CN110947281A - Device and method for treating chlorine-containing tail gas, mixture containing hydrochloric acid and application of mixture - Google Patents
Device and method for treating chlorine-containing tail gas, mixture containing hydrochloric acid and application of mixture Download PDFInfo
- Publication number
- CN110947281A CN110947281A CN201811132708.7A CN201811132708A CN110947281A CN 110947281 A CN110947281 A CN 110947281A CN 201811132708 A CN201811132708 A CN 201811132708A CN 110947281 A CN110947281 A CN 110947281A
- Authority
- CN
- China
- Prior art keywords
- spray
- stage
- hydrochloric acid
- absorption
- tail gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/06—Spray cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
- B01D53/185—Liquid distributors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to the field of chlorine-containing tail gas recovery treatment, and discloses a treatment device and a treatment method for chlorine-containing tail gas, a mixture containing hydrochloric acid and application thereof, wherein the device comprises: a spray absorption tower (1), a first-stage absorption kettle (2) and a hydrochloric acid storage tank (4); the top outlet of the spray absorption tower (1) is communicated with the gas inlet of the first-stage absorption kettle (2), and the bottom outlet of the spray absorption tower (1) is communicated with the liquid inlet of the first-stage absorption kettle (2); a liquid phase outlet of the first-stage absorption kettle (2) is communicated with a liquid phase inlet of the hydrochloric acid storage tank (4); the spray absorption tower (1) is provided with at least two stages of spray trays (5), and at least one stage of spray trays (5) can rotate. The treatment device and the method provided by the invention can effectively remove dust, HCl and other pollutants in the chlorine-containing tail gas, and the recovered mixture containing hydrochloric acid can be used for preparing the catalytic cracking catalyst.
Description
Technical Field
The invention relates to the field of chlorine-containing tail gas recovery and treatment, in particular to a treatment device and a treatment method for chlorine-containing tail gas, a mixture containing hydrochloric acid and application thereof.
Background
At present, alkaline sewage is mostly adopted for treating chlorine-containing tail gas to absorb the chlorine-containing tail gas, although the treatment method can meet the requirement of the tail gas on reaching the standard and discharging, absorption liquid has no recycling value and is directly discharged outside, high-chlorine salt-containing wastewater which is difficult to treat is generated, the index of the total salt content of the discharged sewage is gradually reduced along with the increasingly strict national requirement on environmental protection, the high-chlorine salt-containing wastewater not only increases the burden of a subsequent sewage treatment device, but also improves the difficulty of the sewage on reaching the standard and discharging; meanwhile, the peculiar smell of the trench hydrochloric acid is concentrated due to the discharge of the absorption liquid, which is not beneficial to the environmental and occupational health protection.
CN102198361A relates to a hydrogen chloride tail gas recovery unit, has at least one hydrochloric acid recovery tower and absorption liquid circulating device, and the tail gas import has been seted up to the lower part of hydrochloric acid recovery tower, and the tail gas export has been seted up to the upper end of hydrochloric acid recovery tower, every hydrochloric acid recovery tower in be equipped with the second grade spray set that sprays the absorption liquid, second grade spray set include two atomizers that set up from top to bottom, every atomizer below is equipped with the packing layer respectively, the lower part of hydrochloric acid recovery tower has the circulation liquid case of retrieving second grade spray set spun absorption liquid, circulation liquid case and second grade spray set pass through absorption liquid circulating device pipeline intercommunication. The hydrochloric acid recovery tower of the hydrogen chloride tail gas recovery device of CN102198361A is provided with a secondary spraying device, the effect of absorbing and recovering hydrogen chloride in tail gas is better, a hydrochloric acid product with a useful value is obtained, the device realizes electrification control, the automation degree is high, and the operating cost is greatly reduced compared with that of the original hydrogen chloride tail gas treatment tower.
CN102285641A relates to a waste hydrochloric acid recovery process, which is characterized in that: the waste hydrochloric acid is preheated and then fully mixed with the prepared calcium chloride solution used as the catalyst, the mixture enters a hydrochloric acid desorption tower, the mixture is separated out under the action of a reboiler at the bottom of the hydrochloric acid desorption tower, the separated hydrogen chloride gas is collected through a cooler and a demister, water dissolved with a small amount of hydrogen chloride flows back to the hydrochloric acid desorption tower again to be continuously analyzed, and the calcium chloride solution used as the catalyst is introduced into a flash evaporation shunt tank to be prepared and reused. The waste of hydrogen chloride is avoided, and the sewage treatment cost is also reduced.
CN202193614U discloses concentrated process equipment is retrieved to hydrochloric acid, includes: sour elevated tank of raw materials, cauldron formula evaporimeter, dehydration rectifying column, neutralization apparatus, concentration evaporator, desorption cauldron and hydrochloric acid absorption tower, sour elevated tank of raw materials connects cauldron formula evaporimeter, the cauldron formula evaporimeter is connected respectively and is dewatered rectifying column and neutralization apparatus, the concentration evaporator is connected to the dehydration rectifying column, the concentration evaporator is connected and is desorbed the cauldron, the concentration evaporator with desorption cauldron all are connected with hydrochloric acid absorption tower. Through the mode, the hydrochloric acid recovery and concentration process has the advantages of advanced equipment performance, stable and safe operation, less investment, low energy consumption, high production treatment efficiency and continuous and reliable production process, can concentrate and evaporate the low-concentration hydrochloric acid-containing wastewater, can reach the hydrochloric acid concentration of 25-35% after evaporation, and can be directly used in the chemical industry.
The waste hydrochloric acid process is widely used in various industries, but the main pollution component hydrogen chloride gas in the chlorine-containing tail gas cannot be effectively recycled, the recycling cost is too high, the recycling device is complex, the investment cost is high, and the waste of resources is caused, which is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to overcome the defects of complex chlorine-containing tail gas recovery device and high investment cost in the prior art, and provides a treatment device and a treatment method for chlorine-containing tail gas, a mixture containing hydrochloric acid and application thereof. When the device and the method for treating the chlorine-containing tail gas are used for treating the chlorine-containing tail gas generated in the roasting and spray drying processes in the preparation process of the catalytic cracking catalyst, the dust content and the chlorine root content of the chlorine-containing tail gas can be effectively reduced, and the obtained mixture containing hydrochloric acid can be used in the preparation process of the catalytic cracking catalyst, so that the difficulty and the cost of sewage treatment in the prior art are reduced.
In order to achieve the above object, a first aspect of the present invention provides an apparatus for treating chlorine-containing off-gas, comprising: the spray absorption tower, the first-stage absorption kettle and the hydrochloric acid storage tank; the tower top outlet of the spray absorption tower is communicated with the gas inlet of the first-stage absorption kettle, and the tower bottom outlet of the spray absorption tower is communicated with the liquid inlet of the first-stage absorption kettle; a liquid phase outlet of the first-stage absorption kettle is communicated with a liquid phase inlet of the hydrochloric acid storage tank; the spray absorption tower is provided with at least two stages of spray tower trays, and at least one stage of spray tower tray can rotate.
