CN113209770A - Method for removing odor and application thereof - Google Patents
Method for removing odor and application thereof Download PDFInfo
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- CN113209770A CN113209770A CN202110478049.8A CN202110478049A CN113209770A CN 113209770 A CN113209770 A CN 113209770A CN 202110478049 A CN202110478049 A CN 202110478049A CN 113209770 A CN113209770 A CN 113209770A
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- 238000000034 method Methods 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 397
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 81
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000004332 deodorization Methods 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 17
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 17
- 238000007598 dipping method Methods 0.000 claims description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 39
- 239000003344 environmental pollutant Substances 0.000 abstract description 14
- 231100000719 pollutant Toxicity 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 229920006395 saturated elastomer Polymers 0.000 abstract description 9
- 230000000149 penetrating effect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- 235000019645 odor Nutrition 0.000 description 93
- 239000000243 solution Substances 0.000 description 53
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 39
- 238000002791 soaking Methods 0.000 description 27
- 238000002360 preparation method Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910019029 PtCl4 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 210000000196 olfactory nerve Anatomy 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention relates to a method for removing odor and application thereof, belonging to the technical field of chemistry. The invention provides a method for removing odor, which is characterized in that active carbon with modified metal ions on the surface and/or in pore canals is used for adsorbing the odor; the total penetrating adsorption quantity of the activated carbon used by the method to odor is up to 280mg/g, and the saturated adsorption capacity is up to 400mg/g, so that the deodorization method has the advantages of good deodorization effect, no need of frequently replacing the activated carbon or frequently desorbing and regenerating the activated carbon, and effectively reduces the deodorization cost; the method can select the activated carbon with different types and proportions of metal ions modified on the surface and/or in the pore canal aiming at different odor pollutants, and further improve the deodorization effect; the active carbon used in the method can solidify a certain proportion of odor pollutants on metal ions through chemical reaction, so that the active carbon used in the method is easier to desorb and regenerate, and the deodorization cost is further reduced.
Description
Technical Field
The invention relates to a method for removing odor and application thereof, belonging to the technical field of chemistry.
Background
Odor means a gas containing a malodorous substance, the result of whichThe cause of odour is mainly due to the presence of characteristic odour-emitting groups, such as: -SH, -NH2、CS2、-C(NH3) And the like. The gas molecules containing smelly groups act on olfactory cells to transmit information to brain nerves through olfactory nerves. The odor can be classified according to characteristics into a hydrogen sulfide and methyl mercaptan-rich sewage odor generated from a municipal sewage treatment plant, a putrefactive odor rich in ammonia gas generated from a garbage treatment plant, a pharmaceutical odor rich in formaldehyde and carbon disulfide generated from a pharmaceutical process, and a packaging odor rich in formaldehyde and acetone generated from a packaging plant.
With the rapid development of social economy, the continuous improvement of the living standard of people and the increasingly enhanced public environmental awareness of people, the odor problem has attracted more and more extensive attention of society. The odor has various types, wide distribution and large influence range, and becomes the most complicated air pollution problem at present. In order to prevent and eliminate the influence of odor on the ecological environment and the life quality of residents, the new atmospheric emission standard continuously improves the relevant emission standard, which also puts higher and more comprehensive requirements on the treatment process and level of the odor.
At present, the odor treatment mainly adopts an adsorption method, an absorption method, a catalytic conversion method and a biological treatment method. Because adsorption processes can reduce odor pollutants to trace levels, increasingly stringent environmental quality requirements make adsorption processes increasingly gaining attention as a deodorization process in the deodorization field. The adsorption method has the following advantages in the treatment of the odor gas: (1) a dry process is adopted, and a non-corrosive system is adopted; (2) the process is easy to control, and the adaptability to the fluctuation of the working condition load is strong; (3) the pollutant content in the gas can be reduced to extremely low level, so that the gas reaches the emission standard; (4) the material can be recycled through a recycling process.
There are many adsorption materials such as alumina, molecular sieve, activated carbon, silica gel, etc. most of the adsorbents have a larger adsorption capacity for water in the gas than for malodorous substances, and activated carbon has a larger equilibrium adsorption capacity for malodorous gas and a stronger adsorption capacity for various malodorous gases. In addition, the activated carbon also has the advantages of rich pore structure, low price and rich material. Therefore, activated carbon materials are becoming the most commonly used adsorbent materials in industry and environmental protection.
