UA24147U - Petro-coal-chemical floatation agent - Google Patents

Abstract

A petro-coal-chemical floatation agent contains organic substances as collectors and partially foaming agents. Furthermore, coal-chemical methylnaphthalene fraction and kerosene are used as collectors and partially foaming agents, for example, kerosene TS-1.

Description

Description of the invention

The useful model refers to the field of beneficiation of minerals, specifically by the flotation method and 2 mainly to obtaining high-quality coal concentrates at central beneficiation factories using foam flotation technology with the help of special flotation reagents.

The practical feasibility of the declared useful model is proven by the results of laboratory studies and successful experimental and industrial testing of the flotation reagent at a number of CZFs in relation to coal grades of the Donetsk coal basin. 70 In connection with the development of the mechanization of mining and transport, the content of small grades in the mined coal is increasing. During the movement of coal along the chutes, transshipment devices and beneficiation apparatus, the amount of fines additionally increases. At present, no less than 3,090 coals with a grain size below 1 mm are supplied to the beneficiation factories. This coal trifle can be effectively beneficiated only by flotation. In addition, the use of flotation not only as a method of sludge enrichment, but also as an easily feasible way of cleaning 79 circulating waters, allows solving environmental problems by transferring enrichment factories to work according to rational closed water - sludge schemes.

Flotation of coal fines occurs only with the use of special flotation reagents, although coal is a hydrophobic material. The biggest achievements of flotation are related to discoveries in the field of reagents.

Reagents must meet the following set of requirements: have high efficiency, high selectivity of action and constancy of composition and properties; to be low-toxic, not to have a sharp and unpleasant smell; be well-flowing and low-viscosity at low temperatures; if possible, be flame-resistant and explosion-proof, do not have a corrosive effect on the equipment of the flotation shop, be non-deficient and have a relatively low cost.

Research and selection of reagents that meet these requirements is a difficult task. For different types and compositions of coal, the selection of reagents for flotation is carried out exclusively on the basis of experimental data, since there are no 22 yet firmly established theoretical prerequisites, on the basis of which it would be possible to specify the required flotation reagent in advance.

Flotation is a process of separation of small solid particles, mainly fossil minerals, based on the difference in their wetting with water. Hydrophobic (poorly wettable) particles float. Hydrophilic (well wetted) sink. During flotation, gas bubbles or drops of oil stick to poorly wetted particles and raise them to the surface. "AND

Reagents for flotation are chemical substances that are in the liquid phase of the pulp and, adsorbing at the interface of the liquid-gas and solid-liquid phases, create conditions for the selective (selective) flotation of certain particles - minerals. "Her

There is a lot of literature on this problem. So in section | books: Technology of beneficiation, flotation of coal. G.A. Pickat-Ordynskyi, V.A. Ostryi, Moscow, Nadra publishing house, 1972, pp. 5-27 |1) considered chemical reagents for coal flotation, as well as the state of coal flotation in the USSR and abroad.

All reagents are divided into three groups: collectors, regulators and foaming agents. Collectors (collectors) - organic substances that contribute to the adhesion of mineral particles to gas bubbles. During the flotation of coal particles, the collectors are various apolar (non-polar) oils and other chemical substances. Reagents - collectors are often low-selectivity several minerals float at once. c To improve their effect, reagents-regulators of flotation are used, that is, substances that contribute to the improvement of the flotation of minerals by reagents - collectors and foam generators.

Foaming agents are organic substances that are adsorbed at the water-air interface and contribute to the creation of stable flotation foam.

Pages 8-10 (1) describe the most common apolar reagents and collectors at the beginning of the 70s of the last century (desulfurized kerosene; lighting kerosene; tractor kerosene; reagent AF-2 - fraction 42002 g of Shebelin natural gas condensate, which already at that time there was a shortage; KOJ reagent (KPZH); DGZS reagent; diesel fuel; oil, flotation "0"; motor oil; oxidized kerosene; gas oil).

In particular, "CO" flotation oil is a product of chemical processing of coke pitch and is obtained after its t» 20 neutralization and separation of phenol (contains no more than 495 phenols). that Some collectors (soap, amines, kerosene) have a foaming effect. Various technical alcohols and their mixtures, pyridine bases are used as foaming agents (foaming agents).

Surface-active reagents during coal flotation play the role not only of a foaming agent, but partly also of a collector and peptizer (collector of ultrafine particles). The optimal time of their contact with the pulp 22 small is 1 minute. c The effectiveness of the foaming action of the chemicals used depends on their concentration and molecular structure.

