RU2272061C1 - Preventive means against freezing, sticking and dusting of loose materials (versions) - Google Patents

Abstract

FIELD: preventive means against freezing and sticking of loose materials to walls of mining and transport equipment; prevention of dusting on interim roads, open-cut mining; protection of rolling stock against freezing and blowing-off of loose materials, coal and peat for example.

SUBSTANCE: preventive means is made in form of mixture of solvent and thickening additive of oil nature. Used as solvent are distillation residues of coke and by-product process and/or by-products of production of butadiene, isoprene, isobutylene, ethylene both independently and in mixture with distillation residues of production process of polymers, pyrolysis residues, benzene, styrene and distillation residues of production of butanol, isobutanol, 2-ethyl hexanol acid and 2-ethyl hexanol. Solvent may additionally contain gas oils of thermal and catalytic cracking and gas oils of coking process. Used as thickening additives are mineral and synthetic oils of all kinds, mixture of used oils, oil sludge, oil residues and oil fuel. Components of thickening additive and solvent are used at any combination. Novelty of invention is use of wastes of various processes of oil and petroleum chemistry products.

EFFECT: extended field of application; cut costs; enhanced ecological safety.

5 cl, 1 dwg, 2 tbl, 17 ex

Description

The invention relates to preventive measures to prevent freezing of wet rocks, their adhesion and freezing to the walls of mining and transport equipment, to prevent dust formation on temporary highways, when mining mineral resources by open pit methods, and also to protect the surfaces of rolling stock from freezing and blowing loose materials e.g. coal, peat, etc.

The prophylactic is a solvent-free, oily liquid based on a solvent and a thickening additive of petroleum and petrochemical origin. When this liquid is applied to the processed material, a thin film is formed on its surface, which prevents freezing, dust formation and blowing of loose substances.

The prophylactic should have a high wetting and adhesive ability with respect to the processed material, have a low pour point, and an accessible raw material base.

Preventive compositions for these purposes are widely known in the art.

For example, in ed. St. USSR No. 519467 describes a composition where a light gas oil of catalytic cracking is used as a solvent, and a heavy oil residue is used as a thickening additive. A disadvantage of the known composition is the limited resources of crude oil and not enough low pour point.

To solve the problem of expanding the raw material base on the basis of oil refining products sent ed. St. USSR No. 749878. As a solvent, it is proposed to use fractions of clarified and washing kerosene, a gasoline fraction, a fraction obtained by dewaxing oil with molecular sieves and a distillate residue formed during the reforming process. As a thickening additive, the remainder of the pyrolysis of oil. Despite the good operational characteristics, the use of distillate products of primary oil refining did not solve the problem of creating an affordable raw material base for the production of prophylactic agents.

In the patents of the Russian Federation 2111228, 2132350 and 2155201, a prophylactic is obtained on the basis of oil products such as kerosene-gas oil fractions of catalytic and thermal cracking and tar. Both the previous and these solutions do not eliminate the problem of the shortage of their constituent components.

More promising are the decisions on the creation of preventive products based on production wastes in oil refining and petrochemicals. A prophylactic agent is known (RF patent No. 2196162), in which the problem of a shortage of petroleum feedstock is partially solved by using as a solvent the waste from production - bottoms from the production of butyl and isobutyl alcohols (hereinafter referred to as COBS), and straightening oil as a thickening additive. The disadvantage of this solvent is its limited compatibility with the components of the thickening additive and other solvents, which over time can lead to interfacial separation of the product and, accordingly, to a deterioration in its quality or complete unsuitability for use.

Closest to the claimed solution is the prophylactic agent described in the patent of the Russian Federation No. 2190654, where the bottom residue of the pyrolysis resin processing or absorbent is used as a solvent — a waste from the production of isoprene synthetic rubber monomers (hereinafter referred to as COPSP). As a thickening additive, as in the previous case, straight-run fuel oil was used. This solvent in comparison with the previous one has a higher dissolving ability, however, the resources of this product are insufficient to satisfy all the needs for this kind of components. Another disadvantage is the need to use straight-run fuel oil. It requires constant heating to +80 C, which leads to additional energy costs, complicating the production technology of a prophylactic agent. In addition, the viscosity of the known composition at temperatures below -20 ° C increases sharply, which leads to an increased consumption of prophylactic agents and complicates the technology of their application to obtain a uniform coating.

