CN110841592A - Adsorbent for purifying VOCs waste gas and preparation method and application thereof - Google Patents

Adsorbent for purifying VOCs waste gas and preparation method and application thereof Download PDF

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Publication number
CN110841592A
CN110841592A CN201911056054.9A CN201911056054A CN110841592A CN 110841592 A CN110841592 A CN 110841592A CN 201911056054 A CN201911056054 A CN 201911056054A CN 110841592 A CN110841592 A CN 110841592A
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gas
adsorbent
adsorption
organic
waste gas
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杜先
马洪玺
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Shanghai Lanke Petrochemical Engineering & Technology Co Ltd
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Shanghai Lanke Petrochemical Engineering & Technology Co Ltd
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    • 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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28088—Pore-size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s

Abstract

The invention discloses a preparation method of an adsorbent for purifying VOCs waste gas, which comprises the following steps: s1, drying and crushing the raw material coal to obtain coal powder; s2, mixing an organic solvent, an organic auxiliary agent, an inorganic auxiliary agent and an organic adhesive into the coal powder, and adding polymer resin during mixing; kneading and stirring, and extruding to obtain wet molded adsorbent; and S3, finally, drying, carbonizing and activating the formed adsorbent to obtain the adsorbent for purifying the VOCs waste gas. The adsorbent disclosed by the invention is simple to prepare, has rich mesopores and good hydrophobicity, is excellent in strength, is excellent in adsorption and regeneration performances, and is more energy-saving, so that the adsorption-based deep purification method for VOCs waste gas, which is low in cost, simple in process flow, simple and convenient to operate, excellent in purification effect and safe, can be realized on the basis of the adsorbent.

Description

Adsorbent for purifying VOCs waste gas and preparation method and application thereof
Technical Field
The invention belongs to the technical field of waste gas treatment, relates to an adsorbent for purifying VOCs waste gas in the chemical industry and a preparation method thereof, and relates to an adsorption-based VOCs waste gas deep purification method, which is suitable for purifying and recycling waste gas discharged from pollution sources such as coal chemical industry, petrochemical enterprise process tail gas, chemical loading and unloading occasions, dissipated waste gas, oil product intermediate tank areas and the like.
Background
During the process of processing crude oil in an oil refinery, facilities inevitably emit a large amount of stink polluted waste gas, particularly facilities such as a sulfur-containing sewage storage tank, a semi-finished product storage tank, a dirty oil storage tank, a mercaptan removal tail gas and the like, wherein the stink pollutants emitted by the facilities comprise hydrogen sulfide, organic sulfide, benzene series, other VOCs (volatile organic compounds) and other components. When working personnel move for a long time in the environment polluted by the substances, diseases of respiratory system, digestive system, reproductive system and the like can be caused, and pathological changes and even carcinogenesis of the body can be caused; when the short-term pollution is serious, the acute poisoning symptoms such as dizziness, throat pain, nausea, vomiting and the like can be caused to people.
The waste gas has complex components, causes odor pollution of the surrounding environment and threatens human health; meanwhile, the waste gas has low concentration and complex components, and is difficult to completely purify, so the development of the waste gas treatment is more and more urgent.
The treatment of the odor waste gas discharged by the storage tank has the particularity, and is mainly shown as follows: when the waste gas treatment device is used for purifying waste gas, the normal operation of the storage tank is easily interfered, and the tank is likely to be shrunken or exploded; in addition, the composition of the waste gas discharged by the storage tank is complex, and the purification difficulty is high.
The prior art methods for treating the above pollution source waste gas in petrochemical enterprises include a low-temperature distillate oil absorption method, an adsorption method, a condensation method, a membrane method, an oxidation method and a combination of the above methods. However, with the further strictness of the national emission standard, the conventional waste gas recovery and purification method cannot meet the new emission standard requirements. When waste gas is treated by adopting a non-incineration method, the concentration of organic matters at the outlet of an exhaust funnel of a loading system pollution control device is less than 80mg/m according to the regulation of 'emission control standard of volatile organic matters of industrial enterprises' (DB12524-2014) of local standard in Tianjin City3(ii) a The concentration of organic matters at the outlet of an exhaust cylinder of pollution control equipment of an oil gas recovery device of a loading system is less than or equal to 100mg/m specified in local standard 'emission standard of oil refining and petrochemical industry atmospheric pollutants' (DB 11447-2007) in Beijing City3. Using oxygenAlthough the chemical method can reach the national standard, the energy consumption is high, and the safety control problem exists at the same time.
The method is most suitable for recovering sulfur and hydrocarbon containing waste gas of petrochemical enterprises by adopting a low-temperature distillate oil absorption method, for example, Chinese patent document CN201010222137.3 discloses a method for treating the stink waste gas discharged by a storage tank, Chinese patent document CN201010222122.7 discloses a method for treating the stink waste gas containing sulfides and hydrocarbons, Chinese patent document CN200910011763.5 discloses a method for treating the stink waste gas containing sulfur and hydrocarbon, and Chinese patent document CN201210404088.4 discloses a method for treating the escaping waste gas of an acid water storage tank; the methods all adopt conventional absorption equipment, have large occupied area and energy consumption, can not stably reach 95 percent of purification efficiency of hydrocarbons in the waste gas, and have outlet concentration lower than 15-25 g/m3The new standard cannot be reached.
Chinese patent document CN106362552A discloses a method and an apparatus for treating high concentration organic waste gas, which is to treat high concentration hydrocarbon waste gas by using a method combining diesel oil absorption with a heating furnace, but the method is suitable for forming a relatively stable waste gas, and when the composition and concentration fluctuation of the inlet waste gas are large, the diesel oil absorption efficiency cannot reach the design range, so that there is a safety risk in the oxidation process of the heating furnace. In addition, this method cannot treat exhaust gas having a high hydrogen sulfide concentration.
Liu Zhong and the like adopt a low-temperature diesel oil absorption and catalytic oxidation combined process to treat sulfur-containing and hydrocarbon-containing waste gas in an oil refining sewage treatment plant volatile organic matter and stink waste gas treatment technology (2018, stage 5), and a better effect is achieved.
In the methods, the combined process effect of low-temperature diesel oil absorption and catalytic oxidation is good, but in the design process, a larger safety distance is needed, the technology cannot be adopted in the occasion with tense field, and other technologies mainly have the problems of low purification efficiency or high energy consumption and safety risk.
Therefore, the technical personnel in the field urgently need to develop an adsorbent for purifying the waste gas of the VOCs in the chemical industry, which is simple to prepare, has rich mesopores and good hydrophobicity, has excellent strength, excellent adsorption and regeneration performances, and is more energy-saving, and a preparation method thereof, so that the adsorption-based deep purification method of the waste gas of the VOCs, which has the advantages of cost reduction, simple process flow, simplicity and convenience in operation, excellent purification effect and safety, can be realized on the basis of the adsorbent.
Disclosure of Invention
The invention aims to provide an adsorbent for purifying VOCs waste gas in the chemical industry, which is simple to prepare, has rich mesopores, good hydrophobicity, excellent strength, excellent adsorption and regeneration performance and more energy-saving performance, and a preparation method thereof, so that the adsorption-based VOCs waste gas deep purification method which is low in cost, simple in process flow, simple and convenient to operate, excellent in purification effect and safe can be realized on the basis of the adsorbent.
