CN116999870A - Recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbon - Google Patents
Recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbon Download PDFInfo
- Publication number
- CN116999870A CN116999870A CN202310823216.7A CN202310823216A CN116999870A CN 116999870 A CN116999870 A CN 116999870A CN 202310823216 A CN202310823216 A CN 202310823216A CN 116999870 A CN116999870 A CN 116999870A
- Authority
- CN
- China
- Prior art keywords
- waste
- fluorochlorohydrocarbon
- tower
- recycling
- storage tank
- 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
- 239000002699 waste material Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 238000002485 combustion reaction Methods 0.000 claims abstract description 55
- 239000000047 product Substances 0.000 claims abstract description 47
- 239000002918 waste heat Substances 0.000 claims abstract description 43
- 238000010791 quenching Methods 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 32
- 230000000171 quenching effect Effects 0.000 claims abstract description 32
- 239000006227 byproduct Substances 0.000 claims abstract description 28
- 239000000428 dust Substances 0.000 claims abstract description 23
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims description 77
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 76
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 13
- 239000010865 sewage Substances 0.000 claims description 13
- 239000000779 smoke Substances 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- -1 fluorine-chlorine hydrocarbon Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002893 slag Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 9
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 6
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 6
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 6
- 229940099364 dichlorofluoromethane Drugs 0.000 description 6
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 5
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000010749 BS 2869 Class C1 Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/20—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having rotating or oscillating drums
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/46—Recuperation of heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
- F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
- F23J15/025—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using filters
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of chemical industry, and in particular relates to a recycling and harmless treatment combined system and method of waste fluorochlorohydrocarbon, wherein the combined system comprises a recycling module and a harmless treatment module of the waste fluorochlorohydrocarbon, and the recycling module comprises a fixed bed reactor for hydrodechlorination of the fluorochlorohydrocarbon, a rectifying tower for separating byproducts and a storage tank for storing the products; the harmless treatment module comprises a waste storage tank, a rotary kiln, a secondary combustion chamber, a waste heat boiler, a quenching tower, a dry reaction tower, a bag-type dust remover and a wet deacidification tower which are sequentially connected, and further comprises a fan for sending the fluorocarbon gas in the waste storage tank into the rotary kiln. The invention combines the recycling conversion and the harmless treatment to form a waste fluorochlorohydrocarbon hydrodechlorination-separation-incineration harmless disposal laboratory process route, thereby greatly reducing the harmless disposal amount and disposal difficulty of high-temperature incineration and reducing the energy consumption and disposal cost.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbons.
Background
Chlorofluorocarbons (CFCs), also known as freons, are artificial hydrocarbon chemicals containing chlorine and fluorine, and are widely used in household appliances, heat insulation materials, refrigerants, blowing agents, and the like. CFCs have extremely high chemical stability, have an average life in the atmosphere of hundreds of years, and are not easily decomposed or destroyed. However, when they rise to the stratosphere, chlorine atoms released by decomposition under the action of intense ultraviolet rays and ozone undergo a chain reaction, so that ozone molecules are continuously destroyed, ozone layer cavities are caused, and various serious hazards are brought to human health and ecological environment.
In the conversion of CFCs, chlorofluorocarbons are converted to environmentally benign chemicals, which in some cases are of greater economic value. The hydrodehalogenation research is the most extensive conversion process, and aims to convert the fluorochlorohydrocarbon into products such as Hydrofluorocarbon (HFCs) or unsaturated fluorocarbon, thereby reducing the environmental pressure and obtaining high-added-value products. Catalytic Hydrodechlorination (HDC) is a potentially enormous technology for the treatment and stabilization of organic chlorinated waste. This is a structurally sensitive reaction, mainly by replacing the chlorine atom by a hydrogen atom, with a non-chlorinated cleaning product obtained by means of a suitable catalyst. The waste CFCs gas may also be treated by a pyrolysis process, which involves heating the gas to an elevated temperature to decompose it into simpler compounds such as hydrogen chloride and hydrogen fluoride. These products can then be treated to ensure their safe discharge or further utilization. However, in the existing treatment methods for CFCs, there is no process for combining the recycling conversion of CFCs with innocent treatment.
