CN110314654B - Organic waste gas adsorbent, preparation method thereof and organic waste gas treatment method - Google Patents
Organic waste gas adsorbent, preparation method thereof and organic waste gas treatment method Download PDFInfo
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Abstract
The invention provides an organic waste gas adsorbent, a preparation method thereof and an organic waste gas treatment method, wherein the adsorbent comprises metal salt and a composite organic ligand, the metal salt consists of metal salts of three metal elements of M1, M2 and M3, wherein M1 is selected from one of Cr, Mn, Fe, Co and Ni, and M2 is Cu; m3 is a rare earth element. The organic waste gas treatment method comprises the steps of filling the adsorbent in an adsorption device, allowing the organic waste gas to enter the adsorption device through an inlet for adsorption, discharging the tail gas after adsorption, purging and desorbing by using hot oxygen-poor air or inert gas after the adsorbent is saturated in adsorption, and then burning. The method adopts high-efficiency adsorbent to concentrate the combustible components in the tail gas and then can directly burn the concentrated combustible components, thereby avoiding consuming other fuels; meanwhile, the desorption process is carried out in the microchannel equipment, so that the burning explosion risk can be avoided; the method is efficient, energy-saving and safe, and has a good application prospect.
Description
Technical Field
The invention relates to an organic waste gas adsorbent, a preparation method thereof and an organic waste gas treatment method, and belongs to the field of tail gas treatment.
Background
The gas-liquid two-phase oxidation reaction is a commonly used chemical production process, for example, compounds such as hydrocarbons, alcohols, aldehydes and the like are subjected to oxidation reaction with air to generate products such as aldehydes, ketones, carboxylic acids and the like, reaction tail gas contains a small amount of organic components such as alkanes, alcohols, aldehydes, ketones, carboxylic acids and the like and pollutants such as CO and the like, and the emission of waste gas can cause serious pollution to the surrounding environment and harm human health, and the waste gas needs to be purified. The comprehensive emission standard of air pollutants (GB16297-1996) issued in China in 1996 stipulates emission limits of 33 air pollutants, wherein volatile organic compounds which are not listed are classified into 33 types of non-methane total hydrocarbons, and emission standards of existing and new pollution sources are uniformly stipulated. With the enhancement of the environmental awareness of human beings, in order to promote the technical progress and sustainable development of petrochemical industry, the nation sets up the more demanding discharge standard of pollutants for petrochemical industry (GB 315171-2015). Under the promotion of the requirement, the oxidation reaction process device needs to select a proper oxidation tail gas treatment technology to ensure that the waste gas reaches the emission standard of the environmental protection department.
The treatment technology of organic waste gas can be divided into a recovery method and a destruction method. The recovery method mainly comprises the technologies of adsorption, absorption, condensation, membrane separation and the like; the destroying method mainly comprises thermal incineration, catalytic combustion, photocatalysis technology, biodegradation and the like. The tail gas of the oxidation reaction has low organic content and low recovery value, and is generally destroyed by a thermal oxidation method or a catalytic oxidation method, and the thermal oxidation method needs to add auxiliary fuel into the waste gas during incineration to ensure that pollutants can be fully combusted.
As known in the art, the tail gas adsorption usually adopts activated carbon as an adsorbent, but has the problems of long adsorption time and small saturated adsorption amount, and is generally difficult to adsorb CO; there are generally three ways to desorb after adsorption saturation: heat N2Purging, steam purging, hot air purging, e.g. CN103585854A using activated carbon adsorption, N2Desorption, in patent CN106693939A, activated carbon adsorption and steam desorption are adopted; n is a radical of2Further condensation, concentration and other operations are needed after desorption, the steam desorption easily causes the problems of structural damage of the adsorbent and the like, and the hot air desorption process has the explosion risk.
Therefore, the organic waste gas adsorbent which can be efficiently adsorbed, is simple and safe to desorb, the preparation method of the organic waste gas adsorbent and the organic waste gas treatment method are found, and the method has important significance.
Disclosure of Invention
The invention aims to provide an organic waste gas adsorbent and a preparation method thereof, the adsorbent has high adsorption rate and large adsorption capacity, can efficiently adsorb organic components such as alkane, alcohol, aldehyde ketone, carboxylic acid and the like and pollutants such as CO and the like, and has stable structure and long service life.
