RU2233856C1 - Pond sludge-base binding agent and method for its preparing - Google Patents

Abstract

FIELD: road building, petroleum processing industry.

SUBSTANCE: pond sludge-base binding agent comprises preliminary dehydrated pond sludge, neutralizing agent and plasticizer comprising grease tar as a waste in glycerol manufacture. Powdered dolomite is used as a neutralizing agent in composition of a binding agent, and pond sludge - a waste of furnace mazut from central heating and power plants and asphalt obtained after desasphaltization - non-conditioned product in producing residual oils from petroleum processing plants. In the process for preparing a binding agent the pond sludge is dehydrated preliminary to residual water content 1-3 wt.-% and mixed its at t = 70-90 C with part of asphalt obtained after desasphaltization taken in the amount 50% of the measured amount. Then to the prepared mixture the suspension of grease tar and powdered dolomite prepared preliminary at t = 60-70 C is added at constant stirring and then the prepared composite is brought about to t = 100 C followed by addition of residue asphalt obtained after desasphaltization and pond mazut, and mixture is homogenized at t = 120-130 C. The composition is prepared in the measured amount of components remained.

EFFECT: improved preparing method, enhanced quality of binding agent.

4 cl, 4 tbl, 6 ex

Description

The invention relates to binders based on pond acid tar and a method for its production and can be used in road construction, as well as in the oil refining industry.

Known astringent and method for its preparation [A. St. USSR No. 1281582, cl. C 10 C 3/02, declared 08.23.85, op. 01/07/87], using pond acid tars. The binder contains acid pond tar, a neutralizer - was not available from the lime extinguishing stage, and a plasticizer is a mixture of bottoms from the butyl acrylate rectification stage in the production of butyl acrylate and fat tar - a waste product from glycerol production. A known method aimed at protecting the environment and allowing to simplify the technology of obtaining a binder from production waste, is that in the pond acid tar at a temperature of 60-90 ° C and continuous mixing add 25 ÷ 30 wt.h. I didn’t get from the stage of quenching lime in the production of hydroquinone per 100 parts acid tar and 15-50 parts by weight plasticizer - a mixture of bottoms from the stage of rectification of butyl acrylate in the production of butyl acrylate and fat tar - waste glycerol production per 100 parts by weight neutralized acid tar when their mass ratio in the mixture is 1: 0.6-4, respectively. A binder, completely created by this method from waste, is suitable for obtaining asphalt concrete compositions that meet the requirements of GOST.

A disadvantage of the known binder and the method of its production is the use of lime as a neutralizing agent from the stage of extinguishing, which necessitates its preliminary long-term preparation: drying, crushing, sieving, in addition, it lacks a constant chemical composition.

The presence of a significant amount of water in pond acid tars also leads to an increase in the time to obtain the finished final product.

Known astringent and method for its preparation [A. St. USSR No. 1518353, class C 10 C 3/02, C 10 G 17/10, claimed 11.23.87, op. 30.10.89], using tars previously dehydrated to a residual water content of 1-3 wt.%.

An astringent for road construction includes pre-dehydrated acid tar, a neutralizer - not enough - a waste from the quenching stage of the hydroquinone production, and a plasticizer - a mixture of bottoms from the butyl acrylate rectification stage (butyl acrylate production) and fat tar - a waste from glycerol production.

A method for producing such a binder involves neutralizing pond acid tar with nedopal - leaving the quenching stage of hydroquinone production, mixing with a plasticizer - bottoms of the butyl acrylate distillation stage and with fat tar - manufacturing waste and homogenizing the resulting mixture. The method is characterized in that Nedopal is pre-mixed with fatty tar, then acidic tar is added to the resulting suspension, previously dehydrated to a residual water content of 1 ÷ 3 wt.%, Bottoms are added to the resulting mixture, and then the mixture is homogenized. The process is carried out at a temperature of 60-90 ° C. The known method of producing a binder can reduce the time to obtain the final product compared to the method described above by 5 times while maintaining the quality of the binder at the same level.

