RU2331512C2 - Petroleum preservative for wood preservation treatment (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: the petroleum preservative for wood preservation is described. It is based on the products of processing of crude oil, in the first variant the preservative is the fraction which boils away within the limits of 160-360°C, obtained by rectification absorbent A-2 or A-8, or the mixtures petroleum products containing 10-70 mass% of absorbent A-2 or A-8, 10-70 mass% of the product of pyrolysis of crude oil - resins heavily pyrolised, 10-70 mass% of the fraction of aromatic hydrocarbons, 10-70 mass% of the waste diesel fuel, the second variant of preservatives contains a mixture of the fractions which are boiling away within the limits of 160-250°C and 250-360°C, obtained from residual oil, which boils away within the limits of 160-360°C from rectification of absorbent A-2 or A-8, or the above described mixture of petroleum products at a ratio of fractions 25-75:25-75 mass%.

EFFECT: compositions make it possible to expand the raw-material base and to improve the technical and economic parameters of process due to the involvement of production wastes and increases of flexibility of process of preparation of compositions.

2 cl, 6 tbl, 30 ex

Description

The invention relates to the protection of wood from biodeterioration and can be used for impregnation of wood, in particular for the impregnation of wooden sleepers and beams.

Known impregnating material is coal oil for wood impregnation (GOST 2770), obtained by coking coal based on the 1st and 2nd anthracene fraction and lighter oils - absorption, naphthalene or anthracene filtrate. Coal oil is the main protective agent among oily antiseptics. However, this impregnating material has several disadvantages. Firstly, in terms of toxicity, coal oil belongs to the second hazard class, which negatively affects the sanitary and hygienic condition of sleeper impregnation plants (SHP) and adjacent territories. Coal oil (creosote) has an unpleasant and very persistent smell. Secondly, the pour point of coal oil (minus 5-minus 2 ° C) makes it difficult to work in the winter. In addition, coal oil contains a crystalline precipitate of "raw anthracene" - a mixture of anthracene, phenanthrene, carbazole - which dissolves in hot oil only at a temperature of more than 40 ° C, which complicates the operation of filling and leads to additional energy costs for heating the product. Thirdly, coal oil contains up to 0.3% of substances insoluble in toluene and up to 1.5% water, which negatively affects the process of wood impregnation.

These shortcomings and the limited volume of production of coal oil for wood impregnation sent researchers to search for its substitutes. A replacement was proposed for a coal antiseptic - an oil antiseptic. Oil antiseptics have several advantages, low pour point, low viscosity and water content. Oil antiseptics, as a rule, are classified as low-toxic substances (fourth hazard class), which is important for the sanitary-hygienic state of ShPZ and adjacent territories. Among the shortcomings of petroleum antiseptics, a lower level of fungicidal toxicity, a low density compared with coal antiseptics, can be noted.

Currently known "Oily antiseptic for wood impregnation" (RF patent No. 2050268, CL B27K 3/50, 20.12.1995), containing the product of high-temperature processing of organic raw materials - the product of the pyrolysis of petroleum hydrocarbons with kinematic viscosity at 50 ° C 15-25 mm ² / s and additionally still residue of rectification of benzene alkylation products with kinematic viscosity at 50 ° C 1.8-4 mm ² / s in the following ratio of components, wt.%:

The product of the pyrolysis of petroleum hydrocarbons 0.1-50.0; VAT residue rectification products benzene alkylation rest

The disadvantages of the known oil antiseptic include the following. Firstly, the unstable quality of STP in flash point leads to an unstable, often lowered flash point in an antiseptic, which is unacceptable when impregnating sleepers. The temperature of the protective agent during the period of liquid pressure during the impregnation of wood should be at least 90 ° C and lower than the flash point by 5 ° C. Secondly, a relatively high pour point (up to plus 5 ° С) complicates the processes of discharge and filling, as well as storage in the winter. Thirdly, the density of the antiseptic is less and close in value to the density of water. Fourth, an antiseptic prepared according to the above recipe has a sharp specific smell.