Of great importance is the number of polar groups and their location in relation to the hydrophobic radical and to each other. Most often, surface-active substances have the -OH group, less often -СООН -5053 and -М. The -OH group is part of alcohols, phenols and other compounds. Phenol has a weak foaming effect. 60 A number of waste substances of various productions are widely used as reagents at coal beneficiation factories. However, many wastes from the chemical, oil refining, coal chemical and other industries cannot serve as a stable raw material base, since the improvement or change in the production technology of the target products leads either to a change in the properties of the waste or to the cessation of their production. The group of reagents with a hydroxyl polar group includes phenols, aliphatic alcohols, in particular, fescue oil, which is a mixture of a number of alcohols, terpene alcohols, aromatic alcohols, ethers.

The subgroup of phenols includes: phenol (SeNBONN); cresol (CHzSeNAOnH); coal tricresol, which is a mixture of ortho- (35-4095), meta- (25-2890) and paracresols (35-4095), neutral hydrocarbons, phenols, xylenol derivatives and higher aromatic hydrocarbons; xylenol (dimethylphenol); phenol - cresol fraction; phenols of brown kerosene fraction; light oil; medium oil; absorption oil (it is available in large quantities at coke-chemical plants, therefore it is used at coal-enriching factories of ferrous metallurgy), naphthalene oil, anthracene oil, etc.

Other surface-active substances are also known. Reagent T-66 is a standardized by-product of the production of dimethyl dioxide (toxic substance, MPC in water -0.01mg/l), which should be handled with great 7/0 caution.

The TZF reagent is a heavy ethylidene diacetate fraction, from which the secondary fraction T3F-2 is obtained, which was used as a flotation reagent in the Donbass on the Novo-Uzlovsk, Nikitovsk, Dzerzhynska, Donetsk and

Belovskoy CZF.

In 1975 in the USSR, the flotation reagent PAB-polyalkylbenzene became known and used in 1977-1979. apolar /5 aromatized reagents - AAR-1 and AAR-2 collectors. Fine grades of coal continue to be successfully enriched by flotation.

Float reagents T - 66 (oxal) T - 92 produced by Nizhnekamskneftekhim; AAR - 1 continues to be recommended for sale on the INTERNET network. Also offered: KZTGOL flotation reagent

CJSC "Syburkhimprom"; flotation reagent sodium - butyl (aeroflot); flotation reagent of the RGOMIM series for intensification of separation processes during flotation, etc. Such a variety of types of flotation reagents is due to the fact that, taking into account the peculiarity of the composition of each coal entering enrichment, or a mixture of coals, the composition of the reagents must be selected.

Therefore, the task of further searching for new compounds of known substances to obtain flotation reagents that more fully satisfy the requests of CZF from the point of view of both technical and economic, as well as environmental requirements, is very relevant. WITH

As a prototype, which coincides with the proposed solution, according to the purpose and number of used components, the well-known "petroleum-chemical float reagent" was selected according to TU U 322-00190443-054-2000 developed by the Institute of Chemical Engineering in Ukraine: which was effective from 07.07.2000. until May 1, 2006

Two modifications of the flotation reagent FN and FNU were produced at the Phenol plant and supplied to a number of Central coal beneficiation factories in the Donetsk region of Ukraine.

The following raw materials were used for the production of the flotation reagent: - 1) Polyalkylbenzene resin (PAB) according to TU 38.10396-83; "- 2) Soybean oil according to GOST 17071;

C) Absorbent oil according to TU U 322-00190443-117-97. -

The content of PAB resin in the composition of flotation reagents was in the range of 60-90905 by mass; with

The content of sea buckthorn oil - From it - 1095 mass;

Absorbent oil content - 20 units - 3095 wt.

PAB resin was purchased in Russia and was the main petrochemical component of the specified flotation reagent. However, in recent years, PAB resin has become an acutely scarce product in Ukraine, the price of which has increased significantly.

The basis of the useful model is the task of improving the recipe of the petrochemical flotation reagent - by replacing the main deficient petrochemical component - polyalkylbenzene resin (PAB) with a non-deficient carbon chemical component produced by the Phenol plant, which would allow to ensure the technical characteristics of the new composition of the flotation reagent at the level of the previously produced flotation reagents. and FNU.

The task is solved by the fact that in the petrochemical flotation agent, which includes organic substances as collectors and partially foaming agents, according to a useful model, methylnaphthalene fraction (MNF) and kerosene, for example, TS-1 kerosene, are used as collectors and partially co-foaming agents. with such a ratio of components, parts by mass:

Methylnaphthalene fraction - 85 - 95; - Gasoline TO-1--5 5-15. of them 20 Active beginning of flotation reagent - naphthalene and its derivatives (methyl and dimethyl naphthalene), acenaphthene, fluorene, kerosene.

The specified components of the proposed flotation reagent constitute the essence of a useful model, as they are necessary in any variant of its implementation and are sufficient to achieve the set task.

