Preparation method of chlorinated potassium humate and application of chlorinated potassium humate in agricultural industry
By preparing chlorinated potassium humate, the problems of easy degradation and salinization of traditional potassium humate in high-salt environments have been solved, realizing the function of slow-release chlorine fertilizer and soil improvement, and improving the performance and economic benefits of agricultural and industrial applications.
Patent Information
- Application Number
- CN202511560089.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-29
- Publication Date
- 2026-02-03
AI Technical Summary
Traditional potassium humate does not contain chlorine atoms and cannot provide slow-release chlorine fertilizer, leading to an increased risk of soil salinization and easy degradation and failure in high-salt environments.
Potassium chlorohumate is prepared by reacting potassium humate with a chlorinating agent under specific conditions. The process includes dissolving potassium humate, adding a chlorinating agent, adjusting the pH and removing unreacted reagents, and obtaining solid potassium chlorohumate by dialysis and drying. Various chlorinating agents and solvents are selected to control the reaction conditions.
It enables the efficient preparation of potassium chlorinated humate, providing slow-release chlorine fertilizer, improving soil, enhancing nutrient utilization, reducing the risk of salinization, and increasing crop yield and quality. At the same time, it exhibits excellent high-temperature and high-salt resistance in the treatment of oil drilling fluids and heavy metal wastewater, reducing production costs.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of potassium chlorinated humic acid preparation, specifically a method for preparing potassium chlorinated humic acid and its application in agricultural industry. BACKGROUND
[0002] Potassium humate is a potassium salt generated by the reaction of humic acid and potassium hydroxide. It is a product extracted from natural humic acid and treated by alkalization, widely used in agriculture, industry and environmental protection fields. Potassium humate retains the polycyclic aromatic structure of humic acid and rich functional groups, which endow it with good chelating, adsorbing and ion exchange capacity.
[0003] In agriculture, potassium humate can promote the formation of soil aggregate structure, increase the aeration and water retention of soil, and improve the physical properties of soil. It can chelate metal ions in soil, improve the utilization rate of nitrogen, phosphorus and potassium nutrients in fertilizers, and reduce nutrient loss.
[0004] In industry, potassium humate can be used as a dispersant and stabilizer for drilling fluid, improving the rheological properties and high temperature resistance of drilling fluid; potassium humate can be used for wastewater treatment, adsorbing organic matter, heavy metal ions and dyes and other pollutants in water.
[0005] Traditional potassium humate is prone to flocculation or degradation in high salt (such as >5% NaCl) environment, resulting in loss of function; traditional potassium humate does not contain chlorine atoms, which cannot provide slow-release chlorine fertilizer function, and additional potassium chloride needs to be applied, increasing the risk of soil salinization. SUMMARY
[0006] To solve the above technical problems, the present application provides a method for preparing potassium chlorinated humic acid to solve the problem that traditional potassium humate in the prior art does not contain chlorine atoms, which cannot provide slow-release chlorine fertilizer function, and additional potassium chloride needs to be applied, increasing the risk of soil salinization.
[0007] The method for preparing potassium chlorinated humic acid comprises the following steps:
[0008] Step one: dissolve potassium humate in deionized water or polar solvent to obtain a potassium humate solution with a concentration of 4-20wt%;
[0009] Step two: add chlorinating reagent to the potassium humate solution, and react at a temperature of 20-60℃ and a stirring rate of 200-500rpm for 2-6 hours; the chlorinating reagent is selected from one or more of Cl2 gas, SOCl2 liquid and NaClO liquid, and the molar ratio of chlorine atoms in the chlorinating reagent to humic acid molecules in the potassium humate solution is 1:1 to 500:1;
[0010] Step three: adjust the pH of the reaction solution to neutral, remove the unreacted reagent by dialysis, precipitation or filtration, then dry to obtain the solid of chlorinated humic acid potassium.