Preferably, at least 4 spray nozzles are independently arranged on each stage of spray trays, and the spray nozzles are spiral spray nozzles, and a plurality of holes are arranged on spiral parts of the spiral spray nozzles.
In a second aspect of the present invention, there is provided a method for treating chlorine-containing tail gas, comprising:
1) spraying and absorbing the chlorine-containing tail gas in a spray absorption tower, spraying the bottom of the absorption tower to obtain absorption liquid, and spraying the top of the absorption tower to obtain tail gas;
2) respectively feeding the absorption liquid and the tail gas into a first-stage absorption kettle to absorb chlorine in the tail gas;
wherein, the spray absorption tower is provided with at least two stages of spray tower trays, and at least one stage of spray tower can rotate.
Preferably, at least 4 spray nozzles are independently arranged on each stage of spray trays, and the spray nozzles are spiral spray nozzles, and a plurality of holes are arranged on spiral parts of the spiral spray nozzles.
In a third aspect, the invention provides a hydrochloric acid-containing mixture obtained by the above-described treatment method.
In a fourth aspect, the present invention provides the use of a mixture comprising hydrochloric acid as described above in the preparation of a catalytic cracking catalyst.
According to the device and the method for treating the chlorine-containing tail gas, the adopted spray absorption tower is provided with at least two stages of spray tower trays, and at least one stage of spray tower tray can rotate, so that effective contact between water and the chlorine-containing tail gas can be increased, the absorption effect is improved, and the energy consumption and the water consumption are reduced. Preferably, at least 4 spray nozzles are independently arranged on each stage of spray trays, each spray nozzle is a spiral spray nozzle, and a plurality of holes are formed in a spiral part of each spiral spray nozzle. By adopting the preferable nozzle, part of water can be sprayed out of the small holes, the atomization distribution range of water drops is wider, the contact range with the chlorine-containing tail gas is wider, the effect is better, and the water consumption can be further saved.
The treatment method provided by the invention can effectively remove pollutants such as dust, HCl and the like in the chlorine-containing tail gas, and the dust content in the finally discharged tail gas can be reduced to 30mg/m3The content of HCl gas can be reduced to 5mg/m3The emission standard can be achieved as follows; simultaneously, the obtained chloride is recovered, the discharge of chlorine-containing waste water is reduced, and the concentration of the recovered hydrochloric acid can reach 10-20 wt% (preferably 15-20 wt%). The obtained mixture containing hydrochloric acid can be used for preparing a catalytic cracking catalyst, and the mixture containing hydrochloric acid obtained by the treatment method provided by the invention can partially or completely replace fresh hydrochloric acid in the gelling process of the catalytic cracking catalyst. Surprisingly, the mixture containing hydrochloric acid obtained by the treatment method provided by the invention has higher specific surface area, pore volume, abrasion performance and micro-reaction activity than the catalytic cracking catalyst obtained by using fresh hydrochloric acid.
Drawings
FIG. 1 is a device for treating chlorine-containing off-gas according to an embodiment of the present invention;
FIG. 2 is a nozzle according to one embodiment of the present invention;
fig. 3 is a schematic diagram of a spray tray lateral interface according to an embodiment of the present invention.
Description of the reference numerals
1-spray absorption tower 2-first stage absorption kettle 3-second stage absorption kettle
4-hydrochloric acid storage tank 5-spray tray 51-nozzle
511-spiral part 512-hole 52-water inlet
6-heating unit 7-water storage tank 8-first pump
9-second pump 10-third pump 11-first induced draft fan
12-second induced draft fan 13-fourth pump 14-third induced draft fan
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the use of the terms of orientation such as "top, bottom, up and down" in the absence of a contrary indication generally refers to the top, bottom, up and down shown in the drawings.
In the present invention, "first, second, third, and fourth" are used only for distinguishing the same device or operation used at different locations, and do not limit the device or operation.
In a first aspect, the present invention provides an apparatus for treating chlorine-containing tail gas, as shown in fig. 1, the apparatus comprising: a spray absorption tower 1, a first-stage absorption kettle 2 and a hydrochloric acid storage tank 4; the outlet at the top of the spray absorption tower 1 is communicated with the gas inlet of the first-stage absorption kettle 2, and the outlet at the bottom of the spray absorption tower 1 is communicated with the liquid inlet of the first-stage absorption kettle 2; a liquid phase outlet of the first-stage absorption kettle 2 is communicated with a liquid phase inlet of the hydrochloric acid storage tank 4; wherein, the spray absorption tower 1 is provided with at least two stages of spray tower trays 5, and at least one stage of spray tower trays 5 can rotate.
Chlorine-containing tail gas is sprayed and absorbed in the spraying absorption tower 1, absorption liquid is obtained at the bottom of the spraying absorption tower 1, tail gas is obtained at the top of the spraying absorption tower 1, the absorption liquid is sent into the first-stage absorption kettle 2 through the tower bottom outlet of the spraying absorption tower 1 and the liquid inlet of the first-stage absorption kettle 2, tail gas obtained at the top of the spraying absorption tower 1 is sent into the first-stage absorption kettle 2 through the tower top outlet of the spraying absorption tower 1 and the gas inlet of the first-stage absorption kettle 2, and the tail gas is further absorbed by the absorption liquid in the first-stage absorption kettle 2.
According to the device provided by the invention, at least one stage of spray tray 5 can rotate, preferably, each stage of spray tray 5 can rotate, and by adopting the preferred embodiment, spray water can be fully contacted with chlorine-containing tail gas, so that the problem that the environment pollution is caused by directly discharging untreated tail gas is avoided.
According to the device provided by the invention, preferably, the spray absorption tower 1 is provided with 4-6 stages of spray trays 5. Each stage of spray trays 5 may be the same or different, and the present invention is not particularly limited thereto and is preferably the same.
According to an embodiment of the present invention, at least two stages of spray trays 5 are arranged in parallel up and down along the spray absorber tower 1. Preferably, adjacent spray trays 5 are spaced 1.5-2m apart.
According to a preferred embodiment of the invention, the diameter of each stage of spray trays 5 is independently 2-3.5m, and it is further preferred that the diameter of each stage of spray trays 5 is the same.
The height of the spray absorber column 1 is not particularly limited in the present invention, and those skilled in the art can appropriately select the height according to the number of stages of the spray trays 5 and the interval between adjacent spray trays 5, and for example, the height may be 12 to 20 m.
The inner diameter of the spray absorption tower 1 is not particularly limited in the present invention, and preferably, the inner diameter of the spray absorption tower 1 is larger than the diameter of the spray tray 5, for example, the inner diameter of the spray absorption tower 1 is 3 to 5 m.
According to a preferred embodiment of the present invention, each of the spray trays 5 of each stage is independently provided with at least 4 spray nozzles 51, and further preferably with 4 to 8 spray nozzles 51. According to one embodiment of the invention, the nozzles 51 are evenly distributed on the spray tray 5.
According to a preferred embodiment of the present invention, the nozzle 51 is a spiral nozzle, and the water drops atomized by the spiral nozzle are in a spiral line shape which is continuously reduced, so that the water drops can be distributed in a wider range and can be contacted with the chlorine-containing tail gas more effectively.
