BIFUNCTIONAL PLANT PROMOTER AND PREPARATION THEREOF

Abstract

A bifunctional plant growth promoter and methods of preparing the plant growth promoter. The plant growth promoter comprises nano carbon black modified with carboxyl groups referred to as carbon black acid. The nano carbon black has a structure forming a first functional part of the plant growth promoter and the carboxyl groups form a second functional part of the plant growth promoter. The plant growth promoter has an average particle size in a size range of 5 nm to 200 nm and a mass fraction of carboxyl groups in a mass fraction range of 5% to 25%.

Claims

1. A plant growth promoter, comprising: nano carbon black modified with carboxyl groups; wherein the nano carbon black has a structure forming a first functional part of the plant growth promoter and the carboxyl groups form a second functional part of the plant growth promoter.

2. A plant growth promoter as set forth in claim 1, wherein the plant growth promoter has an average particle size in a size range of 5 nm to 200 nm.

3. A plant growth promoter as set forth in claim 1, wherein the plant growth promoter has a mass fraction of carboxyl groups in a mass fraction range of 5% to 25%.

4. A method of preparing plant growth promoter comprising nano carbon black modified with carboxyl groups, said method comprising controllably oxidizing nano carbon black using at least one oxidizing agent selected from a group of oxidizing agents consisting of ozone, nitric acid, hydrogen peroxide, persulfates, and hypohalites.

5. A method of preparing the plant growth promoter as set forth in claim 4, further comprising: introducing oxygen into a vessel containing nano carbon black in nitric acid dispersion at a preselected pressure until a resulting solution in the vessel has a mass fraction of carboxyl groups in a mass fraction range of 5% to 25%; separating agglomerated solids from the resulting solution; and washing the agglomerated solids with water until the solids are separated into the plant growth promoter.

6. A method of preparing the plant growth promoter as set forth in claim 5, wherein the plant growth promoter has an average particle size in a size range of 5 nm to 200 nm.

7. A method of preparing the plant growth promoter as set forth in claim 5, wherein the preselected pressure is within a pressure range of 1 bar to 10 bar.

8. A method of preparing the plant growth promoter as set forth in claim 5, nano carbon black in nitric acid dispersion is made with nitric acid having a concentration within a concentration range of 10% to 40% nitric acid.

9. A method of preparing the plant growth promoter as set forth in claim 5, wherein the nano carbon black in nitric acid dispersion has a mass ratio within a mass ratio range of 1:1 to 1:30.

10. A method of preparing the plant growth promoter as set forth in claim 5, wherein the step of introducing oxygen into the vessel containing nano carbon black in nitric acid dispersion is performed at a preselected temperature in a temperature range of 60 C. to 150 C.

11. A method of preparing the plant growth promoter as set forth in claim 4, further comprising: introducing ozone into a vessel containing nano carbon black in aqueous dispersion while stirring until a resulting intermediate solution in the vessel has a mass fraction of carboxyl groups in a mass fraction range of 5% to 25%; removing residual ozone from the resulting intermediate solution to produce a final solution; and drying the final solution to produce the plant growth promoter.

12. A method of preparing the plant growth promoter as set forth in claim 11, wherein the plant growth promoter has an average particle size in a size range of 5 nm to 200 nm.

13. A method of preparing the plant growth promoter as set forth in claim 11, wherein the nano carbon black in aqueous dispersion has a mass ratio within a mass ratio range of 1:10 to 1:150.

14. A method of preparing the plant growth promoter as set forth in claim 11, wherein the ozone introduced into the vessel has a concentration within a concentration range of 2% to 10%.

15. A method of preparing the plant growth promoter as set forth in claim 11, wherein the ozone is introduced into the vessel at a gas rate within a gas rate range of 0.3 L/hr/g.sub.carbon black to 15 L/hr/g.sub.carbon black

16. A method of preparing the plant growth promoter as set forth in claim 11, wherein the step of introducing ozone into the vessel is performed at a preselected temperature in a temperature range of 30 C. to 100 C.

