CZ278050B6 - Process for producing special carbon black - Google Patents

Abstract

Soots with big specific surface with developed poroid structure and with high value of interfacial voltage towards water or aqueous solutions are made from soots, which arise as product of gassing of oil and tar matters by partial oxidation in the presence of oxygen and aqueous steam. From gas product of oxidation are soots removed by water washing, from which are then gained by coagulating liquid in this way, that to soots water is added hydrocarbon liquid with starting boiling temperature minimum 20 degrees of Celsius higher as the end of boiling temperature of coagulating liquid and which value of interfacial voltage towards soots water is 20 to 60 mN/m, in mass 0,03 to 1 g for 1 g of soots and that all before or parallel with coagulating liquid originated aglomerates are deprived of coagulating liquid by drying in of inert athmosphery medium or minimum two-stage at temperatures 150 to 280 degrees of Celsius.

Description

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Process for producing special carbon blacks with a large specific surface area, developed porous structure and high interfacial tension against water or aqueous solutions of carbon blacks produced as a product of gasification of petroleum and tar raw materials by partial oxidation in the presence of oxygen and water vapor from which they are obtained by means of a coagulation liquid, comprising adding to the carbon black water a hydrocarbon liquid having a boiling point at least 20 ^° C higher than the end of the boiling point of the coagulating liquid, the interfacial tension of which is 20 to 60 mN / m, in an amount of 0.03 to 1 g per 1 g of carbon black, prior to or simultaneously with the coagulation liquid and the agglomerate formed. The coagulation liquid is dehydrated by drying in an inert atmosphere or at least two stages at temperatures of 100 to 280 ^° C.

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Technical field

The present invention relates to the preparation of special carbon blacks having a large specific surface area, with a developed porous structure from the carbon blacks produced as a product of gasification of petroleum and tar feedstocks by partial oxidation in the presence of oxygen and water vapor and surface modification thereof.

BACKGROUND OF THE INVENTION

The feedstock for the production of surface-modified carbon black is a by-product of the partial oxidation of petroleum and tar feedstocks in the production of hydrogen and synthesis gas, which are separated from the gas stream by scrubbing with water to form an aqueous slurry of carbon black. The carbon black content of the soot water ranges from 5 to 20 g / l. Soot from the aqueous isolated by coagulation of a suspension liquid, such as hydrocarbon solvents having a distillation range of 120 ^e C. Establishing soot macroparticles shedding coagulating liquid drying. The carbon blacks obtained find use as an addition to plastics and elastics as well as as a sorbent or oxidation catalyst for processes carried out predominantly in the aqueous phase. In sorption processes for the disposal of harmful impurities from contaminated waters, their use is not universal, as they may be reintroduced into an aqueous suspension. Known processes for treating activated carbon to modify their surface properties include calcination, partial oxidation at temperatures above 400 ° C, extraction with mineral acids, steam activation at temperatures above 600 ° C, and others. These processes treat the activated carbon or solid feedstock for the production of activated carbon and there is a significant material loss of the treated phases or activated carbon.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The object of the invention is to anchor the auxiliary phase during the production of the carbon black on their surface, thereby modifying the physico-chemical properties of the carbon black and achieving high interfacial tension values of the anchored phase carbon black system against water or aqueous solutions. This results in spontaneous separation of sorbent from water or aqueous solutions after sorption, oxidation, clarification and flotation to the liquid level. The sorbent separated in this way can be separated from the water, for example using mechanical collectors.

We have now found and experimentally verified the method of production of special carbon blacks with surface treatment.