Further preferably, as shown in fig. 2, the spiral part 511 of the spiral nozzle is provided with a plurality of holes 512 (preferably, circular holes). With this preferred embodiment, a portion of the water is allowed to exit the holes 512, so that the overall water atomization is more widely distributed and in greater contact with the chlorine-containing off-gas.
According to an embodiment of the invention, the plurality of holes 512 are evenly distributed on the spiral member 511.
Still more preferably, the opening ratio of the spiral member 511 is 10 to 20%, most preferably 15 to 20%. The open area ratio of the spiral member 511 is defined as the ratio of the total area of the holes 512 on the outer surface of the spiral member 511 to the outer surface of the spiral member 511. By adopting the preferred embodiment, the absorption effect and the service life of the spiral nozzle are better considered.
According to an embodiment of the invention, the apparatus further comprises: and the water storage tank 7 is used for providing water for spraying the spray absorption tower 1. Specifically, a first pump 8 is provided on a communicating line between the water storage tank 7 and the spray absorption tower 1.
As shown in fig. 3, a water inlet 52 is provided on the spray tray 5, and water in the water storage tank 7 enters the spray tray 5 through the water inlet 52, so as to realize spray absorption of the chlorine-containing off-gas.
According to the device provided by the invention, at least one stage of spray tray 5 can rotate, and preferably each stage of spray tray 5 can rotate. The present invention is not particularly limited to the assembly of the shower tray 5. For example, the spray tower tray 5 of the invention is arranged in parallel up and down along the main shaft of the spray absorption tower 1, the main shaft of the spray absorption tower 1 passes through the center of the spray tower tray 5, and the spray tower tray 5 is fixedly connected with the main shaft of the spray absorption tower 1. The main shaft of the spray absorption tower 1 is connected with a motor to drive the main shaft of the spray absorption tower 1 to rotate, and further drive the spray tower tray 5 to rotate. A water flow passage is provided on the shower tray 5 to communicate the water feed opening 52 with the spray nozzles 51, so that the water supplied from the water storage tank 7 enters the water flow passage through the water feed opening 52 to be sent to the spray nozzles 51. The present invention provides a specific way of mounting the spray tray 5 in a rotatable manner, to which the invention is not limited.
According to a preferred embodiment of the invention, the device further comprises: and a tower bottom outlet of the spray absorption tower 1 is communicated with a liquid inlet of the second-stage absorption kettle 3, and a liquid phase outlet of the second-stage absorption kettle 3 is communicated with a liquid phase inlet of the hydrochloric acid storage tank 4. The first stage absorption kettle 2 and the second stage absorption kettle 3 can be alternately used. For example, when the amount of the liquid stored in the first-stage absorption kettle 2 reaches a certain amount, the liquid in the first-stage absorption kettle 2 can be sent into the hydrochloric acid storage tank 4 through the liquid phase outlet of the first-stage absorption kettle and the liquid phase inlet of the hydrochloric acid storage tank 4, and the absorption liquid obtained from the bottom of the spray absorption tower 1 can be sent into the second-stage absorption kettle 3. Specifically, a second pump 9 is arranged on a communicating pipeline of the first-stage absorption kettle 2 and the hydrochloric acid storage tank 4; a third pump 10 is arranged on the communicating pipeline of the second-stage absorption kettle 3 and the hydrochloric acid storage tank 4.
According to a preferred embodiment of the present invention, the first stage absorption vessel 2 and the second stage absorption vessel 3 each independently have a volume of 10 to 15m3。
According to a preferred embodiment of the invention, the device further comprises: and the heating unit 6 is used for heating the hydrochloric acid storage tank 4. By adopting the preferred embodiment, the concentration of the hydrochloric acid collected in the hydrochloric acid storage tank 4 can be increased, the hydrochloric acid storage tank 4 is heated, and gas containing a small amount of volatile hydrochloric acid and a large amount of water vapor can be obtained from the top of the hydrochloric acid storage tank 4. Preferably, a gas phase outlet of the hydrochloric acid storage tank 4 is communicated with a gas phase inlet of the first-stage absorption kettle 2 (preferably, a first induced draft fan 11 is arranged on a communicating pipeline), and the gas containing a small amount of volatile hydrochloric acid and a large amount of water vapor obtained from the top of the hydrochloric acid storage tank 4 is sent to the first-stage absorption kettle 2 through the gas phase outlet of the hydrochloric acid storage tank 4 for re-absorption and utilization. When the device also comprises a second-stage absorption kettle 3, a gas phase outlet of the hydrochloric acid storage tank 4 is communicated with a gas phase inlet of the second-stage absorption kettle 3, and gas containing a small amount of volatile hydrochloric acid and a large amount of water vapor obtained from the top of the hydrochloric acid storage tank 4 is sent to the first-stage absorption kettle 2 and/or the second-stage absorption kettle 3 through the gas phase outlet of the hydrochloric acid storage tank 4 for re-absorption and utilization.
The heating unit 6 may be any of various heating units conventionally used in the art, and may be, for example, a jacket heating unit disposed outside the hydrochloric acid storage tank 4, or a steam heating unit.
According to a specific mode of the invention, the first-stage absorption kettle 2 and the second-stage absorption kettle 3 are respectively and independently provided with a tail gas outlet after absorption. The tail gas after absorption that first order absorption cauldron 2 and 3 upper portions of second level absorption cauldron obtained can discharge alone, also can let in second level absorption cauldron 3 with the tail gas after absorption that first order absorption cauldron 2 obtained (specifically, be provided with third draught fan 14 on first order absorption cauldron 2 and second level absorption cauldron 3's the communicating pipeline), then through the tail gas after absorption export of second level absorption cauldron 3 and discharge.
According to a specific mode of the invention, a second induced draft fan 12 is arranged on a communicating pipeline between the outlet at the top of the spray absorption tower 1 and the gas inlet of the first-stage absorption kettle 2; a fourth pump 13 is arranged on a communicating pipeline between the tower bottom outlet of the spray absorption tower 1 and the liquid inlet of the first-stage absorption kettle 2.
In a second aspect of the present invention, there is provided a method for treating chlorine-containing tail gas, comprising:
1) spraying and absorbing chlorine-containing tail gas in a spray absorption tower 1, obtaining absorption liquid at the bottom of the spray absorption tower 1, and obtaining tail gas at the top of the spray absorption tower 1;
2) respectively feeding the absorption liquid and the tail gas into a first-stage absorption kettle 2 to absorb chlorine in the tail gas;
wherein, the spray absorption tower 1 is provided with at least two stages of spray tower trays 5, and at least one stage of spray tower trays 5 can rotate.
According to the method provided by the present invention, the spray absorption tower 1, the spray tray 5 and the arrangement of the spray nozzles 51 on the spray tray 5 are as described above, and will not be described herein again.
