CS273073B1 - Method of acidic gudrons neutralization - Google Patents

Abstract

The essence of the invention is the effect on acid sludge containing 15 to 70 % by weight sulphuric acid, 5 to 50 % by weight sulphonic acids, 10 to 60 % by weight oil and 5 to 30 % by weight water of at least one substance from the group of urea, dicyanamide, guanidine, semicarbazide, thio-urea, melamine and aldehyde with 1 to 5 carbon atoms or urea-formaldehyde, or phenol formaldehyde resin. The solution can be used by companies refining oil and paraffin, or sulphonating oil distillates for production of sulphonate additives and petroleum fractions for production of tensides.

Description

BACKGROUND OF THE INVENTION The present invention relates to a method for the disposal of acidic gudrons which utilizes free sulfuric acid to produce water-insoluble condensates binding the Salaie component of the present waste.

Acid gudrons are difficult to process secondary raw materials, which are usually not destroyed by high-temperature decomposition to obtain sulfuric acid, resp. low temperature decomposition to obtain bitumen and coke. It is also possible to use it in the production of cement, technical surfactants, concrete and other materials. Each treatment requires some pretreatment of the allbeon based on the neutralization of the alkali with reacting compounds, in particular alkaline earth oxides, hydroxides or carbonates (Z. Grabkowski, Z. Pietrzyk: Czas. Tech. M. 1974-, 2, 34}, Patent Specifications A No. 337). 331} No 346 997}

CS č. 141 622} no. 179 771; no. 180 864} no. 216 181; DE č. 2 241 524} no. 2,642,561;

5. 14.5 471; DD č. 207 217; no. 216 951} no. 21? 534} č. 224 325; SU .336 296} R0 no.

058; JP č. 73 80 495; about. 74 76 904} no. 76,149,173} 0. 78 48,203 atS.).

The above-mentioned drawbacks are solved by the present invention, according to which a method for the disposal of acid gudrons containing 15 to 70 wt. sulfuric acid, 5 to 50 wt.%, sulfoacids, 10 to 60 wt. % oil and 5 to 30 wt. water, neutralization is carried out by contacting gudron with at least one of the urea, dicyanamide, guanidine, semicarbazide, thiourea, melamine and C 1 -C 5 aldehyde, preferably forraaldehyde or glyoxal or urea-formaldehyde formaldehyde, respectively. .

The advantage of the process according to the invention is easier and more universal disposal of fresh as well as accumulated waste, which is derived from refining of oils, paraffins, sulphonation of oil distillates in the production of sulphonated additives, sulphonation of individual hydrocarbons and petroleum fractions in the production of surfactants. and ecological risk from the storage of these products.

Urea, thiourea, guanidine, dicyclohexiamide, melamine and the like are used to prepare the binding component. As a condensation agent can be used? formaldehyde, glyoxal, furfurol, crotonaldehyde, isobutylaldehyde and the like.

Currently, the closest urea-formaldehyde or phenol-formaldehyde resins have been found to be of practical use for reasons of raw material security and cost advantage.

The use of some byproducts of the chemical or woodworking industry, containing at least one condensation component, is also advantageous, which is also a burden for the chemical processing.

The resulting products can be processed * into fertilizers, composite insulating materials, carbonaceous materials, fuels, etc.

The process according to the invention has not been described in the literature so far. Sali is documented by the following examples, which in no way limit the scope and possible variability thereof.

Example 1

960 g of 38% formaldehyde are basified with lime milk to pH = 8.5. While stirring, 360 g of urea are added and the reaction mixture is heated to 95 ° C and kept under stirring for 1 hour. The reaction mixture is then cooled, acidified with dilute aqueous acid gudron extract to pH = 5.1 and carefully heated until viscosity is reached.

2.5 mPas at 75 ° C for 3 hours. Upon completion of the reaction and cooling to pH, the mixture is adjusted to pH = 7 with calcium hydroxide. Mixing with acid gudron follows. Specification as follows:

% free sulfuric acid ............. 37.9 wt.

% of sulfoacids ........................ 25.8 wt.

mineral oil ............................... 24.3% wt.

water ............................. 12.0 wt.

I

CS 273 073 B1 with an ID number of 328.4 mg NaOH / g, a solids mass is dropped in a 1: 1 volume ratio. The ground material is used to produce fertilizer with slowly soluble nitrogen.

The same effect in destroying acidic gudrons is achieved by substituting urea with dicyanamide, guanidine, semicarhazide, thiourea and melamine.

Example 2

180 g of urea and 133.5 g of glyoxal are dissolved in 450 ml of water. The solution is adjusted to pH β 10 and the water is evaporated at atmospheric pressure. At a temperature of 145 ° C, the viscous solution obtained is added to the acid gudron, as in Example 1. The product is worked up as a combustible filler of a brick mixture for the production of ceramics or shards.

Example 3

1120 g of phenol are mixed with 910 g of 38% aqueous formaldehyde solution and heated to boiling for 1 hour. 7 g of 4 H hydrochloric acid are then added. After heating under reflux for 2 hours, 50 g of caprolactam oligomers and 30 ml of 1 N alkaline triethanolamine solution are added. The volatiles were distilled to 120 ° C.

1300 g of product are obtained. This was mixed with 40 g of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacaclooctane-based blowing agent (Chempor G-65) and 300 g of acid gudrone (specified in Example 1). The mixture is allowed to cure in the mold. A porous insulating material is obtained.

Claims (1)

I CS 273 073 B1 has an acid number of 328.4 mg NaOH / g; The milled mass is used to produce fertilizers with slowly soluble boosters. The same acid gudrone disposal effect is achieved by replacing urea-dicyanamide, guanidine, semicarbazide, thiourea and melamine. EXAMPLE 2 180 g of urea and 133 g of glyoxal are dissolved in 450 ml of water. The solution is adjusted to pH e 10 and the water is evaporated at atmospheric pressure. At 145 ° C, the obtained viscous solution is added to the acidic gudrone as in Example 1. The product is incorporated into an acoluble filler of the brick mixture for the production of the ceramic casing. EXAMPLE 3 1120 g of phenol are mixed with 910 g of 3% aqueous formaldehyde solution and heated to boiling for 1 hour. Then 7 g of 4 U hydrochloric acid are added. After heating under reflux for 2 hours, 50 g of caprolactam oligomers and 30 ml of a 1N alkali triethanolamine solution are added. The volatiles were distilled to 120 ° C. 1300 g of product are obtained. This is mixed with 40 g of a 1,5-metano-3,7-di-tris-1,3,5,7-tetraazacaclooctane-based blowing agent (Chempor G-65) and 300 g of acid gudron (Specified in Example 1) ). The mixture is allowed to cure in the mold. A porous lysis material is obtained. BACKGROUND OF THE INVENTION A process for the disposal of acidic gudrons containing 15 to 70 wt. % of sulfuric acid, 5 to 50 wt. % sulfoacids, 10 to 60 wt. % oil and 5 to 30 wt. by water neutralization, characterized in that the gudron is brought into contact with at least one of the urea, dicyanamide, guanidine, semicarbazide, thiourea, melamine aldehyde having 1 to 5 carbon atoms, preferably formaldehyde or glyoxal of the flourformaldehyde and phenol formaldehyde, respectively.