WO2016163911A1

WO2016163911A1 - Method of detoxifying organic waste and sour crude oil

Info

Publication number: WO2016163911A1
Application number: PCT/RU2015/000236
Authority: WO
Inventors: Александр Дмитриевич СИМОНОВ; Николай Алексеевич ЯЗЫКОВ; Юрий Владимирович ДУБИНИН; Сергей Иванович РЕШЕТНИКОВ; Вадим Анатольевич ЯКОВЛЕВ; Валентин Николаевич ПАРМОН
Original assignee: Общество с ограниченной ответственностью "Уникат"
Priority date: 2015-04-10
Filing date: 2015-04-10
Publication date: 2016-10-13
Also published as: RU2015113065A

Abstract

The invention relates to methods of detoxifying liquid organic waste and sour crude oil in a fluidized catalyst bed, and can be used in the chemical, petrochemical, wood chemical and nuclear industries and the thermal power industry. A method of incinerating organic waste and sour crude oil is carried out by oxidation with atmospheric oxygen at a temperature of 700-750°С in the lower part of an organized non-isothermal fluidized bed of a mixture of particles of a catalyst of the deep oxidation of organic substances and particles of an inert material, with a heat exchanger submerged in the bed and a ratio of air to oxidizable organic substances of α = 1.0-1.05 in the lower part of the bed and α = 1.05-1.2 in the upper part of the bed as a result of the introduction of air and the entrapment of acid gases by an alkaline adsorbent in the fluidized bed, wherein the temperature in the upper part of the fluidized bed is maintained at 400-600°С by varying the flow of air. The technical result is a reduction in the consumption of alkaline adsorbent, the absence of secondary pollutants, and a low degree of catalyst attrition.

Description

The method of disposal of organic waste

and sulphurous oil.

The invention relates to methods for neutralizing the flameless combustion of liquid organic waste and sulphurous oil in a fluidized bed of catalyst and can be used in the chemical, petrochemical, wood chemical, nuclear industry and thermal power industry.

A known method of neutralizing organic waste by oxidizing with oxygen in the fluidized bed apparatus, followed by trapping acid gases with an alkaline adsorbent (RU 2209646, A62D3 / 00, B01J8 / 18, 03/29/2003). Organic waste containing extraction mixtures is preliminarily separated into an extractant and a diluent by the introduction of an easily pyrolyzable propellant. The diluent is oxidized in the lower part of the two-zone reactor in a fluidized bed of catalyst at a temperature of 700-750 ° C, and the oxidation of a mixture of extractant and displacer, as well as the capture of acid gases by an alkaline adsorbent, is carried out in the upper part of a two-zone reactor in a fluidized bed of an inert material at a temperature of 700-750 ° FROM; oxidation of the diluent in the fluidized bed of the catalyst and the oxidation of the mixture of extractant and propellant in the fluidized bed of an inert material are carried out alternately. The exhaust gases are further purified from traces of carbon monoxide and hydrocarbons on a honeycomb catalyst at a temperature of 450-500 ° C. The disadvantages of this method are the need for additional purification of flue gases from carbon monoxide in a separate apparatus on a honeycomb catalyst, poisoning and increased wear of the catalyst, a complex system for preliminary separation of organic waste and alternate introduction of easily oxidized and difficultly oxidized components of the waste into separately boiling layers of inert material and catalyst. The closest in technical essence and the achieved result is a method of neutralizing organic waste and sulphurous oil by burning in a fluidized bed (RU 2527238, A62D3 / 38, B01J8 / 18, F23C10 / 01, 05.24.2013) by oxygenation of air in a fluidized bed apparatus with immersed into the layer with a heat exchanger followed by trapping of acid gases with an alkaline adsorbent at a temperature of 700-750 ° C in an organized fluidized bed of a mixture of a catalyst for deep oxidation of substances and inert material in a ratio of 10-20 wt.% and 90-80 wt.% and the ratio of air to oxide schimsya organic components in the bottom layer and 0,95- = 1.05, and the top of a = 1.05-1.2 by introducing additional air. The disadvantage of this method is the high consumption of alkaline adsorbent for the absorption of acid gases.

The invention solves the problem of simplifying the technology of disposal of organic waste, including sulfur oil, The technical result is a reduction in the consumption of alkaline adsorbent, maintaining a low degree of wear of the catalyst, the absence of secondary pollutants.

The problem is solved by the method of burning organic waste and sulfur dioxide by oxidizing with oxygen in air in an organized non-isothermal fluidized bed of a mixture of particles of a catalyst for deep oxidation of organic substances and particles of an inert material in a ratio of 10-20 wt.% And 90-80 wt.% With a heat exchanger immersed in a layer at the ratio of air to oxidized organic substances in the lower zone of the layer is a = 1.0-1.05, and in the upper zone a = 1.05-1.2 due to the introduction of an additional amount of air with the capture of acid gases, while the process dressed in a non-isothermal fluidized bed, including the lower zone of oxidation of organic waste or sulfur dioxide, as well as the capture of acid gases with an alkaline adsorbent, at a temperature of 700-750 ° C, and the upper zone of additional oxidation of organic waste or sulfur oil, as well as the additional capture of acid gases with alkaline adsorbent at a temperature of 400-600 ° C. The necessary temperature in the upper zone of the fluidized bed of 400-600 ° C is created by changing the air flow rate, which is fed into the reactor in a parallel bundle of perforated pipes with holes located between the lower and upper zones of the fluidized bed.