The technical scheme provided by the invention is as follows:
a preparation method of an adsorbent for purifying VOCs waste gas comprises the following steps:
s1, drying and crushing the raw material coal to obtain coal powder;
s2, mixing an organic solvent, an organic auxiliary agent, an inorganic auxiliary agent and an organic adhesive into the coal powder; kneading and stirring, and extruding to obtain wet molded adsorbent;
and S3, finally, drying, carbonizing and activating the formed adsorbent to obtain the adsorbent for purifying the VOCs waste gas.
Preferably, in step S1, the raw material coal is any one or a mixture of anthracite, lignite, peat, petroleum coke, and coal tar pitch.
Preferably, in step S1, the drying temperature is controlled to 50 to 150 ℃, and the water content in the dried raw material coal is 0.5 to 10% by mass.
Preferably, in step S1, the size of the pulverized coal obtained after the pulverization is controlled to be 100 to 350 mesh.
Preferably, in step S2, the organic solvent is an alcohol organic solvent and/or an alkane organic solvent with a boiling point lower than 120 ℃.
Preferably, in step S2, the organic auxiliary agent is an organic acid chelating agent and/or a silane coupling agent.
Preferably, the inorganic auxiliary agent is an alkali metal compound and/or an alkaline earth metal compound.
Preferably, in step S2, the organic binder is any one of coal tar pitch, petroleum residue, coal tar and tar residue binder, and the content of moisture in the organic binder is 0.5 wt% to 4 wt%.
Preferably, in step S2, a polymer resin is further mixed into the pulverized coal.
Furthermore, the addition amount of the polymer resin is 0.01-20% of the mass of the organic adhesive.
Further, in step S2, the polymer resin is any one of phenol resin, butyl phenol resin, p-phenyl phenol resin, poly-cinnamyl alcohol butyral, furan resin, lignin resin glue, carboxymethyl cellulose, and polyvinyl butyral.
Further, in step S2, after the polymer resin and the organic binder are mixed, the mixture is mixed into the coal powder in proportion and stirred uniformly to form coal slurry; then mixing and dissolving the organic solvent, the organic auxiliary agent and the inorganic auxiliary agent in proportion, and uniformly adding the mixture into the coal slime; and kneading and extruding to obtain the wet strip-shaped active carbon with the required diameter.
Preferably, the mixing mass ratio of the organic binder to the pulverized coal is 1: 2-1: 5.
Preferably, the mixing mass ratio of the organic solvent, the inorganic auxiliary agent and the organic auxiliary agent is 100: (4-20): (2-50).
Preferably, the organic solvent, the inorganic auxiliary agent and the organic auxiliary agent account for 0.5-10% of the mass of the organic binder.
Preferably, in step S2, the kneading temperature is controlled to be 0 to 150 ℃.
Preferably, in step S2, the gauge pressure of the extrusion molding after kneading and stirring is controlled to be 0.1 to 2.0MPa, and the diameter of the extrusion is controlled to be 3 to 5 mm.
Preferably, in step S3, the drying temperature for drying after extruding is controlled to be 40 to 120 ℃, and the drying time is 4 to 24 hours.
Preferably, in the step S3, the carbonization temperature is 150 to 650 ℃, and the carbonization time is 30 to 120 min.
Preferably, the carbonization step in the step S3 is to perform first-stage carbonization at 150-350 ℃ for 15-60 min; and then carrying out second-stage carbonization at 300-650 ℃, wherein the carbonization time is 15-60 min.
Preferably, in step S3, the activating medium used for activation after carbonization is water vapor or nitrogen; when water vapor is used as an activation medium, the activation temperature is 600-900 ℃, and the activation time is 3-10 h; when nitrogen is used as an activating medium, the activating temperature is 900-2500 ℃, and the activating time is 3-10 h.
The adsorbent can be prepared by the preparation method, and the specific surface area of the adsorbent can reach 1100m2/g～2500m2(ii) a BET average adsorption pore diameter of 1.5 to 9nm and a pore volume of 0.1 to 1.0cm3The proportion of mesopores with the aperture of 1-50 nm is more than or equal to 65 percent.
The invention also provides an adsorption-based deep purification method for VOCs waste gas, which comprises an adsorption device filled with the adsorbent and comprises the following treatment steps:
s1, pressurizing and pretreating the VOCs waste gas by a pressurizing device and then recovering high-concentration VOCs;
s2, enabling the pretreated waste gas to enter the adsorption equipment for adsorption and purification; wherein, adsorption equipment includes 2 at least adsorption tanks, and is provided with 1 at least layer adsorbent layer in every adsorption tank, adsorbs the regeneration after saturation as wherein a plurality of adsorbent layers, and other adsorbent layers then continue to adsorb waste gas to each layer adsorbent layer adsorbs alternately and desorbs the regeneration, and adsorbs in turn between each adsorbent layer and desorbs the regeneration, makes whole adsorption equipment continuously purify waste gas, and the purified gas is up to standard to be discharged.
Preferably, the pretreatment method in step S1 is any one of a washing method, a low-temperature oil absorption method, a condensation method, an absorption film-coating method, and a condensation film-coating method.
Preferably, in step S1, the pressure boosting device is any one of a screw compressor, a roots blower, a liquid ring compressor, and a scroll compressor.
Preferably, in step S2, the adsorption equipment includes 2 to 4 adsorption tanks, and each adsorption tank is filled with 1 to 6 layers of adsorbents.
Preferably, the adsorption tanks are connected in parallel or in series.
Preferably, in step S2, for the regeneration of the saturated adsorbent, the adsorbent is first desorbed by vacuum, and then purged with inert gas in the later stage of desorption.
Preferably, any adsorbent layer in any adsorption tank is connected with an exhaust gas inlet pipe through an exhaust gas inlet valve and is connected with a desorption gas recovery pipeline with a vacuum pump through a vacuum valve; a gas redistributor with a gas distributing valve is arranged between two adjacent adsorbent layers;
the top of any adsorption tank is connected with a purified gas exhaust pipe through an exhaust valve; and any adsorption tank is connected with a purging air inlet pipe through a gas purging valve.
The invention can bring the following beneficial effects:
1) the invention provides a preparation method of an adsorbent, wherein an inorganic auxiliary agent is used for enabling the adsorbent to generate more mesopores and alkalis in a carbonization process, the organic auxiliary agent and an organic solvent are favorable for enhancing the hydrophobicity of the adsorbent on one hand and promoting the generation of more mesopores on the other hand, and the alkaline functional group can increase the specific surface area and the number of pore channels of the adsorbent; in addition, the invention can further increase the diameter of the hole and improve the strength by adding the polymer. These substances act synergistically to make the adsorbent rich in mesopores and good in hydrophobicity. When the prepared adsorbent is used for adsorbing water-containing macromolecular organic waste gas, the adsorption capacity of the prepared adsorbent to the macromolecular organic waste gas is greatly reduced, so that the adsorption capacity to the macromolecular organic waste gas is enhanced; and because the number of pores in the adsorbent is large, macromolecular organic waste gas is effectively adsorbed.