The chlorine-containing tail gas can be any gas containing chlorine, and is preferably the chlorine-containing tail gas generated in the roasting and/or spray drying process in the preparation process of the catalytic cracking catalyst. The temperature of the chlorine-containing tail gas obtained by roasting in the preparation process of the catalytic cracking catalyst is 200-400 ℃, and the temperature of the chlorine-containing tail gas obtained in the spray drying process is 50-150 ℃. The chlorine-containing off-gases obtained in the roasting and spray drying processes may be treated separately or after mixing, and the invention is not particularly limited thereto. In addition, the chlorine-containing tail gas can also contain a certain amount of dust. The chlorine-containing tail gas in the embodiment of the invention has the HCl content of 19460mg/m3The dust content is 332mg/m3The illustration is for the sake of example.
According to a preferred embodiment of the invention, the rotational speed of each stage of spray trays 5 is independently from 20 to 40r/min, more preferably from 25 to 35 r/min.
According to the present invention, the spray absorption in step 1) can be carried out by a conventional method in the art, for example, chlorine-containing off-gas enters from the lower middle part and exits from the upper part of the spray absorption tower 1. Preferably, in the step 1), the chlorine-containing tail gas is subjected to spray absorption by using water. The chlorine-containing tail gas enters from the middle lower part of the spray absorption tower 1 and contacts with the spray absorption water of at least two stages of spray tower trays 5 in the spray absorption tower 1 to spray and absorb the residual heat, dust and hydrogen chloride of the chlorine-containing tail gas.
The water may be provided by a water storage tank 7. The water is not particularly limited in the present invention, and may be any water conventionally used in the art as long as the purpose of absorbing the chlorine-containing off-gas by spraying is achieved. The water may be deionized water or industrial water. According to a preferred embodiment of the present invention, the water is demineralized water obtained by deionizing industrial water.
According to the method provided by the invention, preferably, in the step 1), the chlorine-containing tail gas is sprayed and absorbed by water, wherein the amount of the chlorine-containing tail gas is 1m3The amount of water used in the chlorine-containing off gas of (2) is 20 to 40L, more preferably 25 to 36L.
The absorption liquid obtained in the step 1) and the tail gas are respectively sent to a first-stage absorption kettle 2. Preferably, the absorption liquid obtained in the step 1) is firstly sent into a first-stage absorption kettle, then the tail gas obtained in the step 1) is introduced into a first-stage absorption kettle 2 in which the absorption liquid is stored, and the absorption liquid is adopted to absorb chlorine in the tail gas.
According to a specific embodiment of the present invention, the method further comprises: sending the liquid in the first-stage absorption kettle 2 into a hydrochloric acid storage tank 4; preferably, when the liquid in the first stage absorption kettle 2 reaches a certain liquid level, the liquid in the first stage absorption kettle 2 is sent to the hydrochloric acid storage tank 4.
Preferably, when the content of hydrochloric acid in the first stage absorption vessel 2 is not less than 10% by weight (preferably 10 to 15% by weight), the liquid in the first stage absorption vessel 2 is sent to the hydrochloric acid storage tank 4.
According to the method provided by the present invention, preferably, the method further comprises: and the second-stage absorption kettle 3 and the first-stage absorption kettle 2 are alternately used. After the first-stage absorption kettle 2 stores a certain amount of liquid, the absorption liquid and the tail gas obtained in the step 1) can be introduced into the second-stage absorption kettle 3 through a pump, and meanwhile, the liquid stored in the first-stage absorption kettle 2 is sent into the hydrochloric acid storage tank 4.
The structures of the first-stage absorption vessel 2 and the second-stage absorption vessel 3 are not particularly limited, and may be appropriately selected according to the actual conditions. The volumes of the first stage absorption vessel 2 and the second stage absorption vessel 3 are as described above, and will not be described in detail.
According to the method provided by the present invention, preferably, the method further comprises: the hydrochloric acid storage tank 4 is heated. The preferred embodiment is more advantageous for increasing the concentration of the hydrochloric acid collected in the hydrochloric acid storage tank 4. The hydrochloric acid storage tank 4 is heated, and gas containing a small amount of volatile hydrochloric acid and a large amount of water vapor is obtained at the top of the hydrochloric acid storage tank 4. Preferably, the obtained gas containing a small amount of volatile hydrochloric acid and a large amount of water vapor is sent to the first-stage absorption kettle 2 and/or the second-stage absorption kettle 3 for absorption and utilization again.
In the present invention, the heating is not particularly limited, and jacket heating or steam heating may be performed outside the hydrochloric acid storage tank 4.
According to a preferred embodiment of the present invention, the heating conditions include: the temperature is 70-100 deg.C, and the time is 1-5 hr, more preferably 75-90 deg.C, and the time is 1.5-3 hr. With this preferred embodiment, the hydrochloric acid concentration of the mixture containing hydrochloric acid collected in the hydrochloric acid storage tank 4 can be increased to 18 to 20% by weight.
According to a specific mode of the invention, the absorbed tail gas obtained from the upper parts of the first-stage absorption kettle 2 and the second-stage absorption kettle 3 can be discharged separately, or the absorbed tail gas obtained from the first-stage absorption kettle 2 can be introduced into the second-stage absorption kettle 3 and then discharged through the absorbed tail gas outlet of the second-stage absorption kettle 3.
By adopting the method provided by the invention, the dust content in the discharged tail gas can be reduced to 30mg/m3The content of HCl gas can be reduced to 5mg/m3The emission standard can be achieved as follows.
In a third aspect, the invention provides a hydrochloric acid-containing mixture obtained by the above-described treatment method. The mixture containing hydrochloric acid obtained by the treatment method provided by the invention can partially or completely replace fresh hydrochloric acid, and surprisingly, the mixture containing hydrochloric acid obtained by the treatment method provided by the invention has higher specific surface area, pore volume, abrasion performance and micro-reverse activity than a catalytic cracking catalyst obtained by using fresh hydrochloric acid. Accordingly, in a fourth aspect the present invention provides the use of a mixture comprising hydrochloric acid as described above in the preparation of a catalytic cracking catalyst.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following steps: the preparation method comprises the steps of pulping a binder, clay and a molecular sieve to obtain catalyst slurry, and carrying out spray drying on the catalyst slurry, wherein the binder contains the mixture containing hydrochloric acid provided by the invention.
The binder of the present invention may contain various binders conventionally used in the art, such as at least one of pseudoboehmite, alumina sol, silica-alumina sol, and magnesium sol, in addition to the hydrochloric acid-containing mixture provided by the present invention, and preferably, the binder of the present invention further contains pseudoboehmite and alumina sol.
According to the present invention, preferably, the method comprises: stirring pseudoboehmite, water and a mixture containing hydrochloric acid and optionally fresh hydrochloric acid to obtain slurry A; pulping a molecular sieve with water to obtain molecular sieve slurry; and adding the alumina sol, the clay and the molecular sieve slurry into the slurry A to obtain catalyst slurry. The order of adding the alumina sol, clay and molecular sieve slurry is not particularly limited, but it is preferable to add the alumina sol and clay first and then add the molecular sieve slurry.
The fresh hydrochloric acid is commercially available with respect to the hydrochloric acid-containing mixture (recovered hydrochloric acid) provided by the present invention. One skilled in the art can determine whether fresh hydrochloric acid needs to be added based on the amount of hydrochloric acid required for pseudoboehmite acidification.