However, the known binder has a low water resistance and increased water saturation. A method of obtaining such a binder does not preclude a preliminary operation of preparing a neutralizing agent, the variability of the chemical composition of which is not excluded.

The objective of the invention is to improve the quality of the binder material, providing increased water resistance of the road surface, as well as simplifying and reducing the cost of the production of a binder based on pond acid tar.

The problem is solved by a binder based on pond acid tar containing pre-dehydrated pond acid tar, a neutralizing agent and a plasticizer, including grease tar - a waste product of glycerin, in which according to the invention dolomite flour is used as a neutralizing agent, and pond fuel oil is additionally introduced as a plasticizer - waste fuel oil from the TPP and asphalt deasphalting - substandard product of the production of residual oils from refineries, taken in mas ovom ratio of 1: 4, with the following component ratio, wt.%:

Pond acid tar 58-79

Dolomite flour 1-2,2

Fat Tar 1-4

Asphalt Deasphalting 13-31.0

Pond fuel oil 3-7.8

The neutralizing agent - dolomite flour - a fine-grained white-gray powder, is a mixture of components and has the following chemical composition, wt.%:

CaCO ₃ 43-51

MgCO ₃ 53-45

Waste rock the rest

A method for producing a binder based on pond acid tar, comprising neutralizing a pre-dehydrated pond acid tar at an elevated temperature and stirring with a neutralizing agent in the presence of a plasticizer containing fatty tar - a waste product from glycerol, and homogenizing the resulting mixture.

Pond acid tar is pre-dehydrated to a residual water content of 1-3 wt.%, Mixed at a temperature of 70-90 ° C with a portion of deasphalting asphalt taken in an amount of 40-50% of the calculated amount, then pre-added to the resulting mixture with constant stirring a suspension of fatty tar and dolomite flour prepared at a temperature of 60-70 ° C, after which the resulting composition is brought to a temperature of 90-100 ° C and the residue of deasphalting asphalt is introduced into it in an amount of 60-50% of the total amount and ponds are added oh oil, and then the mixture is homogenized at a temperature of 120-130 ° C. The second part of the asphalt deasphalting (60-50% of the total) and pond fuel oil (estimated amount) can be introduced simultaneously in the form of a mixture heated to a temperature of 70-90 ° C.

Tar oil, used as one of the components of the plasticizer, is a waste from the distillation stage of the production of glycerol in oil and fat plants, is a paste in black. The composition of fatty tar contains components, wt.%: Polyglycerol (calcium soap) up to 75; alum calcium soap of fatty substances 10; insoluble substances 2; calcium compounds 7; moisture 4.

The deasphalting asphalt, used in the amount of the second component of the plasticizer, is a substandard product of the production of residual oil oils from refineries, is a viscous, hard-moving mass of black. The composition of deasphalting asphalts includes components, wt.%: Paraffin-naphthenic hydrocarbons - 8.33-16.50; aromatic, including: light - 7.05-10.00; medium - 8.55-11.50; heavy - 30.2-36.0; resins 32.32-40.50; asphaltenes - 13.55-20.00; sulfur content - in excess of 100% of the organic component - 2.4-3.7.

Pond fuel oil, used as the third component of the plasticizer, is a waste of heating oil from the CHPP, it is a hard-moving paste-like mass of black color, including up to 89% of the organic mass; water-soluble compounds of not more than 3% and mechanical impurities - the rest, namely, wt.%: paraffin-naphthenic hydrocarbons - 47-50; monocyclic and bicyclic substances: aromatic - 10-20; resins - 5-7; asphaltenes - 3-5; mechanical impurities - the rest.

The composition and physico-chemical characteristics of the acid tar, as well as the neutralizing agent and plasticizer are given in table 1.

The introduction of dolomite flour (DM) is necessary to neutralize sulfuric acid H ₂ SO ₄ , which is in an unbound state in pond acid tar (PCG). The introduction of fat tar (LH) is due to two tasks: obtaining a stable suspension of LH-DM, which is necessary to complete the neutralization reaction and to ensure a homogeneous, non-laminating system PKG-DM-LH, where there is no sedimentation of DM particles and mechanical impurities from PCH, and the neutralization process evenly throughout.

