CN111957273A - System and method for treating industrial waste salt by circulating fluidized bed - Google Patents
System and method for treating industrial waste salt by circulating fluidized bed Download PDFInfo
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- CN111957273A CN111957273A CN202010659701.1A CN202010659701A CN111957273A CN 111957273 A CN111957273 A CN 111957273A CN 202010659701 A CN202010659701 A CN 202010659701A CN 111957273 A CN111957273 A CN 111957273A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
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- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
Abstract
The invention discloses a method for treating industrial waste salt by a circulating fluidized bed, which is characterized in that in a system for treating the industrial waste salt by the circulating fluidized bed consisting of a fluidized reaction zone, a cyclone separation zone and a salt agent separation zone, the industrial waste salt enters the fluidized bed reaction zone to be mixed with an oxygen-adjacent cracking catalyst, air is blown from the bottom of the fluidized reaction zone, so that the industrial waste salt and the oxygen-adjacent cracking catalyst are in a current-carrying fluidized state, and organic matters in the industrial waste salt are subjected to cracking oxidation reaction at a low temperature; the carrier fluid is then tangentially introduced into a cyclone separation zone connected with the fluidized bed reaction zone to realize gas-solid separation, the gas is discharged through a gas collecting pipe, the solid enters a salt separation zone, air is blown from the bottom of the salt separation zone to enable small-particle oxygen-adjacent cracking catalyst to float upwards, the purified large-particle industrial salt sinks to realize the separation of the oxygen-adjacent cracking catalyst and the industrial salt, the upper oxygen-adjacent cracking catalyst returns to the fluidized reaction zone through a return pipe, and the lower industrial salt is extracted. The invention realizes low-temperature purification of industrial waste salt, can be continuously operated and reduces the treatment cost.
Description
Technical Field
The invention belongs to the technical field of waste salt purification, and relates to a system and a method for treating industrial waste salt by a circulating fluidized bed.
Background
In the production process of pesticides, medicines and chemical industry, a large amount of industrial waste salt containing sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium phosphate and sodium phosphate can be generated, and the industrial waste salt contains various organic impurities and cannot be directly utilized, so that resource waste and environmental pollution are caused.
At present, the treatment methods of industrial waste salt mainly comprise two main types, one is wet treatment, and the other is solid treatment. Patent CN104163519A adopts wet method to treat waste brine in glyphosate production, firstly adopts nanofiltration technology to separate and obtain penetrating fluid, then adopts one or more of Fenton oxidation method, hydrogen peroxide active carbon oxidation method, sodium hypochlorite active carbon oxidation method, ozone active carbon or chlorine dioxide oxidation method to treat penetrating fluid to obtain primary salt solution, and then adopts adsorption purification, so that the total carbon in the salt solution is less than 10mg/L, and the total nitrogen is less than 3 mg/L. The wet method for treating the waste salt has long flow, complex process and relatively high treatment cost.
The patent CN1669929A discloses a method for treating waste sodium chloride salt, which adopts a multilayer disc heating furnace with a heating device and a corresponding matched process, and can heat, decompose or volatilize harmful substances such as amine, phenol, ether and the like in industrial salt to remove, wherein the retention time of the waste salt in the heating furnace reaches 4-12 h. Patent CN104014578A discloses a decomposition process system for industrial waste salt organic matter, which comprises drying waste salt in a fluidized bed, adding combustion improver to decompose the organic matter in the waste salt at high temperature in a burning furnace, and packaging the decomposed sodium chloride salt as product. Patent CN106475398A carries out high temperature incineration carbonization with the organic matter in the waste salt in the spouted bed, adopts the steerable carbonization temperature of spouted bed, avoids the material bonding phenomenon, is favorable to serialization production, and this method needs predecomposition in 400 ~ 500 ℃ air-flowing preliminary decomposer, then carbonizes in 500 ~ 700 ℃ carbonization stove, and the export gas carries out gas incineration in 1000 ~ 1100 ℃ incinerator at last, and evacuation after the dust removal again.