However, the total penetrating adsorption amount of the existing activated carbon to the odor is not high, which results in that when the existing activated carbon is used for adsorbing the odor, the activated carbon needs to be frequently replaced or desorbed and regenerated, which undoubtedly increases the cost of deodorization by using the activated carbon. In order to further improve the application performance and advantages of activated carbon in the field of deodorization, a great deal of research and optimization work aiming at the activated carbon is already carried out.
For example, patent document CN211753695U discloses a horizontal activated carbon deodorizing apparatus which improves the placement of the activated carbon and optimizes the air inlet of the adsorption device, reduces the volume of the apparatus and reduces the resistance of the activated carbon layer; patent document CN211585915U discloses a multi-layer activated carbon deodorization device, which combines activated carbon adsorption and spraying processes, and improves the odor absorption effect of the deodorization device; the patent document CN212091561U improves the use efficiency of activated carbon in a limited space and facilitates the replacement of activated carbon by changing the airflow channel of activated carbon. However, the optimization method only optimizes the use process and equipment of the existing activated carbon, and does not fundamentally solve the problem that the total penetrating adsorption capacity of the existing activated carbon to the odor is low, and the problem that the cost is high because the activated carbon needs to be frequently replaced or the activated carbon needs to be frequently desorbed and regenerated when the existing activated carbon is used for adsorbing the odor is not solved.
For another example, patent document CN112121765A mixes activated carbon with graphene oxide, metal oxide and ethanol to obtain a novel graphene material that can be used for removing formaldehyde, so that the graphene material has a good antibacterial effect and a good formaldehyde adsorption removal effect. However, the optimization method is to obtain a novel adsorption material with certain characteristics through a complex mixing preparation process, so that the material cost is greatly increased, the process complexity is greatly increased, and the cost of deodorizing by using activated carbon is increased.
Therefore, it is highly desirable to find a low-cost and simple method for optimizing the existing activated carbon itself to increase the total penetrating adsorption of the active carbon to the odor.
Disclosure of Invention
In order to solve the defects, the invention provides a method for removing odor, which uses active carbon to adsorb the odor; the surface and/or the pore canal of the active carbon are/is decorated with metal ions.
In one embodiment of the invention, the metal ion comprises Zn2+、Fe3+、Cu2+、Cd2+、Ag2+And Ti2+At least one of (1).
In one embodiment of the present invention, the odor contains at least one of hydrogen sulfide, ammonia gas, methyl mercaptan, methyl sulfide, carbon disulfide, acetone, formaldehyde, and acetaldehyde.
In one embodiment of the present invention, when the malodor contains hydrogen sulfide, the metal ion includes Zn2+、Cu2+And Cd2+And Zn is on the surface and/or in the pore channels of the active carbon2+、Cu2+And Cd2+The molar ratio of (A) to (B) is 3-4: 1-2: 0.2-0.5;
when the odor gas contains ammonia gas, the metal ions include Fe3+、Ag+And Pt4+And the surface and/or the inside of the pore canal of the active carbon is Fe3+、Ag+And Pt4+The molar ratio of (A) to (B) is 5-10: 0.1-0.2: 0.5-2;
when the odor contains formaldehyde, the metal ions include Zn2+、Cu2+And Fe3+And Zn is on the surface and/or in the pore channels of the active carbon2+、Cu2+And Fe3+The molar ratio of (A) to (B) is 2-3: 0.5-1: 1-2.
In one embodiment of the present invention, the activated carbon comprises at least one of granular activated carbon, honeycomb activated carbon, fibrous activated carbon, powdered activated carbon, and coconut shell activated carbon.
The invention also provides the activated carbon, and the surface and/or the pore channels of the activated carbon are/is modified with metal ions.
In one embodiment of the invention, the metal ion comprises Zn2+、Fe3+、Cu2+、Cd2+、Ag2+And Ti2+At least one of (1).
