WO2015193779A1 - Barium humate production method - Google Patents

Barium humate production method Download PDF

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WO2015193779A1
WO2015193779A1 PCT/IB2015/054461 IB2015054461W WO2015193779A1 WO 2015193779 A1 WO2015193779 A1 WO 2015193779A1 IB 2015054461 W IB2015054461 W IB 2015054461W WO 2015193779 A1 WO2015193779 A1 WO 2015193779A1
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humate
barium
characterized
coal
humic acid
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PCT/IB2015/054461
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French (fr)
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Hacer DOĞAN
Tülay İNAN
Handan Karakale
Murat Koral
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Tubitak
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Priority to TR2014/07025 priority
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Publication of WO2015193779A1 publication Critical patent/WO2015193779A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/003Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages

Abstract

This invention relates to the production of the insoluble barium humate in alkaline conditions by the directly use of coal having low heating value, and high content of inorganic materials or by using humic acid obtained from the alkaline extraction of coal, and the modification of barium humate by applying heat treatment (calcination).

Description

DESCRIPTION

BARIUM HUMATE PRODUCTION METHOD Technical Field of the Invention

This invention relates to the production of the insoluble barium humate in alkaline conditions by the directly use of coal having low heating value, and high content of inorganic materials or by using humic acid obtained from the alkaline extraction of coal, and the modification of barium humate by applying heat treatment (calcination).

Background of the Invention Various methods such as coagulation, chemical oxidation and reduction, solvent extraction, liquid membrane separation, adsorption and ion exchange have been used in the removal of heavy metals such as copper, cadmium, mercury, lead, nickel, etc. present in the wastewater of various industrial sectors like mining, metal plating and cleaning, battery and paint manufacturing, leather, chior-alkaii, electronic device manufacturing facilities etc.. Because of the use of low cost adsorbent materials, adsorption process is considered to be most promising method. In this context, industrial wastes such as waste tires, fly ash or waste sludge, agricultural products such as starch, tree bark, compressed palm fiber or iignin, or byproducts, natural materials such as coal, turbo, humic acid, pyrite, verrnicuiite or natural zeolite and other biosorbents such as biornass, algae, starch, chitosan or alginate beads have been used as low cost adsorbents. Hence the development of the natural adsorbents according to the present natural resources of the countries should be given weight to. Humic substances constituting the most important part of the coal that is one of the adsorbent materials, occur as a result of chemical and biological (with microorganisms) degradation of the plants. Coal is the formation of advanced stage of decomposed plant residues. Coal represents the many types of humus because the humic substances are intermediate products during coal formation. Coal formation starts with the accumulation of organic material in low oxygen environment, namely the raw material of humic substances.

The chemical and physical properties of humic substances such as molecular weight, size, structure and the number of functional groups vary according to the source of humic substances, extraction methods and natural conditions during formation. Humic substances according to their solubility in water are divided into three major groups called as humic acid, fulvic acid and humin. Humic substances have usually amorphous, brown or black colors, acidic and polydisperse properties, and the molecular weights vary from a few hundred to ten thousands.

Humic acids are organic materials which have high molecular weight, and are soluble in alkaline and insoluble in acidic medium. It has 4 aromatic rings and there are C = O bonds between rings. It also includes O-C-OH functional side groups.

Fulvic acid is a chemical compound soluble in all pH values (acidic or basic) of water and solvents, having short-chain molecules and low molecular weight. Fulvic acids are light yellow to yellow-brown in color. Rather, it is a polycyclic compound and rich with respect to C=0.

Humin is the fraction of humic substances that is not soluble in water at any pH value and in alkali. The molecular structure is too large. It is the most resistant to disintegration between humic substances [1-3]. Humic acid is obtained by acid precipitation of alkali humates which are produced as a result of the extraction with alkaline solution (sodium hydroxide, potassium hydroxide, or ammonium hydroxide) of coal sources such as lignite, leonardite with high humic acid content. Alkali metal humates (Na and K) are defined as the water soluble salts of humic acid. Humic acid used as a soil conditioner in agriculture is not a fertilizer, but is a complement to fertilizer. The benefits are given as follows;

It plays role as a chelating agent for trace elements and nutrient in the soil and it accelerates the absorption of these elements and nutrients by plants. In the absence of chelating agents, iron, copper, zinc, manganese and other trace elements are transformed into insoluble hydroxides. Humic acid causes to keep in the solution phase by chelating of these ions providing biochemical reaction.

Support the transfer of micronutrients from the soil to the plant.

