Catalyst for oxidation of tar and method thereof

 

(57) Abstract:

The invention relates to catalytic chemistry, in particular, to a catalyst for oxidation of tar and method of its production. The invention can be used in the oil industry and building materials industry. Catalyst and process for its production, accelerate the oxidation process of the oil to bitumen desired brand and dispose of waste iron and steel industries. The catalyst contains waste titanium-magnesium production stage chlorination of titanium containing slag and oxygen-containing component, open-hearth slag and/or scale and/or aluminum slag and/or aluminum sludge in the following components, wt.%:

FeCl2- 1,6-10,5

AlCl3- 0,4-17,7

MgCl - 0,3-7,8

KCl - 2,1-12,7

TiO2- 0,6-9,3

MnO - 0,1-4

MgO - 0,9-9,4

FeCl3- 1,2-7,9

CaCl2- 1,4-12,2

NaCl and 0.2 to 7.2

C IS 0.2 TO 7.2

FeO - 2,8-64,5

CaO - 1,2-13,4

SiO2- 0,4-51,2

Al2O3- Not more than 16.5

In accordance with the invention, the catalyst is produced by a joint grinding of waste titanium-magnesium production stage chlorination of titanium containing slag and Martin was going public. 2 S. p. f-crystals, 2 tab.

The invention relates to catalytic chemistry, in particular to catalysts for the oxidation of tar and can be used in the oil industry and building materials industry.

Known catalyst for the oxidation of the tar /1/ represents chloride Plav furnace processing of pulp-waste titanium production. The catalyst has the following composition (mass.): TiCl43.27 to 12,56; FeCl38,12-15,82; SiCl4-2,48-4,25; AlCl3- 10,28-21,19; CaCl23,0-4,25; MgCl20,34-2,35; CrCl3- 0,95-1,06; VOCl30,2-1,02; KCl 22,7-30,0; NaCl 12,0-28,5, else H2O.

In common with the claimed catalyst is the presence of a known catalyst anhydrous chlorides of iron, aluminum, calcium, magnesium, sodium and potassium included in unusable chloride afloat furnace refining of the pulp, which is a waste of titanium production. Depending on the composition and quantity of this catalyst are the different brands of road and construction bitumen. Emissions of hydrogen chloride are removed prior granulation of the used catalyst.

The lack of a developed surface (granules) causes of calevtactu tar, and therefore refractory bitumens are not formed.

It should be noted that due to changing technology titanium production of these wastes is currently lacking.

Closest to the proposed invention is to solve /2/, where the catalyst for the oxidation of tar used titanium waste production (stage chlorination of titanium-containing slag) of the following composition, mass.

FeCl25,2-14,8

AlCl34,7-24,8

TiCl45,2-10,0

CrCl31,0-5,1

FeCl35,4-44,8

SiCl4the 10.1-24,9

MnCl21,0-8,9

C 8,4-24,6

the chlorides and oxides of Ca and Mg the rest.

This solution is chosen as the prototype of the proposed catalyst.

Overall the prototype with the inventive catalyst is the presence of a known catalyst solid chlorides of iron, aluminum, calcium, magnesium, oxides of calcium and magnesium, and carbon included in the composition of waste titanium production stage chlorination of titanium containing slag. Depending on the number and composition of the catalyst are the different brands of road and construction bitumen. However, the presence of this catalyst compared the Ganza, chromium is more conducive to processes of polymerization, polycondensation, i.e. the formation of linear structures that do not lead to structuring of the original tar and, as a consequence, to the formation of refractory bitumen.

A known method of producing a catalyst for oxidation of tar /3/ by mixing solid chlorides titanium waste production stage chlorination of titanium-containing raw materials with kubovy the remainder of the production of synthetic fatty acid, which is selected as a prototype method for producing a catalyst.

Overall the prototype with the inventive method to obtain catalyst is the use of solid chlorides titanium waste production stage chlorination of titanium containing material. In the presence of a known catalyst receive various brands of road and construction bitumen. In addition, the use of this catalyst avoids emissions of hydrogen chloride.