Disclosure of Invention
The invention aims to provide a system for treating industrial waste salt by a circulating fluidized bed, aiming at the problems of long treatment process, complicated process, longer treatment time, higher treatment temperature or complex treatment system of the existing industrial waste salt.
The aim of the invention is realized by the following technical scheme:
a system for treating industrial waste salt by a circulating fluidized bed comprises a fluidized bed reactor 1 and a separation cylinder 2, wherein the middle lower part of the fluidized bed reactor 1 is a fluidized reaction zone, and the height of the fluidized reaction zone accounts for 1/3-2/3 of the height of a straight cylinder section of the fluidized bed reactor; the bottom of the fluidized bed reactor 1 is provided with an air inlet, the air inlet is connected with a fan, air is blown in by the fan, the top of the fluidized bed reactor 1 is provided with a waste salt feeding pipe 3 which is coaxial with the fluidized bed reactor 1, and the waste salt feeding pipe 3 extends into the fluidized reaction zone to enable the outlet end of the waste salt feeding pipe to be immersed in the catalyst and waste salt layer; the separation cylinder 2 comprises an upper cyclone separation area and a lower salt separation area, the cyclone separation area and the salt separation area are not required to be separated, a gas collecting pipe 5 coaxial with the separation cylinder is arranged at the upper part of the separation cylinder, the upper part of the separation cylinder 2 is communicated with the fluidized bed reactor 1 through a tangential feeding pipe 4, so that fluid (including solid particles and gas) in the fluidized bed reactor tangentially enters the separation cylinder 2, a rotational flow is generated in an annular gap of the separation cylinder 2 and the gas collecting pipe 5, so that the solid particles are separated from the gas, the inlet end of the gas collecting pipe 5 is lower than the tangential feeding pipe, the outlet end of the gas collecting pipe is connected with an alkaline cleaning system, and the gas after cyclone separation enters a subsequent alkaline cleaning system through; the bottom of the separation cylinder 2 is provided with an air inlet which is connected with a fan, and the fan blows air to enable catalyst particles and salt particles to generate different fluidization states, so that the separation of the catalyst and the salt particles is realized, the lower part of the separation cylinder is provided with a discharge pipe 6 which is connected with a salt refining working section, the upper part of the salt separation zone is connected with the fluidized bed reactor 1 through an inclined return pipe 7, and the inlet end of the return pipe 7 is higher than the bottom of the fluidized bed reactor to ensure that the catalyst returns to the fluidized reaction zone through self-overflow.
The fluidized bed reactor 1 is a straight cylindrical reactor with the same upper and lower sectional areas.
The waste salt feeding pipe 3 is a straight pipe with a smooth inner wall. The inlet end of the waste salt feeding pipe 3 is connected with a waste salt propeller 8.
The pipe diameter of the waste salt feeding pipe 3 is 10% -15% of the diameter of the fluidized bed reactor 1, the outlet end of the waste salt feeding pipe 3 is as close to the bottom as possible, the distance between the outlet end of the waste salt feeding pipe and the bottom of the fluidized bed reactor 1 is 1/6-1/3 of the height of the straight cylinder section of the fluidized bed reactor, and industrial waste salt particles are prevented from being blown away once entering the reactor.
The height difference between the inlet end of the gas collecting pipe 5 and the tangential inlet pipe 4 (namely the tangential inlet end of the cyclone separation area) is 1-1.5 m, the ratio of the diameter of the gas collecting cylinder 5 to the diameter of the separation cylinder 2 is 1/5-1/10, and sufficient space is ensured for gas and solid particles to realize gas-solid separation through cyclone.