Enhances the retention of water;

Increase the seed germination speed and percentage.

Contributes to the development of microflora in the soil. Except for agricultural uses, humic acid and derivatives have been used in various industries such as in the ceramic industry as dispersants, in wastewater treatment as adsorbents, in drilling fluids as loss prevention additives, in the lead acid batteries as a surfactant material, in black or dark colored inks as a rheology improver, in medicine for treatment of various diseases.

Humic acid produced with alkaline extraction of coal with low heating value and high content of inorganic materials, sent by Turkey Coal Enterprise General Directorate (TKI) has 11-12% percent humidity and more than 30% inorganic content. Ε4/Έ6 ratio was found as 3.26 and this value indicates that the aromatic groups in the sample of TKI humic acid are higher. The cation exchange capacity was determined as 900 meq/IGO g. The total acidity and exchange capacity in the humic substances show the existence of dissociable proton (or H +) in aromatic and aliphatic carboxyi or phenolic hydroxy! groups. The presence of the high amount of carboxyi (COOH) and carbonyl (C = O) groups and the low amount of phenolic groups can be expressed that bumification degree of humic acid is fairly good [1 -7].

Two methods have been used in the production of humic acid based materials which are insoluble in acidic and alkaline media. 1. Cross-linking with aldehydes

2. Cross-linking with polyvalent cations

The cross-linking takes place via the carboxylic groups and the phenolic OH groups present in the structure of humic acid. Humates obtained from divalent metals such as calcium, magnesium and barium have water insoluble property on the contrary of sodium and potassium humates. The compounds obtained with polyvalent metals such as iron, zinc, copper, etc. are called as chelate. In addition to the valence bonding, coordination bonds are also formed. It was shown in the U.S. Patent No. 4,746,442 [10] that alkali salt of humic acids obtained from sub-bituminous coal at 120 to 350°C under oxygen pressure by the dry oxidation could be used in heavy metal adsorption in the range of pH: 1.5-5 .5.

In the patent documents numbered as US 5906960 and US 6143692 applied by Arctech Inc., liquid alkali metal humic acid salt (Humasorb-L) extracted from the coal, and humic acid in a solid form (Humasorb-S) soluble at higher pH values and obtained by precipitation of Humosorb-L with HCl and then by purification were developed. Solid form of humic matter having low solubility at high pH values was obtained by cross-linking of Humasorb-L/Humosorb-S with glutaraldehyde and then immobilization with alginate and shown as Humasorb- CS. It was found that adsorbent material coded as Humasorb-L was effective in the removal of metal ions like Fe, Al, Cr, Pb, Cu, Zn, Co, Hg, Cd, Ni, Mn and organic pollutants like trichlorethylene, tetrakioraetil and benzene. Because it is expressed that huniic acid became insoluble as a result of the adsorption of heavy metal ions. It was indicated that humic acid-based adsorbents containing Fe, Cu, Zn, Mg and Mn can be used as fertilizer with micronutrients in agriculture area.

In the study of the use of the barium humate in the adsorption of organic contaminants, it was observed that 10 and 40 ppm phenol and tetrachloride were adsorbed at a value close to 100%.

As a result of the literature study, alkali metal salts of humic acid (potassium or sodium humate), calcium alginate humate and iron humate have been used for the removal of metal ions and various organic substances causing pollution in the wastewater.

Rubber Production: Rubber which is multi-purpose and has the potential for widespread use is a unique raw material for vital rubber materials in every aspect of life. It is known that rubber is indispensable product for automotive industry (fuel and brake hoses, windshield wipers, suspension parts, etc.), for white ware sector (rubber bellows, gaskets, hoses, etc.), for conveyor belt production, for footwear manufacture, for the industries of food, medical and electronics. The fillers added to the rubber are used for rubber strengthening, for improving workability, for formation of economical mixtures and for coloring. Carbon blacks take the most important place within fillers. The consumption of carbon black in the rubber industry throughout the world is three times more than the consumption of other fillers. Respectively, kaolin, calcium carbonate and silica follow the consumption of carbon black.

In the USA patent documents numbered as US3075931, US3356623, US3533988, US4532260 and US4600728, it has been mentioned that alkali metal humate is added to the rubber formulation and the shaping is performed after vulcanization process [1 1-15].

In the production of ceramic materials: Humic substances are substances in the organic structure having hydrophobic and hydrophilic moieties and defined as amphiphilic substances. Hydrophobic part comprises the aliphatic and aromatic based hydrocarbons structures. Hydrophilic groups include polar or charged groups. As a result, humic acid as well has polar end groups with a hydrocarbon chain like surfactant.