The present invention solves the technical problem of the further expansion of raw materials due to the involvement of production waste and not only refining and petrochemicals, but also other industries, in particular coke chemistry.

Another objective of the present invention is to increase the flexibility of the production process of a prophylactic agent by using such a solvent that would ensure compatibility of the mixed components of the solvent with each other and with the components of the thickening additive.

This problem is solved by the fact that in a prophylactic against freezing, sticking and dusting of bulk materials, which is a mixture of a solvent and a thickening additive of petroleum origin, bottoms of coke production (COCP) or by-products of the production of butadiene, isoprene, isobutylene, ethylene are used as a solvent (hereinafter JOU) or their mixture in arbitrary combination with each other, while the ratio of solvent to thickening additive is, wt.%:

Solvent 40-99.5 Thickener 0.5-60

Another variant of the prophylactic is the use of bottoms of coke oven production (COCP) as a solvent or by-products of the production of butadiene, isoprene, isobutylene and ethylene (ZhOU) or their mixture with bottoms from the production of pyrolymers, pyrolysis resins, benzene, ethylbenzene and styrene (KOPSP) as well as with bottoms from the production of butanol, isobutanol, 2-ethylhexanoic acid, 2-ethylhexanol (COBS) in any combination with each other, while the ratio of solvent and thickening As in the first embodiment, the amount of additive is, wt.%:

solvent 40-99.5 thickening additive 0.5-60

The solvent may further include catalytic and thermal cracked gas oils, as well as coking gas oils.

One of the main requirements for the quality of a prophylactic is the flash point. To meet this requirement, the boiling point of the used bottoms should not be lower than 160 ° C. Since the quality of production wastes is not strictly regulated, this indicator may have lower values. In this case, lighter fractions are distilled off. The distillation residue with a boiling point of 160 ° C and above is used to prepare a prophylactic agent as a solvent.

Another main ingredient of the prophylactic in both variants is a thickening additive of petroleum origin.

As a thickening additive in both variants of the invention, a mixture is used that includes mineral and synthetic oils of all kinds, used oils of all types, oil sludge, oil residues and oil fuel, while the components of the thickening additive are used in any combination with each other.

As oil residues, all types of residues having a viscosity of up to 10 WU at 80 ° C are used.

The fuel obtained from the processing of oil waste is mainly used as petroleum fuel.

As experimental data show, any mixture of these components gives the desired result if COCF and / or JOU are used as a solvent (option 1) or in a mixture of solvents (option 2).

The explanation for this, apparently, lies in the properties of these products. Studies of the physicochemical properties and hydrocarbon composition of these products (see table 1) show that they have a relatively high flash point (+ 85 ° C) and good low-temperature properties (-65 ° C). The hydrocarbon composition of the solvents used: KOKP, ZhOU, KOPSP, KOBS is presented respectively in Appendix 1, 2, 3, 4. From Appendix 1, 2 it is seen that COKP and ZhOU are characterized by the complete absence of paraffin compounds and at the same time high content ( more than 70%) of aromatic hydrocarbons. This is due to the low pour point of these solvents and the possibility of mixing on their basis a wide variety of solvents and components of the thickening additive.

These bottoms are generated in sufficient quantities at domestic petrochemical plants and are burned as heating oil in furnaces to generate heat, and are also used to dilute fuel oils and other needs of industrial enterprises.

The analysis of the prior art carried out by the applicant has made it possible to establish that there are no analogues that are characterized by sets of signs that are identical to all the signs of the declared variants of the prophylactic agent. Therefore, each of the claimed inventions meets the condition of patentability "novelty."

A distinctive feature of the first and second variants of the invention is the use as solvents of KOKP and ZhOU, both independently (option 1), and in a mixture with other solvents (option 2). However, the possibility of using these residues in a mixture with each other does not follow clearly from the existing level of knowledge. Moreover, solvents having a different hydrocarbon base are usually prone to phase separation when mixed. Moreover, it is impossible to predict in advance about the possibility of mixing such poorly studied solvents as waste from petrochemical and coke production. Numerous studies have made it possible to identify such a “universal” source of raw materials as KOKP and ZhOU to obtain a prophylactic from the existing production waste today. These products are not only excellent solvents themselves in relation to thickening additives of various origins (option 1), but also contribute to the compatibility of known solvents with each other (option 2).

