CS276671B6 - Method of production of special carbon black - Google Patents

Abstract

The method of producing special carbon black by partial oxidation of petroleum or/and tar raw materials, whereby the carbon black particles exhibit previously desired values of the average agglomerate size, actual specific gravity, specific surface area from dibutyl phthalate adsorption, ash amount, vanadium content and desired yield consists in that the gasified raw material dispersed into droplets, with an average molecular weight of 400 to 1,100, a specific gravity of 900 to 1,100 kg/m, an ash content of 100 to 900 ppm, a vanadium content of 20 to 250 ppm and a nickel content of 20 to 120 ppm is brought into contact with a mixture of oxygen and water vapor at an oxygen to injected raw material ratio of 0.8 to 0.2 sT/kg under a pressure of 3.2. up to 3.6 MPa, at temperatures of 125°C to 1450°C, while achieving methane in the raw gas at the outlet from the gasification space of 0.18 to 0.38 vol.% and a residence time of 0 to 16 sec.

Description

The present invention relates to a process for the preparation of carbon black as a novel product for the gasification of petroleum tar raw materials in the presence of oxygen and water vapor. ...?

Synthesis gas has hitherto been the main and desired product in the gasification of heavy petroleum and tar fractions in the presence of oxygen and water vapor. In addition, a certain amount of carbon black of variable quality is formed. The carbon black formed during the gasification process is washed out of the gas stream with water and further isolated, for example, by means of hydrocarbon fractions. The properties of these carbon blacks, which vary considerably, have already been described. However, it has not yet been possible to produce carbon black with predetermined values of the 'individual properties' which determine their applicability as a product. Therefore, they must often be disposed of by incineration, or they can only be used for less demanding applications where variable quality parameters do not matter, for example for wastewater treatment. _: .

It has now been found and experimentally verified on existing generators that the basic physicochemical properties of carbon black and their amount can be regulated by adjusting the technological conditions of the gasification process and changing the characteristic properties of the gasified raw material. Characteristics of raw materials. affect the quality of special carbon blacks and their yield, their average molecular weight, specific gravity and ash content, especially heavy metals. . . ·· ../ ·

It has been found that the amount of carbon black formed during the gasification process depends on the type composition of the gasified raw material (paraffinic, naphthenic, aromatic) and on its average molecular weight. Most of the available and used raw materials contain practically all types of hydrocarbons and their composition can be defined by the value of the Watson characterization factor in the range of 10.7 to 12.2. Within this range, a relationship was found between the amount of carbon black formed and the average molecular weight of the gasified feedstock, which can be described by the following mathematical relationship:.

. A. = 0.00124. M + 1.635.

where A is the amount of carbon black formed, expressed in% by weight, and based on the amount of gasified feedstock, and K is the average molecular weight of the gasified feedstock.

This relationship applies to a residence time in the reactor of 12 -0.5 s and to gasification conditions. +, 0.01% by volume, the variation budget, based on the methane content in the gaseous products 0.28 - ^{J of} said dependence, is 0.1% by weight.

At the same time, it was found that the amount of carbon black formed depends on the technological conditions of gasification, which can be easily characterized by the methane content in the generator gas.λ

The determined dependence can be described by a mathematical relation:

A = 8.75. C - 0.125. where A is the amount of carbon black formed, expressed in mass. and based on the amount of gasified raw material and C is the concentration of methane in the gaseous products of gasification expression! in ΐ volumetric ..

Said relationship applies to a gasified feedstock with an average molecular weight of 525 and a residence time in the range of 12 to 12.5 s, the variation range of said dependence being 0.05% by weight.

Furthermore, it was found and experimentally verified that the basic physicochemical properties of carbon black can be controlled by adjusting the specific gravity and ash content of the gasified raw material. It is known that between the ash content of all types of carbon black and the ash content processed

CS 275671 B6 raw material is a direct dependence. -In the case of special carbon blacks, the distribution of ash and heavy metals into individual process streams, ie generator gas, carbon black and wastewater depends on the intensity of carbon black scrubbing from the gas stream and the type of non-polar solvent used to isolate carbon black from their aqueous suspension. Under normal technological conditions, ie operating, 3.4 MPa pressure and gas temperature drop from 280 ° C to 140 ° C, the relationship between the ash content in the carbon black and its content in the gasified feedstock can be expressed by the following equation.

ΡΞ = 16.755. PP - 1073.2.

where PP is the ash content of the gasified feedstock in ppm and PS is the ash content of the carbon black in ppm. .

