Collect natural carbonated hot spring water, filter it, add additives, and concentrate it at low temperature and membrane to obtain mineral concentrated base liquid; (2) Under low temperature conditions, minerals are concentrated and sheared at high speed, while food-grade CO2 is introduced and an amphiphilic polymer stabilizer solution is injected simultaneously. After treatment, a nano bubble dispersion is obtained. (3) The nano bubble dispersion is mineralized, pH adjusted and reduction potential controlled according to the raw water test data.

[0009] The beneficial effects of step (1) are: while enriching the active ingredients, it removes some interfering monovalent ions and prevents the loss of CO2 during the pretreatment process; it also removes key divalent mineral ions (Ca²⁺). + Mg² + ) and HCO3 - The concentration is increased to 3-5 times that of the original solution; The beneficial effect of step (2) is that the low temperature condition is guaranteed by the whole pipeline cooling system, which can suppress the escape of gas thermal expansion and microbial activity to the greatest extent. The beneficial effect of step (3) is that controlling the reduction potential further protects the nanobubbles and active ingredients.

[0010] To improve the interfacial stability of nanobubbles, an amphiphilic polymer stabilizer solution is simultaneously injected into the liquid flow during gas inlet, so that it is adsorbed at the gas-liquid interface the moment the bubble is generated, forming a dual stabilizing layer of steric hindrance and electrostatics.

[0011] Preferred: Step (1) specifically involves: collecting natural carbonated hot spring water, filtering it through a 0.22μm precision filter to remove bacteria, adding 0.05%-0.2% disodium EDTA, and then circulating and concentrating it to 1 / 5 of its original volume through a nanofiltration membrane with a molecular weight cutoff of 200Da at a pressure of 0.8 MPa under a low temperature and closed nitrogen-filled environment of 5-15℃ to obtain a mineral concentrated base liquid.

[0012] Preferred: Step (2) specifically involves: maintaining the mineral concentrate at 4-10℃, pumping it into an ultra-high-speed shear system at a speed of 10000-30000 rpm; simultaneously introducing food-grade CO2 at a pressure of 0.5-1.5 bar, and simultaneously injecting 0.1%-0.5% amphiphilic polymer stabilizer solution; continuing the treatment for 25-30 minutes to obtain a nano-bubble dispersion.

[0013] Preferred: The rotor-stator gap in the ultra-high-speed shearing system is 10-50 micrometers; Amphiphilic polymer stabilizer solution: at least one of hydroxypropyl methylcellulose and polyglycerol ester.

[0014] The beneficial effects are as follows: the gas-liquid mixture undergoes extreme shearing force, cavitation force and impact force in the homogenizing head, is broken and mixed, and carbon dioxide nanobubbles with an average hydrodynamic particle size (Z-average) ≤ 150 nm are generated in situ.

[0015] Preferred: Step (3) specifically involves: transferring the nanobubble dispersion into a 0.5-2 bar pressure-maintaining mixing tank, adding sodium metasilicate according to the raw water test data until the metasilicate content is 25 mg / L; adding a pH and redox potential buffer system: 0.04-0.06% sodium ascorbate, adjusting the pH to 6-6.8 with a trace amount of citric acid, and maintaining the redox potential at -100 to -200 mV; and aseptically filtering through a 0.22 μm filter cartridge.

[0016] The present invention also provides a stabilized product prepared based on the above preparation method.

[0017] The present invention also provides any of the above-described preparation methods and the application of the above-described stabilized products in the preparation of daily chemical products.

[0018] Preferred: Daily chemical products: bath products used for skin care, promoting microcirculation in the body, or relieving fatigue.

[0019] The present invention also provides a bath product containing the above-mentioned stabilized product.

[0020] As can be seen from the above technical solution, compared with the prior art, the present invention discloses a method for preparing carbonic acid nanobubbles based on natural hot springs, its stabilization products, and their applications, achieving the following technical effects: Using ultra-high-speed rotary dispersion and interface modification technology, free carbon dioxide (CO2) and bicarbonate (HCO3) in hot spring water are dispersed. - The system is efficiently transformed into a nanobubble dispersion with ultra-long stability, while retaining the characteristic mineral ions completely, and finally a stabilized product is obtained, which can be directly used as the core raw material for high-end bath and skin care products.