2) In the implementation, the alkali metal and/or alkaline earth metal compound is added as an inorganic auxiliary agent, so that the adsorbent plays a role of a catalyst in a subsequent activation process (especially high-temperature activation with water vapor or nitrogen), carbon reacts with carbon and oxygen in an additive to generate carbon monoxide and/or carbon dioxide at a high temperature to generate gaps, the pore diameter is increased, metal ions and the carbon form a firm framework to play a supporting role, and the strength of the adsorbent is improved.
3) In the invention, carbonization is controlled by two stages of program temperature control, and carbonization in the first stage is controlled to reduce water content and small molecular substance content to form a uniform precursor; in the second stage of carbonization, the unstable heavy component is driven away from the precursor on the basis of the first stage of carbonization, and the precursor is further shaped; therefore, the two-stage carbonization is beneficial to the moderate shaping of each component in the semi-finished product adsorbent, so that the carbonization effect is more uniform, the mesopore diameter is more uniform and reaches more than 65 percent, and the strength of the product is improved.
4) The greatest difference of the adsorbent prepared by the invention compared with the existing activated carbon adsorbent is that the existing activated carbon adsorbent sold on the market has developed pores, and the pores in the invention are developed and have strong hydrophobicity. The influence of the point on the regeneration performance is very important, and the conventional activated carbon adsorbent pore channel in the prior art is filled with water and is very difficult to regenerate; the adsorbent prepared by adopting a special formula and combining the working procedures has good hydrophobicity, excellent adsorption and regeneration performances and more energy conservation. In addition, the adsorbent has large specific surface area and a large number of mesopores, macromolecular hydrocarbons and micromolecular hydrocarbons can respectively enter proper gaps, and the phenomenon that the micromolecular hydrocarbons are replaced by macromolecular hydrocarbon molecules cannot occur before the next desorption period.
5) The deep purification method provided by the invention ensures the service life and purification effect of the adsorbent through the processes of pressure adsorption and pressure reduction desorption on the basis of the adsorbent provided by the invention, the conventional commercial adsorbent has shorter service life and low purification precision by adopting the method provided by the invention, and the conventional activated carbon adsorption purification outlet can not be lower than 4mg/m when purifying the benzene-containing waste gas3But with the adsorbent and purification method of the present invention, the benzene concentration in the purified gas can be less than 1mg/m3The most severe local standards of Shanghai city and the like are achieved; moreover, the method meets the policy requirements of energy conservation, environmental protection and safety。
Drawings
FIG. 1 is a flow chart of the preparation of the adsorbent of the present invention.
FIG. 2 is a flow chart of the adsorption and desorption regeneration process in the deep purification of VOCs waste gas based on the adsorption method.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
As shown in fig. 1, a method for preparing an adsorbent for purifying V0Cs offgas, comprising the steps of:
s1, drying and crushing the raw material coal to obtain coal powder;
s2, mixing an organic solvent, an organic auxiliary agent, an inorganic auxiliary agent and an organic adhesive into the coal powder; kneading and stirring, and extruding to obtain wet molded adsorbent;
and S3, finally, drying, carbonizing and activating the formed adsorbent to obtain the adsorbent for purifying the VOCs waste gas.
According to the invention, the inorganic auxiliary agent is used for enabling the adsorbent to generate more mesopores and alkalinity in the carbonization process, the organic auxiliary agent and the organic solvent are favorable for enhancing the hydrophobicity of the adsorbent on one hand and promoting generation of more mesopores on the other hand, and the substances have synergistic effect to enable the adsorbent to have rich mesopores and good hydrophobicity. When the prepared adsorbent is used for adsorbing water-containing macromolecular organic waste gas, the adsorption capacity of the prepared adsorbent to the macromolecular organic waste gas is greatly reduced, so that the adsorption capacity to the macromolecular organic waste gas is enhanced; and because the number of pores in the adsorbent is large, macromolecular organic waste gas is effectively adsorbed.
In step S1:
as a preferred embodiment, the raw material coal is any one or a mixture of more of anthracite, lignite, peat, petroleum coke and coal tar pitch. More preferably, the raw material coal with the ash content of less than 5 wt% is used. More preferably, anthracite is selected.
As another preferred embodiment, the drying temperature is controlled to be 50-150 ℃, and more preferably 80-120 ℃; the water content in the dried raw material coal is 0.5-10%, preferably 1-5%.
As another preferable embodiment, the size of pulverized coal obtained after pulverization is controlled to be 100-350 meshes, and more preferably 150-200 meshes.
In step S2:
as a preferred embodiment, in step S2, a polymer resin is further mixed into the pulverized coal. More preferably, the addition amount of the polymer resin is 0.01-20% of the mass of the organic binder, and preferably 0.05-0.5%. Preferably, the polymer resin and the organic adhesive are mixed firstly, then mixed into the coal dust in proportion, and stirred uniformly to form the coal slime; then mixing and dissolving the organic solvent, the organic auxiliary agent and the inorganic auxiliary agent in proportion, and uniformly adding the mixture into the coal slime; and kneading and extruding to obtain the wet strip-shaped active carbon with the required diameter. Due to the insolubility of the inorganic auxiliary agent and the resin, the embodiment is implemented in steps, so that various addition auxiliary agents can be mixed more uniformly, and the holes in the final product are distributed very uniformly, thereby improving the integral pore volume of the adsorbent and the adsorption capacity.
Preferably, the mixing mass ratio of the organic adhesive to the coal powder is 1: 2-1: 5.
Preferably, the mixing mass ratio of the organic solvent to the inorganic auxiliary agent to the organic auxiliary agent is 100: (4-20): (2-50).
Preferably, the organic solvent, the inorganic auxiliary agent and the organic auxiliary agent account for 0.5-10% of the mass of the organic adhesive.
As another preferred embodiment, the organic solvent is an organic solvent having a boiling point lower than 120 ℃. Preferably, the organic solvent is an alcohol organic solvent and/or an alkane organic solvent. More preferably, any one or a mixture of plural kinds of methanol, ethanol, propanol, butanol, n-hexane, cyclohexane, n-heptane, etc. may be used. Further preferred are strong hydrogen bonding organic solvents such as absolute ethanol.
As another preferred embodiment, the organic auxiliary agent is an organic acid chelating agent and/or a silane coupling agent. It is preferable to use any one or a mixture of more of citric acid, oxalic acid, dimethyl silicone oil, hexadecyl trimethoxy silane, n-silane ethyl ester, trimethyl chlorosilane, and dimethyl siloxane. More preferably, simethicone is used.
As another preferred embodiment, the inorganic auxiliary is an alkali metal compound and/or an alkaline earth metal compound. Preferably, any one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and calcium chloride is used. More preferably, potassium hydroxide is used. In the implementation, the alkali metal and/or alkaline earth metal compound is added as an inorganic auxiliary agent, so that the adsorbent plays a role of a catalyst in a subsequent activation process (especially high-temperature activation with water vapor or nitrogen), carbon reacts with carbon and oxygen in an additive to generate carbon monoxide and/or carbon dioxide at a high temperature to generate gaps, the pore diameter is increased, metal ions and the carbon form a firm framework to play a supporting role, and the strength of the adsorbent is improved.
As another preferred embodiment, the organic binder is a binder having a colloidal property. Preferably, any one of coal tar pitch, petroleum residue, coal tar and tar residue binder is adopted, and the content of water in the organic binder is 0.5-4 wt%. Preferably, coal tar pitch is used.