The clay of the present invention is a clay raw material well known to those skilled in the art, and any kind of commonly used clay can be used in the present invention, and for the present invention, the clay is preferably one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. For the present invention, the clay is preferably one or more of sepiolite, kaolin and halloysite, and further preferably kaolin.
In the invention, the molecular sieve is a well-known molecular sieve raw material in the field, the molecular sieves commonly used in the field can be used in the invention, and the molecular sieves are preferably REY, REHY, REUSY and USY in the invention, and the gas phase chemical method (SiCl) is adopted4Al removal and Si supplement method), liquid phase chemical method ((NH)4)2SiF6Aluminum extraction and silicon supplement method) and other methods, and ZSM-5 type and β type zeolites with high silica-alumina ratio or their mixtureThe sieve is REY molecular sieve.
According to the method for preparing a catalytic cracking catalyst of the present invention, the solid content of the catalyst slurry is preferably 30% by weight or more, preferably 30 to 40% by weight.
The amounts of binder, clay and molecular sieve used in the present invention are not particularly limited and may be selected by those skilled in the art according to the desired composition of the catalytic cracking catalyst.
The invention also provides a catalytic cracking catalyst prepared by the preparation method. The mixture containing hydrochloric acid obtained by the treatment method provided by the invention has higher specific surface area, pore volume, abrasion performance and micro-reaction activity than the catalytic cracking catalyst obtained by using fresh hydrochloric acid.
The present invention will be described in detail below by way of examples.
The HCl content in the gas is measured by measuring the hydrogen chloride in the ambient air and the waste gas of HJ 549-; the dust content is measured by the method of measuring particulate matters in exhaust gas of a GB/T16157-1996 fixed pollution source and sampling gaseous pollutants.
Example 1
As shown in FIG. 1, chlorine-containing tail gas (HCl content 19460 mg/m) obtained by roasting and spray-drying in the preparation process of catalytic cracking catalyst3The dust content is 332mg/m3) The tower is introduced into a spray absorption tower 1 from the lower part, the height of the spray absorption tower 1 is 15m, the diameter (inner diameter) of the tower is 5m, the spray absorption tower 1 is provided with 4-stage spray tower trays 5, the spray tower trays 5 are sequentially arranged from the top of the tower downwards, the diameter of each spray tower tray 5 is 3m, and the interval between every two adjacent spray tower trays 5 is 2 m. Each stage of spray tray 5 can rotate at a rotational speed of 30 r/min. As shown in fig. 3, the spray tray 5 is provided with 4 uniformly distributed nozzles 51 (spiral nozzles) and with a water feed port 52. As shown in fig. 2, the spiral part 511 of the spiral nozzle is provided with holes 512, and the opening ratio (the ratio of the total area of the holes 512 on the outer surface of the spiral part 511 to the outer surface of the spiral part 511) of the spiral part 511 is 15%.
The multi-stage spray tower tray 5 of the spray absorption tower 1 is communicated with a water storage tank 7, and the spray water of the spray tower tray 5 is provided by the water storage tank 7And a first pump 8 is arranged on a communicating pipeline between the multistage spray tower tray 5 and the water storage tank 7. Relative to each 1m of the spraying absorption tower 13The amount of chlorine-containing tail gas introduced into each stage of spray tray 5 was 7L.
Absorbing the chlorine-containing tail gas by 4-stage spray water, obtaining absorption liquid from the bottom of the spray absorption tower 1, introducing the absorption liquid into the first-stage absorption kettle 2 through a fourth pump 13, tail gas obtained from the top of the spray absorption tower 1 is introduced from the upper part of the first-stage absorption kettle 2 through a second induced draft fan 12, absorbing chlorine in the tail gas, when the content of hydrochloric acid in the first-stage absorption kettle 2 is 13 weight percent, liquid stored in the first-stage absorption kettle 2 is sent into a hydrochloric acid storage tank 4 through a second pump 9, absorption liquid obtained at the bottom of the spray absorption tower 1 is sent into a second-stage absorption kettle 3 through a fourth pump 13 and is introduced from the upper part of the second-stage absorption kettle 3 through a second induced draft fan 12, absorbing chlorine in the tail gas, when the content of hydrochloric acid in the second-stage absorption kettle 3 is 13 weight percent, the liquid stored in the second-stage absorption kettle 3 is sent into a hydrochloric acid storage tank 4 through a third pump 10; the first stage absorption kettle 2 and the second stage absorption kettle 3 are alternately used, and the volume of the first stage absorption kettle 2 and the volume of the second stage absorption kettle 3 are 15m3。
The hydrochloric acid storage tank 4 is heated by a heating unit 6 (steam heating unit) at the temperature of 85 ℃ for 2 hours, so that the hydrochloric acid concentration is increased to 19 wt%.
And gas containing a small amount of volatile hydrochloric acid gas and a large amount of water vapor is introduced into the first-stage absorption kettle 2 and the second-stage absorption kettle 3 from the upper part of the hydrochloric acid storage tank 4 through the first induced draft fan 11 for reabsorption and utilization. And introducing the tail gas obtained from the top of the first-stage absorption kettle 2 into the second-stage absorption kettle 3 through a third induced draft fan 14. Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 4.0mg/m3The dust content is 25.0mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace in Shandong with DB37/2375 and 2013 are met. 99% of the HCl in the chlorine-containing off-gas is recovered.
Example 2
According to the method of example 1, except that the spray absorption tower 1 was 15m in height and 5m in diameter (inner diameter), the spray absorption tower 1 was provided with 5 stages of spray trays5, the spraying tower trays 5 are sequentially arranged downwards from the top of the tower, the diameter of each spraying tower tray 5 is 3m, and the interval between every two adjacent spraying tower trays 5 is 1.8 m. Each stage of spray tray 5 can rotate at a rotational speed of 35 r/min. The spray tray 5 is provided with 6 evenly distributed nozzles 51 (spiral nozzles) and with a water inlet 52. As shown in fig. 2, the spiral member 511 of the spiral nozzle is provided with holes 512, and the opening ratio (the ratio of the total area of the holes 512 on the outer surface of the spiral member 511 to the outer surface of the spiral member 511) of the spiral member 511 is 18%. Relative to each 1m of the spraying absorption tower 13The amount of chlorine-containing tail gas introduced into each stage of spray tray 5 is 5L.
Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 4.3mg/m3The dust content is 26.2mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace in Shandong with DB37/2375 and 2013 are met. 99% of the HCl in the chlorine-containing off-gas is recovered.