[0021] This invention is the first to achieve efficient extraction and extraordinary stabilization of gaseous active ingredients (CO2) from natural hot springs, breaking through the technical limitations of traditional processes that have to passively discard this valuable active component due to the easy escape of gas.

[0022] This invention creates a novel stable material: the resulting stabilized product is a composite system in which gas, liquid, and solid (mineral) phases coexist stably for a long time, possessing both the processability of fluids and the functional activity of gases, providing unprecedentedly highly active raw materials for downstream product development.

[0023] This invention achieves a faithful restoration of efficacy and experience: due to the slow-release properties of nanobubbles, products formulated with this stabilized product can for the first time approach or even surpass the effect of natural open-air hot spring bathing in terms of bubble duration and gentle sensation, solving the core pain point of home-use products. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] This invention discloses a method for preparing carbonated nanobubbles based on natural hot springs, its stabilization products, and their applications.

[0026] In the examples, all raw materials and reagents not mentioned are commercially available, and all process methods not mentioned are conventional processes, which will not be described in detail here. The hot spring involved in the examples: a 1000L carbonated hot spring water in Tengchong, which was tested, had a total CO2 (free + bound) content of 450 mg / L, a calcium hardness (calculated as CaCO3) of 120 mg / L, and a magnesium hardness of 60 mg / L.

[0027] Example 1 A method for preparing carbonated nanobubbles based on natural hot spring water includes the following steps: (1) Collect 1000L of natural carbonated hot spring water, filter it through a 0.22μm precision filter to remove bacteria, add 0.05% disodium EDTA, and concentrate it to 200L through a nanofiltration membrane with a molecular weight cutoff of 200Da at 0.8 MPa under a low temperature and closed nitrogen-filled environment at 5℃ to obtain mineral concentrated base liquid. (2) Maintaining the temperature at 4°C (ensuring the cooling of the entire pipeline), the mineral concentrate is pumped into the ultra-high-speed shearing system (speed 20,000 rpm, the core of which is an ultra-precision homogenizing head with a rotor-stator gap of 10-50 micrometers); at the same time, food-grade CO2 is introduced at a pressure of 0.5 bar, and 0.1% amphiphilic polymer stabilizer solution (hydroxypropyl methylcellulose solution) is injected simultaneously; after continuous treatment for 30 minutes, a nanobubble dispersion is obtained; (3) The nano bubble dispersion was transferred to a 0.5 bar pressure-holding mixing tank. Sodium metasilicate was added according to the raw water test data until the metasilicate content was 25 mg / L. A pH and redox potential buffer system was added: 0.04% sodium ascorbate. The pH was adjusted to 6 with a trace amount of citric acid, and the redox potential was maintained at -100 to -200 mV. The mixture was then sterile filtered through a 0.22 μm filter cartridge.

[0028] To further optimize the technical solution, a stabilized product was obtained after filling.

[0029] The partial detection results of the stabilization products are as follows: Nanobubble concentration: 6.5 × 10⁻⁶ 8 Particles / mL (laser nanoparticle size analyzer).

[0030] Average particle size: 87 nm, PDI=0.15.

[0031] Total dissolved CO2 concentration: 980 mg / L (titration method).

[0032] Accelerated stability (40℃, 30 days): 72% bubble concentration retention, no precipitation.

[0033] Example 2 A method for preparing carbonated nanobubbles based on natural hot spring water includes the following steps: (1) Collect 1000L of natural carbonated hot spring water, filter it through a 0.22μm precision filter to remove bacteria, add 0.1% disodium EDTA, and concentrate it to 200L through a nanofiltration membrane with a molecular weight cutoff of 200Da at 0.8 MPa under a low temperature and closed nitrogen-filled environment at 5℃ to obtain mineral concentrated base liquid. (2) Maintaining the temperature at 8°C (ensuring the cooling of the entire pipeline), the mineral concentrate is pumped into the ultra-high-speed shearing system (speed 20,000 rpm, the core of which is an ultra-precision homogenizing head with a rotor-stator gap of 10-50 micrometers); at the same time, food-grade CO2 is introduced at a pressure of 1.0 bar, and 0.3% amphiphilic polymer stabilizer solution (hydroxypropyl methylcellulose solution) is injected simultaneously; after continuous treatment for 30 minutes, a nanobubble dispersion is obtained; (3) The nano bubble dispersion was transferred to a 1.0 bar pressure-holding mixing tank. Sodium metasilicate was added according to the raw water test data until the metasilicate content was 25 mg / L. A pH and redox potential buffer system was added: 0.05% sodium ascorbate. The pH was adjusted to 6.5 with a trace amount of citric acid, and the redox potential was maintained at -100 to -200 mV. The mixture was then sterile filtered through a 0.22 μm filter cartridge.