The pipe diameter of the return pipe 7 is 1/2 of that of the waste salt feeding pipe 3, so that the series flow of air through the return pipe is avoided; the inlet end of the return pipe 7 is 0.5-1 m higher than the bottom of the fluidized bed reactor 1, and the included angle between the return pipe 7 and the straight cylinder section of the fluidized bed reactor is 30-40 degrees.
The length of the straight cylinder section of the separation cylinder below the return pipe 7 is 20-30% of the length of the straight cylinder section of the salt agent separation zone, so that a sufficient separation space for the catalyst particles of the oxygen cracking and the purified industrial waste salt particles is ensured.
The invention also aims to provide a method for processing industrial waste salt by using the circulating fluidized bed, in a system for processing the industrial waste salt by using the circulating fluidized bed consisting of a fluidized reaction zone, a cyclone separation zone and a salt agent separation zone, under the fluidized state of the industrial waste salt and the temporary oxygen cracking catalyst, organic matters in the waste salt are cracked and oxidized at low temperature, and the temporary oxygen cracking catalyst and the purified industrial salt are separated.
Specifically, a temporary oxygen cracking catalyst is filled in a fluidized bed reaction zone, industrial waste salt enters the fluidized bed reaction zone through a waste salt propeller to be mixed with the temporary oxygen cracking catalyst, air is blown from the bottom of the fluidized reaction zone, so that the industrial waste salt and the temporary oxygen cracking catalyst are in a current-carrying fluidized state in the fluidized reaction zone, and organic matters in the industrial waste salt are subjected to cracking oxidation reaction at low temperature; the carrier fluid is then tangentially fed into the cyclone separation zone connected with fluidized bed reaction zone to implement gas-solid separation, the gas is discharged from gas collecting tube, the solid is fed into salt separation zone, and air is blown from bottom portion of salt separation zone to make the oxygen cracking catalyst float upwards, and the purified industrial salt is sunk so as to implement stratification of oxygen cracking catalyst and purified industrial salt, and the upper oxygen cracking catalyst is returned into fluidized reaction zone by means of return pipe, and the lower purified industrial salt is extracted from system desalting and refining system.
The industrial waste salt is waste salt of sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, sodium phosphate and potassium phosphate containing organic impurities generated in the pesticide, chemical industry and pharmaceutical industry, and can be single salt or mixture of more than two kinds of salt.
The organic impurities in the industrial waste salt at least comprise three elements of carbon, hydrogen and oxygen, and possibly comprise any one or more than two elements of nitrogen, chlorine, sulfur and phosphorus, and the elements are oxidized into inorganic gaseous small molecular substances such as carbon dioxide, water, nitrogen, hydrogen chloride, sulfur dioxide, phosphorus oxide and the like under the action of the temporary oxygen cracking catalyst. Specifically, the organic impurities in the industrial waste salt are o-cresol, o-chlorotoluene, dichloroethane, glyphosate and the like.
The temporary oxygen cracking catalyst is a composite metal oxide loaded on alumina, silica or HY molecular sieve, the metal oxide is 2-3 oxides selected from iron oxide, copper oxide, nickel oxide, cerium oxide, lanthanum oxide, zirconium oxide, cobalt oxide, manganese oxide, vanadium oxide and chromium oxide, and the loading amount (relative to the mass ratio of the carrier) of the oxides on the silica or the molecular sieve is 1-30 wt%.
The temperature of the cracking oxidation reaction in the fluidized bed reaction zone is 400-650 ℃.
The ratio of the average particle size of the industrial waste salt to the average particle size of the temporary oxygen cracking catalyst is 10-20: 1. The particle size of the temporary oxygen cracking catalyst is 1-60 mu m, and the average particle size is about 40 mu m.
The method for treating the industrial waste salt by the circulating fluidized bed can continuously introduce the industrial waste salt, keep the mass ratio of the temporary oxygen cracking catalyst to the industrial waste salt at 0.1-1: 1, preferably 0.2-0.5: 1, and carry out continuous circulating treatment.