17. A method of preparing the plant growth promoter as set forth in claim 11, wherein the step of removing residual ozone from the resulting intermediate solution includes heating the resulting intermediate solution.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] FIGS. 1a and 1b are graphs showing characterization of carbon black and carbon black acid by XPS;

[0020] FIG. 2 is a graph showing the particle size distribution of carbon black acid;

[0021] FIG. 3 is a graph showing the effect of pressure on the carboxylic acid content in nitric acid oxidation;

[0022] FIG. 4 is a graph showing the effect of nitric acid concentration on the carboxylic acid content in nitric acid oxidation;

[0023] FIG. 5 is a graph showing the effect of the mass ratio of reactants on the carboxylic acid content in nitric acid oxidation;

[0024] FIG. 6 is a graph showing the effect of temperature on the carboxylic acid content in nitric acid oxidation;

[0025] FIG. 7 is a graph showing the effect of the ozone source on the carboxylic acid content in ozone acid oxidation;

[0026] FIG. 8 is a graph showing the effect of temperature on the carboxylic acid content in ozone acid oxidation;

[0027] FIG. 9 is a graph showing the effect of the mass ratio of nano carbon black to water on the carboxylic acid content in ozone acid oxidation;

[0028] FIG. 10 is a graph showing the effect of ozone concentration on the carboxylic acid content in ozone acid oxidation;

[0029] FIG. 11 is a photo of carbon black acid in water solution;

[0030] FIG. 12 is a scanning electron microscope image of carbon black acid; and

[0031] FIG. 13 is an atomic force microscope image of carbon black acid.

DETAILED DISCLOSURE

[0032] The present disclosure describes carbon black nano particles, or nano carbon black, being oxidized by controllable chemical oxidation to obtain a bifunctional plant promoter, which this applicant refers to as carbon black acid. The described carbon black acid has an average particle size in a range of about 5 nm to about 200 nm. Further, the described carbon black acid contains about 5 wt % to about 25 wt % carboxyl groups.

[0033] As discussed above, auxins promote plant growth. As reported, the mechanism by which auxins promote growth is that the acidity of the carboxyl structures in auxins promotes plant cell elongation by activating and increasing proton pumping H+-ATPase in cell membranes, leading to the proton efflux, acidification of the cell wall, activation of dilatation proteins in the cell wall, and the weakening of hydrogen bonds between the cell wall polysaccharide groups. In addition, as a nano material, nano carbon has been shown to have a beneficial role in nitrogen fixation, plant growth, and other aspects. Thus, applicant hypothesized that nano carbon material modified with carboxylic acid functional groups, i.e., carbon black acid, would have advantages of both auxins and nano carbon. This hypothesis, however, could not be confirmed before developing reliable methods for modifying nano carbon black with carboxyl groups.

[0034] Nano carbon black is a common nano carbon material having nano-scale particle sizes, but poor dispersibility. Pure water or organic solvents do not stably disperse nano carbon black. Although others developed methods for modifying nano carbon or nano carbon black, the purpose of those methods was to improve the dispersion of nano carbon. Further, the carboxyl content in the nano carbon was not controllable using prior methods. Therefore, the plant growth promoting effects of acidic groups on the surface of nano carbon were not discoverable.

[0035] Having modified nano carbon black with carboxyl groups using controllable chemical oxidation to obtain a bifunctional plant promoter, carbon black acid, applicant was able determine that when carbon black acid had less than about 5 wt % carboxylic acid, the carbon black acid does not cause appreciable plant growth. In addition, applicant was able determine that the nano carbon black readily over-oxidizes, forming small molecules such as aromatic polycarboxylic acids that reduce the yield of carbon black acid, when the carbon black acid had more than about 25 wt % carboxylic acid. Therefore, applicant determined an effective amount of carboxyl group in carbon black acid that was producible and effective as a bifunctional plant promoter. That effective amount of carboxyl group in carbon black acid is in the range of between about 5% and about 25%.

[0036] A plurality of controllable chemical oxidation methods are envisioned for preparing the carbon back acid, including ozone, nitric acids, hydrogen peroxides, persulfates, and hypohalites as oxidants. Two methods for preparing carbon black acid and corresponding procedures for optimizing process parameters in the methods are described below.