Another objective of the present invention is to provide a method for treating organic waste gas, which can make the tail gas from oxidation reaction fully and efficiently contact with the catalyst, enhance the adsorption effect, and avoid the risk of explosion during desorption.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
an organic waste gas adsorbent comprises metal salt and a composite organic ligand, wherein the metal salt is composed of metal salts of three metal elements of M1, M2 and M3, wherein M1 is selected from one or more of Cr, Mn, Fe, Co and Ni, preferably Cr, Co and Fe; m2 is Cu; m3 is a rare earth element selected from one or more of lanthanum, cerium and zirconium, preferably lanthanum.
In the invention, the complex organic ligand comprises two organic ligands of ligand I and ligand II, wherein the ligand I is selected from one of 2,2 '-biquinoline-4, 4' -dicarboxylic acid, 2, 6-pyridinedicarboxylic acid and 2, 5-pyrazinedicarboxylic acid, and preferably 2,2 '-biquinoline-4, 4' -dicarboxylAn acid; the ligand II has the structure
Wherein X1、X2、X3Is a nitrogen-containing heterocyclic group, X1、X2、X3Identical or different, preferably, X1、X2、X3Is selected from
Preference is given to
In the invention, the preparation method of the ligand II comprises the following steps: adding a ligand II precursor into a solvent, uniformly mixing, heating to 60-80 ℃, adding a trivalent phosphorus halide, preferably a normal hexane solvent of phosphorus trichloride, into the system, and stirring to obtain a solution containing a ligand II; the solvent was recovered by distillation and then dried to obtain a solid.
In the invention, the molar ratio of the ligand II precursor to the trivalent phosphorus halide is 1: 1-2: 1.
The precursor of the ligand II is X1、X2、X3The corresponding nitrogen-containing heterocyclic compound, preferably, the ligand II precursor is selected from purine, imidazole or imidazoline.
The molar ratio of the total molar amount of the metal elements in the metal salt to the total molar amount of the composite organic ligand is 1: 1-1: 10, preferably 1: 2-1: 8, and more preferably 1: 3-1: 5; the molar ratio of the metal elements M1 to M2 is 10: 1-1: 1, preferably 8: 1-2: 1, and more preferably 5: 1-3: 1; the molar ratio of the metal element M1 to the metal element M3 is 100: 1-20: 1, preferably 90: 1-40: 1, and more preferably 80: 1-60: 1. The molar ratio of the organic ligand I to the ligand II is 10: 1-1: 1, preferably 8: 1-2: 1, and more preferably 5: 1-3: 1.
The invention also provides a preparation method of the adsorbent, which comprises the following steps: placing an organic ligand I, a ligand II, a salt of a metal element M1, a salt of a metal element M2, a salt of a metal element M3 and distilled water in a container, stirring for 30-100 min at 50-80 ℃, uniformly mixing, adding hydrochloric acid to adjust the pH value to be 2-4, reacting for 48-72 h at 150-200 ℃, naturally cooling to room temperature, filtering, washing, drying to obtain silver gray crystals, and processing into spherical particles with the diameter of 0.1-0.2 mm.
Further, a salt of the metal element M1 is preferably a nitrate, a salt of the metal element M2 is preferably a hydrochloride, and a salt of the metal element M3 is preferably a nitrate.
The invention also provides a method for treating the organic waste gas, wherein the adsorbent is filled in an adsorption device, the organic waste gas enters the adsorption device through an inlet for adsorption, the tail gas after adsorption is discharged, after the adsorption of the adsorbent is saturated, the adsorbent is purged and desorbed by hot oxygen-deficient air or inert gas, and then the organic waste gas is incinerated.
In the invention, the adsorption device is provided with a plurality of lamella and a plurality of baffling micro-channels, and the baffling micro-channels are formed by arranging and separating a plurality of zigzag baffle plates in parallel and at intervals.
In the invention, each sheet layer is formed by two partition plates to sandwich a plurality of baffling micro-channels.
The bending angle of the zigzag baffle plate is 30-150 degrees, preferably 60-120 degrees, and more preferably 90-120 degrees; the width of the micro-channel is 0.01-1 cm, preferably 0.05-0.2 cm; the thickness of the sheet layer is 0.01-1 cm, preferably 0.05-0.2 cm.
The operation temperature of the organic waste gas adsorption process is 25-70 ℃, and preferably 40-60 ℃; the operating temperature of the hot air desorption process is 120-250 ℃, and preferably 150-210 ℃.