The introduction of pond fuel oil (PM) waste and deasphalting asphalt (BP) is due to the following reasons: the introduction of part of the BP in the first stage and mixing it with PCG allows you to get a system that can withstand heating to a temperature of> 100 ° C, and exclude the processes of coke formation of PCG (> 100 ° With the initial PCG, slowly irreversibly cokes); subsequent introduction of the remaining part of blood pressure and PM is necessary to give the system water-repellent properties and provide the binder with the necessary physical and mechanical parameters.

Description of the method for preparing binder compositions based on pond acid tar.

In the mixer, which is an enameled reactor (or a reactor made of stainless steel) with a heating jacket, equipped with an anchor stirrer (40-60 rpm), PCG and part of HELL (40-50%) are introduced, the temperature of the mixture is 70-90 ° С and then add a suspension of LH and DM prepared at 60-70 ° C (the amount of DM is determined from the calculation of the content of H ₂ SO ₄ in the initial PCG). The temperature of the synthesis of binder is gradually increased to 90-100 ° C. Upon completion of neutralization, controlled by rapid acid analysis, the remainder of blood pressure (60-50% of the total amount) and PM are introduced into the reactor. The total ratio of blood pressure: PM in the final composition 4: 1. The content of blood pressure and PM varies based on the composition and amount of neutralized PCG. The mixture is homogenized at a temperature of 120-130 ° C.

Example 1

The composition prepared according to the described scheme contains:

PKG - 1000 g (pond acid tar) (H ₂ O content - 3 wt.%; H ₂ SO ₂ content - 1.3 wt.%);

- DM - 12.27 g (dolomite flour);

- ZhG - 50.6 g (tar);

- HELL - 162.0 g (deasphalting asphalt);

- PM - 40.5 g (pond fuel oil).

Obtained by the above method, the composition contains the material balance is shown in table 2.

Example 2-6 Methods of obtaining analogously to example 1. The experimental results are shown in table 3.

The property of the binder material from PCG and the test results of the finished compositions are shown in table 4.

The amount of neutralizing agent - DM is determined by the content of H ₂ SO ₄ in PCG. The lower and upper boundaries of the DM additive are due to the min and max contents of H ₂ SO ₄ in PCG samples. In the case of incomplete neutralization of H ₂ SO _{4, the} latter has a negative effect on the properties of the binder PCG and the asphalt composition based on it: it increases sensitivity to temperature changes, moisture. Excess DM is also undesirable, because together with mechanical impurities, PCG will have a negative effect on the viscosity and other rheological properties of the binder PCG.

Introduction as a plasticizer GH provides: obtaining a stable suspension - DM-GH; obtaining a homogeneous system PKG-DM-ZhG with the aim of a quick and uniform course of the neutralization reaction of H ₂ SO ₄ in volume.

The introduction of GH less than 1% does not provide the above effects. The introduction of GH more than 4% is irrational, because does not lead to dramatically better results.

The boundaries of the use of AD and PM are determined by obtaining the optimal values of the physicomechanical properties of the binder (softening temperature, extensibility, water resistance).

The joint use of blood pressure and PM is due to the fact that the properties of blood pressure and the properties of PM are mutually complementary. Adding only AD leads to a decrease in the softening temperature of the binder, an increase in extensibility, and a sharp decrease in the viscosity of the binder. The introduction of only PM leads to the opposite result. The joint introduction of AD and PM increases the water resistance of the binder and asphalt concrete composition when using the binder as a bitumen substitute.

The amount of the remaining H ₂ O in PCG (1-3 wt.% By weight of PCG) is determined by the following: when the content of H ₂ O in PCG is less than 1 wt.%, The flowing properties of PCG sharply decrease, which makes it difficult to pump it from the receiving, preparatory tank with selected temperatures; when the content of H ₂ About more than 3 wt.% increases the time of evaporation of water in the reactor. In this case, an additional amount of vaporous water is released, which, with the simultaneous release of carbon dioxide (neutralization process), leads to additional foaming and, as a result, requires more intensive mixing (this is not provided for in standard industrial reactors of this class) and the introduction of antifoam agents of the ПМС-200 type.

