WO2016130039A1

WO2016130039A1 - Apparatus for sterilizing organic waste and sulphur crude oil

Info

Publication number: WO2016130039A1
Application number: PCT/RU2015/000098
Authority: WO
Inventors: Александр Дмитриевич СИМОНОВ; Николай Алексеевич ЯЗЫКОВ; Юрий Владимирович ДУБИНИН; Вадим Анатольевич ЯКОВЛЕВ; Валентин Николаевич ПАРМОН
Original assignee: Общество с ограниченной ответственностью "Уникат"
Priority date: 2015-02-11
Filing date: 2015-02-11
Publication date: 2016-08-18

Abstract

The utility model relates to apparatuses for sterilizing liquid organic waste and sulphur crude oil and can be used in the chemical, petrochemical, wood chemical and atomic industries and in heat and power engineering. An apparatus for incinerating organic waste and sulphur crude oil by oxidation with atmospheric oxygen, with the acid gases being captured by an alkali adsorbent, is described, said apparatus consisting of a reactor with a vertical casing with pipes for supplying the air, the waste and the alkali adsorbent in the lower part, and with pipes for removing smoke fumes and for loading a catalyst in the upper expanded part, and a gas distribution grid is arranged within the casing between the pipes for supplying the air and the pipes for supplying the waste and the adsorbent, on which there is a mixture of particles of a deep-oxidation catalyst and particles of an inert material, with an identical rate at which pseudo-liquefaction begins, and above which are consecutively arranged, in a pseudo-liquefied layer: an organizing nozzle, a non-isothermic grid of parallel perforated tubes connected by a manifold or manifolds to a pipe or pipes for supplying additional air in the upper part of the reactor casing before the expanded portion or in the expanded part thereof, and a heat exchanger. The technical result is a reduction in attrition of the catalyst, and a reduction in the emissions of toxic substances with the smoke fumes without the latter being additionally sterilized in a separate apparatus.

Description

A device for the disposal of organic waste and sulfur dioxide.

The utility model relates to devices for the neutralization of liquid organic waste and sulphurous oil by flameless combustion in a fluidized bed of a catalyst and can be used in the chemical, petrochemical, wood chemical, nuclear industry and thermal power industry. In particular, the proposed installation can be used for burning organic waste containing compounds of one of such elements as sulfur, fluorine, chlorine, phosphorus.

Known reactor for heat treatment of dispersed materials in a fluidized bed of catalyst (Boreskov G. K. Heterogeneous catalysis. - M .: Spider. - 1988. - S. 294). The reactor contains a catalytic oxidation zone of the fuel and a heat treatment zone of the dispersed material. The zones in the reactor are not separated by partitions. The disadvantages of this reactor are the decrease in catalyst activity due to catalyst poisoning when fluorine, chlorophosphorus, and sulfur-containing compounds get into the catalyst bed.

A device for burning waste containing phosphorus in a fluidized bed of chemisorbent (US 4359005, F23G7 / 00, 6.1 1.82). The device includes a reactor, an external fuel source and means for supplying fuel to the reactor, means for supplying air to the reactor for maintaining a fluidized bed and combustion, an external source of waste and means for supplying waste containing phosphorus to the reactor, an external source and means for introducing into the reactor lime, limestone and / or slaked lime, means for heating and maintaining an elevated temperature of the fluidized bed, preferably from 750 to 950 ° C, as well as the space above the fluidized bed from 600 to 900 ° C, as well as a cyclone installed at the outlet from a solid particle capture reactor. During operation, the fluidized bed inside the reactor consists of lime, phosphorus-containing waste and inert calcium phosphate. To control the temperature inside the reactor, a coils, a controlled supply of fuel, waste and air, as well as water injection, can be used. The disadvantages of the known device include the difficulty of controlling the fluidized bed due to the variable particle size, in addition, the complete combustion of fuel and waste due to the short contact time is not ensured. The description provides additional means for cleaning the exhaust gas (filters, adsorbers, scrubbers).