This dependence applies with a variation range of 1,400 ppm. A similar dependence was established between the total content of heavy metals in the carbon black and in the gasified raw material and directly for the main metal components vanadium and nickel. 'These dependences can be described by the following equations:

. KS - 19.99. KP + 26,8 where KP is the content of heavy 'metals in' the gasified feedstock in ppm and.

KS is the content of heavy metals in carbon black in ppm.

. VS = 13.24. VP -I- 107.2 where VP is the amount of vanadium in the feedstock in ppm and VS is the vanadium content in the carbon black also in ppm.

. . Λ. NS = 29.35. NP - 312.5 where NS is the amount of nickel in the carbon black in ppm and.

NP is the nickel content of the gasified raw material in ppm.

The range of variations of these relations is 220 ppm for the total metal content, 130 ppm for vanadium and 145 ppm for nickel.

One of the basic physicochemical properties of carbon black is the value of dibutyl phthalate adsorption, which represents the amount of this substance that the carbon blacks are able to adsorb into each other to form a pasty mass of defined stiffness. It was found, and experimentally verified, that for special carbon black there is a relationship between the specific gravity of the gasified feedstock and the value of their dibutyl phthalate adsorption of the following form:

/. DEP = 0.356. HH + 22.1 ·.

where MH is the specific weight of the gasified raw material, kg / m a

DBF is the value of dibutyl phthalate adsorption in ml of DBF per 100 g of carbon black.

The range of variation of this dependence is 5 DBF units.

The above relations of the dependence of the qualitative parameters of carbon black on the characteristic properties of the gasified raw material apply to the technological conditions of the gasification process characterized by the methane content in _; raw generator gas of 0.28 '''in'> · + '.

0.01 vol.% And the residence time of 12- 0.5 sec. ₇

Based on these newly identified and experimentally verified dependencies, a new way of producing special soot was found. . .

Process for the production of special carbon blacks by partial oxidation of heavy petroleum and / or tar fractions in the presence of a mixture of oxygen and water vapor, followed by washing with water and isoline

CS 27GC71 36, for example by palletizing with the addition of a non-polar solvent, the carbon black particles having predetermined values of the mean size of the agiomers in the range from 50 to 5,000 nm. a,.

actual memo weight 1.7 to 2.15 g / cm, specific surface area.BET in the range of 600 to.

o '..' i- ^r .

200 m 2 / g, dibutyl phthalate adsorption in the range of 300 to 500 ml / 100 g of carbon black, ash amount from 0.05 to 2% by weight, vanadium content in the range of 500 to 9,000 ppm and nickel 300 to 4,000 ppm and yields in the range of 1 According to the invention, the gasified raw material dispersed in droplets, with an average molecular weight of 400 to 1,100, a specific weight of 900 to 1,100 kg / m 2, an ash content of 100 to 900 ppm, a vanadium content 20 to 250 ppm and a nickel content of 20 to 120 ppm are reported with a mixture of oxygen and water vapor at an oxygen to injected feedstock ratio of 0.6 to 0.9 m / kg at a pressure of 3.2 to 3.6 MPa, at temperatures 1,250 to 1,450 ° C, the methane content of the raw gas at the outlet of the gasification space being 0.10 to 0.38% by volume and at a residence time of 8 to 16 sec. The soot particles thus formed, together with the gaseous products of the gasification process, are removed and removed from the gas stream by washing with water, preferably with a hardness of 0.1 min / l, to form a soot suspension from which the soot is isolated. For special carbon blacks formed under technological process conditions characterized by a methane content in gaseous products of 0.28 - 0.01% by volume and a residence time in the reactor of 12 - 0.5 s, there is a relationship between the amount of carbon blacks formed by the gasification process (A ) and the average molecular weight (M) described by the equation (with a variation range of 0.1% by weight) A = 0.00124. M + 1.536. For special carbon blacks formed under the above conditions, the direct ratio between the value of dibutyl phthalate adsorption (DBF) and the specific gravity of the gasified feedstock (MM) is defined! relationship (with a variation range of 5 ml / 100 g of carbon black) DBF = 0.356. MH + 22.1. For carbon black arising under the technological conditions defined above, the relationship between the amount of ash in the carbon black (PS) and the ash content in the gasified feedstock (PP) is described by the equation (with a variation range of 1,400 ppm) PS = 16,775. PP - 1,073.2. For carbon black formed under technological conditions of gasification process characterized by methane content in gaseous products in the range of 0.27 to 0.29% by volume and residence time in the reactor 12 + 0.5 s, the dependence of vanadium content in carbon black (VS) and the content of this component in the gasified feedstock (VP) described by the equation (with a variation range of 130 ppm) VS = 18.24. VP + 107.2, for nickel content (KS) under the same conditions KS = 29.35. HP - 312.5., Where P is the nickel content of the gasified feedstock.