Process for the production of special carbon blacks with a large specific surface area, an unfolded porous structure and a high interfacial tension value against water or aqueous solutions of carbon blacks produced as a product of gasification of petroleum and tar raw materials by partial oxidation in the presence of water vapor. the carbon black from which the carbon black is recovered by means of a coagulating liquid, in particular hydrocarbons having a distillation range up to 120 ° C, which is removed from the carbon black by drying, according to the invention C higher than the end of the boiling point of the coagulation liquid, i. a distillation range of 100 to 550 ° C, preferably 150 to 350 ° C, the interfacial tension value of which is 20 to 60 mN / m, preferably 30 to 50 mN / m, in an amount of 0.03 to 1 g per 1 g of carbon black preferably 0.05 to 0.15 g per 1 g of carbon black prior to or simultaneously with the coagulation liquid and the resulting carbon black agglomerates are freed from the coagulation liquid by drying in an inert atmosphere and / or at least two stages at temperatures of 100 to 280 ° C ..

Industrial applicability

Special surface-modified carbon blacks are used, for example, in sorption processes carried out at water levels, in aqueous solutions, particularly in the liquidation of oil spills, where perfect spontaneous separation of sorbent or absorbent sorbent from water or aqueous solutions by free flotation is required.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

The soot water produced in the synthesis gas production is processed to carbon black by pelletizing using a coagulation liquid which is a hydrocarbon fraction with a distillation range of 60 to 80 ° C. The resulting carbon black agglomerates with coagulation liquid are dried in a stream of superheated steam and coagulation liquid vapor and dried with superheated steam at 240 ° C. The carbon black sorbent is further cooled to 40 ° C and shipped. An analytical evaluation of the carbon blacks thus isolated is given in column 1 of the table below.

The preparation of the surface-treated sorbet differs from the previously described process in that 0.1 g of hydrocarbon fraction is added to the carbon black water per g of carbon black with a distillation range of 150 to 280 ° C with an interfacial tension to water of 49.6 mN / m. In order to achieve an even presorption of the anchored phase on the sorbent surface, the hydrocarbon fraction is metered into the carbon black water with vigorous stirring of the mixture. The isolation of the soot, including the further processing process, is the same as previously described. An analytical evaluation of the carbon black with the surface treated according to the invention is given in Table 1, column 2.

Table 1 column

2

quantity zakot. g / g carbon black phase anal. sorbent evaluation 0 0.1 DBF adsorption ml / 100 g 405 390 iodine adsorption mg / g 1090 1000 specific surface area m ^ / g 910 900 bulk density g / l 132 145 water content% 0.8 0.2 content zakot. phase% 0.0 9.8 koag content. chap. % 0.6 0.3

The carbon black prepared in this way was used in a model oil accident at the water surface, where the water surface was contaminated by an uneven oil spill with a surface contamination of 77.9 g / m ² . The sorbents listed in columns 1 and 2 in an amount of 80 g / m ² were used to remove oil from the surface. The deactivated sorbents were withdrawn from the water surface by a normal wall and the purified water analyzed. The results obtained in the quality of purified water and sorbents with adsorbed substances are given in Table 2 below.

Column 1 shows the results obtained with the carbon black untreated (column 1 of the preceding table), the results with the carbon black treated according to the invention (col 2 of the preceding table) are shown in column 2.

Table 2 column of surface pollution g oil / m consumables g / m ² purified water oil content g / m ² sorbents content g / m ³ purification efficiency. % deactivated water content sorbent% wt.

oil content% wt.

% carbon content

79.9

0,065

99.92

25.0

77.9

0,032

0, -0

99.96

5.0

52.5

42.5

From the above results it can be seen that using the sorbents prepared according to the invention, the residual content thereof in the purified water was zero, in the case of untreated sorbents its content practically eliminated the possibility of direct use of the purified water.

The low water content of the deactivated sorbents prepared according to the invention, separated from the purified water, made it possible to dispose of it by incineration, while direct combustion of the deactivated sorbents from untreated carbon black was unrealistic due to the high water content.

Example 2

The soot water produced in the synthesis gas production by partial oxidation of the vacuum residue is treated to carbon black using a coagulation liquid in the same manner as in Example 1. An analytical evaluation of the obtained carbon black product is given in Table 3, column 1.