Hydrocarbon chain of the humic substances forms micelles surrounded by polar groups dissolved in water. The source of negative charges are partially dissociated carboxylic groups (-COOH), phenolic hydroxyl group (-OH) and phenolic hydroxyl (-OH) groups.

Humic acid is a natural surfactant, because it causes the decrease in the surface tension of the solution and naturally serves as a dispersant when placed in an aqueous alkaline solution. In the USA patent documents numbered as US2007/0149383 and US2008/0300129, it was shown that sodium salt of humic acid, sodium humate, was used as dispersants in the ceramics industry [ 16-17],

The documents cited in the prior technical section are listed below.

1. Stevenson, F.J., Humus Chemistry genesis, Compositions, Reactions, 2nd edition, Wiley, (1984).

2. Ghabbour, E.A., Davies, G., Understanding humic substances: Advanced methods, properties and applications, Northeastern University, USA (1999).

3. Tipping, E., Cation binding by humic substances, Cambridge University Pres, (2002) Sayfa: 8, Klavins, M., Eglite, L., Immobilization of humic substances, Colloids and Surfaces A: Physicochemical and Engineering Aspects 203, 47-54, (2002). Kahalili, F. "Preparation and Characterization of Selected Metal -Humate Complexes", Soil Science, 150, 3, 565-570, (1990).

Seki, H. and Suzuki, A. , Adsorption of Heavy Metal Ions onto Insolubilized Humic Acid, Journal of Colloid and Interface Science, 171, 490-494, (1995).

Havelcova, M., Mizera, J., Sykorova, I, Pekar M., Sorption of metal ions on lignite and the derived humic substances, Journal of Hazardous Materials, 161, 559-564, (2009).

Sanjay, H.G., Srivastava, K.C., Walia, D.S., Adsorbent, US5906960, 1999 Sanjay, H.G., Srivastava, K.C., Walia, D.S., Adsorbent, US6143692, 2000 Davidson, W.L., Levesque, P.E., latourette, H.K., Vulcanizable rubber composition containing as a reinforcing agent, a partial polyvalent metal salt of coal derived humic acids, US3075931, 1963.

Schwartz, N.N., Process for using humic acids and lignin in vulcanizable rubber, US3356623, 1967.

Morris, D.C., Maassen, G.C., Waterman, R.R., Rubber masterbatch containing humic acid, US3533988, 1970.

MacKeighen, H.R., Cortesi, V.T., Elastomer compositions containing humates US4532260, 1985.

MacKeighen, H.R., Cortesi, V.T., Elastomer compositions containing humates US4600728 1986.

Calemma, V., Menicagli, R., Rausa, R., Process for the removal of metals from waters containing them, US4746442 , 1988.

Saleh, E., Ceramic material, compositions and methods for manufacture thereof, US2007/0149383, 2007.

Saleh, E., Ceramic material, compositions and methods for manufacture thereof US2008/0300129, 2008. The citations for aforementioned documents are given with numbers in the previous technique.

Brief Description of the Invention

The object of the invention is related to the production of the insoluble barium humate in alkaline conditions by the directly use of coal having low heating value and high content of inorganic materials or by using humic acid obtained from the alkaline extraction of coal, and after that, the modification of barium humate by applying heat treatment (calcination) to increase the surface area.

Another object of the invention is to realize the production method obtaining low cost barium humate from coal having low heating value and high content of inorganic materials in order to decrease the solubility of humic acid which is soluble under the alkaline conditions, namely at high pH values (>7).

Another object of the invention is to realize a production method realizing the production of the adsorbent material that is humic acid based and inexpensive, and that has the reduced solubility in alkaline conditions and the increased adsorption capacity with the increase of surface area.

Another object of the invention is to realize the production method for the product, used as an adsorbent for the removal of heavy metals and organic contaminants; used as filler in the rubber production; and used as a dispersant in ceramic production.

Another object of the invention is to obtain the production method providing the production of barium humate insoluble in alkaline and acidic medium, without using any agent such as alginate, and the use of it as adsorbent to remove organic pollutants and heavy metals. Another object of the invention is to realize a production method providing the use of alkaline insoluble barium humate in the styrene butadiene rubber production and ensuring better electrical insulation property due to the showing higher resistance of the products containing it.

