HU188653B - Process for manufacturing acid or the alkali salts thereof - Google Patents

Abstract

Processes are alkaline salts of humic acid or humic acid oxidative production of brown coal, lignite, peat, \ t wood chips and cellulose-containing agricultural waste, which is fluidized with oxygen and water vapor gas under oxidative conditions. The starting material narrow sieve fraction with basic material and catalyst the reaction time is about 6 hours, the conversion of organic matter 70-90%.

Description

The present invention relates to a process for the production of humic acid alkaline salts or humic acid by oxidation from lignite, lignite, peat, wood waste, cellulose-containing agricultural derivative material (hereinafter carbon). The powdered feedstock used is oxidized in a fluidized bed with a mixture of air and water vapor affecting the reaction. With the aid of a basic additive and catalyst, the reaction time is kept at an economical level. The reaction product of the invention can be used directly (or after granulation) in agriculture, or after the production of humic acid, for the production of well drilling sludges, adhesive production, etc.

It is known that juvenile carbons may contain humic acid in part and may increase humic acid in part with oxidizing agents. Some of the known methods for increasing the humic acid content of coal utilize potassium permanganate in an alkaline medium, such as Kessler, N. F. (Acta Montana 35 (1975) p. 9) or Tocev D. (Acta Montana 35 (1975) p. 25). During the procedure, only large,

There is a significant transformation at MPa pressure, which is a strong cost-increasing factor. Other processes are similarly oxidized in aqueous media with hydrogen peroxide, nitric acid or mixtures thereof. U.S. Pat. No. 4,013,440 also uses these oxidants, as does U.S. Patent No. 1,950,535 and Hungarian Patent No. 152603. A similar procedure is described in the Borsod Coal Mines research report entitled "Production of Humic Acid from Borsod Brown Coal". The common drawback of these is the environmental impact of the gases released and the high cost of the equipment to be used. However, even when producing humic acid for agricultural purposes, the resulting humic acid has to be separated from the waste, which is a cost-increasing operation.

No. 101612. Air has been used as an oxidizing agent in the patent, however, in a non-air fluidized bed, so the reaction time is extremely long with low conversion. Vincente Aranda et al. (Combustibles 23 p. 29-63 (1964) and 23 p. 73-94 (1964)) achieved a favorable conversion time of about 300-400 hours. A similar procedure is provided by Aleksandra Rusin (KoksSmola-Gaz 18 (1973), pp. 8-9, 219) and Pctrovic, P., Viterovic, D. (Agrohemija, 9-10, (1977), p. 383), who use air as an oxidizing agent in 40 fluidized beds. Thus, a low degree of conversion is achieved and some of the humic acid formed is further oxidized, as described by Suhov VA et al. (Himija Tverdovo Toplive 6 (1977), p. 38). Shrikhande Κ. Y. et al 45 (J.Mines, Metals Fuels N ° 10 L, p. 1-13 (1962) and a fluid-bed oxidation small amounts of water vapor and steam Hn0 ₃ mixed in the air, but they work at low temperatures, the reaction time is 25-50 hours In SU 380687 and in 50 Zhukov NA et al. (Male Tverd. Topl. 1971 (5) p. 63-4), they try to reduce the reaction time at higher temperatures, but the humic acid obtained can only be protected by continuous extraction. oxidation.

The object of the present invention is to overcome the drawbacks of the methods described. This object is achieved by the use of a catalyst and water vapor in addition to the oxidizing medium in the fluidization process.

The invention is based on the discovery that the oxidation of organic material to humic acid with an oxygen-containing gas is carried out on a fluidized bed at maximum intensity, while addition of water vapor is required to avoid the formation of higher oxidation products.

Water vapor significantly slows down the decomposition of the formed carboxyl and existing methoxy groups, while at the same time aiding the formation of the carboxyl groups. All iron compounds that give ferric hydroxide in a basic oxidative atmosphere accelerate the production of humic acids. The combined use of water vapor and iron (III) hydroxide provides a sufficiently high rate of humic acid formation without decomposition of the humic acid formed. Fluid bed has a very good heat and component transfer rate. This is beneficial for the favorable development of unit costs.