Compared with the prior art, the invention has the following advantages:
1. the composite metal organic framework compound has the advantages of large specific surface area, stable pore channel structure and the like, and has higher adsorption rate and larger adsorption capacity compared with traditional adsorbents such as activated carbon and the like; the invention adopts three metals of M1, M2 and M3 to be matched for use, and the prepared adsorbent with the metal organic framework not only has good adsorption effect on organic matters such as hydrocarbons, aldehydes and ketones and alcohols, but also has metal M2(Cu)The metal M3 can enhance the dispersity of the active components M1 and M2 and has synergistic effect with the active components, thereby increasing the stability and the adsorption capacity of the adsorbent. In addition, the invention adopts two organic ligands to synthesize a metal organic framework compound, ligand II
The nitrogen heterocyclic group in the adsorbent can form a coordination bond with active component metal with stronger acting force, so that the formed compound has a more stable structure, the P element at the central position of the ligand II can enhance the hydrothermal stability of the framework, and the damage of moisture in tail gas and high temperature in the desorption process to the adsorbent structure is avoided.
2. The invention adopts a multi-slice multi-baffling microchannel device to carry out adsorption and desorption operations, and an adsorbent is filled in a microchannel. In the adsorption process, the baffling micro-channel can strengthen mass transfer, promote tail gas dispersion, strengthen full contact between the tail gas and the adsorbent, prolong contact time and improve adsorption effect; during the desorption process of the hot oxygen-poor air or the inert gas, the contact between the gas and the adsorbent can be promoted, and the desorption rate is accelerated; according to the mechanism of combustion reaction, combustion can be carried out only by continuously generating new free radicals, and flame cannot propagate after the diameter of a pipeline is smaller than a certain value.
3. The adsorbent can be used for adsorbing tail gas containing hydrocarbon, aldehyde ketone, alcohol organic matters and CO, and is particularly suitable for treating tail gas generated in the reaction of preparing carboxylic acid by oxidizing aldehyde compounds in air.
Drawings
FIG. 1 is a schematic view of the internal structure of an adsorption apparatus according to the present invention;
fig. 2 is a schematic side view of an adsorption apparatus.
Wherein, 1 is a micro-channel, 2 is an adsorbent, 3 is a baffle plate, 4 is a gas inlet, 5 is a sheet layer, and 6 is a clapboard.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.
Examples source of raw materials and analytical instrumentation were as follows:
(1) chemical reagents:
Cr(NO3)3·9H2o: shanghai Aladdin Biotechnology, Inc., AR;
Co(NO3)2·6H2o: shanghai Aladdin Biotechnology, Inc., AR;
Fe(NO3)3·9H2o: shanghai Aladdin Biotechnology, Inc., AR;
CuCl: shanghai Aladdin Biotechnology, Inc., AR;
La(NO3)36H 2O: shanghai Aladdin Biotechnology, Inc., AR;
1,3, 5-trimellitic acid: shanghai Aladdin Biotechnology, Inc., 98%;
2, 6-pyridinedicarboxylic acid: 99% of Shanghai Aladdin Biotechnology, Inc.;
2, 5-pyrazinedicarboxylic acid: shanghai Aladdin Biotechnology, Inc., 97%;
2,2 '-biquinoline-4, 4' -dicarboxylic acid: shanghai Aladdin Biotechnology, Inc., 90%.
And (2) ligand II: the self-made synthesis method comprises the following steps:
(1)
group (b):
mixing 30g of purine
Adding the compound into 300ml of n-hexane solvent, uniformly mixing, heating to 70 ℃, and then dropwise adding 500ml of n-hexane containing 20.6g of phosphorus trichloride into the systemStirring the solvent for 90min to obtain a solution containing the ligand 2 a; distilling to recover the solvent, drying to obtain a white blocky solid, and recrystallizing with ethyl acetate to obtain a white powdery ligand 2a product, wherein the structure is as follows:
(2)
group (b):
adding 9.52g of imidazole compound into 300ml of n-hexane solvent, uniformly mixing, heating to 70 ℃, then dropwise adding 500ml of n-hexane solvent containing 20.6g of phosphorus trichloride into the system, and stirring for 90min to obtain a solution containing the ligand 2 b; distilling to recover the solvent, drying to obtain a white blocky solid, and recrystallizing with ethyl acetate to obtain a white powdery ligand 2b product, wherein the structure is as follows:
(3)
group (b):
adding 18.03g of imidazoline compound into 300ml of n-hexane solvent, uniformly mixing, heating to 70 ℃, then dropwise adding 500ml of n-hexane solvent containing 20.6g of phosphorus trichloride into the system, and stirring for 90min to obtain a solution containing ligand 2 c; distilling to recover the solvent, drying to obtain a white blocky solid, and recrystallizing with ethyl acetate to obtain a white powdery ligand 2c product, wherein the structure is as follows:
(2) BET specific surface area, pore size and pore volume measurement
The specific surface area and the porosity are measured by a specific surface area and porosity measuring instrument. The instrument is a Quadrasorb SI type specific surface area and porosity tester of Conta company in America.