Closest to the proposed invention in technical essence is an “Oil antiseptic for wood impregnation” (RF patent No. 2187429, CL B27K 3/50, 08/20/2002) with a low pour point, containing fractions of heavy catalytic cracking gas oil (140-500 ° C), and the remainder of light thermal cracking, boiling within 380-540 ° C, as an organic depressant. The disadvantages of the known oil antiseptic include the following. Firstly, the boiling point of heavy gas oil reaches 140 ° C, which leads to a significant decrease in the flash point of the final product. The stabilization of heavy gas oil at the boiling point significantly complicates the manufacturing technology and reduces the pour point of the antiseptic. Secondly, the mixing of the two components requires heating to a temperature of 80-90 ° C, which is associated with additional energy consumption. Thirdly, the heavy gas oil fractions of the catalytic and light thermal cracking residues are deficient, which causes a limited raw material base. Currently, with the deepening of oil refining and the introduction of new technologies for the processing of heavy residues, fractions of heavy gas oil catalytic cracking and light residues of thermal cracking are undergoing further processing according to more economical schemes. Fourthly, the technological scheme of most SHPZs is designed for impregnating agents with a density greater than the density of water. This is due to the need for rapid separation and sedimentation of the antiseptic when mixed with water that enters from wood during the treatment. After impregnation, the excess antiseptic in a mixture with water enters the sludge tank, where the impregnating agent should settle, then the antiseptic is re-impregnated. The density of the antiseptic prototype is very close to the density of water, which makes it difficult to separate the water-antiseptic mixture after an impregnation cycle in autoclaves.

Despite the fact that the antiseptic of the prototype has a low pour point (minus 10-minus 35), at temperatures close to pour point, there is a significant increase in the viscosity of the antiseptic, which complicates the process of draining and filling the antiseptic in the winter.

Accordingly, the object of the present invention is to expand the raw material base with the involvement of petrochemical production wastes and further reduce the pour point of the antiseptic.

Another objective of the present invention is the creation of an impregnating composition of petroleum raw materials with a density greater than the density of water sufficient to confidently separate the mixture of antiseptic-water.

The tasks are solved in that a fraction boiling in the range of 160-360 ° C obtained by rectification of absorbent A-2 or A-8 or a mixture containing absorbent A-2 or A- is used as an antiseptic for wood impregnation based on petroleum products. 8, the product of the pyrolysis of crude oil is a heavy pyrolysis resin (SPT), a fraction of aromatic hydrocarbons (FAA), spent diesel fuel in the following ratio of components of a mixture of oil products, wt.%:

absorbent A-2 or A-8 10-70 the specified product of the pyrolysis of crude oil 10-70 aromatic hydrocarbon fraction 10-70 spent diesel fuel 10-70

Absorbent grades A-2 and A-8 is a by-product in the production of monomers for synthetic rubber (butadiene, isoprene). Absorbent grade A-8 is obtained during the production of isoprene by two-stage dehydrogenation of isopentane. A-2 subscriber is obtained in the process of retification of by-products of butadiene and isoprene production. Currently, this product is manufactured according to various regulatory documents, for example, absorbent grade A-2 TU 2411-010-4815319-2001, or TU 38.103349-85, absorbent grade A-8 TU 38.103349-85. The characteristics of these brands of absorbent are presented in table 1.