A. Nitric Acid Oxidation Method

[0037] Using nitric acid oxidation method, oxygen is introduced into a vessel holding nano carbon black in nitric acid dispersion at a specific pressure until the carboxyl content reaches a range of about 5% to about 25%. Bifunctional plant promoter, i.e., carbon black acid, is obtained after separation and washing.

[0038] The average particle size of the nano carbon black held in the vessel is in a range of 5 nm to about 200 nm. The nitric acid concentration is in a range of about 10% to about 40%, and more particularly in some examples, in a range of about 15% to about 30%. The mass ratio of nano carbon black to nitric acid solution is in a range of about 1:1 to about 1:30, and more particularly in some examples, in a range of about 1:5 to about 1:10. Temperature in the vessel maintained in a range of about 60 C. and about 150 C., and more particularly in some examples, in a range of about 100 C. to about 120 C. Pressure in the vessel is maintained in a range of about 1 bar to about 10 bar, and more particularly in some examples, in a range of about 4 bar to about 6 bar. The resulting crude bifunctional plant promoter is washed with water several times until the promoter is no longer agglomerated. The crude bifunctional plant promoter is separated from the solution using conventional methods such as centrifugal separation and/or evaporation.

[0039] The ratio of reactants, the nitric acid concentration, the reaction temperature, and the reaction time were investigated to determine how to control oxidation using the nitric acid oxidation method. High solid-to-liquid ratios caused poor fluidity during the liquid phase, decreasing reaction rate and carboxylic acid content. Low solid-to-liquid ratios negatively impacted reaction efficiency, generating a large amount of waste acid. A nano-carbon-to-nitric-acid mass ratio in a range of about 1:5 to about 1:10 was found to provide a sufficient reaction rate and carboxylic acid content without producing large amounts of waste acid. Further, low nitric acid concentration required high reaction temperature, and high nitric acid concentration resulted in excessive oxidation, potentially causing environmental pollution. A nitric acid concentration in a range of about 15% to about 30% was found to allow appropriate reaction temperatures and suitable excessive oxidation. Temperature also played an important role in the reaction. High temperature caused rapid evaporation and decomposition of nitric acid. In addition, high reaction rates excessively oxidized the nano carbon black. A reaction temperature in a range of about 100 C. to about 120 C. was found to provide satisfactory results. Nano carbon black oxidation increased over time. Stopping the oxidation reaction when the carboxyl group content reaches a range of about 5% to about 25% was found to provide an effective amount of carboxyl groups in the carbon black acid. Further, introducing oxygen into the liquid phase oxidizes nitrogen oxide and nitrogen dioxide to regenerate nitric acid, avoiding environmental pollution by reducing nitric acid and nitrogen oxide emissions.

B. Ozone Oxidation Method

[0040] Using the ozone oxidation method, nano carbon black in aqueous dispersion is stirred in a vessel. Ozone is introduced into the nano carbon black in aqueous dispersion as it is mixed until the carboxyl content reaches a range of about 5% to about 25%. The ozone may be generated from either air or oxygen. The nano carbon black has an average particle size in a range of 5 nm to about 200 nm. The rate at which ozone is introduced is in a range of about 0.3 L/hr/g.sub.carbon black to about 15 L/hr/g.sub.carbon black. The mass ratio of nano carbon black to water is in a range of about 1:10 to about 1:150, and more particularly in some examples, in a range of about 1:20 to about 1:100. The ozone concentration is in a range of about 2% to about 10%, and more particularly in some examples, in a range of about 5% to about 10%. Temperature in the vessel is maintained in a range of about 30 C. and about 100 C., and more particularly in some examples, in a range of about 50 C. to about 100 C. Residual ozone is removed by heating, and evaporation is used to separate the crude bifunctional plant promoter from the solution.

[0041] The ratio of reactants, the reaction temperature, and the reaction time were investigated to determine how to control the amount of oxidation when using the ozone oxidation method. Increasing the amount of solvent to increase the absolute amount of ozone in the reaction system was found to improve the reaction efficiency due to the gas-liquid phases reaction. A mass ratio of nano carbon black to water in a range of about 1:20 to about 1:100 was found to provide a suitable amount of ozone. Holding reaction temperature within a range of about 50 C. to about 100 C. was found to avoid decomposition of ozone.