Modified surface treatment blacks were prepared on the same plant as the carbon black listed in column 1 except that a hydrocarbon mixture with a distillation range of 170 to 360 ° C, a specific gravity of 825 kg / m ³ and an interfacial value was continuously added to the coagulation liquid. a carbon black tension of 28 mN / m in an amount of 0.5 g per 1 g of carbon black. Presorption of the anchored phase coincided with the agglomeration of the carbon black particles by means of a coagulation liquid. The carbon black particle agglomerates were dried in the same manner as Example 1. An analytical evaluation of the surface-modified carbon black is given in Table 3, column 2.

Table 3

column 1 2 quantity, zakot. g / g carbon black phase 0 0.5 anal. values of carbon black - sorbent DBF adsorption ml / 100 g 420 390 iodine ads. mg / g 1 180 1 020 specific surface m / g 940 900 bulk mass, g / l 125 145 water content% 0.7 0.2 content of base phase% 0.0 45 coagulum content. chap. % 0.3 0.7

The carbon black thus prepared was used to purify industrial oily waters with an extractable material content of 60 mg / l. The treatment was carried out on a treatment plant with a treatment capacity of 1 m ³ / h of treated water. Sorption of impurities took place in a vigorously stirred flow vessel into which the sorbent was continuously fed. The mixture was further fed into a cylindrical upright vessel with a residence time of 60 min, where the sorbent spontaneously separated with the adsorptive. Removal of residual amount of sorbent was accomplished by filtration using a drum filter.

The technological conditions and the nanalytic evaluation are given in Table 4 below. Column 1 shows the results using untreated carbon black, column 2 using the carbon black prepared according to the invention, i.e. with a modified surface treatment.

Table 4

column 1 2 raw water for cleaning petroleum content 1. mg / l 50 50 content extracted. 1. mg / l 60 60 obsah pev. 1. mg / l 16 22nd Qty. sorb. for cleaning g / 1 Art. in. . 0.2 0.2 purified water before filtration crude oil content. 1. mg / l 0.4 0.5 extr. 1. mg / l 0.6 0.8 solid content 1. mg / g 52 8.0 separated sorbent prior to filtration sediment% 70 0.0 flotace% 30 100 ALIGN! sludge production% pure, water 9.7 5.1

The tests carried out show that the production of sludge is reduced by using the sorbent prepared according to the invention, and all the deactivated sorbent is separated from the purified water by spontaneous flotation, without having to include the final filtration stage.

Claims (4)

PATENT CLAIMS 1. A process for producing special carbon blacks having a large specific surface area, a developed porous structure and a high interfacial tension value against water or aqueous solutions of carbon black resulting from the gasification of petroleum and tar feedstocks by partial oxidation in the presence of oxygen and water vapor. from which the carbon black is obtained by scrubbing with water to form an aqueous carbon black suspension from which the carbon black is recovered by a coagulation liquid, in particular hydrocarbons having a distillation range up to 120 ° C, which is removed from the carbon black by drying. with an onset of boiling point at least 20 ° C higher than the end of boiling point for the coagulating liquid, the interfacial tension of which is 20 to 20 ° C 60 mN / m, in an amount of 0.03 to 1 g per 1 g of carbon black, prior to or simultaneously with the coagulation liquid, and the resulting carbon black agglomerates are freed from the coagulation liquid by drying in an inert atmosphere and / or at least two stages at 150 to 280 C. 2. Process according to claim 1, characterized in that the hydrocarbon liquid has a distillation range of 100 to 550 [deg.] C, preferably 150 to 350 [deg.] C. 3. The process of claim 1 wherein the hydrocarbon liquid has an interfacial tension value of about 30 to about 50 mN / m. 4. The process of claims 1 to 3 wherein the hydrocarbon liquid is added in an amount of 0.05 to 0.15 per g of carbon black.