In one embodiment of the invention, the metal ion comprises Zn2+、Cu2+And Cd2+(ii) a Zn on the surface and/or in the pore channels of the active carbon2+、Cu2+And Cd2+The molar ratio of (A) to (B) is 3-4: 1-2: 0.2-0.5;
alternatively, the metal ion comprises Fe3+、Ag+And Pt4+(ii) a Fe on the surface and/or in the pore channels of the active carbon3+、Ag+And Pt4+The molar ratio of (A) to (B) is 5-10: 0.1-0.2: 0.5-2;
alternatively, the metal ion comprises Zn2+、Cu2+And Fe3+(ii) a Zn on the surface and/or in the pore channels of the active carbon2+、Cu2+And Fe3+The molar ratio of (A) to (B) is 2-3: 0.5-1: 1-2.
In one embodiment of the present invention, the activated carbon comprises at least one of granular activated carbon, honeycomb activated carbon, fibrous activated carbon, powdered activated carbon, and coconut shell activated carbon.
The invention also provides a method for preparing the activated carbon, which comprises the following steps:
coating: coating the metal ion solution on the surface of the activated carbon to enable the metal ions to be adsorbed on the surface of the activated carbon;
alternatively, the method comprises the steps of:
and (3) dipping: and (3) dipping the activated carbon into the metal ion solution, so that the metal ions are loaded in the pore channels of the activated carbon.
In one embodiment of the present invention, the metal ion solution contains Zn2+、Fe3+、Cu2+、Cd2+、Ag2+And Ti2+At least one of (1).
In one embodiment of the present invention, the metal ion solution contains Zn2+、Cu2+And Cd2+(ii) a In the metal ion solution, Zn2+、Cu2+And Cd2+The molar ratio of (A) to (B) is 3-4: 1-2: 0.2-0.5;
alternatively, the metal ion solution contains Fe3+、Ag+And Pt4+(ii) a In the metal ion solution, Fe3+、Ag+And Pt4 +The molar ratio of (A) to (B) is 5-10: 0.1-0.2: 0.5-2;
alternatively, the metal ion solution contains Zn2+、Cu2+And Fe3+(ii) a In the metal ion solution, Zn2+、Cu2+And Fe3+The molar ratio of (A) to (B) is 2-3: 0.5-1: 1-2.
In one embodiment of the present invention, the total concentration of the metal ion solvent in the metal ion solution is 5 to 200 g/L.
In one embodiment of the present invention, before the impregnation step, a pretreatment step is further included; the pretreatment steps are as follows: firstly, soaking the activated carbon in an acid solution or an alkali solution, then drying the activated carbon, and then soaking the activated carbon in an organic solvent.
In one embodiment of the present invention, the preprocessing step is: firstly, soaking the activated carbon in an acid solution or an alkali solution for 5-100 min, and then soaking the activated carbon in an organic solvent for 2-60 min.
In one embodiment of the present invention, after the impregnation step, a post-treatment step is further included; the post-treatment steps are as follows: firstly, drying the activated carbon, and then soaking the activated carbon in an acid solution or an alkali solution to adjust the pH value of the surface of the activated carbon.
In one embodiment of the present invention, the pH of the surface of the activated carbon is 5.0 to 13.
In one embodiment of the invention, the acid solution comprises HNO3Solution, HSO4Solution, HCl solution and CH3At least one of COOH solution.
In one embodiment of the present invention, the concentration of the acid solution is 1 to 50 g/L.
In one embodiment of the invention, the alkaline solution comprises a NaOH solution,NH3·H2At least one of O solutions.
In one embodiment of the present invention, the concentration of the alkali solution is 0.5 to 30 g/L.
In one embodiment of the present invention, the organic solvent includes at least one of methanol, ethanol, and acetone.
In one embodiment of the invention, the impregnation step is carried out under high pressure compression, suction under negative pressure or heating.
In one embodiment of the invention, the pre-treatment step is carried out under high pressure compression, negative pressure suction or heating.
The invention also provides the application of the method or the activated carbon in deodorization.
The technical scheme of the invention has the following advantages:
1. the invention provides an activated carbon, wherein the surface and/or pore canals of the activated carbon are/is modified with metal ions; after the active carbon adsorbs the odor, the metal ions can react the pollutants in the odor in situ, so that the total penetrating adsorption quantity of the active carbon to the odor is obviously improved, the total penetrating adsorption quantity of the active carbon to the odor is improved to 280mg/g, and the saturated adsorption capacity is improved to 400 mg/g.
Furthermore, the activated carbon can adjust the types and the proportions of modified metal ions on the surface and/or in the pore canal of different odor pollutants, so as to further improve the deodorization effect.
