UA96248C2 - Method for processing furnace coke - Google Patents

Abstract

The invention relates to the coke-chemical and blast-furnace production and concerns a method for processing furnace coke. A method comprises the spraying of 2-20 % aqueous solution of metal pentaborate, selected from the group: sodium, potassium, calcium, on furnace coke pieces at a temperature of more than 20 °C. The solution contains 0.1-0.2 % of nonionic surfactant in the form of mono- and/or dialkyl esters of polyoxyethylene glycol, and is used in the amount providing surfactant content in coke of 0.0035-0.0070 wt %. The solution is sprayed in the amount providing dry pentaborate content in coke of 0.09-0.68 wt %. The technical result is in formation of reliable covering layer on the coke pieces inhibiting reactions of coke carbon with Oand COin the blast-furnace, resulting in reduction of the coke reactivity index (CRI) and increasing its hardness index (CSR) after reaction with CO.

Description

The disadvantages of the known method include insufficient boron content in tetraborate molecules. and an insignificant increase in the surface of coke pieces with a reliable protective indicator of coke strength after the reaction (C5K), neer. the economic efficiency of the technology due to the need to create high temperature (12,850 "С), the complexity is due to the insufficient ability of potassium tetraborates in the hardware design of the process, increased non- (КгВ4О7) or sodium (Ма»28В4О7), or calcium technology for the environment - (Са«О7), used in accordance with the known method - the closest analogue, to improve the quality

A known method of improving the quality indicators of SKI and C5E in accordance with the needs of blast furnace coke (SHA, Me 23560, IPC C10I. 9/10, variable process, due to the replacement of a significant publ. 05.25.2007), which includes processing pieces of part (200 - 220 kg/t of cast iron) of blast furnace coke on blast furnace coke at a temperature of 20 - 50 "C water-PVP. The reason is that during the treatment of coke with a soluble solution of tetraborate selected from the series: tetnom, tetraborate is introduced into the coke a large amount of sodium raborate, potassium tetraborate, tetraborate of an alkaline or alkaline earth metal, which is calcium-negative. At the same time, deactivation takes place, which affects the SKI and C5E indicators of coke, the coke reacts with oxygen (Og) and carbon dioxide, reducing the basicity of the ash. Yes , based on the index (СО»2) due to the formation in the subsequent predominance of ash (Io), which is calculated based on the dependent heating in the blast furnace of coke treated with protection: a film of molten borates on the surface of Io x (РГегОз - Сао i Mao « MagO 4 KgO)D510» 4 pieces of coke. Ag2Oz),

The disadvantage of the known method is its low (Kovalev V.I., Shulga I.V., Ryishchenko A. iY., efficiency due to the use of incomplete copper. for the treatment of coal charge on the reaction improvement of the quality indicators of SKI and SC of coke, which, post-reaction strength of coke is due both to the peculiarities of coke processing, technical and economic indicators of the blast furnace with tetraborates, and to the fact that the surface of the process coke // Uglekhimicheskogo zhurnal.- 2008.- Me 3- is hydrophobic relative to water droplets (tet- 4 solution.- P. 41- 48, it was concluded that the increase in laboratory). This leads to the flow of a part of the value of Io by 0.1 units. deteriorates the quality indicators of the pel solution from the surface of a piece of coke, incomplete coke, namely: it leads to a decrease in its wetting index, and accordingly, non-covering of the molasses by 9.5 95 and an increase in SKI by 7.5 905. Also, tetraborate spheres of the entire surface , which does not allow to fully create a protective layer on the surface of pieces of coke quality after its processing in accordance with the coke. the known method has a low content of boron in the molecule

The closest analogue of the proposed lac tetraborate, which is in the series of potassium tetraborate, according to the invention is a method of processing blast furnace coke with tritium, calcium is, respectively, from 18 to 22 90, improving quality indicators (ША, Me 31186 |, which does not allow fully cover the surface