All these relationships serve to control the process according to the invention in such a way that as the product produces special carbon blacks of specific predetermined properties within the range given by the definition, object of the invention and that their parameters are kept permanently at the required values as required, . ..This way you can get a permanently valuable lure product that does not need to be degraded by incineration.

Special carbon blacks with these properties are used as highly conductive carbon blacks to modify the conductivity properties of plastics and joints, thus enabling the preparation of plastic materials in antistatic or semi-conductive treatment. They are also used as pigment components in paints, varnishes, plastics, elastics, resins, asphalt, bitumen and the like. They can also be used as a sorbent by burning them, in the event of recovery of the metals present, especially vanadium and nickel. .

The invention is further illustrated by the following examples:

CS 276671 B.6 4

He added

The influence of the quality of the gasified raw material on the quality of special carbon black was verified at the operating reactor under the following technological conditions: feed of 9.42 t / h raw material, projected generator power 100%, residence time in the reactor 12 s, methane content in gaseous products 0.28% vol. A mixture of oil fraction II (distillation section from vacuum distillation of primary fuel oil) with primary fuel oil in a weight ratio of 1: 1 was used as a raw material for gasification. The results are given in the column of Table 5. 1.

Example 1 and d 2

The influence of the quality of the raw material used for the gasification process on the quantity and quality of the soot formed was verified at the operating reactor at a methane content in the raw generator gas of 0.27% by volume and a feed of 9.4 t / h of the raw material. Primary fuel oil was used for gasification. The results are shown in column 2 of Table 1.

Example 3

For gasification in the operating reactor, the so-called mixed fuel oil was used as a raw material, prepared by mixing 47% by weight, vacuum residue, 15.2% by weight, black distillate and $ 27.8. masses, oil fractions. The technological conditions of gasification were the same as in Example 1. The obtained qualitative parameters of carbon black and their yield are given in column 3 of Table No. 1. .

He attaches

Black distillate (fraction from vacuum distillation of primary fuel oil) was gasified on the operating generator, technological conditions of the process: methane content 0.29% by volume, feedstock feed 9.45 t / h. The results of the operational gasification experiment are shown in column 4 of Table 1.

Example 5

The influence of the quality of the gasified raw material on the quality of special carbon black was verified at the operating reactor under the following technological conditions: feed of 9.32 t / h raw material, methane content in gaseous products 0.28% by volume. oil distillation). The results are shown in column 5 of Table 1..

Example 6.

A mixture of black distillate and vacuum residue in a weight ratio of 3: 1 was used as raw material for gasification in the operating reactor. The technological conditions of gasification were the same as in Example 2. The obtained qualitative parameters of carbon black and their yield are given in column 1 of Table 2.

CS 275671 B6

Example i d 7 '<

For gasification in the operating reactor, a mixture of black distillate and vacuum residue in a weight ratio of 3:17 was again used as a raw material. The technological conditions of gasification were the same as in Example 2. The results of the operating experiment are given in column 2 of Table 2.

Example 8 ·. '.

The influence of the quality of the gasified raw material on the quality of special carbon black was verified at the operating reactor under the following technological conditions: feed of 9.45 t / h raw material, methane content in gaseous products 0.28% vol. A mixture of black distillate and vacuum residue was used as raw material for gasification. in a weight ratio of 1: 1. The results are shown in Table 2, column 3.

Examples

In the operating reactor, a mixture of black distillate and vacuum residue in a weight ratio of 1: 3 was used, technological conditions of the process: methane content 0.29 5 vol., Feedstock feed 9.5 t / h. The results of the operational gasification experiment are shown in column 4 of Table 2.. . ''. .

Example 10 '; λ ^; . '

The primary fuel oil was gasified on the operating generator under various technological conditions, characterized by the methane content in gaseous products in the amount of 0.22, 0.26, 0.3 S vol. The raw material feed was 9.35 t / h, qualitative parameters specific weight 952 kg / m ⁰ at 20 ° C, average molecular weight 525, ash content 395 ppm, vanadium content 82 pp, nickel content 34 ppm. The quantity of production and the quality of carbon black are listed in the following paragraph.