The method is carried out in a catalytic reactor depicted in

Figure 1, as follows.

A mixture of a catalyst for the deep oxidation of organic substances and inert material (quartz or river sand) is loaded into the reactor -1 on the gas distribution grid -7. Under the gas distribution grill -7, air is supplied through the pipe -3 to fluidize the bed and oxidize the waste or sulfur dioxide. The layer is heated to a temperature of 300-400 ° C due to air heating by an external heat source. Then, through the pipe -4, liquid waste or sulfur dioxide is fed into the bed, and through the pipe -5 an alkaline adsorbent (calcium carbonate). The temperature in the layer is brought to a temperature of 700-750 ° C due to oxidation of the waste, the external heat source is turned off. The temperature in the layer is maintained at 700-750 ° C due to removal of excess heat of oxidation of waste by the heat exchanger -10. The heat exchanger - 10 is supplied with cold water -11 from consumers. Hot water -12 is sent for use by consumers (heat supply and hot water supply). Flue gases through pipe -6 are sent to dust from the cyclone and filter and then discharged into the atmosphere. The fluidized bed is organized by small-volume nozzles -8 and -9, which break the large gas bubbles formed in the layer and provide good mass transfer between gas and catalyst particles, and also alkaline adsorbent particles. The organic components of the waste or sulfur dioxide are oxidized on the surface of the catalyst to products of deep oxidation (C0 ₂ and H ₂ 0). In the lower zone with stoichiometric ratios of waste to oxygen a = 0.95-1.05, the formation of intermediate oxidation products (CO, CH ₄ , etc.) is possible, which are then oxidized in the upper part of the layer at a = 1.05-1, 2 due to the supply of additional air through the pipe -13. Acid gases emitted during waste incineration (SOx, НС1, Р ₂ 0 ₅ ) are bound with alkaline adsorbent particles to sulfates, chlorides or calcium phosphates and are trapped in a cyclone and on a filter. Acid gases adsorbed on the surface of the catalyst are removed by redox reactions of the components of organic fuels and oxygen in the lower zone of the apparatus and then also bind calcium carbonate. The flow of additional air, blown through the perforated tubes -13 with openings -14, increases the flow rate of particles and gas in the cross section of the reactor -1 occupied by perforated pipes and allows maintaining the temperature of the fluidized bed in the lower zone of 700-750 ° C, optimal for burning organic components oil. At the same time, in the upper part of the layer, a temperature of 400-600 ° С is maintained at the expense of the heat exchanger -10, which is optimal for binding sulfur oxides with calcium carbonate and additional oxidation of intermediate products of oil burning.

The binding of sulfur oxides to calcium carbonate proceeds along two routes

CaCO3 + S0 ₂ = CaS0 ₃ + CO2 ₀

CaS0 ₃ + 1/20 ₂ = CaS0 ₄

or

CaC0 ₃ + S0 ₃ = CaS0 ₄ + C0 ₂

The calcium sulfite formed along the first route at a temperature of 600-700 ° C melts and impedes the diffusion of SO2 to the inner part of the calcite granules. The degree of reversible oxidation of S0 ₂ in SO3 is determined by the process temperature and depends on the equilibrium concentration of SO2 and S0 ₃ at a given temperature.

The calculated temperature profile as a function of the equilibrium conversion of sulfur dioxide SO2 to trioxide S0 _{3 is} shown in FIG. 2.

The invention is illustrated by the following examples.

Example 1. The prototype.

In the reactor -1, consisting of a vessel with a diameter of 80 mm in the lower part and 100 mm in the upper, load 5 l of a mixture of a catalyst for deep oxidation of organic substances with a diameter of granules of 2-3 mm, for example, oxide Al-Mg-Cu-Cr catalyst, and granules of river sand with a diameter of 1-2 mm. The ratio of sand to catalyst in the mixture is 80% and 20%, respectively. Under the gas distribution grill -7, air is supplied through the pipe 3 for fluidization and oxidation of fuel in the amount of 10 m 1 h. An external electric heater is used to heat the catalyst layer to 300-400 ° C. Then the pump through the pipe -4 serves in the layer of sulfur dioxide in the amount of 0.76 kg / h When the temperature in the layer reaches 700 ° C, the electric heater is turned off. In the upper part of the layer is a heat exchanger -10, cooled by cold water. The temperature in the layer is controlled by the amount of water supplied for cooling to the heat exchanger, and is maintained at a level of 700-750 ° C. The fluidized bed is organized by organizing grids in the lower part of -9 and in the heat exchange zone -8. The material of the gratings is stainless steel. To bind acidic products (sulfur oxides), an alkaline adsorbent (calcite with a particle size of 50-100 μm) is fed into the reactor through the pipe -5. The coefficient of excess air is a = 1.05-1.20.