[0011] Preferably, in step one, the purity of the potassium humate is ≥ 85%, and the polar solvent is one or more of N,N-dimethylformamide (DMF), water, and ethanol.
[0012] Preferably, in step two, a catalyst is also added to the potassium humate solution, the catalyst is FeCl3, AlCl3 or an ionic liquid, and the addition amount is 0-1wt% of the total mass of the reaction system.
[0013] Preferably, in step two, the chlorinating reagent is Cl2 gas, and the flow rate of Cl2 gas during the reaction is 0.05-0.2L / min.
[0014] Preferably, in step two, the chlorinating reagent is SOCl2 liquid, and the reaction temperature is 50-70℃.
[0015] Preferably, in step three, the dialysis uses a dialysis membrane with a molecular weight cut-off of 500-2000Da, and the dialysis time is 24-72 hours.
[0016] A use of chlorinated humic acid potassium in agriculture.
[0017] A use of chlorinated humic acid potassium in industry.
[0018] Compared with the prior art, the present application has the following beneficial effects:
[0019] By precisely controlling the reaction conditions and raw material ratio, efficient preparation is achieved, and at the same time, various chlorinating reagents and solvents are provided for selection, making the preparation method flexible and variable. The method is environmentally friendly and energy-saving, reduces the generation of harmful by-products and waste, realizes effective utilization of resources, and further improves the yield and reaction rate by adding a catalyst, reduces energy consumption, and finally obtains chlorinated humic acid potassium solid with high purity, excellent application performance and stability. In addition, the preparation method is clear in steps, simple in operation, easy to realize industrial production, and ensures the stability and consistency of product quality.
[0020] The chlorinated humic acid potassium prepared by the present application can significantly improve crop yield and quality, reduce dependence on pesticides and fertilizers, and promote the development of green agriculture by slow-release of chlorine fertilizer, improving nutrient utilization, improving soil, inhibiting bacteria and preventing diseases, and repairing saline-alkali land.
[0021] In petroleum drilling fluid and heavy metal wastewater treatment, chlorinated humic acid potassium exhibits excellent high-temperature resistance, high-salt resistance, efficient chelation and flame retardant performance, while having environmental advantages, reducing production costs and improving industrial economic benefits. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 Preparation flow chart of the present application. DETAILED DESCRIPTION
[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.
[0024] As shown in Figure 1 :
[0025] Example 1: Cl2 gas chlorination method
[0026] Step 1: Dissolution
[0027] 10 g of potassium humate with a purity of ≥85% (molecular weight range of 1000-5000 Da) was dissolved in 200 mL of deionized water to obtain a potassium humate solution with a concentration of 4.76 wt%;
[0028] Step 2: Chlorination reaction
[0029] 0.5 g of FeCl3 catalyst was added to the potassium humate solution, the reaction temperature was controlled at 40℃, the stirring rate was 300 rpm, Cl2 gas was introduced at a flow rate of 0.1 L / min, and the reaction time was 4 hours.
[0030] Step 3: Post-treatment
[0031] The pH of the reaction solution was adjusted to 7 with NaOH, and dialysis was performed using a dialysis membrane with a molecular weight cutoff of 1000 Da for 48 hours. After freeze-drying, the content of chlorine in the chlorinated potassium humate solid was measured to be 12.3%.
[0032] Example 2: SOCl2 liquid chlorination method
[0033] Step 1: Dissolution
[0034] 10 g of potassium humate with a purity of ≥85% (molecular weight range of 1000-5000 Da) was dissolved in 100 mL of DMF to obtain a potassium humate solution with a concentration of 9.09 wt%.
[0035] Step 2: Chlorination reaction
[0036] 5 mL of SOCl2 liquid (without adding catalyst) was added dropwise to the potassium humate solution, the reaction temperature was controlled at 60℃, the stirring rate was 400 rpm, and the reaction time was 3 hours.