Pyrolysis products of crude oil are understood as by-products derived from the pyrolysis of gasoline (straight-run gasoline or hydrocracked gasoline, vacuum distillate of direct distillation of oil), gas (ethane or a mixture of ethane and propane) or a mixture of gasoline and gas raw materials. By-products of pyrolysis (liquid pyrolysis products) are formed in an amount of 2-8% (during gas pyrolysis), 20-25% (during gasoline pyrolysis) and 35-40% (during direct oil distillation vacuum distillate pyrolysis). Their release is carried out by enterprises under various commodity names and according to various regulatory documents, for example, heavy pyrolysis resin (SPT) TU 2451-168-00151727-00, TU 38.1021256-89, TU 38.1021257-89, liquid pyrolysis products (ZhPP) TU 38.402-62 -144-93 amendment 1.2, liquid pyrolysis products (FAC) brand E-13 TU 38.402-62-130-92 with amendment 1-3, fraction of the liquid pyrolysis products (FSPP) TU 38.402-62-144-93 amendment 1, GOST 38-402-62-144-93 amendment 1, 2. Preferred for the preparation of an antiseptic is to use heavy pyrolysis resin (SPT) as the product of oil raw material pyrolysis. Heavy pyrolysis resin (SPT) is obtained in ethylene production as a by-product in the pyrolysis of gasoline or a mixture of gasoline and gas feedstocks; it consists of a mixture of aromatic hydrocarbons C ₈ and higher, including naphthalene, methylnaphthalenes (Akhmetov SA, Oil and Gas Deep Processing Technology. Gilem Publishing House, Ufa, 2002).

The characteristics of the specified pyrolysis product of petroleum feed (heavy pyrolysis resin) are presented in table 2.

Also, to obtain an antiseptic, fractions of aromatic hydrocarbons (FAU) TU 2414-00348082088-2001 of ZAO Kauchuk in Vsevolzhsk and spent diesel fuel (ODT) of TU 6-00-0203335-41-89 of Kazanorgsintez OJSC are used.

The FAA aromatic hydrocarbon fraction is understood to mean a by-product resulting from isobutane dehydrogenation. The characteristics of the specified product are presented in table 3.

Spent diesel fuel is understood to mean a product formed when using diesel fuel as a cooling and flushing agent of pyrogas in the production of ethylene. The characteristics of the specified product are presented in table 4.

The simplification of the task of obtaining an antiseptic with specified parameters by the value of viscosity and density can be achieved if the previously obtained fraction 160-360 ° C is divided by distillation into lighter and heavier, and then mix them in the required proportion.

Thus, another option to achieve the objectives is to use a mixture of fractions boiling in the range 160-250 ° С and 250-360 ° С obtained from the bottom residue boiling in the range 160 for oil impregnation of wood based on petroleum products -360 ° C from rectification of the absorbent A-2 or A-8, or a mixture of petroleum products containing absorbent A-2 or A-8, the product of the pyrolysis of crude oil - heavy pyrolysis resin (SPT), aromatic hydrocarbon fraction (FAA), spent diesel fuel pr the above component ratio, wherein said fraction is used in the following ratio, wt.%:

fraction boiling in the range of 160-250 ° C 25-75 fraction boiling in the range of 250-360 ° C 25-75

Changing the proportions of mixing light and heavy fractions allows you to get an antiseptic exactly according to the specified parameters of viscosity and density, depending on changes in the quality of raw materials and the requirements of sleeper-dressing plants.

The procedure for obtaining the proposed composition for option 1 is as follows. An Engler flask (125 ml) is placed with an absorbent of the A-2 or A-8 grade (table 5, examples 1-2) or a mixture of the components of the invention in various combinations (examples 3-20). Rectification is carried out in an apparatus for distillation of oil products at atmospheric pressure according to the generally accepted method GOST 2177. The device consists of a casing located on a tripod with the Angler bulb mounted in the upper part and in the lower part of a gas or electric heater. A fridge is attached to the Angler flask, into which cooling water is supplied. The flow rate of water is regulated so that its temperature at the drain is not higher than + 30 ° C. A mercury thermometer is inserted into the neck of the flask with raw components. A measuring cylinder is installed under the lower end of the refrigerator tube to receive the distilled product. After assembling the apparatus, the flask is heated evenly so that 5-10 minutes elapse before the first drop of distillate falls. Distillation is carried out at a uniform speed of 4-5 ml per minute. Heating is carried out to a temperature of 160 ° C, after which the heating is stopped and the distillate is allowed to drain for 5 minutes. After rectification, the distillation bottoms (fraction 160-360 ° C), which is in the Angler flask, are cooled to room temperature and subjected to tests. The distillate obtained by distillation (fraction 25-160 ° C) is not used in the preparation of the composition according to the invention. The fraction of 25-160 ° C can be used as a component of motor gasoline or undergo further processing in order to extract benzene, toluene and xylenes.