The total carbon value of the industrial waste salt is reduced to below 20mg/kg through the temporary oxygen cracking reaction.
The linear velocity of gas in the fluidization reaction zone is larger than the carrying-out velocity of the industrial waste salt particles, and the linear velocity of the gas is 1.5-2.5 m/s; the linear velocity of the gas in the salt agent separation zone is smaller than the initial fluidization velocity of the purified industrial salt particles, and the oxygen cracking catalyst particles are in a dispersed fluidization state, wherein the linear velocity of the gas is 0.05-0.1 m/s. The industrial waste salt particles and the oxygen cracking catalyst particles are in a current-carrying state in the fluidized reaction zone, the industrial waste salt particles and the oxygen cracking catalyst particles are distributed in the whole fluidized reaction zone under the action of air, and the two kinds of particles are carried out of the fluidized reaction zone along with the flow of the air, enter the cyclone separation zone connected with the fluidized reaction zone and then are deposited to the salt separation zone, in the salt separation zone, the flow velocity of air makes the catalyst particles in the cracking catalyst in the dispersed fluidized state, and the salt particles have high density, under the action of air, the catalyst particles and salt particles are divided into two phases, the catalyst particles are used for floating to the upper layer when the density and the particles are smaller than those of the salt particles, the salt particles sink to the lower layer due to the larger density and the larger particles, so that the catalyst and salt particles form two phases, and the catalyst on the upper layer returns to the fluidized reaction zone through the return pipe to continuously participate in the oxygen cracking and oxidation of organic matters in the industrial waste salt.
The temperature in the salt agent separation zone is the same as that in the fluidization reaction zone, and the critical oxygen cracking catalyst returning to the fluidization reaction zone from the salt agent separation zone is at the same temperature, so that the temperature of the fluidization zone is prevented from being reduced, and the purification effect is reduced.
As a further preferable technical scheme of the method for treating the industrial waste salt by the circulating fluidized bed, the gas after cyclone separation is discharged by the gas collecting pipe and enters the alkali tank to remove inorganic acidic substances in the gas, so that the standard discharge is realized.
The invention has the beneficial effects that:
in the circulating fluidized bed system comprising fluidizing reaction zone, cyclone separating zone and salt separating zone, industrial waste salt and temporary oxygen cracking catalyst are cracked and oxidized at low temperature, and the TOC eliminating rate is over 99%, so as to purify industrial waste salt and separate temporary oxygen cracking catalyst from purified industrial salt. The invention can realize continuous operation and reduce the treatment cost.
Drawings
FIG. 1 is a schematic diagram of a system for treating industrial waste salt by a circulating fluidized bed.
In FIG. 1, 1-fluidized bed reactor, 2-separator, 3-waste salt feeding pipe, 4-tangential feeding pipe, 5-gas collecting pipe, 6-discharging pipe, 7-reflux pipe, 8-waste salt propeller, 9-first fan, 10-second fan, 11-alkali tank, 12-extraction valve.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
As shown in figure 1, the system for treating industrial waste salt by the circulating fluidized bed comprises a straight tubular fluidized bed reactor 1 and a separation cylinder 2, wherein the middle lower part of the fluidized bed reactor 1 is a fluidized reaction zone, and the height of the fluidized reaction zone accounts for 1/3-2/3 of the height of a straight cylinder section of the fluidized bed reactor; the bottom of the fluidized bed reactor 1 is provided with an air inlet, the air inlet is connected with a fan, air is blown in by a first fan 9, the top of the fluidized bed reactor 1 is provided with a waste salt feeding pipe 3 which is coaxial with the fluidized bed reactor 1, the inlet end of the waste salt feeding pipe 3 is connected with a waste salt propeller 8, the waste salt feeding pipe 3 extends into the fluidized reaction zone, so that the distance from the outlet end of the waste salt feeding pipe to the bottom