[0037] Step three: Post-treatment
[0038] Add 50 mL water to hydrolyze unreacted SOCl2, precipitate with ethanol, and dry to obtain chlorinated potassium humate solid. The chlorine content of the chlorinated potassium humate solid is measured to be 8.7%.
[0039] Example three: Cl2 gas chlorination method
[0040] Step one:
[0041] Dissolve 12 g of potassium humate with purity ≥ 85% (molecular weight range 1000-5000 Da) in 60 mL of ethanol to obtain a potassium humate solution with a concentration of 16.67 wt%.
[0042] Step two:
[0043] Add 0.4 g of AlCl3 catalyst to the solution.
[0044] Control the reaction temperature at 50°C and the stirring rate at 350 rpm.
[0045] Pass Cl2 gas at a flow rate of 0.15 L / min for 5 hours.
[0046] Step three:
[0047] Adjust the pH of the reaction solution to 7 with NaOH and dialyze for 60 hours using a dialysis membrane with a molecular weight cutoff of 1200 Da.
[0048] Freeze-dry to obtain chlorinated potassium humate solid. The chlorine content of the chlorinated potassium humate solid is measured to be 10.5%.
[0049] Example four: NaClO solid chlorination method
[0050] Step one:
[0051] Dissolve 8 g of potassium humate with purity ≥ 85% (molecular weight range 1000-5000 Da) in 150 mL of deionized water to obtain a potassium humate solution with a concentration of 5.06 wt%.
[0052] Add 12 g of solid sodium hypochlorite (NaClO, available chlorine content ≥ 65%) to the solution and stir until completely dissolved.
[0053] Step two:
[0054] No catalyst is added.
[0055] Control the reaction temperature at 30°C and the stirring rate at 300 rpm for 5 hours.
[0056] Step three:
[0057] The pH of the reaction solution was adjusted to 7, and unreacted NaClO and by-products were removed by filtration.
[0058] Dialysis (molecular weight cut-off 800 Da, dialysis time 48 hours) was used to remove residual salts, followed by lyophilization to obtain the potassium chlorohumulate solid;
[0059] The content of chlorine in the potassium chlorohumulate solid was measured to be 7.1%.
[0060] Example Five: Ionic liquid catalyzed SOCl2 chlorination method
[0061] Step One:
[0062] 15 g of potassium humate (molecular weight range 1000-5000 Da) with a purity of ≥ 85% was dissolved in 80 mL of DMF to obtain a potassium humate solution with a concentration of 15.79 wt%.
[0063] Step Two:
[0064] 0.8 g of 1-butyl-3-methylimidazolium tetrafluoroborate was added to the solution.
[0065] 4 mL of SOCl2 liquid was added dropwise.
[0066] The reaction temperature was controlled at 55°C, the stirring rate was 450 rpm, and the reaction time was 2 hours.
[0067] Step Three:
[0068] 40 mL of water was added to hydrolyze the unreacted SOCl2, and ethanol was added for precipitation, followed by drying.
[0069] The content of chlorine in the potassium chlorohumulate solid was measured to be 11.2%.
[0070] Application Example 1: Application of potassium chlorohumulate in agriculture
[0071] A corn planting base, the soil type is sandy loam, there is a problem of mild salinization, and continuous cropping leads to frequent soil-borne diseases (such as fusarium). In order to verify the synergistic effect of potassium chlorohumulate, the following field test was carried out:
[0072] Test group: application of compound fertilizer containing potassium chlorohumulate (prepared by Example One) (addition amount 20%).
[0073] Control group: application of ordinary potassium humate compound fertilizer (addition amount 20%).
[0074] Other conditions: same NPK ratio, consistent irrigation and management measures.
[0075] Comparison table: potassium chlorohumulate vs. ordinary potassium humate
[0076]
[0077] Notes:
[0078] Chloride release period: Chloride ion concentration in soil leaching solution was monitored (slow-release performance test).
[0079] Bacteriostasis rate: Fusarium survival rate in soil was determined by plate culture method.
