CN107876005B - Adsorbent for removing chlorinated pollutants and preparation method and application thereof - Google Patents
Adsorbent for removing chlorinated pollutants and preparation method and application thereof Download PDFInfo
- Publication number
- CN107876005B CN107876005B CN201711046775.2A CN201711046775A CN107876005B CN 107876005 B CN107876005 B CN 107876005B CN 201711046775 A CN201711046775 A CN 201711046775A CN 107876005 B CN107876005 B CN 107876005B
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- molecular sieve
- chlorinated pollutants
- preparation
- removing chlorinated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention relates to an adsorbent for removing chlorinated pollutants, a preparation method and application thereof, wherein the adsorbent adopts a ZSM-5 molecular sieve and an X-type molecular sieve as carriers, active components are loaded through microwave irradiation solid-phase reaction, the obtained material, a binder and a pore-forming agent are mixed and formed to prepare particles, and the adsorbent for removing chlorinated pollutants is obtained after treatment at a certain temperature in an air atmosphere with a certain humidity and can be used for removing various chlorinated pollutants. Compared with the prior art, the preparation method has the advantages of rapidness, controllability, environmental protection, no pollution and the like, and the obtained adsorbent has the advantages of rich pore structure, high dispersion of active components and the like.
Description
Technical Field
The invention relates to an adsorbent, in particular to an adsorbent for removing chlorinated pollutants, and a preparation method and application thereof.
Background
In recent years, the harm of chlorinated pollutants such as persistent organic chlorides and hydrogen chloride to industrial production is receiving more attention, and the development of an effective purification method is urgent. In the field of petroleum refining, the content of organic chlorinated pollutants such as chloralkane in naphtha is obviously increased due to the limitation of mining and refining processes, organic chloride can be converted into hydrogen chloride in the subsequent pre-hydrogenation treatment process, and the corrosion of equipment and pipelines can be caused by the presence of the chlorinated pollutants, so that the catalyst is poisoned or inactivated, and the production enterprises have double risks of safety and operation. In a continuous reforming device, chlorine lost by a reforming catalyst is converted into hydrogen chloride to enter a hydrogen system, so that the content of the hydrogen chloride in the reformed hydrogen exceeds the standard. Meanwhile, trace organic chlorine such as chloroethane, 1-chloropropane, butyl chloride, vinyl chloride and the like exists in the byproduct hydrogen, inorganic chlorine and corresponding hydrocarbon can be generated through decomposition under the low-temperature condition, and in order to avoid corrosion of hydrogen chloride on equipment and pipelines and influence on subsequent hydrocracking reaction, the hydrogen chloride and the organic chlorine must be removed to an extremely low level. At present, various methods for treating chlorinated pollutants exist at home and abroad. The adsorption method has the outstanding advantages of low cost, mature process, easy operation, low energy consumption and the like, and is widely applied to removal of chlorinated pollutants.
CN1064099A discloses a chloride using alkali metal compound or alkaline earth metal compound as active component and natural inorganic clay as binder, but the pore structure distribution of the adsorbent is poor and the chlorine purification degree is low. US5595954 discloses a process for the preparation of dechlorination agents using alumina promoted with an alkaline or alkaline earth metal salt solution, the active component being introduced by impregnation or solution mixing, but in the presence of Al2O3The carrier is unstable in an acid environment, and the penetrating chlorine capacity is low in the actual working condition. CN104437342B discloses a dechlorinating agent obtained by impregnating soluble copper salt, calcium salt, magnesium salt, barium salt, etc. onto a cylindrical carbon molecular sieve and then drying and stabilizing the impregnated product, which is suitable for removing inorganic chlorine in oil products, but the action force between a carbonaceous carrier (such as activated carbon, etc.) and active metal components is weak, the metal active components are easy to lose, and especially the loss is more serious under the condition of liquid phase reaction. US3864243 discloses a process for removing chlorides and other impurities from hydrocarbons using a zeolite molecular sieve, which is carried out by an adsorption process using a 13X or 10X zeolite molecular sieve at normal temperature and pressure, but with low adsorption capacity. CN103830996B discloses a medium-high temperature gas dechlorinating agent using a molecular sieve as a carrier, which is prepared by introducing active ingredients such as calcium nitrate, magnesium nitrate, zinc nitrate, sodium bicarbonate and the like into the carrier in a solution mode, rotating, heating, drying, roasting and forming the carrier to obtain the dechlorinating agent, wherein the dechlorinating agent can efficiently and deeply remove HCl gas in flue gas within the temperature range of 423-1073K.