Therefore, both versions of the invention, in my opinion, meet the condition of patentability "inventive step".

The scheme for obtaining the proposed prophylactic agent is shown in the drawing and includes a tank 1 for solvent (option 1), a tank 2 for solvent (option 2), tanks 3, 4 for thickening additive, a tank for mixing the starting components 5, a commodity tank 6, raw metering pumps 7 and 8, a pump for circulation and pumping of a commodity product 9, a commodity pump 10.

A prophylactic agent is prepared as follows. The solvent from the tank 1 according to the first embodiment or from the tank 2 according to the second embodiment is pumped into the mixing tank 5 with a predetermined capacity. After pump 7 reaches the preset mode, pump 8 is started to pump the thickening additive from reservoirs 3, 4. Pumps 7 and 8 should be monitored to ensure the desired component ratio. 5-10 minutes before the end of solvent injection, pump 7 is stopped. Samples are taken from the upper, middle, and lower layers of mixing tank 5 and are analyzed by quality indicators. In the case of a heterogeneous mixture, it is circulated by pump 9. The duration of circulation should be such that pump 9 passes a twofold volume of liquid in the mixing tank 5. After circulation, re-sampling (layer by layer), after which the finished product is pumped to the commodity tank 6 , a passport is issued for it and the prophylactic is sent to the consumer.

Examples of the production of a prophylactic agent according to embodiment 1. A prophylactic agent is obtained by mixing 90% of the solvent — COCP and 10% of a thickening additive (ZD), including, wt.%:

Examples 1, 2, 3

Thickener Example 1 Example 2 Example 3 Oil synt. 10 5 10 Oil miner. twenty 10 10 The mixture worked out. oils fifty 5 twenty Oil sludge 10 thirty twenty Oil residue (viscosity 8 WU at 80 ° C) 5 twenty twenty Petroleum fuel (fuel oil) 5 thirty twenty

Example 4

Similar to example 1 (90% solvent and 10% ZD), only the thickening additive does not contain an oil component, the rest of its components are taken in the following ratio, wt.%:

oil sludge 40 oil residue thirty oil fuel thirty

Example 5

Similar to example 1 (90% solvent and 10% ZD), only as a thickening additive used a mixture of waste oils (synthetic and mineral).

Examples 6, 7

Similar to example 1, only the solvent and thickening additive included in the prophylactic are taken in the ratio, wt.%:

Trade union Example 6 Example 7 Solvent 99.5 60 Thickener 0.5 40

Example 8

Similar to example 1, only as a solvent used JOW.

Example 9

Similar to example 1, only as a solvent used a mixture of KOKP and JOU, taken in equal quantities.

Examples of the prophylactic preparation according to option 2.

Example 10

A prophylactic is obtained by mixing 90% of the solvent and 10% of a thickening additive (ZD), including, wt.%:

Solvent: Thickener: COCP twenty Oil syn. - 10 JOU 10 Oil min. - 10 KOPSP 40 Mix neg. oils - 20 COBS twenty Oil sludge - 20 Gas oil 10 Oil fuel - 20 Oil residue - 20

Example 11

Similar to example 10, only part of the prophylactic agent solvent includes, wt.%:

COCP 10 JOU twenty KOPSP 10 COBS thirty Gas oil thirty

Example 12 is similar to example 10, only the solvent does not contain gas oil, the remaining components of the solvent are in the following ratio, wt.%:

COCP 40 JOU 10 KOPSP 40 COBS 10

Examples 13, 14

Similar to example 10, only the solvent and thickening additive are taken in the ratio, wt.%:

Trade union Example 13 Example 14

Solvent 99.5 60 Thickener 0.5 40

Example 15

Similar to example 10, only the solvent does not contain COCP, the remaining components of the solvent are in the following ratio, wt.%:

JOU 60 KOPSP twenty COBS 10 Gas oil 10

Example 16

Similar to example 10, only the solvent does not contain KOKP and ZhOU, the remaining components of the solvent are in the following ratio, wt.%:

KOPSP fifty COBS 40 Gas oil 10

Example 17 (according to the prototype), where the bottom residue of the pyrolysis resin processing was used as a solvent, fuel oil in the ratio (wt.%) 90 and 10, respectively, as a thickening additive.