Detailed Description of the Invention

The inventive production method used to obtain barium humate comprises the following steps;

- Obtaining of barium humate solution from coal or humic acid extracted from coal

- Application of decantation and/or centrifuge operations for the solution

- Washing and drying operations after the separation of barium humate from liquid phase

In the inventive methods, coal is directly reacted with barium hydroxide when coal is used. The mentioned reaction temperature changes between 80-95°C. At the end of the treatment, barium humate is obtained and then separated from the solution with decantation and centrifuge and then it is dried. Drying is made between 70-100 °C.

In the inventive methods, when humic acid extracted from coal is used, humic acid without any purification is reacted with sodium hydroxide and sodium humate is obtained. The ion exchange of the obtained sodium humate with barium salt is applied. The mentioned process is realized at the temperature of 25-60 °C, in the concentration of 1-5 % and in the time of 4-24 hours. Then, the barium humate present in the solid phase is separated with decantation or centrifuge operations. After the separation, the chlorine ion from barium humate is removed by washing with water and then barium humate is obtained. As a last step, barium humate is dried. Drying is realized between 70-100 °C. In the inventive method, humic acid derived from coal is obtained from lignite based coal which has 43.04 % high ash content and 31.4 % low humic acid content. The coal is mined in Konya Hgin region. In the preferred application, humic acid is used directly without any purification process.

In the inventive method, the pH value of humic acid solution prepared in the concentration of 1-5 % is adjusted with sodium hydroxide granules. After the necessary adjustment, BaCl2 and/or Ba(N03)2 as barium salts are added to the solution. The studies for the humic acid solutions prepared in the different concentrations (1-5 %) were performed at the different temperatures (25-60 C) and different times (4-24 hours). The reason to use sodium hydroxide instead of potassium hydroxide in the conversion of humic acid to humate is that the diameter of potassium atom is higher than sodium. Barium humate is separated from liquid phase by using decantation and centrifuge operations. The ion exchange of the obtained sodium humate with BaC12 as barium salt is applied. When using BaCl2, the washing with distilled water is carried out until the chlorine ion is removed. In the preferred application, the presence of chlorine ion is controlled with silver nitrate solution. Barium humate after separation is dried in the oven at the temperatures between 70-100 °C. Barium content is determined with ICP. Barium humate that is humic acid salt, obtained by the inventive method is insoluble in acidic and basic conditions and it does not permit the passing of the barium ion confined in its structure to the water phase.

Barium humate obtained in the inventive method is subjected to direct or gradual heating process. In the direct heating, it is calcined at the temperature of 50-440 °C and in the time of 0-4 hours. In the preferred another application, gradual calcination is applied by heating to 50-250 C for 0-4 hours in the first stage and by heating to 150-400°C for 0-4 hours in the second stage. With the application of heat treatment to the barium humate which is the barium salt of humic acid, the highest surface area is obtained. Calcined barium humate is used in the adsorption of As, Cd, Co, Cr, Cu, Hg, Ni and Pb metal ions for different amounts and different times.

The surface area which is an important property affecting the adsorption capacity of the adsorbents, of the synthesized barium humate is obtained as 0.8 m2/ g , the barium humate subjected directly and gradually to heat treatment are obtained about 16 m2/g and about 22 m2/g , respectively. By applying gradually heat treatment to barium humate, surface area increased 30 fold of untreated synthesized barium humate. While the obtained barium humate is used as filler in the rubber production and as a dispersing agent in the production of ceramics and is used as a desiccant, the calcined barium humate is used as adsorbents for the removal of metal ions and organic pollutants in the water. Graphic 1 shows the adsorption percentage after the adsorption process for As, Cd, Co, Cr, Cu, Hg, Ni and Pb metal ions for 2 and 24 hours adsorption time, by using barium humate obtained in the inventive method in the mass of 0.5 and 1 gram.

Figure imgf000013_0001

Graphic 1. Adsorption percentage for barium humate

Adsorption percentage is obtained by using the following equation.

AD % = 1 - C(t)/C(i) * 100

Where Q andCt are the initial and final concentrations, respectively, of metal in solution.

100 % of adsorption percentage is obtained for the adsorption of Cu, Cr, Hg and Pb ions by using 1 g adsorbent obtained with the calcination of the barium humate obtained in the inventive method for 24 hours adsorption time. These values were compared with the commercial product called as Humasorb-CS and the results are given in Graphic 2. As seen from graphic, it is understood that the barium humate obtained by the inventive production method have superior adsorption percentage for a lot of heavy metal ions adsorption.