The procedure for obtaining the proposed composition for option 2 is as follows. The Angler flask (125 ml) was placed fraction 160-360 ° C, obtained according to example No. 19-20. The distillation is carried out in an apparatus for distillation of petroleum products according to the generally accepted method GOST 2177. After assembling the apparatus described in the preparation of the composition according to option 1, the flask is evenly heated so that 10-15 minutes pass before the first drop of distillate falls. Distillation is carried out at a uniform speed of 4-5 ml per minute. Heating is carried out to a temperature of 250 ° C, after which the heating is stopped and the distillate is allowed to drain for 5 minutes. After rectification, the distillate (fraction 160-250 ° C) and the still bottom distillation (fraction 250-360 ° C), which is in the Angler flask, are cooled to room temperature. The obtained fractions 160-250 ° C (30 wt.%) And 250-360 ° C (70 wt.%) Are cooled and mixed in a flask of 150 ml in the ratios shown in table 5, examples 21-30.

The study of the properties of the obtained antiseptic samples was carried out in accordance with known methods: kinematic viscosity at 80 ° C according to GOST 33; pour point according to GOST 20287; flash point determined in an open crucible according to GOST 4333; water content according to GOST 2477; density at 20 ° С according to GOST 3900.

Data on the properties of known and proposed compositions are presented in table 6.

The table shows that regardless of whether they were used separately raw materials (examples 1, 2) or in a mixture (examples 3-20, 21-24, 27-29), the antiseptic meets the requirements of GOST 20022.5-93 “Protection of wood. Autoclave impregnation with oily protective agents ”and in some cases exceeds the prototype in pour point (examples 1-4, 7-8, 11-16, 19-22, 26-28). The interchangeability of the components for the preparation of compositions positively affects the flexibility of the process of their preparation, based on the presence (or absence) of a product.

From tables 5 and 6 it follows that individually the obtained fractions 160-250 ° C and 250-360 ° C do not meet all the requirements of GOST 20022.5-93 and therefore cannot be used as an antiseptic on their own (examples 21, 25, 26, 30 ) When 25% of the heavy residue is already added to the light fraction, an antiseptic of satisfactory quality is obtained (examples 22, 27). An increase in the content of the heavy residue of more than 75% is undesirable due to a significant increase in the viscosity of the antiseptic (examples 24, 29).

From table 6 it is seen that the density of the antiseptic according to the invention in all cases is higher than the density of water and in its value exceeds the prototype. The exceptions are examples 21, 26, where a fraction of 160-250 ° C is considered, cannot be used as an antiseptic on its own.

Thus, the proposed compositions successfully solve the problem of increasing the density of the antiseptic while expanding the raw material base and improving the technical and economic performance of the process by involving production wastes and increasing the flexibility of the preparation process.

Table 1 Physico-chemical characteristics of the absorbent brand A-2 and A-8 Name of indicator A-2 A-8 1. Fractional composition: boiling point, ° С, not lower 65 25 end boiling point, ° С, not higher 370 380 the amount of fraction boiling up to a temperature of 185 ° C, vol.%, not lower - 65 the amount of fraction boiling up to a temperature of 300 ° C, vol.%, not lower 45 - 2. Mass fraction of actual resins at 30-day storage, mg / 100 cm ³ 8000 15,000 4. Flash point in a closed crucible, ° С, not lower 92 minus 55 5. Mass fraction of total sulfur,%, no more 1,0 - 6. Copper plate test withstands withstands 8. The content of free water, wt.% out out 11. Appearance dark liquid without solids brown to black liquid 12. Density at 15 ° C, g / cm ³ 0.800-0.950 0.700-0.950