The role of catalyst in this case, perform the carboxylates of the metals produced by the interaction of the anhydrous chlorides included in these waste components with VAT residue synthetic fatty acids. is prigotovleniya catalyst (50oC) contained in the VAT residue production of synthetic fatty acids fatty acids (mass fraction of not less than 77%) interact with the chlorides of iron, aluminum, chromium, titanium and manganese, forming the corresponding carboxylates and hydrogen chloride (RCOOH+MCln=(RCOO)nM+nHCl), which degrades the Toxicological characteristic of this process.

In addition, the known method does not provide the active catalyst (oxidation tar is carried out at 2105oC), the change of which not allows you to adjust the rheological properties of the produced bitumen in a wide range, including not possible to obtain a refractory bitumen with a softening temperature above 61oC K and W and penetration below 55 mm-1.

In addition, the catalyst obtained in this way is a pasta, passing in the current state at 50-60oC, which requires for its transportation special heated tanks, and storage requires special corrosion-resistant, heated and sealed containers to prevent contact of the catalyst with water vapor.

The basis of the invention the goal of creating catalysis is STV allows you to increase the developed surface of the catalyst components, to intensify the process of oxidation of tar.

This goal is achieved in the catalyst for oxidation of tar containing solid chlorides titanium waste production stage chlorination of titanium containing slag in that it additionally contains oxygen-containing component of open-hearth slag and/or scale and/or aluminum slag and/or aluminum sludge in the following catalyst components, wt.

FeCl21,6-10,5

FeCl31,2-7,9

AlCl30,4-17,7

CaCl21,4-12,2

MgCl20,3-7,8

NaCl from 0.2 to 7.2

KCl 2,1-12,7

C 1,1-6,8

TiO2from 0.6 to 9.3

FeO 2,8-64,5

MnO 0.1 to 4,1

CaO 1,2-13,4

MgO 0,9-9,4

SiO20,4-51,2

Al2O3Not more than 16.5

New in the inventive catalyst is an additional content of the waste to various metallurgical industries, their qualitative and quantitative composition.

In an invention method of producing catalysts the goal is to create a way in which to use as the second component, one of the wastes of metallurgical industries, as well as another principle of mixing the catalyst components can improve the Toxicological characteristics of harmful emissions.

This goal is achieved in a method of producing a catalyst for the oxidation of tar by mixing solid chlorides titanium waste production stage chlorination of titanium containing slag with oxygen-containing component of the fact that as the oxygen-containing component is used open-hearth slag and/or scale and/or aluminum slag and/or aluminum slurry, and mixing is carried out by a joint grinding, while the solid chlorides and oxygen-containing component is taken in the ratio of (10-50): (50-90).

New in the proposed method is used as the oxygen-containing component is one of these wastes of metallurgical industries, as well as the fact that the mixing of the catalyst components is carried out by a joint grinding. Also new is the ratio of the catalyst components.

A causal relationship between the totality of the claimed features and achieve the result can be explained as follows.

In the process of joint grinding produces an additional amount of surface chlorides and chloroxylon and harpertown and chloroaluminate, is actively conducting oxidation processes.

2) during the process of oxidation of tar in the presence of the proposed catalyst.

In addition, facilitates the transport of the catalyst and introducing it into the reactor.

In comparison with the prototype of the proposed catalyst accelerates the oxidation process tar 1.5-6.5 times, while depending on the composition to adjust the rate of change of temperature softening and penetration, i.e., to direct the process towards the formation of bitumen with desired rheological properties.

The proposed composition of the catalyst provides esotericist oxidation of tar, which allows for achieving 180oC to stop the supply of additional heat and thereby in comparison with the prototype to reduce energy in obtaining bitumen with the desired properties. The presence in the composition of the proposed catalyst for a significant share of the oxidation process of tar. Indeed, the oxidation of tar to different grades of road and construction bitumen passes for 1.0 hours

Much smaller in comparison with the prototype of the content of the anhydrous chlorides of iron and aluminum, and oxides of magnesium and calcium leads to the fact that in the process of oxidation of tar not found the selection of hydrogen chloride (conclusion regional SES).