Figure imgf000014_0001

Graphic 2. Comparative results of Barium Humate with Humasorb-CS

The use of humic acid and eight different metal humates in the rubber was investigated and they were used in SBR (styrene butadiene) based rubber as an alternative to carbon black. The curing was realized with the use of ammonium humate, barium humate, potassium humate and sodium humate among 8 different humates. The tensile strength of the samples was obtained 8-9 fold lower than original sample, but elongation and shore strength values were similar. As seen from Table 1, according to the electrical values the samples containing barium humate can be provide better electrical isolation due to the high resistance.

Figure imgf000015_0001

Table 1. Electrical and mechanical properties of the rubber samples

The use of humic acid and 6 different humate mixture in the ceramic production was investigated. Humic acid and barium humate mixture containing 6 different humates showed better property than that of alone sodium humate. Internal and external hardness of the mixture was obtained as ½ of the value of the commercial product (reference), humic acid and sodium humate.

Figure imgf000016_0001

Table 2. Effect of humic acid-based compounds used as dispersant on the ceramic properties

Barium salt of humic acid obtained in the inventive method is produced from humic acid derived from Konya Ilgm coal which have high ash content and low humic acid content, without applying any purification, and may be used as a low cost adsorbent material which is insoluble in alkaline conditions. In this study, humic acid is directly used without any purification step. After applying the modification such as heat treatment to the barium salt of humic acid, it is used in the adsorption of metal ions (As, Cd, Co, Cr, Cu, Hg, Ni, Pb) prepared as synthetically.

The adsorption capacity of the polyvalent humate obtained in the inventive method is increased by applying different treatment such as calcination and it was observed that in the adsortion of heavy metal and organic pollutants it gave better result than the commercial humic acid based products. In addition, it was shown that it can be used as filler in the rubber production and as a dispersant in the ceramic production. Within the basic concepts, it is possible to develop various applications related to the production method of barium humate in the invention and the invention is not limited to the examples described herein and is essentially according to the claims.

Claims

A method of manufacturing barium humate, characterized in that the method comprises the following steps;
- Obtaining of barium humate solution from coal or humic acid extracted from coal
- Application of decantation and/or centrifuge operations for the solution and
- Washing and drying operations after the separation of barium humate from liquid phase,
A method according to claim 1 characterized in that when humic acid extracted from coal is used, humic acid without any purification is reacted with sodium hydroxide and sodium humate is obtained.
A method according to claim 2 characterized in that the ion-exchange of the obtained sodium humate with barium salt is applied.
A method according to claim 3 characterized in that BaCl2 and/or Ba(N03)2 as barium salts are added.
A method according to claim 3 or 4 characterized in that the barium humate present in the solid phase is separated with decantation or centrifuge operations, after the separation, the chlorine ion from barium humate is removed by washing with water and then barium humate is obtained.
6. A method according to any claim 1 to 5 characterized in that humic acid derived from coal is obtained from lignite based coal which has 43.04 % high ash content and 31.4 % low humic acid content.
7. A method according to claim 1 characterized in that coal is directly treated with Ba(OH)2 and barium humate is obtained.
8. A method according to any of the claims given above characterized in that obtained barium humate is exposed to heating process as directly or gradually.
9. A method according to claim 8 characterized in that it is calcined at the temperature of 50-440°C and in the time of 0-4 hours in the direct heating,
10. A method according to claim 9 characterized in that gradual calcination is applied by heating to 50-250°C for 0-4 hours in the first stage and by heating to 150-400°C for 0-4 hours in the second stage.
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Citations (9)

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US3075931A (en) 1959-10-02 1963-01-29 Fmc Corp Vulcanizable rubber composition containing as a reinforcing agent, a partial polyvalent metal salt of coal derived humic acids
US3356623A (en) 1964-03-16 1967-12-05 Fmc Corp Process for using humic acids and lignin in vulcanizable rubber
US3533988A (en) 1967-06-02 1970-10-13 Vanderbilt Co R T Rubber masterbatch containing humic acids
US4532260A (en) 1984-10-18 1985-07-30 Alfred D. Lobo Co., L.P.A. Elastomer compositions containing humates
US4600728A (en) 1984-10-18 1986-07-15 Alfred D. Lobo Co., L.P.A. Elastomer compositions containing humates
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US5906960A (en) 1995-08-15 1999-05-25 Arctech, Inc. Adsorbent
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US3075931A (en) 1959-10-02 1963-01-29 Fmc Corp Vulcanizable rubber composition containing as a reinforcing agent, a partial polyvalent metal salt of coal derived humic acids
US3356623A (en) 1964-03-16 1967-12-05 Fmc Corp Process for using humic acids and lignin in vulcanizable rubber
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