Example 3
According to the method of the embodiment 1, except that the height of the spray absorption tower 1 is 15m, the diameter (inner diameter) of the tower is 5m, the spray absorption tower 1 is provided with 6 stages of spray trays 5, the spray trays 5 are sequentially arranged from the top of the tower downwards, the diameter of each spray tray 5 is 3m, and the interval between every two adjacent spray trays 5 is 1.5 m. Each stage of spray trays 5 can be rotated at a rotational speed of 25/min. The spray tray 5 is provided with 5 evenly distributed nozzles 51 (spiral nozzles) and with a water inlet 52. As shown in fig. 2, the spiral part 511 of the spiral nozzle is provided with holes 512, and the opening ratio (the ratio of the total area of the holes 512 on the outer surface of the spiral part 511 to the outer surface of the spiral part 511) of the spiral part 511 is 20%. Relative to each 1m of the spraying absorption tower 13The amount of chlorine-containing tail gas introduced into each stage of spray tray 5 was 6L.
Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 3.7mg/m3Dust content of 22.5mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace in Shandong with DB37/2375 and 2013 are met. 99% of the HCl in the chlorine-containing off-gas is recovered.
Example 4
The method of example 1 was followed except that the opening ratio of the spiral member 511 was 8%.
Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 44mg/m3Dust content of 61mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace in Shandong with DB37/2375 and 2013 are met. 99% of the HCl in the chlorine-containing off-gas is recovered.
Example 5
The method of example 1 was followed except that the spiral part 511 of the spiral nozzle was not provided with the holes 512. Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 78mg/m3The dust content is 72mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace in Shandong with DB37/2375 and 2013 are met. 99% of the HCl in the chlorine-containing off-gas is recovered.
Example 6
According to the method of example 1, except that each stage of spray trays 5 is capable of rotating at a speed of 15 r/min.
Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 123mg/m3Dust content 70mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace in Shandong with DB37/2375 and 2013 are met. 98% of the HCl in the chlorine-containing off-gas is recovered.
Comparative example 1
According to the method of example 1, except that none of the 4-stage spray trays 5 of the spray absorber tower 1 can rotate. Through detection, the HCl content in the tail gas obtained from the top of the second-stage absorption kettle 3 is 340mg/m3Dust content of 96mg/m3And the requirements of the atmospheric pollutant emission standard of the labor-saving industrial furnace kiln in Shandong with DB37/2375 and 2013 cannot be met. 98% of the HCl in the chlorine-containing off-gas is recovered.
As can be seen from the comparison between the above examples and comparative examples, the method and apparatus provided by the present invention can effectively remove dust, HCl and other contaminants from the chlorine-containing off-gas. From the results of comparing example 1 with examples 4 and 5, it was shown that the HCl content and the dust content were higher in the off-gas discharged in examples 4 and 5 than in example 1, although effective recovery of HCl could be achieved when the opening ratio of the spiral member 511 was low or no holes were provided in the spiral member 511. As can be seen from the comparison between example 1 and example 6, when the rotation speed of the 4-stage spray tray 5 of the spray absorption tower 1 is relatively slow, the HCl content and the dust content in the discharged tail gas are relatively high; as can be seen from the comparison between the example 1 and the comparative example 1, when the 4-stage spray trays 5 of the spray absorption tower 1 cannot rotate, the tail gas discharged by the comparative example 1 has higher HCl content and dust content, and cannot meet the requirements of the atmospheric pollutant discharge standard of the labor-saving industrial furnace in Shandong province of DB 37/2375-.
The following examples illustrate the use of the hydrochloric acid-containing mixtures obtained according to the invention in the preparation of catalytic cracking catalysts.
Wherein, kaolin: a solid content of 81.2% by weight, produced by Kaolin corporation of China (Suzhou);
REY type molecular sieve: produced by Qilu division of China petrochemical catalyst, Inc., and has a solid content of 80 wt%;
pseudo-boehmite: with Al2O3A solids content of 64% by weight, Shandong aluminum industries;
aluminum sol: with Al2O3The solid content was 22% by weight, a product of the Chinese petrochemical catalyst, Qilu division;
fresh hydrochloric acid: solids content as HCl was 36 wt%;
and (3) recycling hydrochloric acid: the hydrochloric acid-containing mixture having a hydrochloric acid concentration of 19% by weight was obtained in the hydrochloric acid storage tank 4 of example 1.
The specific surface area of the catalytic cracking catalyst was measured according to GB/T5816-1995 using an Autosorb-1 nitrogen desorption apparatus from Congta, USA, and the sample was degassed at 300 ℃ for 6 hours before the test.
The pore volume and the abrasion index were measured by RIPP28-90 and RIPP29-90 methods in petrochemical analysis and RIPP test (published by Yangchi, scientific Press, 1990), respectively.
Example 7
55kg of acidic water and 31.25kg of pseudo-boehmite are added into a reaction kettle, stirred for 30min, 8.19kg of recycled hydrochloric acid obtained in example 1 is added, stirred for 40min, 46.8kg of kaolin and 40.91kg of alumina sol are added, stirred for 60min, 112.18kg of REY molecular sieve slurry (the solid content of the slurry is 31.2 wt%) is added, and stirred for 60min, so that catalyst slurry is obtained. And (2) carrying out spray drying on the catalyst slurry, roasting the obtained catalyst microspheres for 1 hour at 500 ℃, washing the catalyst twice by adopting decationized water, wherein the weight ratio of the decationized water to the dry-based catalyst is 8:1, and then drying for 2 hours at 120 ℃ to obtain the catalytic cracking catalyst C-1. The specific surface area, pore volume and attrition index to catalytic cracking catalyst C-1 are shown in Table 1.
Example 8
56.79kg of acidic water and 31.25kg of pseudo-boehmite are added into a reaction kettle and stirred for 30min, 4.09kg of recycled hydrochloric acid obtained in example 1 and 2kg of fresh hydrochloric acid are added and stirred for 40min, 46.8kg of kaolin and 40.91kg of alumina sol are added and stirred for 60min, and then 112.18kg of REY molecular sieve slurry (the solid content of the slurry is 31.2 wt%) is added and stirred for 60min, so that catalyst slurry is obtained. And (2) carrying out spray drying on the catalyst slurry, roasting the obtained catalyst microspheres for 1 hour at 500 ℃, washing the catalyst twice by adopting decationized water, wherein the weight ratio of the decationized water to the dry-based catalyst is 8:1, and then drying for 2 hours at 120 ℃ to obtain the catalytic cracking catalyst C-2. The specific surface area, pore volume and attrition index to catalytic cracking catalyst C-2 are shown in Table 1.
Comparative example 2
58.35kg of acidic water and 31.25kg of pseudo-boehmite are added into a reaction kettle, the mixture is stirred for 30min, 4kg of fresh hydrochloric acid is added, the mixture is stirred for 40min, 46.8kg of kaolin and 40.91kg of alumina sol are added, the mixture is stirred for 60min, then 112.18kg of REY molecular sieve slurry (the solid content of the slurry is 31.2 wt%) is added, and the mixture is stirred for 60min, so that catalyst slurry is obtained. And (2) carrying out spray drying on the catalyst slurry, roasting the obtained catalyst microspheres for 1 hour at 500 ℃, washing the catalyst twice by adopting decationized water, wherein the weight ratio of the decationized water to the dry-based catalyst is 8:1, and then drying for 2 hours at 120 ℃ to obtain the catalytic cracking catalyst D-1. The specific surface area, pore volume and attrition index to catalytic cracking catalyst D-1 are shown in Table 1.