The quality of the product obtained in the above examples is presented in table 2.

As can be seen from the table, the quality of the prophylactic agent obtained according to the invention is not inferior to the quality of the known agent (example 17 is a prototype).

The optimal ratio of solvent to thickening additive is (wt.%) 90 and 10, respectively. A change in this ratio (see examples 6, 7 according to the 1st embodiment and examples 13, 14 according to the 2nd embodiment) leads to some deterioration in the operational characteristics ( pour point in the case of an increase in the proportion of thickening additive or flash point, in the case of an increase in the proportion of solvent). The ratio of solvent to ZD is selected based on the requirements of a particular applicant.

From the above examples it also follows that the presence of certain components practically does not affect the quality of the professional tool, either in a solvent or in a thickening additive, provided that the solvent is COCP and / or ZhOU or these products are included in the solvent mixture.

The absence of these components in the solvent (example 16) leads to delamination of the mixture, lowering its freezing temperature to -41 ° C and freezing of the processed materials.

Thus, the main advantage of the present invention is the flexibility of the prophylactic production process. Due to the use of substances such as bottoms of coke production and / or by-products of the production of butadiene, isoprene, isobutylene, ethylene, on the one hand, a raw material source satisfying the production needs was found, on the other hand, it became possible to mix a wide variety of petroleum and petrochemical products, and most importantly waste from their production and consumption. This circumstance not only expands and reduces the cost of the raw material base for the production of prophylactic agents, but also improves the environmental situation by utilizing waste from a wide variety of industries.

Annex 1

The average hydrocarbon composition of the bottom residue of coke production (COCP),% vol.

1. Alkylbenzenes 8.54 2. Alkenylbenzenes 7.88 3. Oxygen-containing aromatics: 42,44 - benzofurans - benzoethanol - aromatic esters - aromatic ketans 4. Indans, tetralins 15.42 5. Naphthalenes 2,31 6. Quinolines, isoquinolines and other N-soda. connections 3.99 7. Acenaphthenes, phenanthrenes, pyrenes 2.29 8. Dibenzoalkanes 17.13

Appendix 2

The average hydrocarbon composition of by-products of the production of butadiene, isoprene, isobutylene, ethylene (ZhOU),% vol.

1. Paraffins 0 2. Cycloparaffins 12.37 3. Indans, tetralins 13.31 4. Alkylbenzenes 62.87 5. Indenes or C _n H _2n-10 5.77 6. Naphthalene 1.30 7. Naphthalenes 2.01 8. Acenaphthenes, C _n H _2n-14 0.89 9. Acenaphtylenes, C _n H _2n-16 0.96 10. Tricyclic aromatics 0.51 11. Total aromatic 68.54 12. Total naphthenic 18.14

Appendix 3

The average hydrocarbon composition of bottoms

production of pyropolymers, pyrolysis resins, benzene, ethylbenzene and styrene (KOPSP),% vol.

1. Paraffins 3.62 2. Cycloparaffins 7.51 3. Indans, tetralins 26.61 4. Alkylbenzenes 23.52 5. Indenes or With _n H _2n-10 7.4 6. Naphthalene 15.29 7. Naphthalenes 5.42 8. Acenaphthenes, C _n H _2n-14 4.93 9. Acenaphylene, C _n H _2n-16 3.24 10. Tricyclic aromatics 2.26 11. Total aromatic 54.86 12. Total naphthenic 14.91

Appendix 4

The average hydrocarbon composition of the bottoms of the production of butanol, isobutanol, 2-ethylhexanoic acid, 2-ethylhexanol (BBS),% vol.

1. Limit and unsaturated alcohols C ₈ , 65 including 2-ethylhexanol 35 2. The sum of the mass parts of alcohols With ₄ 0.8 3. Mass fraction of butyl ether oily acid 1,5 4. Water 0.3 5. Acetals, monoglinoleic esters of C ₁₂ 32,4