IPC STO. 9/10, publ. 25.03.2008), which includes pieces of coke with a reliable protective layer and protection - post-furnace processing of blast furnace coke by breaking them from oxidation of О?5 and СО». cutting at a temperature of 20 - 50 "C into pieces. The basis of the invention is the task of pouring a 2 - 20 95% aqueous solution of blast furnace coke into sodium or potassium tetraborate or calcium tetraborate, which due to its use for post-baking treatment contains 0.1 - 0.2 wt. 95 of non-inogenous borate surface compounds containing a smaller amount of active substance (surfactant) in the form of mono- and/or alkaline and alkaline earth metals, and in a larger amount - boron , dialkyl ethers of polyethylene glycol. For processing, the creation of a reliable protective agent is ensured by using such an amount of surfactant that its content in the layer on the pieces of coke, which inhibits the reactions of coke carbon, was 0.0035-0.0070 wt. 95. This provides coke with Og and CO." in a blast furnace, which leads to a more complete coverage of the surface of the pieces, as well as a decrease in the coke reactivity index (SC) and a higher penetration into the volume of the coke pieces of dissolution of its strength index (SC) after the tetraborate reaction, providing coverage tation of the surface of schi- from CO". lin and coke pores with tetraborate molecules. At the same time, the problem is solved by the fact that the deactivation (inhibition) of coke takes place in the method of blast furnace coke processing, which includes the reaction oil with O and CO" due to the formation during spraying at a temperature not lower than 20 "C with further heating in the blast furnace of treated pieces of blast-furnace coke 2-20 9-th aqueous de-coking of a protective film of molten tetraborates of a metal borate selected from the series: sodium, ca- on the surface of the coke. tallow, calcium containing 0.1-0, 2 wt. 95 non-ionogen-

The disadvantage of the known method is the insufficient amount of surface-active substance in the form of a mono-degree of improvement of the quality indicators of SKI and CA and/or dialkyl ethers of polyethylene glycol in ki- for the needs of the domain process, due to the attractiveness, which ensures the content of the surface-active substance in a significant part ( 200-220 kg/t of cast iron) additives in coke 0.0035-0.0070 wt. 95, according to mine coke on PVP. according to the invention, as a metal borate selected from:

The reasons for the lack of the known method are sodium, potassium, calcium, pentaborate is used, a portion of the alkaline or alkaline earth metal of one of them, and the solution is used in the tetraborate of this metal, which is negatively identified, the amount that ensures the content of dry pentaborate depends on the value of the indicators SKI and SC of coke. in coke 0.09 - 0.68 wt. 95.

Between the totality of the features of the invention and the technical requirement of pentaborate, the corresponding result achieved during its implementation, metaborate and boron oxide, can be formed. For example, 2КВ5Ов -» there is a cause and effect relationship. К2В2О4 same as 48203. At the same time, metaborate is also ionic

What is new in the developed method is that it is called: К2ВгО4 -» 2 К" and Б2О47. post-furnace treatment of coke uses aqueous Potassium cations can penetrate into the interlayer solution of pentaborate of one of the metals (КВ5Озв, the space of the coke crystallite and remain there (so

MavB»uOz Ca(B5Oz)»2 in the amount that ensures the content of the so-called intercalation reaction). The dimer anion of dry pentaborate in coke is 0.09 - 0.68 wt. 905. These VgO4? forms cycles, i.e. has a cyclic structure: inorganic boron compounds in their composition contain (c) two times less alkaline or alkaline earth bok tv o? metal and 1.2 - 1.3 times more boron than is contained in tetraborate, which makes it possible to significantly (c) improve the quality of blast furnace coke: does the BgO4 anion occur? once on the plane of the framework, an increase in the coke reactivity index of SOK by 9.3, the coke crystallite will be kept on it between 16.1 95 (relative) and a decrease in the strength index due to molecular forces due to overlapping

SNI by 12.3-21.2 te (relative). y , there P-orbitals of boron with corresponding P-