In another preferred embodiment, the polymer resin is any one of phenolic resin, butyl phenolic resin, p-phenyl phenolic resin, poly-cinnamyl alcohol butyral, furan resin, lignin resin glue, carboxymethyl cellulose and polyvinyl butyral. More preferably a phenolic resin. The polymer resins, especially the phenolic resin, can generate high carbon residue under the conditions of high temperature and inert gas, which is beneficial to maintaining the structural stability of the resin; and will slowly decompose to produce hydrogen, hydrocarbons, water vapor. Therefore, after the heat treatment, the pore diameter can be further increased, and the strength can be improved.
In another preferred embodiment, the kneading temperature is controlled to be 0 to 150 ℃, preferably 50 to 80 ℃.
In another preferred embodiment, the gauge pressure of the extrusion after kneading and stirring is controlled to 0.1 to 2.0MPa, and the diameter of the extruded strand is 3 to 5 mm.
In step S3:
as a preferred embodiment, the drying temperature for drying after extruding is controlled to be 40-120 ℃, and the drying time is 4-24 h.
As a preferred embodiment, the carbonization temperature is 150-650 ℃, and the carbonization time is 30-120 min. Preferably, the carbonization step is carried out in two stages, wherein the first-stage carbonization is carried out at 150-350 ℃ for 15-60 min; and then carrying out second-stage carbonization at 300-650 ℃, wherein the carbonization time is 15-60 min. Preferably, the carbonization temperature in the first stage is 200-300 ℃, and the carbonization time is 15-45 min; the second stage carbonization temperature is 350-550 ℃, and the carbonization time is 15-45 min.
In the embodiment, the water content and the content of small molecular substances are reduced under control through carbonization in the first stage to form a uniform precursor; in the second stage of carbonization, the unstable heavy component is driven away from the precursor on the basis of the first stage of carbonization, and the precursor is further shaped; therefore, the two-stage carbonization is beneficial to the moderate shaping of each component in the semi-finished product adsorbent, so that the carbonization effect is more uniform, and the strength of the product is improved.
As a preferred example, the activating medium used for activation after carbonization is water vapor or nitrogen. When water vapor is used as an activation medium, the activation temperature is 600-900 ℃, and the activation time is 3-10 h. When nitrogen is used as an activating medium, the activating temperature is 900-2500 ℃, and the activating time is 3-10 h; preferably, when nitrogen is used as an activating medium, the activating temperature is 1500-2000 ℃, and the activating time is 4-7 hours.
The adsorbent prepared by the embodiment has the specific surface area of 1100m2/g～2500m2(ii) a BET average adsorption pore diameter of 1.5 to 9nm and a pore volume of 0.1 to 1.0cm3The proportion of mesopores (pores with the aperture of 1-50 nm) reaches more than 65 percent.
Accordingly, the greatest difference between the present invention and the conventional activated carbon adsorbent is that the conventional commercially available activated carbon adsorbent has developed pores, whereas the present invention has developed pores and has strong hydrophobicity. The influence of the point on the regeneration performance is very important, and the conventional activated carbon adsorbent pore channel in the prior art is filled with water and is very difficult to regenerate; the adsorbent prepared by adopting a special formula and combining the working procedures has good hydrophobicity, excellent regeneration performance and more energy conservation.
In addition, in chemical enterprises, C3 and C4 hydrocarbons can meet the requirements of relevant national emission standards by adopting common commercial adsorbents. However, when the exhaust gas containing more components of C6 or more is purified, most of the components of C6 or more replace C3 and C4 out of the gaps of the adsorbent due to competitive adsorption, so that the VOC concentration of the purified gas is increased continuously and the excessive emission is realized. The adsorbent has large specific surface area and a large number of mesopores, macromolecular hydrocarbons and micromolecular hydrocarbons can respectively enter proper gaps, and the phenomenon that the micromolecular hydrocarbons are replaced by macromolecular hydrocarbon molecules cannot occur before the next desorption period.
Example 2
An adsorption-based deep purification method for VOCs waste gas, which comprises an adsorption device provided with the adsorbent in the embodiment 1, and comprises the following processing steps:
s1, pretreatment of the VOCs waste gas: pressurizing and pretreating VOCs waste gas by using pressurizing equipment, and then recovering high-concentration VOCs;
s2, enabling the pretreated waste gas to enter the adsorption equipment for adsorption and purification; wherein, adsorption equipment includes 2 at least adsorption tanks, and is provided with 1 at least layer adsorbent layer in every adsorption tank, adsorbs the regeneration after saturation as wherein a plurality of adsorbent layers, and other adsorbent layers then continue to adsorb waste gas to each layer adsorbent layer adsorbs alternately and desorbs the regeneration, and adsorbs in turn between each adsorbent layer and desorbs the regeneration, makes whole adsorption equipment continuously purify waste gas, and the purified gas is up to standard to be discharged.
The deep purification method provided by the invention ensures the service life and purification effect of the adsorbent through the processes of pressure adsorption and pressure reduction desorption on the basis of adopting the adsorbent provided by the invention, and is conventionalThe method of the invention adopted by the commercial adsorbent has short service life and low purification precision, and when the benzene-containing waste gas is purified, the conventional activated carbon adsorption purification outlet can not be lower than 4mg/m3But with the adsorbent and purification method of the present invention, the benzene concentration in the purified gas can be less than 1mg/m3And the most severe local standards of Shanghai city and the like are achieved.
As a preferred embodiment, in step S1, the pressure boosting device is any one of a screw compressor, a roots blower, a liquid ring compressor, and a scroll compressor. The air entraining device has to be designed explosion-proof, preferably a liquid ring compressor. The supercharging device has the function of safely conveying the waste gas besides improving the pressure for waste gas purification. More preferably, the operation pressure of the supercharging device is controlled to be 0.02 MPaG-0.8 MPaG (gauge pressure, the same below). More preferably, the concentration is controlled to be 0.1 to 0.5 MPaG.
As another preferable example, the pretreatment method in step S1 is any one of a washing method, a low-temperature oil absorption method, a condensation method, an absorption coating method, and a condensation coating method. After pretreatment, the hydrocarbon concentration in the VOCs waste gas is lower than 25g/Nm3. Specifically, the foregoing methods are all common treatment methods in the prior art, the washing method generally comprises spraying, washing and absorbing the VOCs with an alkaline liquid, filling the washing tower with a filler, and washing to purify acidic, alkaline or solid particles such as hydrogen sulfide, ammonia gas, dust, etc. in the VOCs. The low-temperature oil absorption method is to cool the absorption liquid to low temperature by using a refrigerator and then send the absorption liquid into an absorption tower to spray and absorb the mixed gas. The condensing method is a kind of oil gas recovery method which utilizes the partial pressure of vapor of hydrocarbon material at different temperatures to reach saturation state and gradually condenses into liquid state, generally adopts precooler and serial mechanical refrigerating device (divided into high temperature section and low temperature section) to gradually condense into liquid state and recover it. The absorption film-adding method is characterized by that it combines the absorption method with membrane separation method, in which the membrane separation method utilizes the preferential permeability of polymer membrane to oil gas, and makes the oil gas-air mixed gas pass through the membrane under the action of a certain pressure difference and make the oil gas in the mixed gas pass through the membrane, and can be removed and recovered, and the air can be selectively retained, and adopts a compressor,And the absorption tower and the rolling curtain type membrane component series device realize the recovery of VOCs. The condensation and membrane-adding method combines a membrane separation method on the basis of a condensation method, and realizes the recovery of VOCs by adopting a compressor, a condensation device and a rolling curtain type membrane component series device. The pretreated waste gas contains various components of C2-C20, and the concentration of VOCs in the purified gas can be lower than 50mg/Nm after the waste gas is treated by oxidation equipment such as an incinerator, a catalytic oxidation equipment, a heat storage oxidation equipment, a heating furnace and the like3And meets the requirements of national relevant standards. However, not all pollution source treatments can be adapted to oxidation equipment due to site, safety control and other restrictions, and in such cases, if a recovery method can be used to meet the requirements of deep purification, the method has obvious advantages in the technical field. The present invention meets the above-described need based on a specially developed adsorbent and the above-described deep purification method.