table 2 Physico-chemical characteristics of the pyrolysis product of petroleum feed Name of indicator Heavy Pyrolysis Resin (SPT) 1. Fractional composition: boiling point, ° С 155 temperature 3% distillation, ° С 170 2. Kinematic viscosity at 50 ° C, mm ² / s thirty 3. Kinematic viscosity at 80 ° C, mm ² / s 5 4. Flash point in an open crucible, ° С 106 5. The flash point in a closed crucible, ° C 74 6. Mass fraction of mechanical impurities, wt.% 0.01 7. Mass fraction of water, wt.% 0.5 8. Density at 20 ° C, g / cm ³ 1,064 9. Mass fraction of sodium ions,% 0.01 10. Mass fraction of potassium ions,% 0.001 11. Coking ability,% 16

Table 3 Physico-chemical characteristics of the fraction of aromatic hydrocarbons (FAA) Name of indicator Aromatic Hydrocarbon Fraction (FAA) 1. Appearance Yellow to brown fluid with no mechanical impurities 2. Density at 20 ° C, within 0.8-0.9 3. Mass fraction of actual resins, mg / 100 cm ³ , not more than 4.0 4. Fractional composition: boiling point, ° С fifty temperature 90% distillation, ° С 175 5. The xylene content, wt.% 68-72 6. The content of benzene, wt.% 6 7. The content of toluene, wt.% 10-14

Table 4 Physico-chemical characteristics of spent diesel fuel (ODT) Name of indicator Spent Diesel Fuel (ODT) 1. Density at (20 ± 1) "C, g / cm ³ , not more than 0.9 2. Flash point, determined in a closed crucible, ° С, not lower thirty 3. Mass fraction of water,%, no more 1,0 4. Mass fraction of mechanical impurities,%, no more 1,0 5. Kinematic viscosity at (50.0 ± 0.1) ° С, mm ² / s (cSt), not more than 12 6. Ash content,%, no more 0.2 7. Mass fraction of sulfur,%, no more 0.5

Table 5 Data on the content of ingredients in the studied formulations Example No. The content of raw materials to obtain a fraction of 160-360 ° C in the mixture before distillation, wt.% (Option 1) The ratio of fractions obtained by distillation of the still bottom 160-360 ° C, wt.% (Option 2) absorbent Tsp FAA ODT 160-250 ° C 250-360 ° C A-2 A-8 one one hundred - - - - - 2 - one hundred - - - - - 3 70 - 10 10 10 - - four - 70 10 10 10 - - 5 10 - 70 10 10 - - 6 - 10 70 10 10 - - 7 10 - 10 70 10 - - 8 - 10 10 70 10 - - 9 10 - 10 10 70 - - 10 - 10 10 10 70 - - eleven 49 - 17 17 17 - - 12 - 49 17 17 17 - 13 17 - 49 17 17 - - fourteen - 17 49 17 17 - - fifteen 17 - 17 49 17 - - 16 - 17 17 49 17 - - 17 17 - 17 17 49 - - eighteen - 17 17 17 49 - - 19 25 - 25 25 25 - - twenty 25 25 25 25 - - 21 - - - - - one hundred - 22 - - - - - 75 25 23 - - - - - fifty fifty 24 - - - - - 25 75 25 - - - - - - one hundred 26 one hundred - 27 75 25 28 fifty fifty 29th 25 75 thirty - one hundred