According to the present invention, the process involves grinding the starting material and producing a uniform sieve fraction (e.g., 0.2-0.3 mm) which is mixed with a basic additive and an iron-containing catalyst to provide an alkaline reaction medium. The material thus prepared is fluidized in a fluidization reactor with an air-water vapor mixture at a temperature of about 160 ° C for about 6 hours. The basic additive is 0.3-20% sodium carbonate, potassium hydroxide, etc., the iron-containing catalyst is 0.5-10% iron (III) chloride, iron (III) hydroxide and the like. used. The fluidization medium has a water vapor content of 25-90%, depending on the starting material and the progress of the reaction. Occasionally, an oxygen-water vapor mixture may be used to reduce ballast nitrogen. A significant proportion of the air / water mixture is recyclable and only the blown gas needs to be replaced with fresh mixture. The proportion of fresh mixture (which decreases to 100-40% depending on the progress of the reaction) is determined by the minimum oxygen content required. When the reaction temperature rises sharply, the reaction can be stopped by blowing inert gas (N ₂ , CO ₂ ).

As a result of this oxidation, 70-92% of the organic material is converted to humic acid. After removal of humic acid e.g. The lignite residue itself is recommended for fertilization purposes (Hungarian Patent No. 152603), the final product leaving the fluidization reactor can be used directly for agricultural purposes (sometimes after granulation). For non-agricultural applications, pure humic acid can be recovered by any of the known methods (e.g., NaOH dissolution and ITCl precipitation).

By reducing the particle size of the carbon used, the reaction time can be reduced. However, this requires an increase in the water vapor content of the reaction mixture.

Example 1

Use of Powder Coal in Hole Mines for the Production of Humic Acid. 1 kg of carbon 0.2-0.3 mm in diameter was mixed with 50 g of soda and 50 g of ferric iron and placed in the fluidization reactor.

The flow rate of the gas mixture to be used is between the minimum and maximum fluidization rates. Air at a flow rate of 1000 zel ¹ was saturated with water vapor at 80 ° C (about 1: 1 air: H ₂ O) and then heated to 160 ° C. With this gas precursor, the carbon powder was kept in a floating state for 6 hours, during which time humic acid formation was 90% complete.

320 g of the product obtained are insoluble in 0.5 N NaOH, of which 270 g are ash constituents. About 650 g of crude humic acid are dissolved in NaOH by precipitation with kT hydrochloric acid (83% yield).

Example 2

Berentei classifier! waste use humic acid

-2188 653. 1 kg of 0.3-0.4 mm diameter carbon was mixed with 50 g of powdered KOH and 50 g of iron oxide and placed in a drying oven preheated to 100 ° C in a fluidization reactor preheated to 140 ° C.

Air at a flow rate of 1700 l'h ¹ was saturated with steam at 80 ° C and heated to 210 ° C. With this gas mixture, the carbon powder was kept floating at a fluid bed temperature of 160 ° C for 6 hours, during which time the production of humic acid was 95% complete.

From the product obtained, 610 g of crude humic acid was dissolved in 0.5 N NaOH, of which 452 g of ash constituent. After evaporation and precipitation of humic acid in NaOH, about 392 g of crude humic acid were obtained in 63% yield.

Example 3

Using mixed (pine and oak) sawdust to produce humic acid. 1 kg of sawdust, 0.3-0.4 mm in diameter, was soaked in 250 cm ^{3 of} 4 η KOH solution and dried in a vacuum oven at 60 ° C for 2 hours. 70 g FeCl _{3 was} mixed and placed in a fluidization reactor preheated to 110 ° C.

1500 l * h ^_1 flow rate of air saturated with the first two hours C head temperature conditioning tower 92 ° with steam and this is further achieved by heating the fluidized bed temperature of 160 C ° linear heat-up program at the end of the second hour. Subsequently, the reaction was carried out at a temperature of 85 ° C for a conditioning tower and 160 ° C for a further 5 hours.

The product obtained is soluble in 720 g of 0.5N NaOH and precipitated with HCl to yield 695 g of humic acid in 73% yield.

Claims (5)

A process for the preparation of humic acid alkaline salts or humic acid from coal, lignite, peat, wood chips and cellulose-containing agricultural wastes in a fluidization reactor, characterized in that the comminuted starting material (s) having a particle size of 0.05-5 mm with alkaline additive - carbonate or hydroxide. And coupled with an iron containing catalyst, the mixture is added to a fluidization reactor where it is oxidized with oxygen and water vapor containing gas for up to 10 hours at 100 to 200 ° C and then precipitated with hydrochloric acid. Process according to claim 1, characterized in that 0.5 to 20% of an alkaline additive, preferably sodium carbonate or potassium hydroxide, is added to the starting material. 3. The process according to claim 1, wherein the gas mixture comprises 25-90% preferably 50% water vapor. 4. characterized in that the fluidization is carried out with a gas-water vapor mixture containing 2 to 50% oxygen, 5. The process according to claim 1, wherein the starting material comprises a catalyst containing from 0.5 to 10% iron. iron (III) hydroxide is preferably added.