Dechlorination agents in the current market are usually developed aiming at single chlorine species, most of the dechlorination agents are selected from single carrier types, and the dechlorination agents have the defects of poor pore structure distribution, weak acid resistance, small specific surface area, low active component content, narrow application range and the like. In the preparation process, the addition of the active components generally adopts a method of impregnation or direct solid mixing, wherein the impregnation method has the advantages of uniform distribution of the active components, wastewater pollution, obvious reduction of the surface area and the pore volume of the adsorbent, and the solid mixing method has the advantages of nonuniform distribution of the active components and low utilization efficiency of the pore channels of the carrier material, thereby influencing the adsorption effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the adsorbent for removing chlorinated pollutants, which has the advantages of rapidness, controllability, environmental protection, no pollution and the like, and the obtained adsorbent has the advantages of rich pore structure, high dispersion of active components and the like, and the preparation method and the application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an adsorbent for removing chlorinated pollutants comprises the following steps:
(1) uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component and trace moisture, and fully grinding;
(2) performing microwave irradiation treatment on the material obtained in the step (1) to uniformly disperse active components on the surface of the molecular sieve, and performing solid phase ion exchange on part of metal ions and cations of the molecular sieve;
(3) uniformly mixing the material obtained in the step (2), an organic pore-forming agent and an inorganic binder, and forming to prepare a granular adsorbent;
(4) and (4) activating the granular adsorbent obtained in the step (3) in a low-humidity air atmosphere to obtain the adsorbent for removing chlorinated pollutants.
Preferably, the weight ratio of the ZSM-5 molecular sieve, the X-type molecular sieve, the active component and the trace moisture in the step (1) is (20-60): (20-50): (0.5-5), and the X-type molecular sieve is at least one of a 13X molecular sieve, a 10X molecular sieve and a NaLSX molecular sieve.
In the invention, the ZSM-5 molecular sieve and the X-type molecular sieve are modified together through microwave solid-phase reaction.
Preferably, the active component is a metal salt selected from at least one of nitrate, formate, acetate, carbonate, bicarbonate and basic carbonate of a metal element selected from at least one of zinc, sodium, potassium, calcium, iron, copper, nickel and magnesium.
Further preferably, the active component is at least one selected from carbonates and acetates of metal elements, and the metal elements are zinc.
In the invention, the metal salt modifies the ZSM-5 molecular sieve and the X-type molecular sieve through microwave solid-phase reaction, promotes the active component to carry out solid-phase ion exchange by utilizing the heat effect of a microwave field, and promotes the dispersion of the active component on a molecular sieve carrier by utilizing the heat effect and the action of a special electric field. The method ensures that the active component is highly dispersed in the pore canal of the carrier molecular sieve and on the surface of the carrier, and part of unconsumed metal salt can still be remained in the powder material to play a role as the active component without being removed.
Preferably, the microwave irradiation frequency in the step (2) is 2450MHz, the power is 600W-1200W, and the treatment time is 3 min-20 min.
Further preferably, the treatment time of the microwave irradiation in the step (2) is 5min to 15 min.
Preferably:
the organic pore-forming agent in the step (3) is selected from at least one of starch, dextrin, lignin and cellulose;
the inorganic binder in the step (3) is at least one selected from kaolin, attapulgite, bentonite, water glass, alumina sol and silica sol.
The organic pore-forming agent selected by the invention is an organic pore-forming agent with a macromolecular structure, and is mainly used for increasing the macroporous distribution of the adsorbent material, enriching the pore channel structure, reducing the diffusion resistance in the adsorption process and improving the adsorption efficiency.
The adhesive is an essential component for forming the adsorbent so as to maintain the strength and abrasion resistance of the granular adsorbent in application, the inorganic adhesive listed in the invention is a commercially common adhesive type, and other products with similar properties can be applied to the forming process of the adsorbent in the invention.