The most preferred from the point of view of the applicant are also the following specific compositions of the specified petrochemical flotation reagent. The specific composition of the flotation reagent: MNF - 9095 mass; TO-1 - 1095 mass 59 In order to improve the foaming properties of the flotation reagent, which is applied at a reduced content of kerosene, it is advisable to add it to another specific composition of safflower oil. The composition of the flotation reagent 9o mass:

Methylnaphthalene fraction - 90;

Gasoline TO-1-5;

Soybean oil - 5.6 o In order to reduce the solidification temperature, which allows the use of a flotation reagent, which is applied in the winter season, it is advisable to add an additional introduction into the two-component and three-component compositions of oil and coal flotation reagent up to 2 - 595 wt. due to part of the content of other fuel components of the petrochemical furnace, mainly produced by the Phenol plant.

The specific composition of the flotation reagent with such a content of 95 mass components: because Methylnaphthalene fraction - 85 - 90;

Gasoline TO-1-5 10;

Soybean oil - 2 and 5;

Petrochemical furnace fuel - 2.5.

Obtaining the stated compositions of the petrochemical flotation reagent is carried out by dosing the raw components in certain ratios with continuous mixing. The time of mixing the components - From an hour; standing time - 2 hours. Production form: liquid; color is dark brown; boiling point 100h 360 2; density at 202, kg/m?, no more than 1.06; when stored for a year or more, the product does not change its properties. The characteristics of the raw materials used are given in 70 Tables 1-4 and - Bo (volume), not less

The methylnaphthalene fraction was not previously used as a basis for the flotation reagent. щ и- " - з " and that does not contain fur. impurity When shaking, it should not form a turbidity.

The temperature limit of distillation at a pressure of 120 en NI NN nn: ю о

I

. and?

Petrochemical furnace fuel

It is intended for burning in boilers of small and medium productivity and other technological units of industrial purpose.

Depending on the cooking recipe, the stove fuel is produced of two brands of TPNA, its TPnN B. - According to physical and chemical parameters, the fuel must meet the requirements and norms of TU U - 322-00190443-102-2000, indicated in the Table. 4 t i dark brown color dark- brown color 5 - about b5

The decision based on a useful model was based on the results of comparative experimental studies of activity, flotation of known and two experimental samples of flotation reagents. The study of the flotation properties of reagent samples was carried out in laboratory conditions on a flotation machine with a chamber volume of 750 cm 3.

As a raw material during the enrichment, the material that is the feed for the flotation of the "Krasnolimanska" CZF, indicated in Table 5, was used.

Before conducting the research, a control screening was carried out on the sieves of the English company Epdesov

And tkea with the size of the holes in Timm. The average ash content of the raw material sample was about 24,965.

For each experiment, a suspension with a weight of 0.1 kg was selected, which ensured the pulp density during flotation at the level of 13Okg/mU. In the chamber of the floating machine, the suspension was mixed with water (1 min.), then the reagent was supplied (dropwise) and its contact with the pulp was made (1 min.). After preparing the pulp for flotation, the density of the pulp was adjusted to the working density, air was supplied and enrichment was carried out for 2 minutes.

The enrichment products were filtered, dried and prepared for chemical analysis.

The obtained qualitative and quantitative results of flotation of coal sludge of the "Krasnolimanska" CZF are given in

Tables 6. and Sivash; 00 vyyudf|Freedom 0 Vytannyavkt; From 77231435 5

Met 64.9 294 vd (zanozvecha zodova vis - zv | vd, hola) taov sch vodo zve vdo (zvyuyu « to 90.8 35.6 - s vdo oovv| vv? .

B Mag 114 A 38.5 vd vv tya 4 g vdoyatyao| zt t» vd ovlv| I will take up the gold Visual observation of the flotation process showed that the process of enrichment with reagents proceeds quite intensively. Some difference can be seen (at higher costs) in the flotation time. The highest flotation rate is observed when using the Mo2 reagent. In the final stage of the process with this reagent, foaming is slightly increased (reagent excess). 60 A comparison of qualitative and quantitative indicators confirms the very high flotation properties of the Me2 reagent. It should be noted its higher activity in relation to related minerals (or growths), which somewhat increases the ash content of concentrates.

The activity of Moi and Mo3Z reagents at a consumption of kg/t is practically the same. The reagent works somewhat more actively at higher costs, which may be a consequence of lower foaming ability. This drawback can be reduced in the conditions of circulating water supply at operating factories.

The results show that when replacing 50 parts of PAB with 50 parts of methylnaphthalene fraction in sample Mo2 and 30 parts of PAB with 30 parts of methylnaphthalene fraction in sample Mo1-30, good results were obtained.