[0042] As those skilled in the art will appreciate, other methods of oxidation could be used. The investigations and optimization procedures outlined above are representative of the investigations and procedures needed to confirm and optimize the other methods. Thus, it is believed that the other methods are sufficiently reduced to practice by this disclosure to provide support for these methods if recited in claims of applications having priority to this application.

[0043] Surprisingly, nano carbon black can be functionalized by controlled oxidation to form certain numbers of carboxyl functional groups on the surface of the nano carbon black particles and to provide a macromolecular carbonic acid similar to auxin structure can be obtained. Applicant refers to this macromolecular carbonic acid as carbon black acid. Carbon black acid comprises nano carbon black particles having a carboxylic acid functional group on its surface and has both nanostructure and acidic functional groups. After being functionalized, the nano carbon black provides the dual functions of auxin analogs and nano carbons, such as improving nutrients, nitrogen, fat, and far-infrared absorption, as well as, removing or adsorbing impurities and moisture, and providing anti-bacterial benefits.

[0044] As noted above, the particle size of nano carbons used in the processes is in a range of about 5 nm to about 200 nm. After functionalizing the nano carbon black, e.g., using the methods described above, most of the nano carbon black continues to have particle sizes in the specified range, thereby meeting the particle sizes necessary for nano carbons. In addition, the carbon black acid readily disperses uniformly in water for extended periods of time due to the acidic hydrophilic groups on the surface.

[0045] Using the methods described above allow oxidation and the number of carboxyl functional groups on the surface of the nano carbon black to be controlled. When the mass fraction of carboxyl group in the carbonic acid is less than about 5%, the dispersion performance of carbon black acid is poor. The low acid value and few carboxylic acid functional groups prevent carbon black acid from functioning as an auxin analog. When the mass fraction of carboxyl groups in carbon black acid is above about 25%, due to excessive oxidation, a large amount of nano carbon black is oxidized into carbon dioxide discharged into the atmosphere, wasting raw materials and emitting greenhouse gases. In addition, higher oxidation amounts produce small molecular aromatic polycarboxylic acid by-products that are harmful to the environment and pose a risk of cancer. Controlling the mass fraction of the carboxyl group in carbon black acid to be within a range of about 5% to about 25% reduces these harmful effects.

[0046] The present disclosure describes preparing the bifunctional plant promoter, carbon black acid, having an average particle size range of about 5 nm to about 200 nm and a mass fraction of carboxyl groups in range of about 5% to about 25% by controllably oxidizing nano carbon black. The carbon black acid contains two functional parts, the nano carbon structure and carboxyl groups, to efficiently promote plant growth.

EXAMPLES

[0047] The following examples are intended to be illustrative only and are not intended to restrict the scope of the claims or disclosure.

Example 1

[0048] 20.0 g nano carbon black having an average particle size of 50 nm was combined with 200.0 g 30% HNO.sub.3 solution in a reactor and heated to 110 C. Reaction occurred under a fixed pressure of 3 bar while adding oxygen for 19 hours. After cooling, the reactants were separated by centrifugal separation at 4000 rpm to obtain crude bifunctional plant promoter. Then the crude bifunctional plant promoter was washed with water three times until the promoter was not agglomerated and could not be separated by centrifugal separation. The final bifunctional plant promoter, carbon black acid, was obtained after evaporating the solution and drying. The carboxyl content of the resulting bifunctional plant promoter was 17.8% as measured using the Boehm titration method. The nano carbon black and the carbon black acid were characterized by XPS. The results are shown in FIG. 1. After the nano carbon black controllably oxidized, the peak representing carbon in carboxyl group, COO, at 289 eV increased, indicating the carboxyl groups were introducing to the nano carbon black after oxidation. The oxygen atom content also increased from 8.63% to 25.18%. The particle size distribution of the carbon black acid was characterized by zeta-potential analysis. The average size of the carbon black acid was 124.7 nm as shown in FIG. 2.

Example 2

[0049] The effects of nitric acid concentration, oxygen pressure, reaction temperature and mass ratio of nano carbon black to nitric acid in the nitric acid oxidation were investigated using the procedure described in Example 1. FIGS. 3-6 illustrate carboxyl content as a function of oxidation time for noted reagents and conditions.