EXAMPLE 1 preparation of Metal organic framework Compound adsorbents
a) Preparation of adsorbent A
2gCr (NO)3)3·9H2O、0.099gCuCl、0.027gLa(NO3)3·6H2O, 5.73g2,2 '-biquinoline-4, 4' -dicarboxylic acid, 1.165g ligand 2a
200g of distilled water is placed in a beaker, stirred for 90min at 70 ℃, mixed uniformly, titrated to pH 3 with 1mol/L hydrochloric acid, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted for 60h at 180 ℃, naturally cooled to room temperature, filtered, washed and dried to obtain silver gray crystals, and then processed into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 5g of the adsorbent A.
b) Preparation of adsorbent B
1.16g of Co (NO)3)2·6H2O、0.099gCuCl、0.026gLa(NO3)3·6H2O, 6.1g of 2,2 '-biquinoline-4, 4' -dicarboxylic acid, 1.553g of ligand 2a and 200g of distilled water are placed in a beaker, stirred for 90min at 70 ℃, mixed uniformly, titrated to pH 3 with 1mol/L hydrochloric acid, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted for 60h at 180 ℃, naturally cooled to room temperature, filtered, washed and dried to obtain silver gray crystals, and then processed into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 4.9g of adsorbent B.
c) Preparation of adsorbent C
1.21g Fe (NO)3)3·9H2O、0.099gCuCl、0.022gLa(NO3)3·6H2O, 5.73g2,2 '-biquinoline-4, 4' -dicarboxylic acid, 1.942g ligand 2a
Placing 200g of distilled water in a beaker, stirring for 90min at 70 ℃, mixing uniformly, titrating to pH 3 with 1mol/L hydrochloric acid, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting 1%Reacting at 80 ℃ for 60h, naturally cooling to room temperature, filtering, washing and drying to obtain silver gray crystals, and processing the silver gray crystals into spherical particles with the diameter of 0.1-0.2 mm to obtain about 4.7g of the adsorbent C.
d) Preparation of adsorbent D
1.21g Fe (NO)3)3·9H2O、0.099gCuCl、0.022gLa(NO3)3·6H2O, 5.73g2,2 '-biquinoline-4, 4' -dicarboxylic acid, 1.16g ligand 2b
200g of distilled water is placed in a beaker, stirred for 90min at 70 ℃, mixed uniformly, titrated to pH 3 with 1mol/L hydrochloric acid, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted for 60h at 180 ℃, naturally cooled to room temperature, filtered, washed and dried to obtain silver gray crystals, and then processed into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 4.3g of the adsorbent D.
e) Preparation of adsorbent E
1.21g Fe (NO)3)3·9H2O、0.099gCuCl、0.022gLa(NO3)3·6H2O, 5.73g)2,2 '-biquinoline-4, 4' -dicarboxylic acid, 1.22g ligand 2c
200g of distilled water is placed in a beaker, stirred for 90min at 70 ℃, mixed uniformly, titrated to pH 3 with 1mol/L hydrochloric acid, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted for 60h at 180 ℃, naturally cooled to room temperature, filtered, washed and dried to obtain silver gray crystals, and then processed into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 4.3g of the adsorbent E.
f) Preparation of adsorbent F
1.21g Fe (NO)3)3·9H2O、0.099gCuCl、0.022gLa(NO3)3·6H2O, 2.51g2, 6-pyridinedicarboxylic acid, 1.942g ligand 2a
200g steamed stuffed bunDistilled water is placed in a beaker, stirred for 90min at 70 ℃, mixed evenly, titrated to pH 3 with 1mol/L hydrochloric acid, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted for 60h at 180 ℃, naturally cooled to room temperature, filtered, washed and dried to obtain silver gray crystals, and then processed into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 2.7g of the adsorbent F.