Disclosure of Invention
Aiming at the defect that the prior art does not combine the resource conversion and the harmless treatment of the fluorochlorohydrocarbon, the invention provides a system and a method for combining the resource utilization and the harmless treatment of the waste fluorochlorohydrocarbon, which have the following specific technical scheme:
in a first aspect, the invention provides a waste fluorochlorohydrocarbon recycling and harmless treatment combined system, which is characterized by comprising a waste fluorochlorohydrocarbon recycling module and a harmless treatment module;
the recycling module comprises:
a fixed bed reactor for hydrodechlorination of fluorochlorohydrocarbons;
a rectifying tower connected with the fixed bed reactor for separating the gas flowing out of the fixed bed reactor, thereby obtaining recoverable products and non-fully reacted fluorochlorohydrocarbon;
a storage tank for storing a recoverable product flowing from the rectifying column;
the innocuous treatment module comprises:
a waste storage tank connected to the rectifying tower for storing the non-reacted fluorochlorohydrocarbon flowing out of the rectifying tower;
the combustion module comprises a rotary kiln and a secondary combustion chamber which are connected in sequence and is used for carrying out combustion treatment on the fluorine-chlorine hydrocarbon which is stored in the waste storage tank and is not completely reacted;
the cooling module comprises a waste heat boiler and a quenching tower which are connected in sequence and is used for cooling high-temperature gas flowing out of the combustion module and recovering heat energy;
the tail gas treatment module comprises a dry reaction tower, a bag-type dust remover and a wet deacidification tower which are sequentially connected, so that acid gas and smoke dust in gas flowing out of the cooling module are removed;
and the fan is used for providing kinetic energy for fluorine and chlorine which are not completely reacted to pass through each part in the harmless treatment module in sequence.
The combined system comprises a waste chlorofluorocarbon recycling module and a harmless treatment module, wherein a fixed bed reactor in the waste chlorofluorocarbon recycling module can perform catalytic hydrogenation dechlorination on the chlorofluorocarbon to convert the chlorofluorocarbon into main products of Hydrofluorocarbon (HFCs), the products comprise the hydrofluorocarbon, HCl, alkane, hydrochlorocarbon and the hydrochlorofluorocarbon which is not completely reacted, and a rectifying tower in the waste chlorofluorocarbon recycling module can separate the products and can be recycled to enter a storage tank as the products. After catalytic hydrogenation dechlorination, the fluorocarbon which is not fully reacted is filled into a waste storage tank after separation, the fluorocarbon is treated by a harmless treatment module, the product which cannot be recycled is conveyed by a fan, the product is conveyed into a rotary kiln for incineration reaction through a pipeline, wherein freon gas is combusted and decomposed at high temperature, the obtained flue gas is subjected to waste heat utilization in a waste heat boiler, then the flue gas is cooled in a quenching tower, then the flue gas is subjected to desulfurization and defluorination through a dry reaction tower, smoke dust with smaller particle size is intercepted by a bag-type dust remover, the generated flue gas is subjected to harmless treatment such as deacidification through a wet deacidification tower, and the rest empty waste storage tank is put into an incinerator for complete incineration after being replaced by water.
In a second aspect, the invention provides a method for recycling and harmlessly disposing of waste fluorochlorohydrocarbons, wherein the disposing method is performed in a combined system and comprises the following steps:
s1: the waste fluorochlorohydrocarbon is subjected to hydrodechlorination reaction through a fixed bed reactor;
s2: separating the product generated in the step S1 by a rectifying tower, purifying the separated main product, and storing;
s3: introducing the byproduct fluorochlorohydrocarbon in the step S2 into a waste storage tank;
s4: after the fluorocarbon in the waste storage tank is conveyed and fed by a fan, the fluorocarbon enters a rotary kiln for incineration treatment, and a secondary combustion chamber arranged at the tail part of the rotary kiln completely incinerates dangerous waste and discharges slag;
s5: the high-temperature flue gas generated in the secondary combustion chamber in the step S4 enters a waste heat boiler to exchange waste heat, and the low-temperature flue gas after heat exchange is cooled by a quenching tower;
s6: and (3) enabling the cooled flue gas in the step (S5) to enter a dry reaction tower for deacidification, then entering a bag-type dust remover for further purification of the flue gas, then entering a wet deacidification tower for deacidification, and discharging the rest waste water into a sewage station for treatment, wherein the waste water reaches the standard and is discharged.