Depending on the composition of the catalyst, its amount and time of the process, you can get a wide range of different brands of road, building and roofing asphalts.

The use of the catalyst mixture of the above components, taken in different ratio determined by their influence on the physico-chemical properties forming bitumen.

Thus, the catalysts with a high content of aluminium (table. 1, samples 7-9, 13-16) significantly reduce the rate of descent of penetration, and the ratio of iron/aluminum catalyst under otherwise equal conditions significantly affects the speed change softening temperature and penetration (table. 1).

Varying thus the mass fraction and the composition of the catalyst, it is possible in a wide range to adjust as the rate of oxidation of tars, that is m To the solid chloride - titanium waste production stage chlorination of titanium containing slag add in a ball mill with constant stirring oxygen-containing component, which take the open-hearth slag and/or scale and/or aluminum slag and/or aluminum sludge and conduct a joint grinding. The ratio of solid waste and oxygen-containing components take in the ratio of (10-50):(50-90), respectively.

Example 1. To 10 kg of solid chlorides titanium waste production stage chlorination of titanium containing slag, the composition of which is specified in the table. 1, sample 1, with stirring in a ball mill, add 90 kg open-hearth slag and get a sample of the catalyst, the composition of which is specified in the table. 1, sample 4.

Example 2. To 30 kg of solid chlorides titanium waste production stage chlorination of titanium containing slag, the composition of which is specified in the table. 1, sample 1, with stirring in a ball mill, add 70 kg open-hearth slag and get a sample of the catalyst, the composition of which is specified in the table. 1, sample 5.

Example 3. To 50 kg of solid chlorides titanium waste production stage chlorination of titans the g open-hearth slag and get a sample of a catalyst, the composition of which is specified in the table. 1, sample 6.

The remaining samples of the catalysts were obtained similarly, mixing of solid chlorides titanium waste production, the composition of which is given in the table. 1, samples 1-3, or with aluminum slag (table. 1, samples 7, 8, 9), or scale (table. 1, samples 10, 11, 12), or with aluminum sludge (table. 1, samples 13, 14, 15) in ratios that provide the content of the components listed in table. 1.

Example 4. To 10 kg of solid chlorides titanium waste production stage chlorination of titanium containing slag, the composition of which is specified in the table. 1, sample 1, with stirring in a ball mill type 45 kg open-hearth slag and 45 kg of aluminum sludge and receive a sample of the catalyst, the composition of which is specified in the table. 1, the sample 16.

Example 5. To 55 kg of solid chlorides titanium waste production stage chlorination of titanium containing slag, the composition of which is specified in the table. 1, sample 1, with stirring in a ball mill, add 25 kg of open-hearth slag and 20 kg of aluminum dross and get a sample of the catalyst, the composition of which is specified in the table. 1, the sample 17.

Example 6. To 5 kg of solid chlorides titanium waste of product is assured in a ball mill to add 40 kg scale and 55 kg of aluminum sludge and get a sample of a catalyst, the composition of which is specified in the table. 1, the sample 18.

Example 7. In laboratory disperser with engine speed 600 rpm, with a capacity of 15 liters, equipped with a heater load of 10 kg of oil tar (density at 20oC 0,985 g/cm3, viscosity at 80oC 28, softening temperature by Kish 30oC) heated to 185oC. the oxidation Process is conducted at 185-190oC for 7 o'clock Get oil bitumen with the indicators shown in the table. 2.

Example 8. In laboratory disperser with engine speed 600 rpm, with a capacity of 15 liters, equipped with a heater load of 10 kg of oil tar (density at 20oC 0,985 g/cm3, viscosity at 80oC 28, softening temperature by Kish 30oC) heated to 185oC and 50 g (0.5%) solid chlorides titanium waste production stage chlorination of titanium containing slag, the composition of which is specified in the table. 2, the sample 1. The process is conducted at 185-190oC for 1 h Get oil bitumen with the indicators shown in the table. 2.