Known installation with a fluidized bed for burning waste containing chlorine compounds (US 5379705, F23G5 / 00, 10.01.95), with the supply of chemosorbents to bind the resulting HO. The installation includes: a gasification furnace with a 1 fluidized bed consisting of at least alkali metal oxide (CaO), means for supplying air to the fluidized bed, means for supplying chlorine-containing waste, means for removing unburned waste particles from the 1st fluidized bed Thus, the waste is gasified and the resulting software turns into salt; and - a fluidized bed combustion furnace connected at the bottom to the named gasification furnace in such a way that gases from the gasification of waste are supplied to it and having a second fluidized bed for burning these gases; said salt is discharged from the gasification furnace to the iodine combustion furnace by gas pressure; the combustion furnace is equipped with a nozzle for loading alkali metal carbonate (CaCO3), which forms the 2nd fluidized bed, with means for supplying air to the 2nd fluidized bed, as well as with means for withdrawing the alkali metal oxide (CaO) formed as a result of combustion and feeding it to 1 the fluidized bed of the gasification furnace. In addition, the combustion furnace may be equipped with a heat exchanger immersed in the 2nd fluidized bed. In the upper part, the incinerator is equipped with an exhaust gas outlet.

The disadvantages of the known device: the difficulty of controlling the fluidized bed of a gasification furnace due to the small particle size of the sorbent, as well as the generation of secondary contaminants, for example, nitrogen oxides in the exhaust gases due to the oxidation of atmospheric nitrogen.

Known catalytic reactor for the treatment of sewage sludge (RU 2456248, C02F1 1/06, 07.20. 2012), consisting of a vertical casing with catalyst discharge pipes, air and fuel supply pipes in the lower part, flue gas discharge pipes and catalyst loading pipes in the upper part, a gas distribution grid is located between the air and fuel supply pipes, on which the oxidation catalyst or a mixture of catalyst and inert material is located in the ratio of 10- 20% and 80-90%, the organizing nozzle and tehloobmenny surfaces are sequentially placed above the grate, the reactor vessel has an expansion in the upper part and is equipped with a discharge sludge supply pipe water, located at the level of the connection of the lower and upper expanded part of the reactor vessel.

A disadvantage of the known reactor is the difficulty of starting it, requiring the shipment of the catalyst from the expanded part of the body below the level of the heat exchanger, followed by loading of the catalyst upon reaching the reactor operating mode. Additionally, during unloading and overloads, the degree of abrasion of the catalyst increases.

A known installation for the neutralization of organic waste by fluidized bed burning (RU 2198024, A62D3 / 00, B01J8 / 18, 02/10/2003), containing two interconnected reactors equipped with means for supplying air, air distribution grilles and partially filled with a layer of solid particles, located axially, while the output of the first reactor is connected to the inlet of the second reactor, as well as means for supplying organic waste and means for introducing chemisorbent into at least one of the reactors, as well as means for trapping and circulation of solid particles, characterized in that the first reactor for burning fuel as solid particles is filled with a catalyst and equipped with means for supplying fuel and air, as well as a catalyst dust supply system, the second reactor for neutralizing waste as solid particles is filled with an inert material and equipped with means for delivering neutralized waste and chemisorbent, wherein the inlet of the second reactor is provided with a cyclone and a hopper for collecting catalyst dust, and the hopper for collecting catalyst dust is connected to the system odachi dust to the first reactor.

The disadvantages of the known installation are the large energy consumption for blowing equipment to maintain in a fluidized state the catalyst layer in the nerve reactor and the inert material layer in the second reactor, increased catalyst wear, the difficulty of maintaining the temperature necessary for neutralization in two reactors, a complex system of preliminary separation of organic waste into easily oxidized and difficultly oxidized components of the waste and feeding them into separately boiling layers of inert material and catalyst, the need for additional purification of flue gases after the second reactor with a layer inert material from toxic impurities in a separate apparatus.