The method for recycling and harmless disposal of the waste fluorochlorohydrocarbon is realized through a combined system, and the recycling conversion and harmless treatment are combined to form a laboratory process route of hydrodechlorination-product separation-incineration harmless disposal of the waste fluorochlorohydrocarbon, so that the harmless disposal amount and disposal difficulty of high-temperature incineration are greatly reduced, the energy consumption and disposal cost are reduced, waste is turned into wealth, and the method has great social and economic benefits.
Further, in S1, the catalyst used in the hydrodechlorination reaction is a noble metal catalyst.
Further, the noble metal catalyst is a Pd catalyst.
The catalytic hydrodechlorination reaction is a reaction in which a C-CI bond in the fluorochlorohydrocarbon is reduced to a C-H bond by an H atom under the action of a catalyst. Especially, with the abandon of the atmospheric ozone layer consumable (ODS) fluorochlorohydrocarbon, the demand of the fluorochlorohydrocarbon substitute HFCs gradually increases, and the route of synthesizing the HFCs by using CFCs as raw materials and carrying out the dechlorination reaction under the action of a catalyst is a more effective way for realizing the utilization of CFCs with the coordinated development of environment and economy.
In the catalytic hydrogenation dechlorination reaction of the fluorochlorohydrocarbon, the selectivity of different catalysts to the product is also different, and the selectivity of the hydrofluorocarbon on the palladium catalyst is higher so as to obtain more HFCs with high added value. In this reaction, the palladium catalyst is supported on a carrier, and the carrier species include metal oxides, metal fluorides, activated carbon, and the like.
Further, in S1, the hydrodechlorination reaction temperature is 200-500 ℃, the reaction pressure is 0-3 mpa, and H 2 The volume flow rate ratio of the fluorine-chlorine hydrocarbon to the waste fluorine-chlorine hydrocarbon is 1-6: 1.
along with the increase of the hydrogen gas velocity, the catalyst carrier layer is well fluidized, the mass transfer speed of the whole reaction is improved, reactants are fully contacted with the catalyst, and the catalytic hydrogenation dechlorination reaction is more thoroughly carried out.
Further, in S2, the pressure of the rectifying tower is 0-2 Mpa, the number of theoretical plates is 25-35, the reflux ratio is 1.1-2.0, and the feeding temperature is 25-45 ℃.
Further in S4, the kiln head temperature in the rotary kiln is 550-700 ℃, the kiln tail temperature is 850-950 ℃, the secondary combustion chamber temperature is 1100-1200 ℃, the residence time in the rotary kiln is 0.5-2 h, and the residence time of flue gas in the secondary combustion chamber is 2-5S.
Further, in S5, the injection temperature of the quenching tower is 500-600 ℃, and the discharge temperature is 150-200 ℃.
In S6, the dry reaction tower is internally provided with fluorine fixing and desulfurizing, wherein the fluorine fixing and desulfurizing agent is Ca (OH) 2 The alkaline neutralizer used in the wet deacidification tower is NaOH.
The method comprises the steps that the partially abandoned fluorochlorohydrocarbon is subjected to hydrodechlorination reaction through a fixed bed reactor, products generated by the reaction are separated through a rectifying tower, and the products which can be recycled are fed into a storage tank as products; the harmless treatment part is used for introducing the byproducts which cannot be recycled into a waste storage tank, conveying the byproducts through a fan, conveying the fluorocarbon gas into a kiln through a pipeline for incineration reaction, adding water into the remaining empty waste storage tank for replacement, and then putting the waste storage tank into an incinerator for complete incineration.