of the fluidized bed reactor 1 is 1/6 of the height of the straight cylinder section of the fluidized bed reactor, and the outlet end of the; the separation cylinder 2 comprises an upper cyclone separation area and a lower salt separation area, the cyclone separation area and the salt separation area are not required to be separated, a gas collecting pipe 5 coaxial with the separation cylinder is arranged at the upper part of the separation cylinder, the ratio of the diameter of the gas collecting pipe 5 to the diameter of the separation cylinder 2 is 1/10, the upper part of the separation cylinder 2 is communicated with the fluidized bed reactor 1 through a tangential feed pipe 4, so that fluid in the fluidized bed reactor tangentially enters the separation cylinder 2, rotational flow is generated in an annular space of the separation cylinder 2 and the gas collecting pipe 5, solid particles are separated from gas, the inlet end of the gas collecting pipe 5 is lower than the tangential feed pipe by 1.5m, the outlet end of the gas collecting pipe is connected with an alkaline cleaning system, and gas after cyclone separation enters a subsequent alkaline cleaning system; the bottom of the separation cylinder 2 is provided with an air inlet, the air inlet is connected with a second fan 10, the fan blows air to enable catalyst particles and salt particles to generate different fluidization states, so that the separation of the catalyst and the salt particles is realized, the lower part of the separation cylinder is provided with a discharge pipe 6 which is connected with a salt refining working section, the discharge pipe 6 is provided with a production valve 12, the upper part of the salt separation zone is connected with the fluidized bed reactor 1 through an inclined return pipe 7, and the length of a straight cylinder section of the separation cylinder below the return pipe 7 is 30% of the length of a straight cylinder section of; the inlet end of the return pipe 7 is 0.5m higher than the bottom of the fluidized bed bottom reactor and forms an included angle of 30 degrees with the straight cylinder section of the fluidized bed reactor.
The waste salt feeding pipe 3 is a straight pipe with a smooth inner wall, and the pipe diameter of the waste salt feeding pipe 3 is 15% of the diameter of the fluidized bed reactor 1.
The pipe diameter of the return pipe 7 is 1/2 of that of the waste salt feeding pipe 3.
The alkali washing system comprises an alkali tank 11, an air outlet is arranged at the top of the alkali tank, and a discharge hole is arranged at the bottom of the alkali tank and connected with a salt recovery system.
The system for treating the industrial waste salt based on the circulating fluidized bed is used for treating the industrial waste salt, an oxygen-critical cracking catalyst is filled in a fluidized bed reaction zone, the industrial waste salt enters the fluidized bed reaction zone through a waste salt propeller to be mixed with the oxygen-critical cracking catalyst, air is blown from the bottom of the fluidized reaction zone to enable the industrial waste salt and the oxygen-critical cracking catalyst to be in a current-carrying fluidized state in the fluidized reaction zone, organic matters in the industrial waste salt are cracked and oxidized at low temperature, carrier fluid enters a cyclone separation zone connected with the fluidized bed reaction zone in a tangential way, rotational flow is generated in an annular space of a separation cylinder and an air collecting pipe, solid particles are separated from gas, gas and solid are separated, the gas is discharged through a gas collecting pipe, the solid particles sink to enter a salt separation zone, air is blown from the bottom of the salt separation zone, and different fluidized states are generated by changing the gas velocity, floating the low-density oxygen cracking catalyst upwards, and sinking the high-density salt particles to realize layering of the oxygen cracking catalyst and the purified industrial salt; the upper layer of the temporary oxygen cracking catalyst floats to the upper part of the salt agent separation zone and returns to the fluidized reaction zone through a return pipe to be continuously used for carrying out catalytic cracking oxidation reaction, and salt particles sink to the lower part of the salt agent separation zone and are extracted through an extraction valve to enter an extraction system desalting refining system of a salt refining section.