Examples 9-61 (PL. 2) illustrate the obtaining of bitumen oxidation of tar under conditions analogous to example 8, with the only difference that would change the amount of catalyst (table. 2) and e is. the. USSR N 1616693 (analog) on the oxidation of tar in a known manner at 200-210oC using as a catalyst solid chlorides titanium waste production stage chlorination of titanium containing slag (example 62, the process of oxidation of 2 h) and chloride afloat furnace processing of pulp (example 63, the oxidation time 2 h).

Example 64. In industrial bitumen spraying machine with a capacity of 15 m3with two dispersers, load 10 tons of oil of tar. Raise the temperature of fuel oil injector 180oC. Disconnect the nozzle and through 12 h are petroleum bitumen grade BND 90/130 with a softening temperature in KISH 56oC and 110 penetration mm-1.

Example 65. In industrial bitumen spraying machine with a capacity of 15 m3with two dispersers, load 10 tons of oil of tar. Raise the temperature of fuel oil injector 130oC, load at the working dispersers 100 kg of catalyst (table. 1, sample 7). Raise the temperature to 180oC, turn off the burner and after 1 h 15 min get oil bitumen grade BND 90/130 with a softening temperature in KISH 56oC and 110 penetration mm-1.

Example 66. In industrial disperser with a capacity of 15 fuel oil injector 130oC, load at the working dispersers 100 kg of catalyst (table. 1, the sample 16). Raise the temperature to 180oC, turn off the burner and through 2 h are petroleum bitumen grade BNK 90/30 (roofing) with a softening temperature in KISH 89oC and penetration 40 mm-1. As can be seen from the table. 2, the reduction catalyst to 0.5 wt. also speeds up the process, however, obtained only low-melting (road and building) bitumen. Increasing the amount of catalyst above the claimed impractical because no significant effect on the speed of the process that it becomes less manageable. As follows from the data presented, the catalyst samples 4-16 in quantities of 0.5-1.0 wt. accelerate the process of oxidation of tars to bitumen desired brand. In the preparation of catalysts for the reduction of the solid content of chlorides titanium waste production stage chlorination of titanium containing slag below 10 wt. and above 90 wt. it is impractical. In the first case, the acceleration of the oxidation of tar is not observed (examples 59-61, PL. 2), in the second case, the efficiency of the prepared catalyst similar solid chlorides (examples 56-58, PL. 2).

Predlagaemom waste of various metallurgical industries, causing thereby the production of such catalysts available in a particular region of the relevant raw materials of man-made waste.

Oxidation of tars in the presence of the proposed catalysts of ectothermic and therefore requires less energy consumption in comparison with existing technologies.

The temperature reduction process to 180-195oC and time consuming process 4-6 times leads, in addition to saving energy, reduce toxic emissions into the atmosphere.

1. Catalyst for oxidation of tar on the basis of solid chlorides titanium waste production stage chlorination of titanium containing slag, characterized in that it additionally contains oxygen-containing component

open-hearth slag, and/or scale and/or aluminum slag, and/or aluminum sludge when the mass ratio of the quantities of solid chlorides and oxygen-containing component 10 50 50 90 at the following content, wt.

FeCl21,6 10,5

AlCl30,4 17,7

MgCl20,3 7,8

KCl 2,1 12,7

TiO20,6 9,3

MnO 0,1 4,1

MgO 0,9 9,4

Al2O3Not more than 16.5

FeCl31,2 7,9

CaCl21,4 12,2

NaCl 0,2 7,2

C 1,1 6,8

FeO 2,8 64,5
the solid chlorides titanium waste production stage chlorination of titanium containing slag with oxygen-containing component, characterized in that as the oxygen-containing component used open-hearth slag, and/or scale and/or aluminum slag, and/or aluminum sludge and mixing is carried out by a joint grinding, while the solid chlorides and oxygen-containing component of the charge / mass ratio 10 50 50 90 respectively.

 

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