In a preferred embodiment, in step S2, for the regeneration of the saturated adsorbent, the adsorbent is first desorbed by vacuum, and then purged with inert gas for the last 10-60 min of desorption.
More preferably, the vacuum degree is controlled to be-80 to-99 kPa (gauge pressure) during vacuum desorption, and preferably-95 to-99 kPa (gauge pressure); the purging amount of the inert gas is 1-50 times (volume ratio) of the adsorbent, and the longer the purging amount of the nitrogen is, the better the desorption effect is. The inert gas may be nitrogen.
As a preferred embodiment, from the comprehensive consideration of the aspects such as throughput, equipment volume, etc., the adsorption equipment include 2 ~ 4 adsorption tanks, each adsorption tank loads 1 ~ 6 layers of adsorbent. Preferably, a gas redistributor with a gas distributing valve is arranged between the adjacent adsorbent layers; the gas redistributor 3 is used for uniformly distributing the waste gas, so that the stable treatment of the adsorbent is facilitated. More preferably, the adsorbent is preferably packed in 1 to 3 layers. In addition, in practical application, a plurality of adsorption tanks can be used in parallel in groups, can also be used in series in groups, and can adopt different modes according to different treatment components and purification requirements.
In a preferred embodiment, any adsorbent layer in any adsorption tank is connected with an exhaust gas inlet pipe through an exhaust gas inlet valve, and is connected with a desorption gas recovery pipeline with a vacuum pump 10 through a vacuum valve;
the top of any adsorption tank is connected with a purified gas exhaust pipe through an exhaust valve A4/B4; and any adsorption tank is connected with a purge air inlet pipe through a gas purge valve A8/B8/A5/B5.
The embodiment provides a reproducible adsorption device capable of continuously purifying, and more preferably, the waste gas inlet valve and the waste gas inlet pipe are arranged at the bottom of the corresponding adsorbent layer, so that waste gas can be fully purified through the adsorbent layer after being introduced; the purified gas reaches the standard and is discharged. For the adsorbent layer with saturated adsorption, the adsorbent layer can be sucked back to a desorption gas recovery pipeline through a vacuum pump, so that desorption regeneration is realized, and the adsorption purification of the next period can be recovered; while desorbing, can switch over another adsorption layer and adsorb the purification to do not influence the stable purifying effect of whole device. And the gas purge valves can be arranged at different positions of the adsorption tank corresponding to the adsorbent layer, for example, in fig. 2, the gas purge valves a5/B5 and A8/B8 are respectively arranged at the middle part and the top part, and in practical application, the gas purge valves can be adaptively adjusted according to purge requirements.
More preferably, as shown in fig. 2, the number of the adsorption tanks is 2, and each adsorption tank is filled with 2 layers of adsorbents; a gas redistributor with a gas distributing valve A3 is arranged between the 2 layers of adsorbent layers;
in step S2, the step of alternately performing adsorption and desorption regeneration includes:
s20, in canister a: organic waste gas containing macromolecules firstly enters the first adsorbent layer through a waste gas inlet valve A1, gas after adsorption enters the gas redistributor through a gas distribution valve A3 and then enters the second adsorbent layer, and after secondary adsorption, purified gas reaches the standard and is discharged from an exhaust valve A4;
s21, adsorption tank A: after the first adsorbent layer is penetrated by adsorption, the waste gas inlet valve A1 and the gas distribution valve A3 are closed, meanwhile, the waste gas inlet valve A2 is opened, and the waste gas of the VOCs is switched to pass through the second adsorbent layer of the adsorption tank A for adsorption; desorbing and regenerating the first adsorbent layer, starting a vacuum valve A6, starting a vacuum pump 10, desorbing the organic molecules adsorbed on the surface of the adsorbent, and sending desorbed gas into a recovery system for recovery through the vacuum pump 10; in the later desorption stage, closing the vacuum valve A6, opening the gas purging valve A5, purging by inert gas, closing the gas purging valve A5 after purging is finished, ending the whole desorption process, and waiting for the next adsorption period by the first adsorbent layer of the adsorption tank A;
s22, penetrating the second adsorbent layer of the adsorption tank A; in canister B: opening an exhaust gas inlet valve B1, and switching the VOCs exhaust gas to the first adsorbent layer of the adsorption tank B for adsorption; the gas after adsorption enters a gas redistributor through a gas distribution valve B3 of the adsorption tank B and then enters a second adsorbent layer, and after secondary adsorption, the purified gas reaches the standard and is discharged; desorbing and regenerating the second adsorbent layer of the adsorption tank A, starting a vacuum valve A2, starting a vacuum pump 10, desorbing the organic molecules adsorbed on the surface of the adsorbent, and sending the desorbed gas into a recovery system for recovery through the vacuum pump 10; in the later desorption stage, closing the vacuum valve A7, opening the gas purging valve A8, purging by inert gas, closing the gas purging valve A8 after purging is finished, ending the whole desorption process, and waiting for the next adsorption period by the second adsorbent layer of the adsorption tank A;
s23, in adsorption tank B: after the first adsorbent layer has penetrated, sequentially: adjusting corresponding valves (closing an exhaust gas inlet valve B1 and a gas distribution valve B3, simultaneously opening an exhaust gas inlet valve B2; opening a vacuum valve B6, starting a vacuum pump 10 for desorption regeneration, closing a vacuum valve B6 and a gas purging valve B5 in the later desorption period, purging by adopting inert gas, closing a gas purging valve B5 after purging is finished), switching the exhaust gas to a second adsorbent layer for adsorption purification, and performing desorption regeneration on the first adsorbent layer according to the step S21; after the second adsorbent layer in the adsorption tank B penetrates, adjusting corresponding valves (closing an exhaust gas inlet valve B2, opening an exhaust gas inlet valve A1 and a gas distribution valve A3; opening a vacuum valve B7, starting the vacuum pump 10 for desorption regeneration, in the later period of desorption, closing a vacuum valve B7, opening a gas purging valve B8, purging by adopting inert gas, and after purging is completed, closing the gas purging valve B8) to switch to the first adsorbent layer of the adsorption tank A for adsorption purification, and performing desorption regeneration on the second adsorbent layer of the adsorption tank B according to the step S22;
therefore, the steps S21-S23 are continuously circulated, so that alternate adsorption and desorption regeneration are realized, and the purification treatment of the VOCs waste gas is continuously carried out.