The positive effect of pentaborates on the improvement of coke carbon orbitals, which contributes to high-quality c and SERIES indicators, is due to the reduced donor-acceptor interaction between the atoms of the ash basicity index (Io) due to the variable and carbon. Being on the crystallization surface of the content of alkaline or alkaline earth tu coke in them, B2O22 anions are firmly held on the neo-metal. In addition, upon exposure to the pentabom solution, it creates a protective film of BgO47 anions, which adheres to the surface of a piece of coke and prevents the penetration and interaction of the gaseous coating with a layer of pentaborate molecules, which are impregnated with oxidizing agents and coke carbon, as in the case of on the surface due to adhesion forces. Parts of the gasification of coke in the blast furnace, as well as in the equipment, pentaborate solution also penetrates into the cracks and not according to the determination of SZV and SVI indicators of coke at the pores of a piece of coke and covers their surface with molecules of pentaborate. Formed from pen molecules at a temperature of 1100 2С. The taborate layer blocks the access of oxidizing The that between the carbon of the coke crystallite and the co-gases Ог and СО» to the surface of the coke and is manifested by boron deposits, which are formed during the borate spots to deactivate the coke by reactions with Ог and СО» regrouping ( i.e., metaborate and boron oxide), even at a temperature below the melting temperature, a chemical reaction takes place, the radiation of pentaborate is confirmed. This is confirmed by the genostructural analysis. On the basis of the X-ray data of the 1-ray spectra, we showed that the crystallites of nitrogen adsorption-desorption term at 77 K, under dopocoke treated with potassium pentaborate, which were characterized by the parameters of the porous structure, are characterized by a greater length of the polyarene structure experimental samples of coke. The number of layers in the crystallite (n) was used to characterize the layers (Ha) and height (Ic) of the crystals, as well as the particles of the porous structure of the coke. The following X-ray parameters, dent IM and pore volume, Mt, structural parameters of the initial coke crystallites are: dog 0.356 nm, av8.32 nm, c 4.07 nm, p 12, 4,

Mta (cm'/)) - respectively, the volume of micro-, mesa- and mac- coke treated with potassium pentaborate: oo? mouthpiece For untreated coke, these parameters are 0350 NM Iaogonm 1s509nm, p 15 5, wet 1.695 m?/g, M» 0.021cm3/g, Mti 1.6x10-5! Coke strength index after reaction with CO" cmo/g, Mte 8.2x109 cm'/g, Mta 1.3x107 cm'/g. Dpya (SB), obtained by the proposed method from coke treated with a solution of potassium tetraborate: using pentaborates, increases in proportion

Zvet 0.743 mg/g, Mx 0.0086 cm'/g, Mti 7.1x1079 bands, compared with the nearest analog at 9.3-16.1 95 (from

Mte 3.3x107 cm'/u, Mta 5.3x107 cm'ug. For coke, bearing), in comparison with the original coke - by 18.8, moat in potassium tyrorate: bvet 38.5 96 (relative). The reactivity index of coke (SR) 1x103 cm3/g mta 1x103 cm3/g ' decreases by 12.3-21.2 k (relative) and ' , t, 17.2-35.2 905 (relative), respectively. Such an improvement in performance

Taking into account the given data, it is possible to draw the conclusion that the treatment of coke with borates with the addition of surfactant significantly increases its pore volume. With this treatment of coke, borax, in comparison with the indicators of coke, you cover with a protective layer not only the surface of the piece of coke treated in a known way - the closest nu, but also penetrate into the cracks and the like, due to the fact that during the treatment of coke, the pores are covered them, thereby limiting the access of pentaborate to the coke, contribute half the amount of alkaline oxidizing gases to the carbon of the coke, deactivating its metal, which negatively affects the indicators of SB and oxidation. The obtained results show that the SVI of coke, and 1.2-1.3 times more boron, which allows

In pentaborate-treated coke, the pore volume is 8 times less than in the original coke, and 3.3 times less, compared to the protective layer, than in tetraborate-treated coke. which is formed when coke is treated with tetraborate.

Along with this, at melting temperatures, such a protective layer reliably prevents the penetration of borates, subject to the so-called borate transfer and the influence of oxidizing gases on coke, degrouping (Borates! inorganic // Khimicheskii correspondingly reducing the reactivity index of SVI and sub-encyclopedic dictionary. - M: Sovetskaya znchischiving the strength index of SV. blast furnace coke. Klopedia, 1983. - p. 79), as a result of which from mole-

An essential feature of the claimed method is a temperature not lower than 20 "С, it is carried out on the way that for coke processing, a solution of pentaborate is sent to the hopper after it is crushed and used in an amount that ensures the content of the coke in terms of size and directly in the bunker, which contains pentaborate in coke, equal to 0.09 - 0.68 mass, where coke is stored for its further processing. It has been proven experimentally that when the content is loaded into wagons. The prepared solution of dry pentaborate in coke, less than 0.09 wt. is melted in an amount that ensures the content of dry to, there is an insufficient improvement in the performance of pentaborate in coke 0.09 - 0.68 wt. 905, which is sufficient for SZEK and CE. Obviously, this amount of pentaborate - for wetting the surface of the pieces of coke, which is insufficient to create a reliable protect- to be treated. The given amount of solution of the pentane layer over the entire surface of the pieces of coke, which borate is sprayed with the use of a pump and to be treated. hundred dry pen nozzles. taborate in coke greater than 0.68 wt. 95, techno- Example. logically difficult and economically impractical. The blast furnace coke processing method was tested