TABLE 1
| Analyzing data | C-1 | C-2 | D-1 |
| Specific surface area, m2·g-1 | 275 | 268 | 252 |
| Pore volume, mL/g | 0.41 | 0.40 | 0.38 |
| Abrasion index, m%/h | 1.3 | 1.4 | 1.8 |
Test examples
The catalysts C-1, C-2 and D-1 are aged and deactivated for 12 hours at 800 ℃ by 100 percent of water vapor. The loading of the catalyst is 9g, the reaction raw material is Wu-MI-Sanyuan oil, and the raw materials are shown in Table 2. The reaction temperature was 500 ℃ and the catalyst-to-oil ratio (by weight) was 6, and the measured catalyst performance parameters are shown in Table 3.
Wherein, the conversion rate is gasoline yield, liquefied gas yield, dry gas yield and coke yield;
the yield of light oil is gasoline yield and diesel oil yield;
the liquid yield is the liquefied gas yield, the gasoline yield and the diesel oil yield;
coke selectivity is coke yield/conversion;
TABLE 2
TABLE 3
As can be seen from the data in Table 2, the compositions of the catalysts (C-1, C-2) prepared with the recovered hydrochloric acid according to the invention (examples 7, 8) are substantially equivalent to the catalyst (D-1) prepared with fresh hydrochloric acid: the specific surface area, pore volume and attrition index are all obviously better than those of the catalyst (D-1) prepared by fresh hydrochloric acid in the prior art. As can be seen from the data of the results in Table 3, when heavy crude oil processing is carried out, the catalysts (C-1, C-2) obtained by using the recovered hydrochloric acid of the present invention can obtain higher conversion, liquid yield and light oil yield than the catalyst (D-1) obtained by using the fresh hydrochloric acid of the prior art under the same solvent-oil ratio conditions, and the coke amount is reduced.
The device and the method for treating the chlorine-containing tail gas provided by the invention can effectively recover hydrochloric acid, and the catalytic cracking catalyst is prepared by using the recovered hydrochloric acid, so that the production cost of the catalyst is reduced, the environmental-friendly emission requirement is met, and the reaction performance of catalytic cracking can be improved.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A treatment device for chlorine-containing tail gas is characterized by comprising: a spray absorption tower (1), a first-stage absorption kettle (2) and a hydrochloric acid storage tank (4); the top outlet of the spray absorption tower (1) is communicated with the gas inlet of the first-stage absorption kettle (2), and the bottom outlet of the spray absorption tower (1) is communicated with the liquid inlet of the first-stage absorption kettle (2); a liquid phase outlet of the first-stage absorption kettle (2) is communicated with a liquid phase inlet of the hydrochloric acid storage tank (4); the spray absorption tower (1) is provided with at least two stages of spray trays (5), and at least one stage of spray trays (5) can rotate.
2. The apparatus according to claim 1, wherein the spray absorber (1) is provided with 4-6 stages of spray trays (5); preferably, the interval between adjacent spray trays (5) is 1.5-2 m;
preferably, the diameter of each stage of spray trays (5) is independently 2-3.5 m;
preferably, the height of the spray absorption tower (1) is 12-20m, and the inner diameter is 3-5 m.
3. The device according to claim 2, wherein each stage of spray trays (5) is provided with at least 4 spray nozzles (51), further preferably with 4-8 spray nozzles (51), independently from each other;
preferably, the nozzle (51) is a spiral nozzle;
further preferably, the spiral part (511) of the spiral nozzle is provided with a plurality of holes (512), preferably, the plurality of holes (512) are uniformly distributed on the spiral part (511); still more preferably, the opening ratio of the spiral member (511) is 10 to 20%.
4. The apparatus of any one of claims 1-3, wherein the apparatus further comprises: a tower bottom outlet of the spray absorption tower (1) is communicated with a liquid inlet of the second-stage absorption kettle (3), and a liquid phase outlet of the second-stage absorption kettle (3) is communicated with a liquid phase inlet of the hydrochloric acid storage tank (4);
preferably, the volumes of the first stage absorption kettle (2) and the second stage absorption kettle (3) are respectively and independently 10-15m3。
5. The apparatus of any one of claims 1-3, wherein the apparatus further comprises: the heating unit (6), the said heating unit (6) is used for heating the hydrochloric acid storage tank (4);
preferably, a gas phase outlet of the hydrochloric acid storage tank (4) is communicated with a gas phase inlet of the first-stage absorption kettle (2).
6. A method for treating chlorine-containing tail gas, comprising the following steps:
1) carrying out spray absorption on the chlorine-containing tail gas in a spray absorption tower (1), obtaining absorption liquid at the bottom of the spray absorption tower (1), and obtaining tail gas at the top of the spray absorption tower (1);
2) respectively feeding the absorption liquid and the tail gas into a first-stage absorption kettle (2) to absorb chlorine in the tail gas;
the spray absorption tower (1) is provided with at least two stages of spray trays (5), and at least one stage of spray trays (5) can rotate.
7. The method of claim 6, wherein,
in the step 1), the chlorine-containing tail gas is sprayed and absorbed by water, wherein the amount of the chlorine-containing tail gas is 1m3The amount of water used in the chlorine-containing tail gas is 20-40L, preferably 25-36L;
preferably, the spray absorption tower (1) is provided with 4-6 stages of spray trays (5); preferably, the interval between adjacent spray trays (5) is 1.5-2 m;
preferably, the diameter of each stage of spray trays (5) is independently 2-3.5 m;
preferably, the height of the spray absorption tower (1) is 12-20m, and the inner diameter is 3-5 m;
preferably, the rotational speed of each stage of spray trays (5) is independently 20-40 r/min.
8. A method according to claim 7, wherein each stage of spray trays (5) is provided independently with at least 4 nozzles (51), further preferably with 4-8 nozzles (51);
preferably, the nozzle (51) is a spiral nozzle;
further preferably, the spiral part (511) of the spiral nozzle is provided with a plurality of holes (512), preferably, the plurality of holes (512) are uniformly distributed on the spiral part (511); still more preferably, the opening ratio of the spiral member (511) is 10 to 20%.
9. The method of claim 6, wherein the method further comprises: sending the liquid in the first-stage absorption kettle (2) into a hydrochloric acid storage tank (4);
preferably, when the content of hydrochloric acid in the first stage absorption kettle (2) is not less than 10 weight percent, the liquid in the first stage absorption kettle (2) is sent to a hydrochloric acid storage tank (4);
preferably, the method further comprises: a second-stage absorption kettle (3) and the first-stage absorption kettle (2) are alternately used;
preferably, the volumes of the first stage absorption kettle (2) and the second stage absorption kettle (3) are respectively and independently 10-15m3。
10. The method of claim 9, wherein the method further comprises: heating the hydrochloric acid storage tank (4), preferably, the heating conditions comprise: the temperature is 70-100 ℃, and the time is 1-5 h;
preferably, the gas obtained from the top of the hydrochloric acid storage tank (4) is sent to the first-stage absorption kettle (2) and/or the second-stage absorption kettle (3).