After entering a secondary combustion chamber, the fluorochlorohydrocarbon gas is decomposed into gases such as hydrogen fluoride, hydrogen chloride and the like at high temperature in the secondary combustion chamber, the gases firstly pass through a waste heat boiler and a quenching tower, then pass through a dry reaction tower for dry sulfur removal and fluorine fixation, then intercept smoke dust in the gases through a bag-type dust remover, and finally enter a wet deacidification tower for wet treatment of acid gases.
The invention has the following beneficial effects:
(1) The invention combines the recycling conversion and the harmless treatment to form a process route of a waste fluorochlorohydrocarbon hydrodechlorination-separation-incineration harmless disposal laboratory, thereby not only greatly reducing the harmless disposal amount and disposal difficulty of high-temperature incineration and reducing the energy consumption and disposal cost, but also changing waste into valuables, which is a potential industrialized route with strong feasibility and has great social benefit and certain economic benefit;
(2) The resource utilization part of the invention adopts Pd catalyst to convert the waste fluorochlorohydrocarbon, the condition is mild, no secondary pollutant is produced, no more toxic dioxin substance is produced, the treated pollutant can be reused, only HCl in the reaction product is a byproduct, the product is easy to recycle, the invention is a green catalytic process with higher atom economy, the whole dechlorination process is simple, safe and effective, and the invention has strong industrial application prospect.
Drawings
Fig. 1: the invention relates to a schematic diagram of a resource utilization and harmless treatment combined system of waste fluorochlorohydrocarbon.
Wherein: waste fluorochlorohydrocarbon, hydrogen, slag, up to standard flue gas, waste water, 1 fixed bed reactor, 2 rectifying tower, 3 storage tank, 4 waste storage tank, 5 fan, 6 rotary kiln, 7 secondary combustion chamber, 8 waste heat boiler, 9 quench tower, 10 dry reaction tower, 11 bag dust collector, 12 wet deacidification tower.
Detailed Description
The invention is further described below in connection with specific embodiments. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
General examples
S1: the waste fluorochlorohydrocarbon a is subjected to hydrodechlorination reaction in a fixed bed reactor 1, the catalyst is Pd catalyst, the reaction temperature is 200-500 ℃, the reaction pressure is 0-3 mpa, and H 2 The volume flow rate ratio of the fluorine-chlorine hydrocarbon to the waste fluorine-chlorine hydrocarbon is 1-6: 1, a step of;
s2: separating the products generated by the reaction through a rectifying tower 2, wherein the pressure of the rectifying tower 2 is 0-2 Mpa, the number of theoretical plates is 25-35, the reflux ratio is 1.1-2.0, the feeding temperature is 25-45 ℃, and the main products after separation are purified and stored in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, the temperature of the kiln head in the rotary kiln 6 is 550-700 ℃, the temperature of the kiln tail is 850-950 ℃, a secondary combustion chamber 7 is arranged at the tail of the rotary kiln 6, hazardous waste can be completely incinerated, the temperature of the secondary combustion chamber 7 is 1100-1200 ℃, the retention time in the rotary kiln 6 is 0.5-2 h, and the retention time of flue gas in the secondary combustion chamber 7 is 2-5 s; adding water into the residual empty waste storage tank 4 for replacement, then putting the waste storage tank into an incinerator, and discharging slag c;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is subjected to waste heat utilization, the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9, the sample injection temperature of the quenching tower 9 is 500-600 ℃, the discharge temperature is 150-200 ℃, and the temperature of the gas is reduced to about 200 ℃ in 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 1
This example is directed to the treatment of waste chlorofluorocarbons of the class C1 CFC-12 (difluorodichloromethane) as follows:
s1: the waste fluorochlorohydrocarbon aCFC-12 (difluoro methylene dichloride) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 2