Preferably, in the step (3), the weight ratio of the material obtained in the step (2), the inorganic binder and the organic pore-forming agent is (80-90): (10-20): 1-3).
The adsorbent of the present invention is formed by extrusion or rolling into cylindrical, clover, tablet or granule of different particle sizes by methods well known in the art, and the particle forming mode can be adjusted according to application requirements.
Preferably, the relative humidity of the low-humidity air in the step (4) is 10-30% RH (25 ℃), that is, the relative humidity of the low-humidity air at 25 ℃ is 10-30% RH.
The invention does not need to fully dry the air (activated) in the roasting process, saves energy consumption, simultaneously keeps trace moisture in the structure of the adsorbent, and improves the water resistance when the adsorbent is applied to a water environment.
Preferably, in the step (4), the temperature of the activation treatment is 350-650 ℃, and the activation time is 30 min-3 h.
Further preferably, the temperature of the activation treatment is 400-500 ℃, and the heating device preferably uses a moving bed so as to uniformly activate the adsorbent particles.
Further preferably, the activation time is 1h to 3 h.
An adsorbent for removing chlorinated pollutants, which is obtained by adopting the preparation method.
The application of the adsorbent for removing chlorinated pollutants is applied to the removal of various chlorinated pollutants including organic chlorides and hydrogen chloride.
Compared with the prior art, the invention has the following advantages:
1) the adsorbent carrier is compounded by two molecular sieves, the size difference of pore channels among different types of molecular sieves can be utilized, the distribution of the pore channel structure is effectively improved, and the enrichment of trace pollutants is realized by utilizing the pore channel structure of the molecular sieves. Meanwhile, the polarity difference of the surface of the carrier can be used for removing chlorinated pollutants with different polarities, so that the application range of the product is improved, and the product can be applied to removing hydrogen chloride in a gas-liquid phase and also can be used for removing trace organic chloride in an oil product or a water body. Meanwhile, the carrier has high temperature resistance and acid resistance, and the dechlorination efficiency reduction caused by the structural damage of the carrier in the application process can be avoided.
2) Compared with the traditional impregnation or solid-phase mixing method, the preparation method has the advantages that the microwave solid-phase reaction technology is adopted in the preparation process, the production process avoids the generation of sewage, the environment-friendly characteristic is realized, the uniform immobilization of the active components on the surface of the carrier is rapidly realized, the adsorption effect of the adsorbent is enhanced, and the utilization efficiency of the active components is improved.
3) The micro-moisture is introduced into the materials of the microwave solid-phase reaction, so that on one hand, the solid-phase reaction efficiency is improved, on the other hand, the steam reaming treatment is carried out on the molecular sieve carrier by utilizing the quickly generated steam, the richness of the pore structure is improved, and the blockage of the internal pore is avoided.
4) Roasting under certain humidity can increase the water resistance of the adsorbent and avoid the adsorbent from being cracked when applied to a water body environment.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, zinc acetate and trace moisture according to a weight ratio of 20:50:40:5, fully grinding, and performing 600W microwave irradiation treatment for 20min under the condition of 2450 MHz. The mixed material, the attapulgite and the cellulose are mixed and formed according to the weight ratio of 80:20:3, and the mixture is roasted for 3 hours at 350 ℃ and 20% RH (25 ℃) to obtain the adsorbent I.
Example 2
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, calcium nitrate and trace moisture according to the weight ratio of 20:60:50:0.5, fully grinding, and carrying out 1200W microwave irradiation treatment for 3min under the condition of 2450 MHz. The mixed material, kaolin and starch are mixed and molded according to the weight ratio of 90:10:2, and the mixture is roasted for 2 hours at the temperature of 550 ℃ and the humidity of 30 percent RH (25 ℃) to obtain an adsorbent II.
Example 3
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, potassium carbonate and trace moisture according to a weight ratio of 60:20:30:2, fully grinding, and carrying out 800W microwave irradiation treatment for 3min under the condition of 2450 MHz. Mixing the mixed material, bentonite and dextrin according to a weight ratio of 85:15:1, forming, and roasting at 650 ℃, 10% RH (25 ℃) and humidity air for 1h to obtain the adsorbent III.