[0034] To further optimize the technical solution, a stabilized product was obtained after filling.

[0035] The partial detection results of the stabilization products are as follows: Nanobubble concentration: 8.2 × 10⁻⁶ 8 Particles / mL (laser nanoparticle size analyzer).

[0036] Average particle size: 112 nm, PDI=0.18.

[0037] Total dissolved CO2 concentration: 1250 mg / L (titration method).

[0038] Accelerated stability (40℃, 30 days): 78% bubble concentration retention rate, no precipitation.

[0039] Example 3 A method for preparing carbonated nanobubbles based on natural hot spring water includes the following steps: (1) Collect 1000L of natural carbonated hot spring water, filter it through a 0.22μm precision filter to remove bacteria, add 0.2% disodium EDTA, and concentrate it to 200L through a nanofiltration membrane with a molecular weight cutoff of 200Da at 0.8 MPa pressure under a low temperature and closed nitrogen-filled environment at 15℃ to obtain mineral concentrated base liquid. (2) Maintaining the temperature at 10°C (ensuring the cooling of the entire pipeline), the mineral concentrate is pumped into the ultra-high-speed shearing system (speed 20,000 rpm, the core of which is an ultra-precision homogenizing head with a rotor-stator gap of 10-50 micrometers); at the same time, food-grade CO2 is introduced at a pressure of 1.5 barr, and 0.5% amphiphilic polymer stabilizer solution (polyglycerol ester solution) is injected simultaneously; after continuous treatment for 25 minutes, a nano bubble dispersion is obtained; (3) The nano bubble dispersion was transferred to a 2 bar pressure-maintaining mixing tank. Sodium metasilicate was added according to the raw water test data until the metasilicate content was 25 mg / L. A pH and redox potential buffer system was added: 0.06% sodium ascorbate. The pH was adjusted to 6.8 with a trace amount of citric acid, and the redox potential was maintained at -100 to -200 mV. The mixture was then sterile filtered through a 0.22 μm filter cartridge.

[0040] To further optimize the technical solution, a stabilized product was obtained after filling.

[0041] The partial detection results of the stabilization products are as follows: Nanobubble concentration: 9.7 × 10⁻⁶ 8 Particles / mL (laser nanoparticle size analyzer).

[0042] Average particle size: 134 nm, PDI=0.16.

[0043] Total dissolved CO2 concentration: 1500 mg / L (titration method).

[0044] Accelerated stability (40℃, 30 days): 81% bubble concentration retention rate, no precipitation.

[0045] Based on the test results of Examples 1-3 and in conjunction with actual production, the technical standards of this invention meet the following requirements: 1. Characteristics of nanobubbles: Nanobubble number concentration: ≥ 5×10 8 (particles / mL) (laser nanoparticle size analyzer).

[0046] Average particle size (Z-average): 50 - 150 nm, and particle size polydispersity index (PDI) < 0.25.

[0047] Absolute value of interface zeta potential: ≥ 35 mV (usually negative).

[0048] 2. Chemical composition characteristics: Total dissolved CO2 (including free nanobubbles and HCO3) - Concentration: ≥ 800 mg / L (as CO2).

[0049] Characteristic mineral ions (Ca²⁺) + Mg² + HCO3 - The concentration ratio of metasilicic acid is consistent with the source hot spring water quality test report, with a variation rate of <15%.

[0050] 3. Stability: After being stored at 25°C in the dark for 6 months, the concentration of nanobubbles remained at ≥ 85%, and there was no visible layering or sedimentation.

[0051] After being stored for one month in an accelerated destructive test at 40°C, the concentration retention rate of nanobubbles is ≥ 70%.