Preferably, the switching time of adsorption and desorption regeneration is 0.5-60 min, preferably 30-60 min. As known in the art, competitive adsorption exists among mixed components due to the difference of adsorption energy on the surface of the adsorbent, generally speaking, adsorption of heavier components is easier, and desorption is also more difficult, and the adsorbent can reach more than 99% of desorption rate within 30-60 min, so that the purification efficiency of adsorption equipment is ensured.
As a preferred embodiment, vacuum desorption is effected by means of a vacuum desorption apparatus; the vacuum desorption equipment is a dry vacuum pump. In practical applications, any one of a screw vacuum pump, a membrane vacuum pump, a molecular pump, a turbo pump, and a roots vacuum pump may be used, but the pump is not limited to the above pump.
The invention is suitable for deep purification of VOC waste gas with complex components in refining enterprises, especially for purification of VOCs waste gas containing a large number of macromolecules, and is particularly suitable for deep purification treatment of VOCs in occasions which cannot be purified by oxidation equipment, such as oil product middle or raw material tank areas, aromatic hydrocarbon tank areas and loading and unloading occasions with limited sites. Specifically, in the prior art, the oxidation equipment adopted for deep purification needs to keep a safe distance of more than 30 meters with the middle of an oil product or a raw material tank area, an aromatic hydrocarbon tank area and a loading and unloading occasion, and a device supported by the adsorption method can be close to the raw material tank area and the like.
Application example 1
S1, selecting anthracite with ash content of 4.56 wt%, drying at 120 ℃ until the water content is 4 wt%, and crushing to 200 meshes to obtain coal powder;
s2, mixing absolute ethyl alcohol, dimethyl silicone oil, potassium hydroxide and coal tar pitch into coal dust according to a proportion, wherein the mass content of water in the organic adhesive coal tar pitch is 1%, and the mass ratio of the water to the coal dust is 1: 3; wherein the mass ratio of the absolute ethyl alcohol to the potassium hydroxide to the dimethyl silicone oil is 100: 5: 10, the dosage of the three components is 5 percent of the mass of the organic adhesive; kneading and stirring at 60 ℃, and extruding and molding under the pressure of 1MPa (gauge pressure) to obtain a molded adsorbent with the diameter of 4 mm;
s3, drying at 60 ℃ for 10h, and then carbonizing in a carbonization furnace at 500 ℃ for 60 min; then, introducing water vapor for activation, and activating for 5 hours at 900 ℃ to obtain the adsorbent product.
Application example 2
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S1, coal pitch with ash content of 0.6 wt% is adopted as raw material coal, the raw material coal is dried at 120 ℃ until the water content is 0.3 wt%, and the raw material coal is crushed to 150 meshes to obtain coal powder.
Application example 3
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S2, sodium carbonate is used as the inorganic auxiliary.
Application example 4
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
the adding sequence of the components in the step S2 is different, specifically, firstly, the organic adhesive coal tar pitch is mixed into the coal dust according to the proportion and is stirred uniformly to form coal slime; then mixing and dissolving an organic solvent absolute ethyl alcohol, an organic auxiliary agent dimethyl silicone oil and an inorganic auxiliary agent potassium hydroxide according to a proportion, and uniformly adding the mixture into the coal slime; and kneading and extruding to obtain wet strip-shaped active carbon with the diameter of 4 mm.
Application example 5
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S3, the carbonization process adopts two-stage program temperature control carbonization, firstly, the first-stage carbonization is carried out at 250 ℃, and the carbonization time is 30 min; then, the second stage of carbonization is carried out at 500 ℃, and the carbonization time is 45 min.
Application example 6
The preparation process and the operation conditions are the same as those of application example 4, and the differences are only that:
in step S2, firstly, mixing organic binder coal tar pitch into coal dust according to the mass ratio of 1:2, wherein the mass content of water in the organic binder is 0.5%, and uniformly stirring to form coal slime; then mixing and dissolving an organic solvent anhydrous ethanol, an organic auxiliary agent dimethyl silicone oil and an inorganic auxiliary agent potassium hydroxide in proportion, wherein the mass ratio of the anhydrous ethanol to the potassium hydroxide to the dimethyl silicone oil is 100: 4: 2, the dosage of the three is 0.5 percent of the mass of the organic adhesive, and then the three are uniformly added into the coal slime; and kneading and extruding to obtain wet strip-shaped active carbon with the diameter of 4 mm.
Application example 7
The preparation process and the operation conditions are the same as those of application example 4, and the differences are only that:
in step S2, firstly, mixing organic binder coal tar pitch into coal dust according to the mass ratio of 1:5, wherein the mass content of water in the organic binder is 4%, and uniformly stirring to form coal slime; then mixing and dissolving an organic solvent anhydrous ethanol, an organic auxiliary agent dimethyl silicone oil and an inorganic auxiliary agent potassium hydroxide in proportion, wherein the mass ratio of the anhydrous ethanol to the potassium hydroxide to the dimethyl silicone oil is 100: 20: 50, the dosage of the three is 10 percent of the mass of the organic adhesive, and then the three are uniformly added into the coal slime; and kneading and extruding to obtain wet strip-shaped active carbon with the diameter of 4 mm.
Application example 8
The preparation process and the operation conditions are the same as those of application example 4, and the differences are only that:
in step S2, the phenolic resin is first mixed with the organic binder coal tar pitch and then mixed into the coal dust, wherein the amount of the added phenolic resin is 0.5% of the mass of the organic binder.
Application example 9
The preparation process and the operation conditions are the same as those of application example 8, and the differences are only that:
in step S3, the carbonization process adopts two-stage program temperature control carbonization, firstly, the first-stage carbonization is carried out at 300 ℃, and the carbonization time is 15 min; then, the second stage of carbonization is carried out at 550 ℃, and the carbonization time is 15 min.
Comparative example 1
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S1, anthracite coal having an ash content of 6 wt% is used as the raw material coal.
Comparative example 2
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S2, no organic auxiliary is added.
Comparative example 3
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S2, no inorganic auxiliary is added.
Comparative example 4
The preparation process and the operation conditions are the same as those of application example 1, and the differences are only that:
in step S2, the inorganic additive is ferric hydroxide.
Comparative example 5
The preparation process and the operation conditions are the same as those in application example 6, and the differences are only that:
in step S2, firstly, mixing organic binder coal tar pitch into coal dust according to the mass ratio of 1:2, wherein the mass content of water in the organic binder is 0.5%, and uniformly stirring to form coal slime; then mixing and dissolving an organic solvent anhydrous ethanol, an organic auxiliary agent dimethyl silicone oil and an inorganic auxiliary agent potassium hydroxide in proportion, wherein the mass ratio of the anhydrous ethanol to the potassium hydroxide to the dimethyl silicone oil is 100: 2: 2, the dosage of the three is 0.5 percent of the mass of the organic adhesive, and then the three are uniformly added into the coal slime; and kneading and extruding to obtain wet strip-shaped active carbon with the diameter of 4 mm.