[0080] Saline-alkali soil remediation: Soil electrical conductivity (EC value) decreased from 2.8 dS / m to 1.5 dS / m before and after the test.
[0081] Application Example 2: Application of Potassium Chlorinated Humic Acid in Industry
[0082] In deep-sea oil field drilling operations, the drilling depth exceeds 4500 meters, the downhole temperature is as high as 220℃, and the formation contains high-concentration salt water (Ca 2+ / Mg 2+ concentration > 8%). To verify the performance advantages of potassium chlorinated humic acid, the following comparison scheme was adopted:
[0083] Test group: 3% potassium chlorinated humic acid (prepared by Example 1) was added to the drilling fluid.
[0084] Control group: Conventional sulfonated asphalt treatment agent (addition amount 5%) was used.
[0085] Operation conditions: Same drilling parameters (rotation speed, pump pressure), well depth, and temperature environment.
[0086] Comparison table: Potassium chlorinated humic acid vs. conventional sulfonated asphalt
[0087]
[0088] Notes: Filtration loss and temperature resistance: API standard test.
[0089] Salt resistance: Filtration loss comparison test in simulated high-salt environment (8% NaCl).
[0090] Environmental friendliness: OECD301 B biodegradability test (28 days).
[0091] Application Example 3: Application of Potassium Chlorinated Humic Acid in Sewage Treatment
[0092] A plating plant discharged wastewater containing high concentrations of heavy metals (lead, cadmium, mercury) and organic dye pollutants. The traditional chemical precipitation method had low treatment efficiency and was prone to secondary pollution. To verify the chelation and catalytic degradation ability of potassium chlorinated humic acid, the following experiments were carried out:
[0093] Test group: 0.5% chlorinated humic acid potassium (prepared in example one) was added to wastewater, supplemented by UV light catalysis condition.
[0094] Control group: conventional polyaluminum chloride (PAC) treatment agent (addition amount 1%) was used.
[0095] Treatment condition: same reaction time (2 hours), temperature 25°C.
[0096]
[0097] Notes:
[0098] Heavy metal removal rate: residual concentration was determined by atomic absorption spectrometry.
[0099] Organic dye degradation rate: HPLC was used to analyze degradation products.
[0100] Sludge amount: centrifugation method was used to determine the dry weight of precipitate.
[0101] Application example 4: application of chlorinated humic acid potassium in the development of flame retardant materials
[0102] A plastic product factory needs to develop a biological-based flame retardant to replace traditional halogen-based flame retardants (such as brominated epoxy resin) to reduce the release of toxic gases during combustion. The flame retardant properties of chlorinated humic acid potassium modified polypropylene (PP) were tested:
[0103] Test group: 10% chlorinated humic acid potassium (prepared in example one) was added to PP.
[0104] Control group: 10% brominated epoxy resin was added.
[0105] Test conditions: UL-94 vertical burning test, oxygen index (LOI) determination.
[0106]
[0107] Notes:
[0108] Combustion test: vertical burning time and dripping under UL-94 standard.
[0109] Toxicity test: Fourier transform infrared spectroscopy (FTIR) was used to analyze the composition of combustion gases.
[0110] Application example 5:
[0111] A saline farmland (soil EC value 3.5 dS / m, Na + content > 30%) needs to restore soil ecological function. The repair effect of chlorinated humic acid potassium and conventional gypsum (CaSO4) was compared:
[0112] Test group: 50 kg of chlorinated potassium humate (obtained by preparing Example 1) was applied per mu.
[0113] Control group: 100 kg of gypsum was applied per mu.
[0114] Repair period: 6 months, same irrigation and management measures.
[0115]
[0116] Note:
[0117] Soil EC value: determined by conductivity method.
[0118] Granular structure: wet sieve method to determine the proportion of >0.25 mm aggregates.