11. A mixture comprising hydrochloric acid obtained by the treatment method of any one of claims 6 to 10.
12. Use of a mixture comprising hydrochloric acid as claimed in claim 11 in the preparation of a catalytic cracking catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811132708.7A CN110947281A (en) | 2018-09-27 | 2018-09-27 | Device and method for treating chlorine-containing tail gas, mixture containing hydrochloric acid and application of mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811132708.7A CN110947281A (en) | 2018-09-27 | 2018-09-27 | Device and method for treating chlorine-containing tail gas, mixture containing hydrochloric acid and application of mixture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110947281A true CN110947281A (en) | 2020-04-03 |
Family
ID=69967881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811132708.7A Pending CN110947281A (en) | 2018-09-27 | 2018-09-27 | Device and method for treating chlorine-containing tail gas, mixture containing hydrochloric acid and application of mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110947281A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2089429A5 (en) * | 1970-04-10 | 1972-01-07 | Steuler Industriewerke Gmbh | Multistage scrubber |
| US5008225A (en) * | 1984-05-24 | 1991-04-16 | The B. F. Goodrich Company | Catalytic dehydrohalogenation catalyst |
| US20060204407A1 (en) * | 2005-03-09 | 2006-09-14 | Mcwhorter Edward M | Coal flue gas scrubber |
| US20080146854A1 (en) * | 2004-12-22 | 2008-06-19 | Harald Hafenscher | Method for Producing 1,2-Dichloroethane by Means of Direct Chlorination |
| CN201147730Y (en) * | 2008-01-30 | 2008-11-12 | 齐忠华 | Porous helical spray nozzle |
| CN202625835U (en) * | 2012-04-11 | 2012-12-26 | 中国恩菲工程技术有限公司 | System for recovering hydrogen chloride from reduction exhaust gas |
| CN204522718U (en) * | 2015-03-04 | 2015-08-05 | 中国石油化工股份有限公司 | Hydrochloric acid tank hydrogen chloride tail gas treating apparatus |
| CN105503513A (en) * | 2015-12-08 | 2016-04-20 | 天津利安隆新材料股份有限公司 | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid |
| CN206823477U (en) * | 2017-06-07 | 2018-01-02 | 宁夏龙江化工科技有限公司 | A kind of light hydrocarbon etherifying industrial water washes tower |
| CN107961645A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of processing method of chloride tail gas |
| CN108031260A (en) * | 2017-11-13 | 2018-05-15 | 扬州荣辉化工设备有限公司 | A kind of adjustable desulfurizing tower |
| CN108147491A (en) * | 2017-11-29 | 2018-06-12 | 金华市纳德棠生物科技有限公司 | A kind of wastewater zero discharge equipment |
-
2018
- 2018-09-27 CN CN201811132708.7A patent/CN110947281A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2089429A5 (en) * | 1970-04-10 | 1972-01-07 | Steuler Industriewerke Gmbh | Multistage scrubber |
| US5008225A (en) * | 1984-05-24 | 1991-04-16 | The B. F. Goodrich Company | Catalytic dehydrohalogenation catalyst |
| US20080146854A1 (en) * | 2004-12-22 | 2008-06-19 | Harald Hafenscher | Method for Producing 1,2-Dichloroethane by Means of Direct Chlorination |
| US20060204407A1 (en) * | 2005-03-09 | 2006-09-14 | Mcwhorter Edward M | Coal flue gas scrubber |
| CN201147730Y (en) * | 2008-01-30 | 2008-11-12 | 齐忠华 | Porous helical spray nozzle |
| CN202625835U (en) * | 2012-04-11 | 2012-12-26 | 中国恩菲工程技术有限公司 | System for recovering hydrogen chloride from reduction exhaust gas |
| CN204522718U (en) * | 2015-03-04 | 2015-08-05 | 中国石油化工股份有限公司 | Hydrochloric acid tank hydrogen chloride tail gas treating apparatus |
| CN105503513A (en) * | 2015-12-08 | 2016-04-20 | 天津利安隆新材料股份有限公司 | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid |
| CN107961645A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of processing method of chloride tail gas |
| CN206823477U (en) * | 2017-06-07 | 2018-01-02 | 宁夏龙江化工科技有限公司 | A kind of light hydrocarbon etherifying industrial water washes tower |
| CN108031260A (en) * | 2017-11-13 | 2018-05-15 | 扬州荣辉化工设备有限公司 | A kind of adjustable desulfurizing tower |
| CN108147491A (en) * | 2017-11-29 | 2018-06-12 | 金华市纳德棠生物科技有限公司 | A kind of wastewater zero discharge equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111013328B (en) | Treatment method of gas-phase ultrastable molecular sieve tail gas, obtained mixture and application thereof, and preparation method of catalytic cracking catalyst | |
| CN1070731C (en) | Process for preparing a modified Y-zeolite | |
| CN108786375A (en) | A kind of method and system of discharge gas of the processing containing volatile organic matter | |
| CN109225320B (en) | Method for crystallization regeneration of waste molecular sieve with MFI structure | |
| CN1915486A (en) | Hydrated alumina with structure of similar to thin diaspore of containing additive | |
| CN113289679B (en) | Method for regenerating waste catalyst framework containing molecular sieve by supplementing aluminum and reactivating | |
| CN105251525A (en) | Recycling method of vanadium-containing waste FCC (fluid catalytic cracking) equilibrium catalyst | |
| CN1059701A (en) | High-silicon beta zeolite | |
| CN1192993C (en) | Removal of phosphorus-contg. compounds from olefin feedstock | |
| CN110947281A (en) | Device and method for treating chlorine-containing tail gas, mixture containing hydrochloric acid and application of mixture | |
| CN1861754A (en) | Catalytic cracking cocatalyst and preparation method thereof | |
| CN1157465C (en) | Catalytic cracking catalyst for preparing light oil with high yield and its preparing process | |
| CN109529917B (en) | Preparation method of TiO2, CuO/ZSM-5 molecular sieve catalyst | |
| CN1879960A (en) | Heavy metal resistant catalytic cracking auxiliary agent and preparation method thereof | |
| CN108097288A (en) | A kind of method for preparing rare earth Y type molecular sieve | |
| US2430289A (en) | Process for ammoniating an acid treated clay | |
| CN1195014A (en) | Process for modifying kaolin | |
| CN113952978B (en) | Catalytic cracking catalyst and preparation method and application thereof | |
| CN1900226A (en) | Catalytic cracking cocatalyst for producing diesel oil in high yield and preparation method thereof | |
| CN115920589B (en) | Treatment method of low-concentration sewage pool waste gas | |
| CN112717985B (en) | Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof | |
| CN109692676B (en) | Macroporous kaolinite and preparation and application thereof | |
| CN1048427C (en) | Laminar column molecular sieve catalyst of high yield olefines | |
| CN113952969B (en) | Catalytic cracking catalyst and preparation method and application thereof | |
| CN112717961B (en) | Filter residue and preparation method thereof, and catalytic cracking catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200403 |
|
| RJ01 | Rejection of invention patent application after publication |