Comparative example 6
The preparation process and the operation conditions are the same as those of application example 7, and the differences are only that:
in step S2, firstly, mixing organic binder coal tar pitch into coal dust according to the mass ratio of 1:5, wherein the mass content of water in the organic binder is 4%, and uniformly stirring to form coal slime; then mixing and dissolving an organic solvent anhydrous ethanol, an organic auxiliary agent dimethyl silicone oil and an inorganic auxiliary agent potassium hydroxide in proportion, wherein the mass ratio of the anhydrous ethanol to the potassium hydroxide to the dimethyl silicone oil is 100: 22: 50, the dosage of the three is 10 percent of the mass of the organic adhesive, and then the three are uniformly added into the coal slime; and kneading and extruding to obtain wet strip-shaped active carbon with the diameter of 4 mm.
In the above-mentioned specific examples of the production of the adsorbent, the specific surface area, pore volume and pore diameter of the produced adsorbent were analyzed by a American Mike ASAP 2020 physical surface adsorption apparatus. The equilibrium adsorption capacity of saturated water vapor is the static saturated adsorption capacity of the adsorbent to air with the humidity of 90 percent at 25 ℃, and the weight of the adsorbent after water vapor adsorption is WRear endThe weight of the adsorbent before adsorption is WFront sideThe saturated water vapor equilibrium adsorption quantity is calculated according to the following formula: saturated water vapor equilibrium adsorption capacity (wt%) (W)Rear end-WFront side)/WFront sideX 100%. The main properties of the adsorbent products prepared in the application examples of the present invention and the comparative examples are shown in table 1.
TABLE 1 Main Properties of the respective adsorbent products
Figure BDA0002256583060000201
In the present invention, the mesopore diameter formed by each adsorbent product is concentrated between 1 to 50nm, and even if the average pore diameter value in Table 1 is not more than 5nm (in the range of 1.5 to 9 nm), the proportion of mesopores between 1 to 50nm is more than 65%. In addition, as can be seen from table 1 above, the polymer resin, the inorganic assistant, and the organic assistant all promote the formation of mesopores and micropores, and increase the hydrophobicity. Comparative examples 1-3 show that the hydrophobic and mesoporous performances of the adsorbent are directly affected by the raw material coal, the organic auxiliary agent and the inorganic auxiliary agent. In comparative example 4, since the aqueous solution of iron hydroxide was colloidal and difficult to mix uniformly, iron oxide solids were more likely to form during the heat treatment, which not only did not promote the formation of mesopores, but also occupied effective adsorption channels. Therefore, the product cannot effectively increase the mesopore volume. Comparison of comparative examples 5 and 6 with application examples 6 and 7 shows that when the ratio of the organic solvent, the inorganic additive and the organic additive exceeds a certain range, the synergistic mesoporous promotion effect of the components may be adversely affected, specifically, the amount of the potassium hydroxide inorganic additive is too low, so that the gas and water formed with carbon are less, and abundant mesopores are difficult to form, and conversely, when the amount of the inorganic additive is too much, more metal salt occupies the volume of the mesopores, and the adsorbent per unit volume is not favorable for forming more channels.
Application example 8
By adopting the adsorbent prepared in application example 4 and the process flow shown in figure 2, the recovery and treatment are carried out on the benzene and xylene loaded and dissipated waste gas, wherein the concentration of the benzene is 1.5 multiplied by 105mg/m3Xylene concentration 4.5X 104mg/m3。
The method specifically comprises the following steps:
s1, carrying out pressure increase on the waste gas through a liquid ring compressor, and recovering high-concentration VOCs after pretreatment through a condensation method;
s2, the concentration of hydrocarbons in the pretreated waste gas is 5000mg/m3The purified gas enters the adsorption equipment filled with the adsorbent to be adsorbed and purified, and the purified gas reaches the standard and is discharged;
the adsorption equipment comprises adsorption equipment which is divided into an adsorption tank A and an adsorption tank B, wherein the A series is started firstly, and the B series is standby; organic waste gas containing macromolecules firstly enters a first adsorbent layer of the A series, gas after adsorption enters a second adsorbent layer through a gas redistributor, and purified gas is discharged after reaching the standard after secondary adsorption; switching to the A series second adsorbent layer for adsorption after the first adsorbent layer is penetrated by adsorption; the first adsorbent layer enters a vacuum desorption regeneration procedure, organic molecules adsorbed on the surface of the adsorbent are desorbed, and desorption gas is sent to a mixed aromatic low-temperature absorption tower through a vacuum pump for recovery; and in the later desorption stage, nitrogen purging is adopted, after the purging is completed, the whole desorption process is finished, and the first adsorbent layer waits for the next adsorption period. After the A series second adsorbent layer penetrates, switching to the B series, and desorbing in the same way;
and controlling the operation pressure of 0.2MPaG and the adsorption temperature of 25 ℃ in the adsorption process; the switching time of adsorption and regeneration is 40min, and the vacuum degree of regeneration is-97 kPaG.
After 6 months of operation according to this example, the outlet concentration of the apparatus was 1.8mg/m3The concentration of the dimethylbenzene is less than or equal to 8.3mg/m3。
The embodiment solves the defect that an oxidation device needs to be added at the rear end of the traditional absorption device, has simple process and avoids the potential safety problem of the oxidation process.
Application example 9
The process flow of the adsorbent and the adsorption and desorption regeneration of the application example 1 is adopted for 1.5 multiplied by 104mg/m3The styrene-containing waste gas is subjected to adsorption and regeneration treatment.
The method specifically comprises the following steps:
s1, increasing the pressure of the waste gas through a liquid ring compressor, and recovering high-concentration VOCs after pretreatment by a low-temperature oil absorption method;
s2, the hydrocarbon concentration in the pretreated waste gas is 8000mg/m3The purified gas enters the adsorption equipment filled with the adsorbent to be adsorbed and purified, and the purified gas reaches the standard and is discharged;
the adsorption equipment comprises adsorption equipment which is divided into three adsorption series of an adsorption tank A, an adsorption tank B and an adsorption tank C, wherein the A series is started firstly, and the B series is regenerated and the C series is standby; each series has 3 adsorption layers, wherein after two series (such as A, C) complete adsorption, the other series (such as B) completes regeneration for standby, and according to bed calculation, 6 beds are in regeneration state while one bed is adsorbing. The adsorption and the regeneration desorption are sequentially and continuously carried out through the switching of a valve;
and controlling the adsorption gauge pressure to be 0.15MPaG, and carrying out normal-temperature adsorption for 3min and regeneration for 18 min. Regenerating vacuum degree of-97 kPaG, adopting nitrogen to blow, condensing desorbed gas, sending liquid into a storage tank for storage, and returning non-condensable gas to the inlet of the adsorption equipment.
The calibration is carried out after the operation of the embodiment for 6 months, and the concentration of the styrene at the adsorption outlet is less than 4mg/m3Far below the relevant national emission standards.
The embodiment solves the bottleneck problem that the conventional adsorption method can not recover the styrene waste gas, obtains ideal recovery, and the device outlet can stably reach the standard.
Application example 10
By adopting the adsorbent prepared in application example 4 and the process flow shown in figure 2, the waste gas dissipated by the sump oil storage tank is recycled and treatedThe concentration of non-methane total hydrocarbon discharged from the storage tank is 3.5 multiplied by 105mg/m3。
The steps specifically adopted are basically the same as those in application example 8, and the differences are only that:
in step S2, the operating pressure in the adsorption process is 0.25MPaG, and the adsorption temperature is 25 ℃; regenerating the vacuum degree of-97 kPaG, and purging with nitrogen; the switching time of adsorption and regeneration is 8min, and the desorbed gas in the process enters a gas tank for further recovery.