The closest in technical essence and the achieved result is the installation of neutralization of organic waste by oxidation with air oxygen in a fluidized bed apparatus followed by trapping of acid gases with an alkaline adsorbent (RU 2209646, A62D3 / 00, VO 1.18 / 18, 03.29.2003). Organic waste containing extraction mixtures is first separated into an extractant and a diluent by the introduction of an easily hydrolyzable propellant. The diluent is oxidized in the lower part of the two-phase reactor in the fluidized bed of the catalyst at a temperature of 700-750 ° C, and the oxidation of the mixture of extrahept and propellant, as well as the capture of acid gases with an alkaline adsorbent, are carried out in the upper part of the two-phase reactor in the fluidized bed of an inert material at a temperature of 700-750 ° FROM; the oxidation of the diluent in the fluidized bed of the catalyst and the oxidation of the mixture of the extract and the propellant in the fluidized bed of an inert material are carried out alternately. The exhaust gases are additionally cleaned of 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 utility model solves the problem of increasing the efficiency of the device for the disposal of organic waste and sulfur dioxide.

EFFECT: reduction of catalyst wear, simplification of the technology of neutralizing organic waste, including sulphurous oil, reduction of toxic substances emissions with flue gases without their additional neutralization in a separate apparatus.

Organic waste and sulphurous oil are neutralized by oxygen oxidation of air in a fluidized bed apparatus at a temperature of 700 - 750 ° C in an organized fluidized bed of a mixture of particles of a catalyst for deep oxidation of substances and an inert material with the same fluidization onset rate with the ratio of air to oxidizing organic components in the lower part of the layer α ^~ 0.95-1, 05 with trapping of acid gases with an alkaline adsorbent and additional oxidation of toxic substances at a - 1, 05-1, 2 in the upper part of the fluidized bed with t an heat exchanger over a non-isothermal grill made of parallel perforated pipes connected by a collector or collectors to a pipe or pipes for supplying additional air.

The problem is solved by a device for burning organic waste and sulfur dioxide by oxygen oxidation of the air with the capture of acid gases by an alkaline adsorbent, which consists of a reactor with a vertical casing with air supply pipes, waste and alkaline adsorbent in the lower part, flue gas discharge pipes and catalyst loading in the upper the expanded part, inside the housing between the air supply pipes and the waste and adsorbent supply pipes there is a gas distribution grill, on which there is a mixture of particles of a deep oxidation catalyst and particles of an inert material in a ratio of 10% and 90%, above which an organizing nozzle, a non-isothermal grate and a heat exchanger are sequentially placed in the fluidized bed, a non-isothermal grating of parallel perforated pipes connected by a collector or collectors to the nozzle is placed inside the housing above the organizing nozzle or nozzles for supplying additional air in the upper part of the reactor vessel before expansion or in its expanded part, and to the gas distributor The lattice contains a mixture of catalyst particles and an inert material with the same rate of onset of fluidization.

The device consists of a catalytic reactor, a cooling system and the cleaning of flue gases from the acne, air supply systems, adsorbent supply. supply of neutralized waste or sulphurous oil.

A diagram of the catalytic reactor is shown in FIG. one.

The reactor 1 consists of a vertical casing with an extension in the upper part. In the housing, there are nozzles for supplying air 2 and 3, a nozzle for introducing waste 4, a nozzle for introducing sulfur dioxide 5, a nozzle for introducing adsorbent 6, a nozzle for removing flue gases 7, nozzles for entering 8 and leaving water 9 from the heat exchanger 10. Inside the reactor vessel between the nozzles the air supply 2 and the inlet pipes of the adsorbent 6 are located gas distribution grill 1 1. Above the grill are organizing nozzle 12. Above the nozzle is a non-isothermal grille 14 of parallel pipes with holes 15 connected by a collector or a collector Ktorov a nozzle or nozzles for supplying additional air 3. Above the grate 14 there is a heat exchanger 10. The branch pipe is provided for loading the catalyst on the lid of the reactor vessel 13 and inert material.