This example is directed to the treatment of the C1 class of waste chlorofluorocarbons CFC-21 (dichlorofluoromethane) as follows:
s1: the waste fluorochlorohydrocarbon aCFC-21 (dichloro-fluoro methane) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 3
This example is directed to the treatment of the C1 class of waste chlorofluorocarbons CFC-22 (difluoromethane) as follows:
s1: the waste fluorochlorohydrocarbon aCFC-22 (difluoro chloromethane) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 4
This example is directed to the treatment of waste chlorofluorocarbon CFC-113 (trifluorotrichloroethane) of the C2 class, comprising the following steps:
s1: the waste fluorochlorohydrocarbon aCFC-113 (trifluorotrichloroethane) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 5
This example is directed to the treatment of waste chlorofluorocarbons CFC-114 (tetrafluorodichloroethane) of the C2 class, comprising the following steps:
s1: the waste fluorochlorohydrocarbon aCFC-114 (tetrafluorodichloroethane) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 6
This example is directed to the treatment of waste chlorofluorocarbons of the C2 class CFC-115 (pentafluoro-chloroethane) as follows:
s1: the waste fluorochlorohydrocarbon aCFC-115 (pentafluoro-chloroethane) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3; s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 7
This example is directed to the treatment of waste fluorochlorohydrocarbons CFC-12 (difluorodichloromethane) +cfc-115 (pentafluoro-chloroethane) of the c1+c2 class, comprising the following steps:
s1: the waste fluorochlorohydrocarbon aCFC-12 (difluorodichloromethane) +CFC-115 (pentafluoro-chloroethane) is subjected to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 8
This example is directed to the treatment of waste chlorofluorocarbons CFC-21 (dichloromonofluoromethane) +cfc-114 (tetrafluorodichloroethane) of the c1+c2 class, and comprises the following steps:
s1: the waste fluorochlorohydrocarbon aCFC-21 (dichloro-fluoro methane) +CFC-114 (tetrafluoro dichloroethane) is subject to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 9
This example is directed to the treatment of waste chlorofluorocarbons CFC-22 (difluoromethane) +cfc-113 (trifluorotrichloroethane) of the c1+c2 class, comprising the following steps:
s1: the waste fluorochlorohydrocarbon aCFC-22 (difluoro chloromethane) +CFC-113 (trifluoro trichloroethane) is subject to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
Example 10
This example is directed to the treatment of waste chlorofluorocarbons CFC-21 (dichloromonofluoromethane) +cfc-114 (tetrafluorodichloroethane) of the c1+c2 class, and comprises the following steps:
s1: the waste fluorochlorohydrocarbon aCFC-21 (dichloro-fluoro methane) +CFC-114 (tetrafluoro dichloroethane) is subject to hydrodechlorination reaction through a fixed bed reactor 1;
s2: separating the product generated by the reaction through a rectifying tower 2, purifying the separated main product, and storing in a storage tank 3;
s3: introducing the reacted by-product fluorochlorohydrocarbon into a waste storage tank 4;
s4: in the waste storage tank 4, the fluorocarbon gas is conveyed by a fan 5 and is sent into a rotary kiln 6 through a pipeline to be incinerated, a secondary combustion chamber 7 is arranged at the tail part of the rotary kiln 6, so that dangerous waste can be completely incinerated, and the residual empty waste storage tank 4 is put into an incinerator after being replaced by water, and slag c is discharged;
s5: the high-temperature flue gas generated in the secondary combustion chamber 7 enters the waste heat boiler 8 for waste heat exchange, the generated steam is used for waste heat utilization, and the low-temperature flue gas with the temperature of about 550 ℃ after heat exchange is cooled by the quenching tower 9 and is cooled to about 200 ℃ within 1 second;
s6: the cooled flue gas of the quenching tower 9 enters a dry reaction tower 10 for deacidification treatment, then enters a bag-type dust remover 11 for further purification of the flue gas, then enters a wet deacidification tower 12 for deep deacidification treatment by using an alkaline neutralizer, and finally the residual wastewater e is discharged into a sewage station for treatment, and the discharged flue gas reaches the standard. Complete combustion hydrolysis of CFCs is achieved.