Further, after the activated carbon is used for deodorization, because a certain proportion of odor pollutants are solidified on metal ions through chemical reaction, the odor pollutants physically adsorbed in the activated carbon are more easily desorbed through heating and other modes in the process of desorbing and regenerating the activated carbon, so that the performance of the activated carbon is recovered again.
2. The invention provides a method for removing odor by using the active carbon; the total penetrating adsorption quantity of the activated carbon used by the method to odor is up to 280mg/g, and the saturated adsorption capacity is up to 400mg/g, so that the deodorization method has the advantages of good deodorization effect, no need of frequently replacing the activated carbon or frequently desorbing and regenerating the activated carbon, and effectively reduces the deodorization cost.
Furthermore, the method can select the activated carbon with different types and proportions of metal ions modified on the surface and/or in the pore canal aiming at different odor pollutants, thereby further improving the deodorization effect.
Further, the activated carbon used in the method can solidify a certain proportion of odor pollutants on metal ions through chemical reaction, so that the activated carbon used in the method is easier to desorb and regenerate, and the deodorization cost is further reduced.
3. The invention provides a method for preparing the activated carbon, which comprises the steps of coating a metal ion solution on the surface of the activated carbon to enable metal ions to be adsorbed on the surface of the activated carbon, or soaking the activated carbon in the metal ion solution to enable the metal ions to be loaded in pore channels of the activated carbon; the method for preparing the activated carbon only needs simple dipping or coating, does not need to mix and mold the activated carbon powder and other active components, and has the advantages of simple preparation process, small using amount of the active components and low economic cost.
Further, in order to improve the load uniformity and load capacity of metal ions, the method adopts an organic solvent to firstly modify the surface of the internal pore channels of the activated carbon, so that the subsequent active component load is easier and more uniform.
Further, in order to enhance the loading process of the solvent and the active component, the method improves the capacity of the solvent and the metal ions entering the pore channels by means of high-pressure compression, negative-pressure suction and heating.
Further, the method enables metal ions to grow in situ on the surfaces of internal pore channels of the activated carbon to form the active substance with the deodorization performance by adjusting the pH value of the surface of the activated carbon.
Furthermore, the surfaces of the internal pore channels of the activated carbon are mainly C ═ C nonpolar bonds and certain-OH polar bonds, the method prepares the supported activated carbon by a multi-step impregnation process, can change the surface tension and polarity of the supported activated carbon, adjusts the proportion of the polar bonds and the nonpolar bonds, and achieves comprehensive treatment on polar pollutants and nonpolar pollutants in odor.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The following examples do not show specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1: modified active carbon and preparation method thereof (aiming at odor containing hydrogen sulfide)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Zn2+、Cu2+And Cd2+And the surface of the modified activated carbon, Zn2+、Cu2+And Cd2+The molar ratio of (A) to (B) is 3.0: 1.5: 0.5.
The preparation method of the modified activated carbon comprises the following steps: preparing ZnCl containing 1.5mol/L2、0.75mol/L CuCl2And 0.25mol/L CdCl2The metal ion solution of (4); and soaking the honeycomb activated carbon in the metal ion solution for 30min to obtain the modified activated carbon.
Example 2: modified activated carbon and preparation method thereof (aiming at odor containing ammonia gas)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Fe3+、Ag+And Pt4+And the surface of the modified activated carbon, Fe3+、Ag+And Pt4+The molar ratio of (A) to (B) is 5.0: 0.1: 1.5.
The preparation method of the modified activated carbon comprises the following steps: preparation of a solution containing 2.5mol/L FeCl30.05mol/L AgCl and 0.75mol/L PtCl4The metal ion solution of (4); and soaking the honeycomb activated carbon in the metal ion solution for 45min to obtain the modified activated carbon.
Example 3: modified activated carbon and preparation method thereof (aiming at odor containing formaldehyde)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Zn2+、Cu2+And Fe3+(ii) a Zn on the surface and/or in the pore channels of the active carbon2+、Cu2+And Fe3+The molar ratio of (A) to (B) is 2.5: 0.8: 1.8.
The preparation method of the modified activated carbon comprises the following steps: preparing ZnCl containing 1.25mol/L2、0.4mol/L CuCl2And 0.9mol/L FeCl3The metal ion solution of (4); and soaking the honeycomb activated carbon in the metal ion solution for 20min to obtain the modified activated carbon.