[0052] Comparative experiment Comparative Example 1: Traditional thermal concentration method: Take the same batch of hot spring water and concentrate it using vacuum evaporation at 60℃ (to 200L).

[0053] Compare with Example 2: Step (2) omits pumping into the ultra-high-speed shear system; Comparative Example 3: Step (2) omits the addition of the amphiphilic polymer stabilizer solution; Comparison with Example 4: Step (3) omits the addition of pH and redox potential buffer system.

[0054] The total dissolved CO2 concentration of the concentrate obtained in Control Example 1 dropped to <50 mg / L, completely losing its bubble activity and becoming merely a mineral salt solution. Control Example 2 could not produce sufficient nanobubbles, making further experimentation unnecessary. In Control Example 3, after one month, the nanobubble concentration retention rate was less than 50%, potentially making commercial preservation impossible. In Control Example 4, after approximately four months, the nanobubble concentration retention rate was less than 50%, and the user experience significantly declined.

[0055] Example 4 The stabilized product can be used as a 100% active stock solution, or as a core ingredient, added at a rate of 5%-30% in formulations. 1. Home Bath Essence (How to use: Dilute in hot water in the bathtub to provide fine bubbles and a warm feeling for more than 25 minutes). 2. Shower gel, body lotion, face mask (leave-on or short-stay skincare products that provide skincare benefits by promoting microcirculation); 3. Local care gels or patches (for targeted relief of joints and muscles).

[0056] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0057] Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing carbonated nanobubbles based on natural hot spring water, comprising the following steps: (1) Collect natural carbonated hot spring water, filter it, add additives, and concentrate it at low temperature and membrane to obtain mineral concentrated base liquid; (2) Under low temperature conditions, minerals are concentrated and sheared at high speed, while food-grade CO2 is introduced and an amphiphilic polymer stabilizer solution is injected simultaneously. After treatment, a nano bubble dispersion is obtained. (3) The nano bubble dispersion is mineralized, pH adjusted and reduction potential controlled according to the raw water test data.

2. The preparation method according to claim 1, characterized in that, Step (1) is as follows: collect natural carbonated hot spring water, filter it through a 0.22μm precision filter to remove bacteria, add 0.05%-0.2% disodium EDTA, and concentrate it to 1 / 5 of the original volume through a nanofiltration membrane with a molecular weight cutoff of 200Da at a pressure of 0.8 MPa under a low temperature of 5-15℃ and a closed nitrogen-filled environment to obtain a mineral concentrated base liquid.

3. The preparation method according to claim 2, characterized in that, Step (2) is as follows: Under the condition of 4-10℃, the mineral concentrate is pumped into the ultra-high speed shear system at a speed of 10000-30000rpm; at the same time, food-grade CO2 is introduced at a pressure of 0.5-1.5bar, and 0.1%-0.5% amphiphilic polymer stabilizer solution is injected simultaneously; the treatment is continued for 25-30 minutes to obtain nano bubble dispersion.

4. The preparation method according to claim 3, characterized in that, The rotor-stator gap in the ultra-high-speed shearing system is 10-50 micrometers; the amphiphilic polymer stabilizer solution is at least one of hydroxypropyl methylcellulose and polyglycerol ester.

5. The preparation method according to claim 4, characterized in that, Step (3) is as follows: the nano bubble dispersion is transferred to a 0.5-2 bar pressure-maintaining mixing tank, and sodium metasilicate is added according to the raw water test data until the metasilicate content is 25 mg / L; a pH and redox potential buffer system is added: 0.04-0.06% sodium ascorbate, and the pH is adjusted to 6-6.8 with a trace amount of citric acid, and the redox potential is maintained at -100 to -200 mV; and then aseptically filtered through a 0.22μm filter cartridge.

6. The stabilized product prepared by the preparation method according to claims 1 to 5.

7. The preparation method according to any one of claims 1-5, and the application of the stabilized product according to claim 6 in the preparation of daily chemical products.

8. The application as described in claim 7, characterized in that, The aforementioned daily chemical products are bath products used for skin care, promoting microcirculation in the body, or relieving fatigue.

9. A bath product comprising the stabilized product as described in claim 6.