g) Preparation of adsorbent G
1.21g Fe (NO)3)3·9H2O、0.099gCuCl、0.022gLa(NO3)3·6H2O, 2.52g2, 5-pyrazinedicarboxylic acid, 1.942g ligand 2a
200G of distilled water is placed in a beaker, stirred for 90min at 70 ℃, mixed uniformly, titrated to pH 3 with 1mol/L hydrochloric acid, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacted for 60h at 180 ℃, naturally cooled to room temperature, filtered, washed and dried to obtain silver gray crystals, and then processed into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 2.6G of the adsorbent G.
h) Preparation of adsorbent H (comparative adsorbent)
1.21g Fe (NO)3)3·9H2O、0.099gCuCl、0.022gLa(NO3)3·6H2Placing O, 3.99g1,3, 5-trimellitic acid and 200g distilled water in a beaker, stirring for 90min at 70 ℃, mixing uniformly, titrating to pH 3 with 1mol/L hydrochloric acid, transferring to a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 60H at 180 ℃, naturally cooling to room temperature, filtering, washing and drying to obtain silver gray crystals, and processing the silver gray crystals into spherical particles with the diameter of 0.1 mm-0.2 mm to obtain about 3.3g of the adsorbent H.
The adsorbents A to H8 prepared in example 1 were characterized by the parameters shown in Table 1:
TABLE 1
Example 2 adsorption Effect test
(1) Experimental equipment
The self-made experimental adsorption equipment is shown in figures 1 and 2, and is provided with a plurality of lamella 5 and a plurality of baffling micro-channels 1, wherein the baffling micro-channels 1 are formed by arranging and separating a plurality of zigzag baffle plates 3 in parallel at intervals. The bending angle of the zigzag baffle plate 3 is 100 degrees, the width of the formed microchannel 1 is 0.1cm, the length of the baffle plate 3 is 5cm, the distance between the sheet layer partition plates 6 is 0.2cm, the length of each sheet layer is 5cm, the number of the sheet layers is 5, and 7g of the adsorbent prepared by the method of the embodiment is filled in the microchannel.
(2) The adsorption effect is verified by taking the reaction tail gas generated in the process of preparing isononanoic acid (3,5, 5-trimethylhexanoic acid) by oxidizing isononanoic acid (3,5, 5-trimethylhexanoic acid) in air as an example, the temperature of the tail gas is 40 ℃, and the gas composition is as follows: CO: 0.4 mol%, CO21.3 mol%, isooctane: 0.26 mol%, isononanal: 0.01 mol%, isononanoic acid: 0.01 mol%, C8 aldehyde ketol: 0.02 mol%, other organic components: 0.01 mol%, water: 0.8 mol% of O2：2.7mol％，N2: 94.49mol percent. The tail gas flow rate is 8L/h (space velocity 800 h)-1)。
(3) The adsorption effect is as follows:
adsorbent A:
note: "-" undetected
Adsorbent B:
note: "-" undetected
Adsorbent C:
note: "-" undetected
Adsorbent D:
note: "-" undetected
Adsorbent E:
note: "-" undetected
Adsorbent F:
note: "-" undetected
Adsorbent G:
note: "-" undetected
Adsorbent H:
example 3 Desorption Effect test
After the adsorbent is adsorbed and saturated, blowing by hot oxygen-poor air (oxygen content is 5%) at 180 ℃, wherein the flow rate of the blowing air is 8L/h,
adsorbent A:
note: "-" undetected
Adsorbent B:
note: "-" undetected
Adsorbent C:
note: "-" undetected
Adsorbent D:
note: "-" undetected
Adsorbent E:
note: "-" undetected
Adsorbent F:
note: "-" undetected
Adsorbent G:
note: "-" undetected
Adsorbent H:
Claims (18)
1. an organic waste gas adsorbent is characterized by comprising metal salt and a composite organic ligand, wherein the metal salt is composed of metal salts of three metal elements of M1, M2 and M3, wherein M1 is selected from one or more of Cr, Mn, Fe, Co and Ni, and M2 is Cu; m3 is rare earth element selected from one or more of lanthanum and cerium;
the composite organic ligand comprises two organic ligands, namely a ligand I and a ligand II, wherein the ligand I is selected from one of 2,2 '-biquinoline-4, 4' -dicarboxylic acid, 2, 6-pyridinedicarboxylic acid and 2, 5-pyrazinedicarboxylic acid; the ligand II has the structure
Wherein X1、X2、X3Is a nitrogen-containing heterocyclic group, X1、X2、X3Identical or different, X1、X2、X3Is selected from