Example 4: modified active carbon and preparation method thereof (aiming at odor containing hydrogen sulfide and ammonia gas)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Zn2+、Cd2+And Pt4+And the surface of the modified activated carbon, Zn2+、Cd2+And Pt4+The molar ratio of (A) to (B) is 3.0: 0.3: 0.8.
The preparation method of the modified activated carbon comprises the following steps:
a pretreatment step: firstly, soaking granular activated carbon in a sulfuric acid solution with the volume fraction of 5% for 25min, then drying the granular activated carbon at 80 ℃ for 2h, and then soaking the granular activated carbon in acetone with the volume fraction of 5% for 15 min;
and (3) dipping: preparing ZnCl containing 1.5mol/L2、0.15mol/L CdCl2And 0.4mol/L PtCl4The metal ion solution of (4); soaking the granular activated carbon in a metal ion solution for 40 min;
post-treatment: drying the granular activated carbon at 105 ℃, then soaking the granular activated carbon in a sodium hydroxide solution with the pH of 8.5 for 1.5h, and adjusting the pH of the surface of the granular activated carbon to obtain the modified activated carbon.
Example 5: modified active carbon and preparation method thereof (aiming at odor containing hydrogen sulfide and formaldehyde)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Zn2+、Cd2+And Fe3+And the surface of the modified activated carbon, Zn2+、Cd2+And Fe3+The molar ratio of (A) to (B) is 2: 0.6: 1.
The preparation method of the modified activated carbon comprises the following steps:
a pretreatment step: firstly, soaking granular activated carbon in a nitric acid solution with the volume fraction of 10% for 30min, then drying the granular activated carbon at 90 ℃ for 0.5h, and then soaking the granular activated carbon in methanol with the volume fraction of 10% for 15 min;
and (3) dipping: preparing ZnCl containing 2.0mol/L2、0.6mol/L CdCl2And 1.0mol/L FeCl3The metal ion solution of (4); soaking the granular activated carbon in a metal ion solution for 50 min;
post-treatment: drying the granular activated carbon at 100 ℃, then soaking the granular activated carbon in a sodium hydroxide solution with the pH of 9.0 for 1.0h, and adjusting the pH of the surface of the granular activated carbon to obtain the modified activated carbon.
Example 6: modified active carbon and preparation method thereof (aiming at odor containing ammonia gas and formaldehyde)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Pt4+、Cu2+And Fe3+And the surface of the modified activated carbon, Pt4+、Cu2+And Fe3+The molar ratio of (A) to (B) is 0.5: 1.2: 1.8.
The preparation method of the modified activated carbon comprises the following steps:
a pretreatment step: firstly, soaking granular activated carbon in a sulfuric acid solution with the volume fraction of 5% for 25min, then drying the granular activated carbon at 95 ℃ for 1.0h, and then soaking the granular activated carbon in methanol with the volume fraction of 5% for 0.5 h;
and (3) dipping: the preparation contains 1.0mol/L PtCl4、2.4mol/L CuCl2And 3.6mol/L FeCl3The metal ion solution of (4); soaking the granular activated carbon in a metal ion solution for 50 min;
post-treatment: drying the granular activated carbon at 110 ℃, then soaking the granular activated carbon in a sulfuric acid solution with the pH of 6.5 for 1.0h, and adjusting the pH of the surface of the granular activated carbon to obtain the modified activated carbon.
Example 7: modified active carbon and preparation method thereof (aiming at odor containing hydrogen sulfide, ammonia gas, formaldehyde and acetone)
The embodiment provides modified activated carbon, which is honeycomb activated carbon with a surface modified with metal ions; the metal ion is Zn2+、pt4+、Cd2+And Fe3+And the surface of the modified activated carbon, Zn2+、Pt4+、Cd2+And Fe3+The molar ratio of (A) to (B) is 2.0: 0.5: 0.8: 1.8.