The flue gases treated in examples 1 to 10 were tested, and the results of each test are shown in tables 1 to 10 below:
table 1: smoke record table for R12 byproduct incineration experiment
Table 2: flue gas record table of R21 accessory substance burning experiment
Table 3: smoke record table for R22 by-product incineration experiment
Table 4: smoke record table for R113 byproduct incineration experiment
Table 5: smoke record table for R114 by-product incineration experiment
Table 6: smoke record table for R115 by-product incineration experiment
Table 7: smoke record table for R12+R115 byproduct incineration experiment
/>
Table 8: flue gas recording table for R21+R114 byproduct incineration experiment
Table 9: smoke record table for R22+R113 byproduct incineration experiment
/>
Table 10: flue gas recording table for R21+R114 byproduct incineration experiment
From tables 1 to 10, it can be seen that the detection results of incineration flue gas of the byproducts of C1, C2 and C1+C2 meet the national standard, so that all freons in the incineration process are safely and harmlessly treated, the experimental project achieves the expected experimental target, and the process meets various environmental protection requirements.
In summary, the byproducts of the C1 and C2 compounds in the experimental process can be completely decomposed after undergoing the process conditions of resource utilization and incineration.
Claims (10)
1. The system for recycling and innocent treatment of the waste fluorochlorohydrocarbon is characterized by comprising a waste fluorochlorohydrocarbon recycling module and a innocent treatment module;
the recycling module comprises:
a fixed bed reactor (1) for hydrodechlorination of fluorochlorohydrocarbons;
a rectifying column (2) connected to the fixed bed reactor (1) for separating the gas flowing out from the fixed bed reactor (1) to obtain a recoverable product and a non-fully reacted fluorochlorohydrocarbon;
a storage tank (3) for storing a recoverable product flowing out of the rectifying column (2);
the innocuous treatment module comprises:
a waste storage tank (4) connected to the rectifying tower (2) for storing the non-fully reacted fluorochlorohydrocarbon flowing out of the rectifying tower (2);
the combustion module comprises a rotary kiln (6) and a secondary combustion chamber (7) which are connected in sequence and is used for carrying out combustion treatment on the fluorine-chlorine hydrocarbon which is stored in the waste storage tank (4) and is not completely reacted;
the cooling module comprises an exhaust-heat boiler (8) and a quenching tower (9) which are connected in sequence and is used for cooling high-temperature gas flowing out of the combustion module and recovering heat energy;
the tail gas treatment module comprises a dry reaction tower (10), a bag-type dust remover (11) and a wet deacidification tower (12) which are sequentially connected, so that acid gas and smoke dust in gas flowing out of the cooling module are removed;
and the fan (5) is used for providing kinetic energy for fluorine and chlorine which are not completely reacted to pass through each part in the harmless treatment module in sequence.
2. A method for recycling and harmless disposal of waste fluorochlorohydrocarbon is characterized in that: the treatment method is performed in a combined system and comprises the following steps:
s1: the waste fluorochlorohydrocarbon is subjected to hydrodechlorination reaction through a fixed bed reactor (1);
s2: separating the product generated in the step S1 by a rectifying tower (2), purifying the separated main product, and storing;
s3: introducing the byproduct fluorochlorohydrocarbon in the S2 into a waste storage tank (4);
s4: after the fluorocarbon in the waste storage tank (4) is conveyed and fed by a fan (5), the fluorocarbon enters a rotary kiln (6) for incineration treatment, and a secondary combustion chamber (7) arranged at the tail part of the rotary kiln (6) completely incinerates dangerous waste;
s5: the high-temperature flue gas generated by the secondary combustion chamber (7) in the step S4 enters the waste heat boiler (8) to exchange waste heat, and the low-temperature flue gas after heat exchange is cooled by the quenching tower (9);
s6: and (3) enabling the cooling flue gas in the step (S5) to enter a dry reaction tower (10) for deacidification treatment, then entering a bag-type dust remover (11) for further purification of the flue gas, then entering a wet deacidification tower (12) for deacidification treatment, and discharging the rest wastewater (e) into a sewage station for treatment, wherein the flue gas reaches the standard (d) and is discharged.
3. The method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: in S1, the catalyst used in the hydrodechlorination reaction is a noble metal catalyst.
4. The method for recycling and harmlessly disposing of waste fluorochlorohydrocarbons according to claim 3, wherein the method comprises the steps of: the noble metal catalyst is a Pd catalyst.
5. The method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: in S1, the hydrodechlorination reaction temperature is 200-500 ℃, the reaction pressure is 0-3 mpa, and H 2 The volume flow rate ratio of the fluorine-chlorine hydrocarbon to the waste fluorine-chlorine hydrocarbon (a) is 1-6: 1.