Obtaining 2 - 20 95% aqueous solution was performed on coke samples of the Makiiv coke chemical plant and spraying at a temperature of 2070 at the plant. For the treatment of coke, an aqueous solution was prepared and above, due to the properties of the solution, potassium pentaborate, sodium pentaborate, pentabogs of the technological use of coke in calcium domate, to which 0.1 - 0.2 wt. 95 of her process (the temperature of the coke in the hopper to obonogenic surfactants of the "DB" and "OP" brands. The working solution is 200-100 C), the surface of the coke pieces was applied by spreading the most complete distribution of pentaborate throughout the forging through nozzles Determining the quality of the surface of coke pieces to create a reliable coke cutter was carried out in accordance with the protective layer standard, which would more fully cover IBO 18894:2006. Blast furnace coke from a piece of coke was to be processed. The use of 2 - 20 95% aqueous with the following initial quality indicators: SC 50.4 90, pentaborate solution at a temperature not lower than 20 SVI 34.4 95. Table 1 shows the results of choosing safely for the environment and testing coke samples with determining the health indicators of service personnel. SE and SKI: raw coke (example 1), sample

It was experimentally proven that the use of 2 - 8 (examples 2 - 8), processed in accordance with the nonionic surfactant in the amount that provides the conditions of the known method (closest analogue). content in coke 0.0035 - 0.0070 wt. 96 is optimal. Samples according to examples 2 - C - coke treated to achieve complete wetting of the pieces with a 2.0 Uon solution of potassium tetraborate with the calculation of coke with an aqueous solution of pentaborate. nku 45 l/t of coke, i.e. 0.09 wt. 9o tetraborate

The claimed method of processing potassium blast furnace gas containing 0.1 wt. 96 South Africa "DB" for the sample is carried out as follows. 210.2 wt. 95 SAR "DB" for sample 3, corresponding to

After unloading from the coke oven, quenching gives 0.0035 and 0.0070 wt. 9о in accordance with the conditions for sorting by size class of the fraction of pieces of the closest analogue. A sample according to example 4 - coke with a size of 25 - 80 mm, which is used in coke, treated with a 7 95 solution of tetraborate in a blast furnace, is treated by spraying 2 - 20 potassium containing 0.2 wt. 96 South African Republic "DB", with the calculation

A concentrated aqueous solution of pentaborate, selected from a volume of 35 l/t, i.e. 0.25 wt. 9 o of potassium tetraborate in a row: potassium pentaborate, sodium pentaborate, pen- 1 t of coke. The sample according to example 5 is coke, treated with calcium taborate, containing 0.1 - 0.2 wt. 95 with a nonionic 15 F5 solution of potassium tetraborate, which contains 0.2 wt. 96 "DB" surfactant, at the rate of 45 l/t polyethylene glycol ethers ("DB" or "OP" brands) of coke, i.e. 0.68 wt. 95 potassium tetraborate per 1 ton in the amount that provides a surfactant content in coke of 0.0035 coke. - 0.0070 wt. 95. Processing of pieces of coke having

Table 1 for processing coke mass. 70 wt. 7o 11711111 1111 |unprocessed./////77 | -1117171717171717171 and 1344 504 otetraboratkalui DB | 009 | 0035 330), 53.7 dB 009 | 00070 |325)| 548

The closest anapog 6 8 9 | opentaboratkalyu DB. | 009 | 00035 /|303)1| 5850

Applicant (Lentaboratkalui dB 1 009 | 00070 2851 599

Continuation of table 1

Example Method of processing - Components of an aqueous solution | Amount of borate, Amount of surfactant,