A mixture of a catalyst (mixed chromite of copper and magnesium supported on alumina) and an inert material (quartz or river sand) is loaded into a reactor 1 onto a gas distribution grid 1 1 through a nozzle 13. The velocity of the start of fluidization of particles of an inert material and particles of a catalyst is the same. Under the gas distribution grid 1 1 air is supplied through the pipe 2 for fluidization of the bed and the oxidation of waste or sulfur dioxide. Air is introduced into the pipe 3 and further into the perforated pipes of the non-isothermal grate 14 to fluidize the bed above the grate in the expanded part of the reactor vessel and to provide the necessary temperature gradient between the layer below and above the non-isothermal grate. Cold water 8 is supplied to the heat exchanger 10 from consumers. Hot water 9 is directed to consumer use (heat supply and hot water supply). The iodine layer is heated with a non-isothermal lattice to a temperature of 300-400 ° C due to the heating of the air by an external heat source. Then, sulfur dioxide oil is fed into the bed through pipe 5 or organic waste is fed through pipe 4, and alkaline adsorbent (calcium carbonate) is supplied through pipe 6. The temperature in the layer is brought to a temperature of 700-750 ° C due to the oxidation of waste. After reaching a temperature of 700 ° C, the external heat source is turned off. The temperature in the layer is maintained at 700-750 ° C for due to removal of excess heat of oxidation of waste by the heat exchanger 10. Flue gases through the pipe 7 are sent to clean the dust in a cyclone and filter and then discharged into the atmosphere. The fluidized bed is organized by a low-volume nozzle 12, which breaks the large gas bubbles formed in the layer and provides good mass transfer between the gas and the particles of the catalyst and alkaline adsorbent. Acid gases emitted during waste incineration (SO _x , HO, P ₂ 0 ₅ ) bind to alkaline CaO adsorbent particles in calcium sulfates, chlorides or phosphates and are trapped in the cyclone and on the filter. CaO particles are formed upon decomposition of CaCO ₃ in the lower zone of the fluidized bed. Acid gases adsorbed on the surface of the catalyst are removed due to redox reactions of the components of organic fuels and atmospheric oxygen in the lower zone of the apparatus, and CaO is also bound. 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, SP ₄ , etc.) is possible, which are then oxidized in the upper part of the layer at α ^ 1, 05-1, 2 due to the supply of additional air through the nozzles 3. The degree of abrasion of the catalyst (mixed chromite of copper and magnesium deposited on alumina) is significantly lower than the degree of abrasion of quartz or river sand - 0.4-0.5 may. % per day and 0.8-1, May 0. % per day, respectively. When using a mixture of sand and catalyst in the ratio of 90% of sand and 10% of the catalyst, the degree of abrasion of the catalyst decreases to 0.02 May. % day. This can significantly reduce the pollution of solid waste neutralization products with catalyst dust containing chromium compounds.

The construction of the isothermal lattice 14 of parallel pipes with holes 15 is shown in FIG. 2.

The essence of the utility model is illustrated by the following examples and illustrations.

Example 1 (prototype).

In the reactor, consisting of a vessel with a diameter of 80 mm at the bottom and 100 mm in the top, load 2.5 l of a catalyst for deep oxidation of organic substances, for example, mixed chromite of copper and magnesium deposited on alumina, with a diameter of granules of 2-3 mm and 2.5 l of inert material (quartz sand) with a particle size of 0.5-0.8 mm . Under the gas distribution grill, air is supplied through the pipe for fluidization and oxidation of the fuel in an amount of 10 m ³ / h. Due to the difference in the particle size of the catalyst and the inert material, the fluidized bed is divided into two zones — the boiling zone of the catalyst (lower zone) and the boiling zone of the inert material (upper zone). An external electric heater heats the catalyst bed to 300-400 ° C. Then the pump through the nozzle serves in the lower part of the layer of kerosene in the amount of 0.16 kg / h When the temperature in the layer reaches 700 ° C, tributyl phosphate is fed to the upper part of the layer in an amount of 0.22 kg / h. At the same time, an alkaline adsorbent (calcite with a particle size of 50-100 μm) in the amount of 0.12 kg / h is introduced into the lower part of the reactor, and the electric heater is turned off. In the upper part of the layer is a coil-type heat exchanger 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 coefficient of excess air is 2.0. The content of toxic substances in the exhaust gases: СО - 800-1000 mg / m ³ , NO _x - 5 mg / m ³ , SO _x 0 MI / M ^J. The degree of abrasion of the catalyst is 0.4 may. % per day.