The preparation method of the modified activated carbon comprises the following steps:
a pretreatment step: firstly, soaking granular activated carbon in a nitric acid solution with the volume fraction of 10% for 25min, then drying the granular activated carbon at 105 ℃ for 0.5h, and then soaking the granular activated carbon in ethanol with the volume fraction of 10% for 1.0 h;
and (3) dipping: preparing ZnCl containing 2.0mol/L2、0.5mol/L PtCl4、0.8mol/L CuCl2And 1.8mol/L FeCl3The metal ion solution of (4); soaking the granular activated carbon in a metal ion solution for 45 min;
post-treatment: drying the granular activated carbon at 105 ℃, then soaking the granular activated carbon in a nitric acid solution with the pH of 7.5 for 1.5h, and adjusting the pH of the surface of the granular activated carbon to obtain the modified activated carbon.
Comparative example 1: modified activated carbon and preparation method thereof
The comparative example provides a modified activated carbon, the surface of which was modified with an acid, alkali solution.
The preparation method of the modified activated carbon comprises the following steps:
firstly, soaking the granular activated carbon in a sulfuric acid solution with the volume fraction of 10% for 25min, then drying the granular activated carbon at 80 ℃ for 2.0h, and then soaking the granular activated carbon in a sodium hydroxide solution with the volume fraction of 10% for 15 min.
Experimental example 1: penetration test of activated carbon
The total penetration adsorption amount of the modified activated carbon in the examples 1-6 and the modified activated carbon in the comparative example 1 to different odors is detected by taking commercially available honeycomb activated carbon (purchased from Henan green Posson environmental protection materials Co., Ltd.) and granular activated carbon (purchased from Nanping plain activated carbon Co., Ltd.) as a comparison, and the detection results are shown in Table 1;
the detection method comprises the following steps: detecting the concentration of the odor entering and exiting the odor with the total concentration of the odor of 500ppm by using the activated carbon at the height of the fixed bed layer, and when the concentration of the odor at the outlet is higher than 10ppm, considering that the odor penetrates the activated carbon, the activated carbon is invalid and needs to be replaced;
the odor is as follows:
odor A: the odor gas A comprises 50 percent of hydrogen sulfide, 25 percent of ammonia gas, 16 percent of formaldehyde and 9 percent of acetone in percentage by total volume of the odor gas A;
odor B: the odor gas B comprises 40 percent of hydrogen sulfide, 40 percent of ammonia gas, 10 percent of formaldehyde and 10 percent of acetone in percentage of the total volume of the odor gas B;
odor C: the odor gas C comprises 25 percent of hydrogen sulfide, 50 percent of ammonia gas, 9 percent of formaldehyde and 16 percent of acetone in percentage of the total volume of the odor gas C;
odor D: contains 100% hydrogen sulfide in percentage by total volume of the odor D.
As can be seen from table 1, the total permeation adsorption amount of each of examples 1 to 6 against different odors was much higher than that of the commercially available honeycomb activated carbon, the commercially available granular activated carbon, and the modified activated carbon of comparative example 1, and among them, the modified activated carbon of example 1 had the best odor a adsorption effect, the modified activated carbon of example 2 had the best odor C adsorption effect, and the modified activated carbon of example 7 had the best odor B adsorption effect.
TABLE 1 Total breakthrough adsorption of different active carbons to different odors
Note: "-" is not detected.
Experimental example 2: saturated adsorption performance experiment of activated carbon
The saturated adsorption capacity of the modified activated carbon in the examples 1-6 and the modified activated carbon in the comparative example 1 to different odors is detected by taking commercially available honeycomb activated carbon (purchased from Henan green Posson environmental protection materials Co., Ltd.) and granular activated carbon (purchased from Nanping plain activated carbon Co., Ltd.) as a comparison, and the detection results are shown in Table 2;
the detection method comprises the following steps: placing the activated carbon in an odor container with the total odor concentration of 800ppm, continuously introducing odor pollutants in the adsorption process to keep the total odor concentration and the proportion of each pollutant unchanged, when the odor concentration in the container is not changed, considering that the adsorption is saturated, and weighing the weight of the activated carbon before and after the adsorption to obtain the saturated adsorption capacity of the activated carbon;
the odor is as follows:
odor A: the odor gas A comprises 50 percent of hydrogen sulfide, 25 percent of ammonia gas, 16 percent of formaldehyde and 9 percent of acetone in percentage by total volume of the odor gas A;
odor B: the odor gas B comprises 40 percent of hydrogen sulfide, 40 percent of ammonia gas, 10 percent of formaldehyde and 10 percent of acetone in percentage of the total volume of the odor gas B;
odor C: the odor gas C comprises 25 percent of hydrogen sulfide, 50 percent of ammonia gas, 9 percent of formaldehyde and 16 percent of acetone in percentage of the total volume of the odor gas C;
odor D: contains 100 percent of hydrogen sulfide in percentage of the total volume of the odor D;
odor E: contains 100% ammonia gas in percentage of the total volume of the odor E.