Example 1
The waste sodium chloride salt to be treated is waste salt generated in the production of herbicide 2-methyl-4-chloro-phenoxyacetic acid, contains 0.23% of o-cresol, has total TOC of 4628mg/kg, and is crushed to have a particle size of 300-1000 mu m, and the average particle size is about 600 mu m.
The oxygen cracking catalyst takes alumina as a carrier, zirconium oxide and cerium oxide as active components, the loading capacity of iron oxide is 15%, and the loading capacity of copper oxide is 15%; the particle size of the temporary oxygen cracking catalyst is 1-60 μm, and the average particle size is about 40 μm.
In the fluidized reaction zone, the mass ratio of the temporary oxygen cracking catalyst to the sodium chloride waste salt is 0.5: 1.
The temporary oxygen cracking catalyst is put into a fluidized reaction zone, and the temperature in the fluidized reaction zone is controlled to be 400 ℃. The waste sodium chloride salt is conveyed into a fluidized reaction zone by a waste salt propeller, air is introduced from the bottom of the fluidized reaction zone by a fan to control the linear velocity of gas in the fluidized reaction zone to be 2m/s so that the waste salt and a catalyst are in a current-carrying state, after a gas-solid mixture tangentially enters a cyclone separation zone, catalyst and sodium chloride particles are subjected to cyclone separation and then swirl to a salt separation zone, the temperature in the salt separation zone is the same as the temperature in the fluidized reaction zone, the air is introduced from the bottom of the salt separation zone by the fan to control the linear velocity of gas in the salt separation zone to be 0.05m/s, so that the oxygen cracking catalyst floats upwards to an upper layer to be separated from sodium chloride under the action of airflow, the upper oxygen cracking catalyst returns to the fluidized reaction zone by a return pipe, and sodium chloride with the Total Organic Carbon (TOC) of 9.2mg/kg is collected from the lower part. The concentration of VOCs in the gas discharged from the gas collecting pipe is only 12mg/m3And the waste water can be directly drained without entering an alkali liquor tank.
Example 2
The sodium chloride waste salt to be treated is waste salt generated in the production of o-chlorobenzaldehyde, and contains 0.18 percent of o-chlorotoluene and 0.04 percent of dichloroethane, the total TOC in the waste salt is 3133mg/kg, and the salt is crushed to the particle size of 500-1100 mu m, and the average particle size is about 800 mu m.
The temporary oxygen cracking catalyst takes HY molecular sieve as a carrier, iron oxide and copper oxide as active components, the loading of zirconium oxide is 5%, the loading of cerium oxide is 25%, the particle size of the temporary oxygen cracking catalyst is 1-60 mu m, and the average particle size is about 40 mu m.
In the fluidized reaction zone, the mass ratio of the temporary oxygen cracking catalyst to the sodium chloride waste salt is 0.1: 1.
The temporary oxygen cracking catalyst is put into a fluidized reaction zone, the temperature in the fluidized reaction zone is controlled to be 650 ℃, meanwhile, the waste salt is input into the fluidized reaction zone by a propeller and is automatically fed by a fanIntroducing air into the bottom of the fluidization reaction zone to control the linear velocity of gas in the fluidization reaction zone to be 1.5m/s so that waste salt and catalyst are in a current-carrying state, tangentially introducing a gas-solid mixture into a cyclone separation zone, then cyclone-separating the catalyst and sodium chloride particles to a salt separation zone, wherein the temperature in the salt separation zone is the same as the temperature in the fluidization reaction zone, introducing air from the bottom of the salt separation zone by a fan to control the linear velocity of gas in the salt separation zone to be 0.1m/s, so that the temporary oxygen cracking catalyst floats upwards to the upper layer to be separated from sodium chloride under the action of airflow, returning the upper layer of the temporary oxygen cracking catalyst into the fluidization reaction zone through a return pipe, and collecting sodium chloride with the Total Organic Carbon (TOC) of 16mg/kg from the lower part of the salt separation zone. The concentration of VOCs in the gas leaving the header is only 15mg/m3And the gas containing hydrogen chloride enters an alkali liquor tank to absorb the hydrogen chloride and then is emptied.