Example 2

5 l of a mixture of a catalyst for deep oxidation of organic substances with a diameter of granules of 2-3 mm and granules of river sand with a diameter of 1-2 mm are loaded into a reactor consisting of a vessel with a diameter of 80 mm in the lower part and 100 mm in the upper part. The ratio of sand to catalyst in the mixture is 90% and 10%, respectively. Under the gas distribution grill 1 1 serves air through the pipe 2 for the fluidization and oxidation of the fuel in an amount of 10 m ³ / h An external electric heater heats the catalyst bed to 300-400 ° C. Then 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, I turn off the electric heater. In the upper part of the layer there is a coil type 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 700 - 750 ° C. The fluidized bed is organized by a small wire nozzle 12. Above the nozzle in the expanded part of the housing is an additional air inlet 3 connected through a collector with parallel pipes 14 with holes 15. To bind acidic products (sulfur oxides), an alkaline adsorbent (calcite with particle size 50-100 microns) with a weight ratio of calcite / S equal to 3.44. The coefficient of excess air a = 1.05-1.20. 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, ^* 02 May. % per day.

Example 3. Similar to example 2.

The burning of crude oil is carried out with a coefficient of excess air a 1.0-1.05. The content of toxic substances in the exhaust gases: СО 200-400 MI7M ^j , ΝΟχ 4 mg / m ³ , SO _x 0 mg / m ³ . The degree of abrasion of the catalyst is 0.02 May. % per day.

Example 4. Similar to example 3.

The burning of crude oil is carried out in the lower part of the reactor with an air excess coefficient α ~ 1.0-1.05. In the upper part of the reactor due to the supply of additional air, an excess air coefficient of 1.05-1.20 is maintained. The content of toxic substances in the exhaust gases: СО 30 mg / m ', NO _x 4 mg / m ³ , SO _x 0 mg / m ³ . The degree of abrasion of the catalyst is 0.02 May. % per day.

Example 5. Similar to example 4.

A mixture of kerosene and tributyl phosphate in the amount of 0.16 kg / h and 0.22 kg / h, respectively, is fed into the lower part of the layer. The content of toxic substances in the exhaust gases: СО - 30 mg / m ³ , NO _x - 4 mg / m ³ , SO _x 0 mg / m ³ . The degree of abrasion of the catalyst is 0.02 May% per day.

As can be seen from the above examples, the proposed device can reduce catalyst wear, simplify the technology of neutralization of organic waste, including sulfur dioxide, reduce emissions of toxic substances with flue gases without additional neutralization in a separate apparatus.

Claims

The utility model formula.

A device for burning organic waste and sulfur dioxide by oxidizing oxygen with trapping acid gases with an alkaline adsorbent, consisting of a reactor with a vertical casing with air inlets, waste and alkaline adsorbent in the lower part, flue gas exhaust pipes and catalyst loading in the upper expanded part, inside the casing between the air supply pipes and the waste and adsorbent supply pipes there is a gas distribution grill, on which there is a mixture of catalyst particles deep oxidation and particles of inert material in the ratio of 10% and 90%, above which the organizing nozzle, psizothermal grate and heat exchanger are sequentially placed in the fluidized bed, characterized in that a non-isothermal grating of parallel perforated pipes connected by a collector or collectors is placed inside the body above the organizing nozzle with a nozzle or nozzles for supplying additional air in the upper part of the reactor vessel before expansion or in its expanded part, and on the gas distribution lattice is a mixture of the catalyst particles per hour and the inert material at the same speed the start of fluidization.