From the data given in table 4, it can be seen that the number of compounding and plasticizing components (LF, HELL, PM) allows you to get a cementitious material for road construction and use it as a bitumen substitute in the preparation of asphalt mixes. The latter in their parameters comply with the standards in accordance with GOST 9128-84 “Mixtures of asphalt road, airfield and asphalt concrete”.

Thus, the proposed binder allows you to increase the water resistance of asphalt mixtures, as well as to exclude from the known composition of a similar mixture a toxic and flammable component - still bottoms from the stage of rectification of butyl acrylate.

The above method of producing a binder allows to reduce the time of production of the finished product by reducing preparatory operations, to reduce the cost of the binder due to the use of cheap production waste in the composition.

Sources of information

1. A.S. USSR No. 1281582, cl. C 10 C 3/02, declared 08.23.85, op. 01/07/87, “Binder and a method for producing a binder” (analogue).

2. A.S. USSR No. 1518353, class C 10 C 3/02; With 10 G 17/10, decl. 11/23/87; op. 10.30.89, “A binder and a method for producing a binder (prototype).

Claims (4)

1. A binder based on pond acid tar containing pre-dehydrated pond acid tar, a neutralizing agent and a plasticizer, including grease tar - a waste product of glycerin, characterized in that it contains dolomite flour as a neutralizing agent, and additionally used as a plasticizer in it pond fuel oil - waste fuel oil from the TPP and asphalt deasphalting - substandard product of the production of residual oils from refineries, taken in mass quantities solution 1: 4, with the following ratio of components wt.%: Pond acid tar 58 ÷ 79 Dolomite flour 1 ÷ 2.2 Fat tar 1 ÷ 4 Asphalt deasphalting 13 ÷ 31,0 Pond fuel oil 3 ÷ 7.8 2. The binder according to claim 1, characterized in that the neutralizing agent is dolomite flour has the following chemical composition, wt.%: CaCO ₃ 43 ÷ 51 MgCO ₃ 53 ÷ 45 Waste rock the rest 3. A method of producing a binder based on pond acid tar, comprising neutralizing a pre-dehydrated pond acid tar at an elevated temperature and mixing with a neutralizing agent in the presence of a plasticizer containing fatty tar - glycerol production waste, and homogenizing the resulting mixture, characterized in that it is dehydrated to a residual content water 1-3 wt.% pond acid tar, mix it at a temperature of 70-90 ° C with a portion of deasphalting asphalt taken in an amount of 40-50% of the calculation amount, then, with constant stirring, add a suspension of fat tar and dolomite flour previously prepared at a temperature of 60-70 ° C, after which the resulting composition is brought to a temperature of 90-100 ° C and the remainder of deasphalting asphalt in an amount of 60- 50% of the total amount and add pond fuel oil, and then the mixture is homogenized at a temperature of 120-130 ° C and get an astringent of the following composition, wt.%: Pond acid tar 58-79 Dolomite flour 1-2,2 Fat Tar 1-4 Asphalt Deasphalting 13-31.0 Pond fuel oil 3-7.8 4. The method of producing a binder according to claim 3, characterized in that 1-3 wt.% Pond acid tar is dehydrated to a residual water content, mixed at a temperature of 70-90 ° C with a portion of deasphalting asphalt taken in an amount of 40-50% from the calculated amount, then the suspension of fatty tar and dolomite flour previously prepared at a temperature of 60-70 ° C is added to the resulting mixture with constant stirring, after which the resulting composition is brought to a temperature of 90-100 ° C and the residue of deasphalting asphalt is introduced into it in an amount of 60 -fifty% of the total amount and add pond fuel oil, and then the mixture is homogenized at a temperature of 120-130 ° C and get an astringent of the following composition, wt.%: Pond acid tar 58-79 Dolomite flour 1-2,2 Fat Tar 1-4 Asphalt Deasphalting 13-31.0 Pond fuel oil 3-7.8

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