Example 3
The waste sodium chloride salt to be treated is waste salt generated in glyphosate production, and contains 0.15% of glyphosate, the total TOC in the waste salt is 1814mg/kg, and the salt is crushed to the particle size of 500-1100 mu m, and the average particle size is about 800 mu m.
The temporary oxygen cracking catalyst takes silicon dioxide as a carrier, copper oxide and manganese oxide as active components, the loading amount of the copper oxide is 10%, the loading amount of the manganese oxide is 10%, the particle size of the temporary oxygen cracking catalyst is 1-60 mu m, and the average particle size is 40 mu m.
In the fluidized reaction zone, the mass ratio of the temporary oxygen cracking catalyst to the sodium chloride waste salt is 0.2: 1.
The method comprises the steps of placing a temporary oxygen cracking catalyst into a fluidized reaction zone, controlling the temperature in the fluidized reaction zone to be 650 ℃, simultaneously conveying waste salt into the fluidized reaction zone by a propeller, introducing air from the bottom of the fluidized reaction zone by a fan to control the linear velocity of gas in the fluidized reaction zone to be 1.5m/s so that the waste salt and the temporary oxygen cracking catalyst are in a current-carrying state, enabling a gas-solid mixture to enter a cyclone separation zone in a tangential direction, then enabling the temporary oxygen cracking catalyst and sodium chloride particles to swirl to a salt separation zone after cyclone separation, enabling the temperature in the salt separation zone to be the same as the temperature in the fluidized reaction zone, and introducing air from the bottom of the salt separation zone by the fan to control the linear velocity of gas in the salt separation zoneThe Total Organic Carbon (TOC) of the sodium chloride is 12.7mg/kg from the lower part of the salt separation zone. The concentration of VOCs in the gas leaving the header is only 18mg/m3The gas contains phosphorus pentoxide vapor, and the gas enters an alkali liquor tank to be absorbed and then is emptied.
Claims (10)
1. A system for treating industrial waste salt by a circulating fluidized bed is characterized by comprising a straight cylindrical fluidized bed reactor and a separating cylinder; the middle lower part of the fluidized bed reactor is a fluidized reaction zone, and the height of the fluidized reaction zone accounts for 1/3-2/3 of the height of the straight cylinder section of the fluidized bed reactor; the bottom of the fluidized bed reactor is provided with an air inlet, the air inlet is connected with a fan, air is blown in by the fan, the top of the fluidized bed reactor is provided with a waste salt feeding pipe which is coaxial with the fluidized bed reactor, and the waste salt feeding pipe extends into the fluidized reaction zone so that the outlet end of the waste salt feeding pipe is immersed in the catalyst and waste salt layer; the separation cylinder comprises an upper cyclone separation area and a lower salt separation area, the upper part of the separation cylinder is provided with a gas collecting pipe coaxial with the separation cylinder, the upper part of the separation cylinder is communicated with the fluidized bed reactor through a tangential feed pipe, so that fluid in the fluidized bed reactor tangentially enters the separation cylinder and generates rotational flow in an annular space of the separation cylinder and the gas collecting pipe, solid particles are separated from gas, and the inlet end of the gas collecting pipe is lower than the tangential feed pipe; the bottom of the separating cylinder is provided with an air inlet, the air inlet is connected with a fan, the fan blows air to enable catalyst particles and salt particles to generate different fluidization states, so that the catalyst and the salt particles are separated, the lower part of the separating cylinder is provided with a discharge pipe connected with a salt refining section, the upper part of the salt agent separating zone is connected with the fluidized bed reactor through an inclined return pipe, and the inlet end of the return pipe is higher than the bottom of the fluidized bed bottom reactor to ensure that the catalyst has self-refluxing capacity.