6. the method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: in S2, the pressure of the rectifying tower (2) is 0-2 Mpa, the theoretical plate number is 25-35, the reflux ratio is 1.1-2.0, and the feeding temperature is 25-45 ℃.
7. The method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: in S4, the temperature of the kiln head in the rotary kiln (6) is 550-700 ℃, the temperature of the kiln tail is 850-950 ℃, the temperature of the secondary combustion chamber (7) is 1100-1200 ℃, the residence time in the rotary kiln (6) is 0.5-2 h, and the residence time of the flue gas in the secondary combustion chamber (7) is 2-5S.
8. The method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: s5, the injection temperature of the quenching tower (9) is 500-600 ℃, and the discharge temperature is 150-200 ℃.
9. The method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: s6, carrying out fluorine fixation and desulfurization in the dry reaction tower (10), wherein the fluorine fixation and desulfurization agent is Ca (OH) 2 。
10. The method for recycling and harmlessly disposing the waste fluorochlorohydrocarbon according to claim 2, which is characterized in that: in S6, the alkaline neutralizer used by the wet deacidification tower (12) is NaOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310823216.7A CN116999870A (en) | 2023-07-06 | 2023-07-06 | Recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310823216.7A CN116999870A (en) | 2023-07-06 | 2023-07-06 | Recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116999870A true CN116999870A (en) | 2023-11-07 |
Family
ID=88568179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310823216.7A Pending CN116999870A (en) | 2023-07-06 | 2023-07-06 | Recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116999870A (en) |
-
2023
- 2023-07-06 CN CN202310823216.7A patent/CN116999870A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100766749B1 (en) | An apparatus and method for treatment waste gas contains perfluoro compounds | |
| JP5192617B2 (en) | Production of one or more effective products from low-value halogenated materials | |
| RU2095131C1 (en) | Method for rendering harmless of effluent gases of waste burning units and device for its embodiment | |
| JP5721832B2 (en) | Process for pyrolysis of PVC and other waste containing halogen containing polymer waste | |
| CN116999870A (en) | Recycling and harmless disposal combined system and method for waste fluorochlorohydrocarbon | |
| WO2001038787A1 (en) | Improved chlorinated hydrocarbon waste incinerator an d valorization of chlorinated residuals process unit | |
| CN210645852U (en) | High-temperature pyrolysis gas disposal device | |
| JP2008031328A (en) | Liquefaction treatment process and apparatus for plastic waste | |
| CN110508122B (en) | High-temperature pyrolysis gas treatment device and treatment method | |
| CN113048480B (en) | Harmless treatment method for garbage in high-altitude low-oxygen area | |
| RU2684263C1 (en) | Method of recycling solid medical wastes | |
| CN111853832A (en) | Plasma harmless treatment method of polychlorinated biphenyl waste liquid | |
| Blake | Solar thermal technology for the destruction of CFC waste | |
| RU2014346C1 (en) | Method of processing wastes | |
| JP3734963B2 (en) | Detoxification method for organochlorine compounds, etc. with mixed molten salt | |
| CN111828993A (en) | Plasma environment-friendly treatment method of polychlorinated biphenyl waste liquid | |
| JPH1192590A (en) | Disposal method or disposal device of waste containing expandable plastic | |
| JP3725889B2 (en) | Method and apparatus for promoting reaction of chemical substance using ultrasonic wave, and method for producing fluororesin using ultrasonic wave | |
| CN117419343A (en) | Dangerous waste treatment system and treatment method | |
| JP2000167514A (en) | Exhaust gas treatment for reducing discharge of dioxins | |
| RU2232943C1 (en) | Method for reclamation of chemical weapon, contaminated containers and grounds | |
| JPH08215566A (en) | Decomposing method of fluorocarbon | |
| JPH10265413A (en) | Treatment of halogenated methane into harmless methane | |
| CN114409001A (en) | Sucralose waste liquid treatment device and method | |
| CN115340069A (en) | Method for recycling byproduct hydrogen chloride containing organic matters |
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 |