Ki for processing coke mass. because mass. Uo

Claimed

Samples according to examples 6 and 7 - coke samples, treated with a solution of potassium pentaborate. Made in accordance with the conditions of the closest analogue, as in examples 13 and 14 - coke, processed as in example 4, only as borate was used under the same conditions as in examples 6 and 7, only rolled sodium tetraborate, containing 0.2 wt. 95 sodium pentaborate solution was prepared. Sample

Surfactant brand "OP" according to example 6 and 0.2 wt. 905 according to example 15 - coke processed according to the same

Surfactant of the "DB" brand according to example 7. The sample, according to the same conditions as in example 12, was only used according to method 8 - a sample of coke, processed according to the solution of sodium pentaborate. Samples based on examples of conditions of the closest analogue, as in example 4, 16 and 17 - coke, processed under the same conditions, only tetraborate was used as borate, and in examples 11 and 12, only calcium was used. solutions of calcium pentaborate.

Samples according to examples 9 - 17 were processed according to Table 2 shows the indicators of SUK and SR depending on the conditions of the claimed processing method, depending on the amount of potassium pentaborate, used blast furnace coke. Samples 9 - 12 - coke, processed by towing for processing. under the same conditions as in examples 2 - 5, only

Table 2 719 HH 777717171717171717117120 77777777 1777717171717171717171717171711009077777777777777771 128.51 5959 23 | .Y.YUBK«KYDrDYiY7I0s0sil1ab1111111171171111117171717171717171115407777777171717123.01 6950 | шЮБ«...ЮЮЮЮЙг0.|777Й7Й77111сп90077777777717123,3| 686

Example 18 - raw coke. Samples for (relative). In comparison with the yield indicators - examples 19 - 25 - coke samples processed for one foot of coke, the SKI value decreases under the same conditions as in example 10, only for processing according to the claimed method, by 17.2 - coke processing used solutions with different 35.2 95 (relative), and the C5K value increases with the concentration of potassium pentaborate, respectively, 2 by 18.8 - 38.5 905 (relative). оо, 5 bo, 7 90, 10 90, 12 95, 15 95, 20 95. Quantity As can be seen from the data in Table 2, coke treatment of the solution for treatment in examples 19 - 25 with a standard solution of potassium pentaborate of various concentrations, 45 l/ tons of coke. Each of these solutions contained, i.e. by introducing into the coke, different amounts of pentabo- 0.2 wt. 906 South Africa brand "DB". rate, allows you to vary the values of quality indicators

As can be seen from the data in Table 1, the processing of CE domain names. and SE and it is predicted to improve the quality of coke with water solutions of pentaborates (examples 19 - 25). of lithium, sodium and calcium (examples 9 - 17) significantly. Therefore, the use of the proposed method increases the quality indicators of SUK and SKI coke. It allows, in comparison with the known method, the highest indicators of the quality of coke SE and SVI by a closer analogue: achieved during the treatment of coke with potassium pentaborate - to increase the strength of coke after re- (examples 11 and 12). So, coke processing, which has shares of it with SO" (SBK) at 9.3 - 16.5 905 (relative); initial indicators of CE 50.4 95 and SKI 34.4 95 calculated - to reduce the reactivity index of SKI by 12.3 - potassium pentaborate in the amount that provides 21.2 95 (relative); the content of dry pentaborate in coke is 0.09 - 0.68 wt. - to improve the quality of coke with initial indicators, contributes to the improvement of SKI and SC indicators in SKI 34 - 36 95 and less, and S5K- 50 - 55 95 before comparison with the indicators of the same coke, values of indicators corresponding to the best according to the known method - the closest analogue to international standards: SKI is less than 25 - 22 9b and log: SKI decreases by 12.3 - 21.2 95 (the ratio of C5E is more than 65 - 70 905; them), and the value of C5K increases by 9, 3 - 16.5

- to prove the use of PVP in the blast furnace - to reduce coke consumption in the blast furnace from 520 to 200 - 220 kg/t of cast iron due to the improvement of the quality - to 300 kg/t of cast iron due to the improvement of the quality indicators of the coke; indicators of coke; - to purposefully obtain coke with specified indicators of C5K and SKI.

Computer layout D. Sheverun Signature Circulation 23 approx.

State Intellectual Property Service of Ukraine, st. Urytskogo, 45, Kyiv, MSP, 03680, Ukraine

SE "Ukrainian Institute of Industrial Property", str. Glazunova, 1, Kyiv - 42, 01601