Concentration ΐ nethan (-i vol.) 0.22 . 0.26 0.3 Soot Production (ϊ wt.) 1.81 2.14 2.50 DBF adsorption (ml / 100 g) 379 368 353 Iodine number (mg / g) 1 126 1 092 1 074 Ash content (ppm) 6 200 '5 190 3 350 vanadium (ppm) 2 115 '1 690 1 148 nickel (ppm) 980 785 624

CG 276671 B6

TABLE 2

Column 1 2 4 Example 5 7 M · 9 S u r o v i n a (mixture of black dent. + vacuum residue) viscosity at 120 ° c (cSt) 58 31 135 ° C (cSt) 32 n 155 ° C (cSt) 30 specific weight at 20 ° C (kg / m) 531 1 012 595 1 007 average molecules, mass. 337 904 34 5 095 ash content (ppm) • 140 GOO 480 500 total metals (ppm) 210 239 2? n 231 vanadium (ppm) 143 148 144 14 G nickel (ppm). 53 74 59 G3 Conradson's test (%) ' _: 14.1 17.5 15.1 15.9

Soot

production (ΐ wt.). . 2, ⁷ 2.67 2.67 . 2.75 (based on raw material) · DB? adsorption (ml / 100 g): 375 380 378 331 Iodine number (mg / g); . / 1 110 1 116 1 102 1 119 ash content (ppm). . '-. 6,000 10,000 7,000 8 400 total metals (ppm) · .. ^: 4,005 4 980 4 400 4 680 vanadium (ppm). 2 520 2 800 2 730 2 770 nickel (ppm) ... . . 1 100 1 900 1 420 1 730

TABLE 1 Example 1 . 2 3 4 5 raw material OP + M M SM CD VZ viscosity at 100 ° C (¢ 35) 21.9 50 53 96 120 ° C / 135 ° C ’. 12.7 28 31 90 155 ° C 44 specific weight at 20 ° C (kg / m 2) 942 950 9G0 968 1 020 medium molecule mass . . 400 520 595 800 550 ash content (ppm) <. . ¹³⁰ 410 450 330 700 total metals (ppm). 64 124 150 159 283 vanadium (ppm) 4 36 88. 90 103 1 35 nickel (ppm) 29 / 36 35 39 78 Conradson's test (¾). 4.8 9.3 13 10 20 Soot. . - -. production (¾ hmct.). 2.20 2.32 2.35 2.7 2.84 (based on raw material) DBF adsorption (ml / 100 g) · 358. 356 3G6 3G5 384

Claims (1)

Iodine value (mg / g) 1 042 1 040 1 070 . 1 070 1 .126 ash content (ppm) 3 140 4 700 5 100 4 700 11 000 total metals (ppm) 1 140 2 360 2 991 3 236 Ú 710 vanadium (ppm) 745 1 585 1,998 2 107 3 500 nickel (ppn) 545 780 773 300 1 990 Process for the production of special carbon blacks by partial oxidation of heavy petroleum nobols and / or tar. fractions in the presence of a mixture of oxygen and water vapor followed by washing with water and isolation, for example by palletisation with the addition of a non-polar solvent, the carbon black particles having predetermined values, mean agglomerate sizes in the range 50 to 5 000 nm, actual vain weights 1.7 to 2, 15 g / cm ”, BET specific surface area in the range of 600 to 1,200 m / g. butyl phthalate adsorption in the range of 300 to 500 ml / 100 g of carbon black, ash amount from 0.05 to 2% by weight, vanadium content in the range of 500 to 9,000 ppm and nickel 300 to 4,000 ppm and yields in the range of 1.0 to 4 , 2% by weight, characterized in that the gasified feedstock dispersed in droplets, with an average molecular weight of 400 to 1,100, a specific weight of 1,000 to 100 kg / m 2, an ash content of 100 to 900 ppn, a vanadium content of 20 to 250 ppn. and a nickel content of 20 to 120 ppm is contacted with a mixture of oxygen and water vapor at an oxygen to injected feedstock ratio of 0.6 to 0.0 πιζ / kg at a pressure of 3.2 to 3.6 UP; ^1. , At temperatures of 1,250 to 1,450 ⁱⁿ c, the methane content of the raw gas at the outlet of the gasification space reaching 0.1 to 0.30% by volume and at a yield of 0 to 16 sec.