2. The adsorbent of claim 1, wherein M1 is selected from one or more of Cr, Co, Fe; m3 is lanthanum.
3. The adsorbent of claim 1 wherein ligand i is selected from 2,2 '-biquinoline-4, 4' -dicarboxylic acid and ligand ii has the structure
Wherein X1、X2、X3Is composed of
4. The adsorbent according to claim 1, wherein the ligand II is prepared by the following method: adding a ligand II precursor into a solvent, uniformly mixing, heating to 60-80 ℃, adding a trivalent phosphorus halide and a normal hexane solvent into the system, and stirring to obtain a solution containing a ligand II; the solvent was recovered by distillation and then dried to obtain a solid.
5. The adsorbent of claim 4, wherein the molar ratio of the ligand II precursor to the trivalent phosphorus halide is 1:1 to 2: 1.
6. An adsorbent according to claim 4, wherein the trivalent phosphorus halide is phosphorus trichloride.
7. The adsorbent according to claim 1 or 2, wherein the molar ratio of the total molar amount of the metal elements in the metal salt to the total molar amount of the composite organic ligand is 1: 1-1: 10; the molar ratio of the metal elements M1 to M2 is 10: 1-1: 1; the molar ratio of the metal elements M1 to M3 is 100: 1-20: 1; the molar ratio of the organic ligand I to the ligand II is 10: 1-1: 1.
8. The adsorbent according to claim 7, wherein the molar ratio of the total molar amount of the metal elements in the metal salt to the total molar amount of the complex organic ligand is 1:2 to 1: 8; the molar ratio of the metal element M1 to the metal element M2 is 8: 1-2: 1; the molar ratio of the metal elements M1 to M3 is 90: 1-40: 1; the molar ratio of the organic ligand I to the ligand II is 8: 1-2: 1.
9. The adsorbent according to claim 8, wherein the molar ratio of the total molar amount of the metal elements in the metal salt to the total molar amount of the complex organic ligand is 1:3 to 1: 5; the molar ratio of the metal element M1 to the metal element M2 is 5: 1-3: 1; the molar ratio of the metal element M1 to the metal element M3 is 80: 1-60: 1; the molar ratio of the organic ligand I to the ligand II is 5: 1-3: 1.
10. The method for preparing the adsorbent according to claim 1, characterized by comprising the steps of: putting a ligand I, a ligand II, a salt of a metal element M1, a salt of a metal element M2, a salt of a metal element M3 and distilled water into a container, stirring for 30-100 min at 50-80 ℃, uniformly mixing, adding hydrochloric acid to adjust the pH value to be 2-4, reacting for 48-72 h at 150-200 ℃, naturally cooling to room temperature, filtering, washing and drying to obtain silver gray crystals.
11. A method for treating organic waste gas, characterized in that the adsorbent according to any one of claims 1 to 9 or the adsorbent prepared by the method according to claim 10 is filled in an adsorption device, the organic waste gas enters the adsorption device through an inlet for adsorption, the tail gas after adsorption is discharged, after the adsorption of the adsorbent is saturated, the adsorbent is purged and desorbed by hot oxygen-deficient air or inert gas, and then the desorbed waste gas containing organic matters is incinerated.
12. The method as claimed in claim 11, wherein the adsorption device has a plurality of sheets and a plurality of baffling micro-channels, and the baffling micro-channels are formed by a plurality of zigzag baffles which are arranged in parallel and spaced apart from each other.
13. The method of claim 12, wherein each of the plurality of layers is formed by two baffles sandwiching a plurality of baffled microchannels.
14. The organic waste gas treatment method according to claim 12, wherein the zigzag baffle has a bending angle of 30 to 150 ° and the microchannel has a width of 0.01 to 1 cm; the thickness of the sheet layer is 0.01-1 cm.
15. The method for treating organic waste gas according to claim 14, wherein the bending angle of the zigzag baffle is preferably 60 to 120 °; the width of the micro-channel is 0.05-0.2 cm; the thickness of the sheet layer is 0.05-0.2 cm.
16. The method for treating organic waste gas according to claim 15, wherein the zigzag baffle has a bending angle of 90 to 120 °.
17. The method of claim 11, wherein the tail gas adsorption process operating temperature is 25-70 ℃; the operating temperature of the desorption process is 120-250 ℃.
18. The method of claim 17, wherein the tail gas adsorption process operating temperature is 40-60 ℃; the operating temperature of the desorption process is 150-210 ℃.
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