Table 6 Data on the properties of known and proposed compounds Example No. (according to Table 6) Name of indicator Kinematic viscosity at 80 ° С, mm ² / s, according to GOST 33 Pour point, ° C, according to GOST 20287 Flash point, determined in an open crucible, ° С, according to GOST 4333 Water content,%, according to GOST 2477 Density at 20 ° С, g / cm ³ , GOST 3900 According to GOST 2770 with rev. 1-4 "Coal oil for wood impregnation" - - 110 No more than 1,5 No more than 1,13 According to GOST 20022.5-93 “Protection of wood. Autoclave impregnation with oily protective agents. " No more than 5 - Not less than plus 95 No more than 5 - According to the prototype 3.81-4.04 minus 10-35 120-152 0.1-0.5 0.998-1.001 one 4.95 Minus 50 97 0.3 1,120 2 4,52 Minus 52 95 0.12 1.05 3 4.75 Minus 49 106 0.25 1,081 four 4.70 Minus 52 104 0.21 1,070 5 4.40 Minus 31 135 0.09 1,035 6 4.31 Minus 35 132 0.09 1,031 7 3,5 Minus 59 102 0,07 1.017 8 3.4 Minus 60 one hundred 0.08 1.015 9 4,5 Minus 17 118 0.3 1,041 10 4.3 Minus 19 114 0.27 1,037 eleven 4.3 Minus 45 108 0.14 1,072 12 4.0 Minus 47 105 0.11 1,050 13 4.3 Minus 43 119 0.1 1,028 fourteen 4.2 Minus 45 115 0.09 1,024 fifteen 3.8 Minus 49 105 0.09 1,020 16 3,7 Minus 51 103 0,07 1.015 17 4,5 Minus 15 112 0.21 1,033 eighteen 4.3 Minus 17 110 0.19 1,030 19 4.2 Minus 37 110 0.1 1,045 twenty 4.1 Minus 40 106 0.09 1,040

Table 6 (continued) Data on the properties of known and proposed compounds Example No. (according to Table 6) Name of indicator Kinematic viscosity at 80 ° С, mm ² / s, according to GOST 33 Pour point, ° C, according to GOST 20287 Flash point, determined in an open crucible, ° С, according to GOST 4333 Water content,%, according to GOST 2477 Density at 20 ° С, g / cm ³ , GOST 3900 According to GOST 2770 with rev. 1-4 "Coal oil for wood impregnation" - - 110 No more than 1,5 No more than 1,13 According to GOST 20022.5-93 “Protection of wood. Autoclave impregnation with oily protective agents. " No more than 5 - Not less than plus 95 No more than 5 - According to the prototype 3.81-4.04 Minus 10-35 120-152 0.1-0.5 0.998-1.001 21 1,1 Minus 50 75 0.05 1.001 22 2,5 Minus 45 96 0,07 1.015 23 4.3 Minus 35 107 0.1 1,036 24 5.2 Minus 17 126 0.12 1,047 25 19 Minus 5 140 0.1 1,112 26 1,0 Minus 52 70 0.06 1,000 27 2,4 Minus 43 95 0.08 1.010 28 4.1 Minus 37 105 0.1 1,030 29th 5.1 Minus 20 120 0.11 1,042 thirty 17 Minus 7 135 0.1 1,062

Claims (2)

1. Petroleum antiseptic for wood impregnation based on petroleum refined products, characterized in that it is a fraction boiling in the range 160-360 ° C, obtained by rectification of the absorbent A-2 or A-8 or a mixture of oil products containing absorbent A-2 or A-8, the product of the pyrolysis of petroleum feeds is a heavy pyrolysis resin, a fraction of aromatic hydrocarbons, spent diesel fuel in the following ratio of components of a mixture of petroleum products, wt.%: absorbent A-2 or A-8 10-70 the specified product of the pyrolysis of crude oil 10-70 aromatic hydrocarbon fraction 10-70 spent diesel fuel 10-70 2. Petroleum antiseptic for wood impregnation based on products of petroleum feed processing, characterized in that it contains a mixture of fractions boiling in the range of 160-250 ° C and 250-360 ° C, obtained from the bottom residue boiling in the range of 160-360 ° C from rectification of absorbent A-2 or A-8, or a mixture of oil products containing absorbent A-2 or A-8 10-70 wt.%, heavy pyrolysis resin 10-70 wt.%, fraction of aromatic hydrocarbons 10-70 wt.% , spent diesel fuel 10-70 wt.% in the following ratio, wt.%: fraction boiling in the range of 160-250 ° C 25-75 fraction boiling in the range of 250-360 ° C 25-75