Example 3

[0050] 20.0 g nano carbon black having an average particle size of 50 nm was combined with 2000.0 g water in a 2000 mL reactor with ozone bubbling at 100 C. The concentration of ozone generated by oxygen was 8%, and the gas flow rate was 1 L/min. The reaction was stopped after 2.5 hours. The residual ozone in the solution was removed by heating. The bifunctional plant promoter, i.e., carbon black acid, was obtained after evaporation. The carboxyl content of the bifunctional plant promoter was 17.5% as measured using the Boehm titration method.

Example 4

[0051] The effects of ozone source, ozone concentration, reaction temperature, and mass ratio of nano carbon black to water in the ozone oxidation were investigated using the procedure described in Example 3. FIGS. 7-10 illustrate carboxyl content as a function of oxidation time for noted reagents and conditions.

Example 5

[0052] Wheat seeds were soaked in the experimental solution for 6 hr. After soaking, 30 seeds of the same size were selected for each group of experiments and cultured in filter dishes with filter paper. One week later, the data of radicle length and germ length in each group were counted. Light was used to maintain temperature in the incubator at 25 C. The humidity was in the range of 80% to 90%. The statistical results are shown in Table 1. The results show that adding carbon black acid has obvious growth promoting effects on radicle and germ, and carbon black acid exerts a bifunctional effect.

TABLE-US-00001 TABLE 1 Results for carbon black acid containing 20.3% carboxyl groups promoting wheat seed germination Radicle Radicle Germ Germ Average Experimental Length Length Length Length Rhizome Sample Solution (cm) growth rate (cm) growth rate Ratio 1 No Additive 4.46.sub.0.32.sup.+0.32 2.73.sub.0.11.sup.+0.12 1.63 2 0.03% 4.52.sub.0.29.sup.+0.31 1.35% 2.86.sub.0.11.sup.+0.10 4.76% 1.58 Carbon Black Solution 3 0.03% 4.80.sub.0.28.sup.+0.28 7.62% 3.07.sub.0.11.sup.+0.12 12.5% 1.56 Carbon Black Acid Solution 4 0.06% 4.62.sub.0.31.sup.+0.30 3.59% 3.16.sub.0.10.sup.+0.12 15.8% 1.46 Carbon Black Acid Solution

Example 6

[0053] Cotton and sugar beet field experiments were performed using 0.3% carbon black acid solution. On the basis of normal planting, 0.3% carbon black acid (carboxyl content 18.3%) solution was added with water, and a blank control group was also set up. The results are shown in Table 2. After the use of carbon black acid, the cotton leaves were larger and darker in color, the stems were thicker, the growth of individual plants was higher, the growth was lush, and the number of bolls per plant was large. It took longer time to fruit comparing to the blanks. The cotton plants were strong lodging resistance after using carbon black acid. During the growth of sugar beet, the leaves are darker and larger. The production of sugar beets was increased by carbon black acid.

TABLE-US-00002 TABLE 2 Effect of the carbon black acid containing 18.3% carboxyl groups on cotton and sugar beet yield Fertilizer Carbon Black Acid (kg/mu) Area Solution Nitrogen Phosphate Production Crop (mu) (mu/dosage/kg) Fertilizer Fertilizer Potash growth ratio Cotton 30 25 44 45 26 15.6% Sugar Beet 20 20 31 20 25 8.2%

[0054] It will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

[0055] Insofar as the description above and the accompanying drawings disclose any additional subject matter that is not within the scope of the claims below, the disclosures are not dedicated to the public and the right to file one or more applications to claims such additional disclosures is reserved.

[0056] Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring its steps be performed in a specific order. This construction holds for possible non-express bases for interpretation, including matters of logic with respect to arrangement of steps or operational flow, or plain meaning derived from grammatical organization or punctuation.

[0057] When introducing elements in this description, the articles a, an, the, and said are intended to mean that there are one or more of the elements. The terms comprising, including, and having are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0058] As those skilled in the art could make various changes to the above constructions, products, and methods without departing from the intended scope of the description, all matter in the above description and accompanying drawings should be interpreted as illustrative and not in a limiting sense.