Then similar studies of two samples of reagents were carried out:

Reagent 1: 8895 methylnaphthalene fraction; 5905 kerosene, 590 furnace petro-carbon chemical fuel, 290 safflower oil.

Reagent 2: 9395 methylnaphthalene fraction; 590 kerosene; 2960 fescue oil.

Heavy floated slags of Russian coal were used (Raspadskaya mine, Kemerovo region)

The results of flotation of samples are given in Table 7

Almost the same results were obtained. The introduction of 595% of furnace fuel into the flotation reagent 1 made it possible to increase its solidification temperature by 720%.

Reagent consumption, g/t! The product of

All subsequent comparative experiments were carried out on three compositions of reagents:

And - kerosene (collector) - absorbing oil POD (foaming agent);

II - Moi's reagent (collector and foaming agent) in the composition: 87-889% methylnaphthalene fraction, 1095% kerosene and 2-396% sow oil;

IP - reagent Мо1 (collector in the composition: 9095 methylnaphthalene fraction, 1095 kerosene) called ФН-1 and reagent Мо2 called ФНП (foaming agent in the composition: 5095 methylnaphthalene fraction, 5095 safflower oil) as an additive 2-395 to che

From the amount of MO1 reagent.

The costs of reagents were: -

And - kerosene: 800g/t and 1000g/t; oil POD: 80g/t. "-

II - reagent Mo1: 80Og/t, 100Og/t and 120Og/t.

Sh - reagent Mo1: 80Og/t and 100Og/t; -

Reagent Mo2: ZOg/t. Foaming agent: 5095 of methyl naphthalene fraction - 5095 of sow oil). with

The slags of the "Dobropolska", "Stepova", "Yuvileina", "Giivdenno-Donbassivska Mo3", "Zakhidno - Donbassovska" mines were studied. For conducting experiments, screening with a size of 0-0.5 mm (primary sludge) obtained from coal samples weighing 2 kg was used. The research was carried out in laboratory conditions in a flotation machine of the type

FL-1 with a chamber volume of 750 cm? For the experiments, a suspension of the starting material with a weight of 90 g was prepared, which ensured the pulp density during flotation at the level of 120 kg/m? . Sludge flotation was carried out under the same conditions at different values of reagent consumption. The enrichment products were filtered, dried and prepared for chemical analysis. Experiments were duplicated to increase the reliability of conclusions. is" The analysis of the obtained data when using different reagents showed that the efficiency of the flotation process is higher in experiment I when using the Moi reagent (as a collector) and in experiment I with the Mo2 reagent called FNP (as a foaming agent) in comparison with kerosene and POD absorbing oil ( experiment I). At the same time, better values of ash content of concentrate and waste were achieved in experiments I and IYI. Their use of the Moi reagent also allows obtaining sufficiently high indicators, but at greater costs. - The reliability of comparative tests of flotation reagents carried out in laboratory conditions was checked in 50 conditions of experimental and industrial tests at a number of CZF.

According to the results of the experimental inspection, a corresponding change of Me2 was made and approved in TU U that 322-00190443-054-2000 with the date of introduction of 01.07.2006 to "Petroleum-chemical flotation agent", which includes two compositions: ФН-1 and ФНП using the carbon-chemical methylnaphthalene fraction and the toxicological and hygienic passport of the flotation reagent is also approved.

Thus, the presented data indicate that the flotation reagent declared as a useful model meets the regulatory requirements for novelty and industrial applicability.

Claims (4)

The formula of the invention 1. Petrochemical flotation reagent, which contains organic substances as collectors and partially foaming agents, which differs in that as collectors and partially foaming agents, coal chemical methylnaphthalene fraction and kerosene, for example TS-1 kerosene, are used at this ratio of components, wt. parts: 65 coal-chemical methylnaphthalene fraction 85-95 kerosene TO-1 5-15. 2. Petrochemical flotation reagent according to claim 1, which differs in that it uses the following quantitative ratios of components, wt. parts: 2 coal-chemical methylnaphthalene fraction 90 gas TS-1 10. 3. Petrochemical flotation agent according to claim 1, which is distinguished by the fact that it additionally contains safflower oil with the following quantitative ratio of components: coal chemical methyl naphthalene fraction 90 gas TO-1 5-8 safflower oil 2-5. 4. Petrochemical flotation agent according to item C, which is distinguished by the fact that it additionally contains petrochemical furnace fuel with the following ratio of components: coal chemical methylnaphthalene fraction 85-95 kerosene TO-1 5-10 safflower oil 2-5 fuel petrochemical furnace 2-5. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2007, M 9, 25.06.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. - in « - « p - I.Y and? name) Chek" - Chek" that 60 b5