Table 1
Physico-chemical characteristics of the components of the solvent prophylactic Indicator VAT residues of coke production (COCP) VAT residues for the production of pyropolymers, pyrolysis resins, benzene, ethylbenzene and styrene (KOPSP) By-products of the production of butadiene, isoprene, isobutylene, ethylene (JOU) VAT bottoms production of butanol, isobutanol, 2-ethyl-hexanoic acid, 2-ethylhexanol (COBS) Density at 20 ° C, g / cm ³ 0,990 0.986 0.892 0.86 Conditional viscosity, ° VU at 20 ° C 1.94 1.90 1.10 1.71 at 50 ° C 1.40 1.39 1,04 1.10 at 80 ° C - - - - at 100 ° C - - - - Flash point, ° С +85 +83 +81 61 Pour point, ° C -65 -65 -71 -60 The content of mechanical impurities,% wt. 0.05 0,062 out out Fractional composition: Start of boil 152 151 155 158 10% 159 157 161 178 twenty% 162 162 167 210 thirty% 169 168 170 238 40% 170 170 176 260 fifty% 180 180 179 280 60% 189 188 185 285 70% 214 212 187 294 80% 288 288 195 305 90% 335 330 224 318 96% yield 96.5 320 98% End of boil 354 350 245 324

table 2
Quality prophylactic Examples Viscosity 50 ° С ° ВУ Pour point, ° C Temperature closed crucible flash Mechanic impurities mass no, not> Water% Mass. Density 20 ° C The freezing strength of coal with a moisture content of 9%, treated with 1% of the composition at -40 ° C, kg / cm ² Example 1 1,62 -60 78 0.6 Traces 0.989 Not freezing Example 2 1.79 -54 76 0.5 Ots. 0.986 Not freezing Example 3 1.68 -56 76 0.57 Traces 0.987 Not freezing Example 4 1.81 -49 81 0.5 Ots. 0.989 Not freezing Example 5 1,6 -62 78 0.48 Traces 0.984 Not freezing Example 6 1.42 -63 75 0.6 Ots. 0,990 Not freezing Example 7 1.98 -46 81 0.5 0.08 0.978 Not freezing Example 8 1.81 -64 78 0.48 0.1 0.986 Not freezing Example 9 1.55 -55 84 0.3 Traces 0.987 Not freezing Example 10 1,59 -58 66 0,096 Traces 0.984 Not freezing Example 11 1.72 -52 78 0.008 Traces 0.980 Not freezing Example 12 1,60 -57 64 0,096 Traces 0.980 Not freezing Example 13 1.40 -65 75 0.1 Ots. 0.981 Not freezing Example 14 1.95 -45 89 0.4 0.14 0.976 Not freezing Example 15 1.65 -68 86 0.009 Traces 0.970 Not freezing Example 16 1,62 -41 78 0.3 Traces 0,900 freezes Prototype 1,60 -53 87 0.005 0.10 0,906 Not freezing

Claims (5)

1. A prophylactic against freezing, sticking and dusting of bulk materials, which is a mixture of a solvent and a thickening additive of petroleum origin, characterized in that bottoms of coke production (COCP) or by-products of butadiene, isoprene, isobutylene, and ethylene are used as a solvent ( JOU) or their mixture in the following ratio of solvent and thickening additive, wt.%: Solvent 40-99.5 Thickener 0.5-60 2. The prophylactic agent according to claim 1, characterized in that all types of mineral and synthetic oils, a mixture of used oils of all types, oil sludge, oil residues and oil fuel are used as a thickening additive, while the components of the thickening additive are used for their arbitrary combination with a friend. 3. A prophylactic against freezing, sticking and dusting of bulk materials, which is a mixture of a solvent and a thickening additive of petroleum origin, characterized in that bottoms of coke production (COCP) and / or by-products of butadiene, isoprene, isobutylene are used as a solvent, ethylene (ZhOU) in a mixture with bottoms from the production of pyrolymers, pyrolysis resins, benzene, ethylbenzene, styrene (KOPSP), as well as bottoms from the production of butanol ., Isobutanol, 2-ethylhexanoic acid, 2-ethylhexanol (MFC), in an arbitrary combination with each other at the following ratio of the solvent and thickening additive, wt%: Solvent 40-99.5 Thickener 0.5-60 4. The prophylactic agent according to claim 3, characterized in that the solvent may further comprise thermal and catalytic cracking gas oils, as well as coking gas oils. 5. The prophylactic agent according to claim 3, characterized in that all types of mineral and synthetic oils, a mixture of used oils of all types, oil sludge, oil residues and oil fuel are used as a thickening additive, while the components of the thickening additive are used when randomly combined. with a friend.