With a mass ratio of calcite / S = 3.44, the content of toxic substances in the exhaust gases: СО - 30 mg / m ³ , NO _x - 5 mg / m ³ , SO _x - 0 mg / m. The degree of abrasion of the catalyst is 0.04 May. % per day.

Example 2 .. According to the invention.

In the reactor -1, consisting of a vessel with a diameter of 80 mm in the lower part and 100 mm in the upper, load 5 l of a mixture of a catalyst for deep oxidation of organic substances, for example, an oxide Al-Mg-Cu-Cr catalyst with a diameter of granules of 2-3 mm and granules of river sand with a diameter of 1-2 mm. The ratio of sand to catalyst in the mixture is 80% and 20%, respectively. Under the gas distribution grill -7, air is supplied through the pipe -3 for fluidization and oxidation of the fuel in an amount of 10 m 1h. An external electric heater is used to heat the catalyst layer to 300-400 ° C. Then the pump through the pipe -4 serves in the layer of sulfur dioxide in the amount of 0.76 kg / h When the temperature in the layer reaches 700 ° C, the electric heater is turned off. In the upper part of the layer is a heat exchanger -10, cooled by cold water. The temperature in the layer is controlled by the amount of water supplied for cooling to the heat exchanger, and maintained at a level of 700-750 ° C. The fluidized bed is organized by organizing grids in the lower part of -9 and in the heat exchange zone -8. The material of the gratings is stainless steel. To bind acidic products (sulfur oxides), an alkaline adsorbent (calcite with a particle size of 50-100 μm) is fed into the reactor through the pipe -5. The coefficient is maintained in the lower zone of the fluidized bed excess air α = 1.05. Additional air is supplied - in 4 perforated pipes -13 with openings -14 with a diameter of 10 mm. By changing the flow rate of additional air and the amount of water supplied to the heat exchanger -10, set the temperature in the upper part of the fluidized bed 600 ° C.

With a mass ratio of calcite / S = 3.00, the content of toxic substances in the exhaust gases: СО - 30 mg / m ³ , ΝΟ _χ - 5 mg / m ³ , SO _x - 0 mg / m ³ . The degree of abrasion of the catalyst is 0.04 May. % per day.

Example 3. Similar to example 2.

By changing the flow rate of additional air and the amount of water supplied to the heat exchanger, the temperature in the upper part of the fluidized bed is set at 500 ° C.

With a mass ratio of calcite / S = 2.50, the content of toxic substances in the exhaust gases: СО - 30 mg / m ³ , NO _x - 5 mg / m ³ , SO _x - 0 mg / m ³ . The degree of abrasion of the catalyst is 0.04 May. % per day.

Example 4. Similar to example 2.

By changing the flow rate of additional air and the amount of water supplied to the heat exchanger, the temperature in the upper part of the fluidized bed is set at 400 ° C.

With a mass ratio of calcite / S = 2.00, the content of toxic substances in the exhaust gases: СО - 30 mg / m ³ , NO _x - 5 mg / m ³ , SO _x - 0 mg / m ³ . The degree of abrasion of the catalyst is 0.04 May. % per day.

Example 5. Similar to example 4.

Organic waste containing sulfur is fed to the bottom of the reactor.

With a mass ratio of calcite / S = 2.00, the content of toxic

3 3 3 substances in the exhaust gases: СО - 30 mg / m, NO _x - 5 mg / m, SO _x - 0 mg / m. The degree of abrasion of the catalyst is 0.04 May. % per day.

As can be seen from the above examples, the proposed method allows to reduce the consumption of alkaline adsorbent, to simplify the technology of disposal of organic waste, including sulfur dioxide, in the absence of secondary pollutants.

Claims

Claim.

1. A method of burning organic waste and sulfur dioxide by oxidizing with atmospheric oxygen in an organized fluidized bed mixture of a catalyst for deep oxidation of organic substances and inert material in a ratio of 10-20% and 80-90% in May. with a heat exchanger immersed in the layer with the ratio of air to oxidizing organic substances in the lower part of the layer a = 1.0-1.05, and in the upper part a = 1.05-1.2 with the capture of acid gases with an alkaline adsorbent, characterized in that the process is carried out in a non-isothermal fluidized bed, including the lower zone of oxidation of organic waste or sulfur oil, as well as the capture of acid gases with an alkaline adsorbent at a temperature of 700-750 ° C, and the upper zone of additional oxidation of organic waste or sulfur oil, as well as additional trap pouring acid gases with an alkaline adsorbent at a temperature of 400-600 ° C.

2. The method according to p. 1, characterized in that the temperature in the upper part of the fluidized bed 400-600 ° C create due to changes in air flow, which is fed into the reactor in a parallel bundle of perforated pipes with holes located between the lower and upper parts of the fluidized bed .