2. The system for treating industrial waste salt by using the circulating fluidized bed as claimed in claim 1, wherein the diameter of the waste salt feeding pipe is 10% -15% of the diameter of the fluidized bed reactor, and the distance from the outlet end of the waste salt feeding pipe to the bottom of the fluidized bed reactor is 1/6-1/3 of the height of the straight cylinder section of the fluidized bed reactor.
3. The system for treating industrial waste salt by using the circulating fluidized bed according to claim 1, wherein the height difference between the inlet end of the gas collecting pipe and the tangential feeding pipe is 1-1.5 m, and the ratio of the diameter of the gas collecting cylinder to the diameter of the separation cylinder is 1/5-1/10.
4. The system for treating industrial waste salt by using the circulating fluidized bed as claimed in claim 1, wherein the pipe diameter of the return pipe is 1/2 of that of the waste salt feeding pipe; the inlet end of the return pipe is 0.5-1 m higher than the bottom of the fluidized bed reactor, and the included angle between the return pipe and the straight cylinder section of the fluidized bed reactor is 30-40 degrees; the length of the straight cylinder section of the separation cylinder below the return pipe is 20-30% of the length of the straight cylinder section of the salt separation zone.
5. A method for treating industrial waste salt by circulating fluidized bed includes such steps as mixing industrial waste salt with temporary oxygen cracking catalyst in fluidized-bed reaction region, blowing air from the bottom of fluidized-bed reaction region to make them in current-carrying fluidized state, cracking and oxidizing reaction of organic substance in industrial waste salt at low temp, introducing carrier fluid to cyclone separation region, gas-gas separation, introducing solid to salt separation region, blowing air from the bottom of salt separation region to make the temporary oxygen cracking catalyst float upward, depositing purified industrial salt, layering temporary oxygen cracking catalyst and purified industrial salt, returning the upper temporary oxygen cracking catalyst to fluidized-bed reaction region, and extracting purified industrial salt from lower layer.
6. The method of claim 5, wherein the industrial waste salt is one or more of sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, sodium phosphate, and potassium phosphate containing organic impurities; the organic impurities in the industrial waste salt at least comprise carbon, hydrogen and oxygen elements, or carbon, hydrogen and oxygen elements and any one or more than two elements selected from nitrogen, chlorine, sulfur and phosphorus elements;
the temporary oxygen cracking catalyst is a composite metal oxide loaded on alumina, silicon oxide or a molecular sieve; the metal oxide is selected from 2-3 oxides of iron oxide, copper oxide, nickel oxide, cerium oxide, lanthanum oxide, zirconium oxide, cobalt oxide, manganese oxide, vanadium oxide and chromium oxide, and the load capacity of the oxide on silicon oxide or a molecular sieve is 1-30 wt%.
7. The method of claim 5, wherein the ratio of the average particle size of the industrial waste salt to the average particle size of the temporary oxygen cracking catalyst is 10-20: 1; the particle size of the temporary oxygen cracking catalyst is 1-60 mu m, and the average particle size is 40 mu m.
8. The method for treating industrial waste salt by using the circulating fluidized bed according to claim 5, wherein the mass ratio of the temporary oxygen cracking catalyst to the industrial waste salt in the fluidized reaction zone is 0.1-1; the temperature of the cracking oxidation reaction is 400-650 ℃.
9. The method of claim 5, wherein the linear velocity of the gas in the fluidized reaction zone is greater than the carry-over velocity of the industrial waste salt particles, and the linear velocity of the gas is 1.5-2.5 m/s.
10. The method of claim 5, wherein the linear velocity of the gas in the salt separation zone is lower than the initial fluidization velocity of the purified industrial salt particles, and the oxygen cracking catalyst particles are in a dispersed fluidization state, and the linear velocity of the gas is 0.05-0.1 m/s.
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| CN111957273B (en) | 2022-03-22 |
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