As can be seen from table 2, the saturated adsorption capacities for different odors of examples 1 to 6 were much higher than those of the commercially available honeycomb activated carbon, the commercially available granular activated carbon, and the modified activated carbon of comparative example 1, and among them, the modified activated carbon of example 1 had the best odor a adsorption effect, the modified activated carbon of example 2 had the best odor C adsorption effect, and the modified activated carbon of example 7 had the best odor B adsorption effect.
TABLE 2 saturated adsorption capacities of different activated carbons for different odors
Note: "-" is not detected.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method for removing odor is characterized in that the method is to use active carbon to adsorb the odor; the surface and/or the pore canal of the active carbon are/is decorated with metal ions.
2. The method of claim 1, wherein the metal ion comprises Zn2+、Fe3+、Cu2+、Cd2+、Ag2+And Ti2+At least one of (1).
3. The method of claim 1 or 2, wherein the odor gas contains at least one of hydrogen sulfide, ammonia gas, methyl mercaptan, methyl sulfide, carbon disulfide, acetone, formaldehyde, and acetaldehyde;
when the odor contains hydrogen sulfide, the odor can be reducedThe metal ion comprises Zn2+、Cu2+And Cd2+And Zn is on the surface and/or in the pore channels of the active carbon2+、Cu2+And Cd2+The molar ratio of (A) to (B) is 3-4: 1-2: 0.2-0.5;
when the odor gas contains ammonia gas, the metal ions include Fe3+、Ag+And Pt4+And the surface and/or the inside of the pore canal of the active carbon is Fe3+、Ag+And Pt4+The molar ratio of (A) to (B) is 5-10: 0.1-0.2: 0.5-2;
when the odor contains formaldehyde, the metal ions include Zn2+、Cu2+And Fe3+And Zn is on the surface and/or in the pore channels of the active carbon2+、Cu2+And Fe3+The molar ratio of (A) to (B) is 2-3: 0.5-1: 1-2.
4. The method of any one of claims 1 to 3, wherein the activated carbon comprises at least one of granular activated carbon, honeycomb activated carbon, fibrous activated carbon, powdered activated carbon, and coconut shell activated carbon.
5. The activated carbon is characterized in that the surface and/or the pore canals of the activated carbon are modified with metal ions.
6. The activated carbon of claim 5, wherein the metal ion comprises Zn2+、Fe3+、Cu2+、Cd2+、Ag2+And Ti2+At least one of (1).
7. The activated carbon of claim 5 or 6, wherein the metal ion comprises Zn2+、Cu2+And Cd2+(ii) a Zn on the surface and/or in the pore channels of the active carbon2+、Cu2+And Cd2+The molar ratio of (A) to (B) is 3-4: 1-2: 0.2-0.5;
alternatively, the metal ion comprises Fe3+、Ag+And Pt4+(ii) a Surface of the activated carbon and/orIn the pore canal, Fe3+、Ag+And Pt4+The molar ratio of (A) to (B) is 5-10: 0.1-0.2: 0.5-2;
alternatively, the metal ion comprises Zn2+、Cu2+And Fe3+(ii) a Zn on the surface and/or in the pore channels of the active carbon2+、Cu2+And Fe3+The molar ratio of (A) to (B) is 2-3: 0.5-1: 1-2.
8. The activated carbon according to any one of claims 5 to 7, wherein the activated carbon comprises at least one of granular activated carbon, honeycomb activated carbon, fibrous activated carbon, powdered activated carbon, and coconut shell activated carbon.
9. A method for preparing the activated carbon according to any one of claims 5 to 7, comprising the steps of:
coating: coating the metal ion solution on the surface of the activated carbon to enable the metal ions to be adsorbed on the surface of the activated carbon;
alternatively, the method comprises the steps of:
and (3) dipping: and (3) dipping the activated carbon into the metal ion solution, so that the metal ions are loaded in the pore channels of the activated carbon.
10. Use of the method of any one of claims 1 to 4 or the activated carbon of any one of claims 5 to 7 for deodorization.
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