The device is calibrated again after running for 1 year, and the concentration of non-methane total hydrocarbon in the outlet is 60mg/m3And the purification efficiency is 99.98 percent.
The method for deeply purifying the VOCs waste gas based on adsorption has the advantages of excellent purification effect, stable long-period operation and suitability for industrial application.
It should be noted that the above embodiments can be freely combined as necessary. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (11)

1. A preparation method of an adsorbent for purifying VOCs waste gas is characterized by comprising the following steps:
s1, drying and crushing the raw material coal to obtain coal powder;
s2, mixing an organic solvent, an organic auxiliary agent, an inorganic auxiliary agent and an organic adhesive into the coal powder; kneading and stirring, and extruding to obtain wet molded adsorbent;
and S3, finally, drying, carbonizing and activating the formed adsorbent to obtain the adsorbent for purifying the VOCs waste gas.
2. The method of claim 1, wherein:
in step S1, the raw material coal is any one or a mixture of more of anthracite, lignite, peat, petroleum coke, and coal tar pitch; and/or the presence of a gas in the gas,
in the step S1, the drying temperature is controlled to be 50-150 ℃, and the mass content of water in the dried raw material coal is 0.5-10%; and/or the presence of a gas in the gas,
in step S1, the size of the pulverized coal obtained after crushing is controlled to be 100-350 meshes.
3. The method of claim 1, wherein:
in step S2, the organic solvent is an alcohol organic solvent and/or an alkane organic solvent with a boiling point lower than 120 ℃; and/or the presence of a gas in the gas,
in step S2, the organic auxiliary agent is an organic acid chelating agent and/or a silane coupling agent; and/or the presence of a gas in the gas,
in step S2, the inorganic auxiliary is an alkali metal compound and/or an alkaline earth metal compound; and/or the presence of a gas in the gas,
in step S2, the organic binder is any one of coal tar pitch, petroleum residue, coal tar, and tar residue binder, and the content of water in the organic binder is 0.5 wt% to 4 wt%.
4. The method of claim 1, wherein:
in step S2, polymer resin is also mixed into the pulverized coal; and the addition amount of the polymer resin is 0.01-20% of the mass of the organic adhesive.
5. The method of claim 4, wherein:
in step S2, firstly, polymer resin and organic adhesive are mixed, then mixed into coal powder according to a certain proportion, and stirred uniformly to form coal slurry; then mixing and dissolving the organic solvent, the organic auxiliary agent and the inorganic auxiliary agent in proportion, and uniformly adding the mixture into the coal slime; kneading and extruding to obtain wet strip-shaped active carbon with the required diameter;
and/or the presence of a gas in the gas,
in step S2, the polymer resin is any one of phenol resin, butyl phenol resin, p-phenyl phenol resin, poly-cinnamyl alcohol butyral, furan resin, lignin resin glue, carboxymethyl cellulose, and polyvinyl butyral.
6. The method of claim 1, wherein:
in the step S2, the mixing mass ratio of the organic binder to the pulverized coal is 1: 2-1: 5; and/or the presence of a gas in the gas,
in step S2, the mixing mass ratio of the organic solvent, the inorganic auxiliary agent, and the organic auxiliary agent is 100: (4-20): (2-50); and/or the presence of a gas in the gas,
in step S2, the organic solvent, the inorganic auxiliary agent and the organic auxiliary agent account for 0.5-10% of the mass of the organic adhesive; and/or the presence of a gas in the gas,
in the step S2, the temperature of the kneading and stirring is controlled to be 0-150 ℃; and/or the presence of a gas in the gas,
in the step S2, the gauge pressure of the extrusion molding after kneading and stirring is controlled to be 0.1-2.0 MPa, and the diameter of the extrusion is 3-5 mm;
in the step S3, the drying temperature for drying after extruding is controlled to be 40-120 ℃, and the drying time is 4-24 h;
in the step S3, the carbonization temperature is 150-650 ℃, and the carbonization time is 30-120 min.
7. The method of claim 1, wherein:
the carbonization step in the step S3 is that the first stage carbonization is carried out at 150-350 ℃ for 15-60 min; then carrying out second-stage carbonization at 300-650 ℃, wherein the carbonization time is 15-60 min;
and/or the presence of a gas in the gas,
in step S3, the activating medium used for activation after carbonization is water vapor or nitrogen; when water vapor is used as an activation medium, the activation temperature is 600-900 ℃, and the activation time is 3-10 h; when nitrogen is used as an activating medium, the activating temperature is 900-2500 ℃, and the activating time is 3-10 h.
8. The adsorbent for purifying waste gases of VOCs prepared by the preparation method according to any one of claims 1 to 7, wherein:
the specific surface area of the prepared adsorbent can reach 1100m2/g～2500m2(ii) a BET average adsorption pore diameter of 1.5 to 9nm and a pore volume of 0.1 to 1.0cm3The proportion of mesopores with the aperture of 1-50 nm is more than or equal to 65 percent.
9. The application of an adsorbent for purifying VOCs waste gas is characterized in that: used for carrying out deep purification on VOCs waste gas.
10. A method for the advanced purification of waste gases containing VOCs based on adsorption, comprising an adsorption apparatus containing the adsorbent of claim 8, and performing the following steps:
s1, pressurizing and pretreating the VOCs waste gas by a pressurizing device and then recovering high-concentration VOCs;
s2, enabling the pretreated waste gas to enter the adsorption equipment for adsorption and purification; wherein, adsorption equipment includes 2 at least adsorption tanks, and is provided with 1 at least layer adsorbent layer in every adsorption tank, adsorbs the regeneration after saturation as wherein a plurality of adsorbent layers, and other adsorbent layers then continue to adsorb waste gas to each layer adsorbent layer adsorbs alternately and desorbs the regeneration, and adsorbs in turn between each adsorbent layer and desorbs the regeneration, makes whole adsorption equipment continuously purify waste gas, and the purified gas is up to standard to be discharged.
11. The purification method according to claim 10, characterized in that:
the pretreatment method in step S1 selects any one of a washing method, a low-temperature oil absorption method, a condensation method, an absorption film-adding method, and a condensation film-adding method; and/or the presence of a gas in the gas,
in step S1, the supercharging device is any one of a screw compressor, a roots blower, a liquid ring compressor, and a scroll compressor; and/or the presence of a gas in the gas,
in the step S2, the adsorption equipment comprises 2-4 adsorption tanks, and each adsorption tank is filled with 1-6 layers of adsorbents; and/or the presence of a gas in the gas,
the adsorption tanks are used in parallel or in series; and/or the presence of a gas in the gas,
in step S2, for the regeneration of the saturated adsorbent, the adsorbent is desorbed first by vacuum, and then purged with an inert gas in the later stage of desorption; and/or the presence of a gas in the gas,
in the adsorption apparatus: any adsorbent layer in any adsorption tank is connected with a waste gas inlet pipe through a waste gas inlet valve and is connected with a desorption gas recovery pipeline with a vacuum pump through a vacuum valve; a gas redistributor with a gas distributing valve is arranged between two adjacent adsorbent layers; the top of any adsorption tank is connected with a purified gas exhaust pipe through an exhaust valve; and any adsorption tank is connected with a purging air inlet pipe through a gas purging valve.
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