[0119] Application Example 6: Potential application of chlorinated potassium humate in the field of medicine
[0120] A livestock farm broke out of bacterial diarrhea (pathogen is Escherichia coli), and it is necessary to verify the bacteriostatic effect and safety of chlorinated potassium humate as a feed additive:
[0121] Test group: 0.1% chlorinated potassium humate (obtained by preparing Example 1) was added to the feed.
[0122] Control group: 0.05% antibiotic (oxytetracycline) was added.
[0123] Test period: 30 days, same feeding conditions.
[0124]
[0125] Note:
[0126] Cure rate: clinical symptoms observation combined with pathogenic bacteria PCR detection.
[0127] Bacterial diversity: 16S rRNA sequencing analysis of intestinal microbial composition.
[0128] Application Example 7: Application of chlorinated potassium humate in battery materials
[0129] A new energy company developed sodium ion battery, and needed to develop low-cost and high-conductivity cathode materials. The electrochemical performance of chlorinated potassium humate composite material was tested.
[0130] Test group: 10% chlorinated potassium humate (obtained by preparing Example 1) was added to the cathode material.
[0131] Control group: traditional hard carbon cathode material.
[0132] Test conditions: 0.5C charge and discharge rate, 100 cycles.
[0133]
[0134]
[0135] Notes:
[0136] Specific capacity: Constant current charge-discharge test.
[0137] Cycle stability: Capacity fade rate calculation.
[0138] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "an example", "a specific example" or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Furthermore, the person skilled in the art can combine and combine the different embodiments or examples described in the present specification and the features of the different embodiments or examples, without contradiction.
[0139] Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can modify the technical solutions recorded in the foregoing embodiments or make equivalent replacements for part of the technical features, and any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A method for the preparation of chlorinated potassium humate, characterized in that, The method comprises the following steps: Step 1: Dissolve potassium humate in deionized water or a polar solvent to obtain a potassium humate solution with a concentration of 4-20wt%; Step 2: Add a chlorinating agent to the potassium humate solution, and react at a temperature of 20-60℃ and a stirring rate of 200-500rpm for 2-6 hours; the chlorinating agent is selected from one or more of Cl2 gas, SOCl2 liquid, and NaClO liquid, and the molar ratio of chlorine atoms in the chlorinating agent to humic acid molecules in the potassium humate solution is 1:1 to 500:1; Step 3: Adjust the pH of the reaction solution to neutral, remove unreacted reagents by dialysis, precipitation, or filtration, and then dry to obtain a chlorinated potassium humate solid.
2. The method for preparing potassium chlorohumate as described in claim 1, characterized in that, In step 1, the purity of the potassium humate is ≥85%, and the polar solvent is one or more of N,N-dimethylformamide (DMF), water, and ethanol.
3. The method for preparing potassium chlorohumate as described in claim 2, characterized in that, In step 2, a catalyst is further added to the potassium humate solution, and the catalyst is FeCl3, AlCl3, or an ionic liquid, and the addition amount is 0-1wt% of the total mass of the reaction system.
4. The method of claim 3, wherein the potassium chlorohuminic acid is prepared by the process of: (a) mixing humic acid with potassium hydroxide; (b) adding chlorine gas to the mixture; and (c) recovering the potassium chlorohuminic acid. In step 2, the chlorinating agent is Cl2 gas, and the flow rate of Cl2 gas during the reaction is 0.05-0.2L / min.
5. The method for preparing potassium chlorohumate as described in claim 4, characterized in that, In step 2, the chlorinating agent is SOCl2 liquid, and the reaction temperature is 50-70℃.
6. The method of claim 1, wherein the potassium chlorohuminic acid is prepared by the process of: (a) mixing humic acid with potassium hydroxide; (b) adding chlorine gas to the mixture; and (c) recovering the potassium chlorohuminic acid. In step 3, dialysis is performed using a dialysis membrane with a molecular weight cut-off of 500-2000Da, and the dialysis time is 24-72 hours.
7. Use of chlorinated potassium humate in agriculture.
8. Use of chlorinated potassium humate in industry.