Example 4
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, iron acetate and trace moisture according to the weight ratio of 40:30:40:4, fully grinding, and carrying out 900W microwave irradiation treatment for 20min under the condition of 2450 MHz. Mixing the mixed material, water glass and starch according to the weight ratio of 88:12:1, forming, and roasting for 2 hours at 500 ℃ and 10% RH (25 ℃) humidity air to obtain the adsorbent.
Example 5
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, sodium formate and trace moisture according to the weight ratio of 20:50:40:3, fully grinding, and carrying out 1000W microwave irradiation treatment for 3min under the condition of 2450 MHz. Mixing the above mixed materials, attapulgite and cellulose at a weight ratio of 80:20:1.5, molding, and calcining at 400 deg.C and 20% RH (25 deg.C) in humidity air for 3 hr to obtain adsorbent.
Comparative example 1
The adsorbent was prepared as described in example 1, with no addition of trace moisture, to give (i-II) adsorbent.
Comparative example 2
The adsorbent is prepared according to the proportion described in example 1, and after full grinding, the adsorbent is directly formed without microwave irradiation, and the adsorbent (i-III) is obtained by adopting the same roasting condition.
The test of the first to fifth examples and the comparative example was carried out by using a physical adsorption apparatus ASAP2020, and the test method was a low-temperature nitrogen adsorption-desorption method. The pore structure is tested, the specific surface area of the sample is measured, and the data is shown in table 1.
The removal performance of the adsorbents prepared in examples 1 to 5 on organic chlorides was evaluated by a static adsorption method, and organic chlorides were characterized by n-heptane as a simulated solvent and dichloroethane as a simulated oil with a concentration of 100 ppm. Mixing 100ml of simulated oil with 10g of adsorbent, shaking for 2 hours at normal temperature, taking out and testing. The chloride removal rates are shown in table 1.
TABLE 1
| Sample name | Specific surface area (m)2/g) | Pore volume (cm)3/g) | Removal efficiency (%) |
| ① | 340 | 0.43 | 89.5 |
| ② | 317 | 0.39 | 82.4 |
| ③ | 350 | 0.40 | 94.9 |
| ④ | 329 | 0.39 | 85.6 |
| ⑤ | 342 | 0.46 | 92.0 |
| ①-II | 325 | 0.35 | 81.9 |
| ①-III | 310 | 0.32 | 70.2 |
Example 6
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, nickel acetate and trace moisture according to a weight ratio of 20:30:50:1, fully grinding, and performing 700W microwave irradiation treatment for 10min under the condition of 2450 MHz. Mixing the mixed material, silica sol and starch in the weight ratio of 85 to 15 to 3, forming, and roasting at 550 deg.c and 30% RH (25 deg.c) humidity for 2 hr to obtain adsorbent.
Example 7
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, magnesium carbonate and trace moisture according to a weight ratio of 50:30:20:1, fully grinding, and performing 700W microwave irradiation treatment for 10min under the condition of 2450 MHz. Mixing the mixed material, attapulgite and dextrin according to a weight ratio of 90:10:2, molding, and roasting at 450 ℃ and 20% RH (25 ℃) for 2h to obtain the adsorbent.
The prepared adsorbent is applied to removing trace organic chloride in water, 10g of the adsorbent is placed in 100mL of aqueous solution containing 50ppm of trichloromethane, and after oscillation for 2 hours at normal temperature, separation test is carried out, so that the trichloromethane content can be reduced to less than 1 ppm.
Example 8
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component (zinc acetate: sodium formate: 1) and trace moisture according to the weight ratio of 40:30:50:1, fully grinding, and performing 600W microwave irradiation treatment for 15min at 2450 MHz. Mixing the mixed material, kaolin and lignin according to a weight ratio of 85:15:3, forming, and roasting at 600 ℃ and 30% RH (25 ℃) in humidity air for 1.5h to obtain the adsorbent (b).
Example 9
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component (zinc acetate: sodium bicarbonate: potassium bicarbonate: 1:0.5:0.5) and trace moisture according to a weight ratio of 40:30:50:1, fully grinding, and performing microwave irradiation treatment for 10min under the condition of 2450 MHz. Mixing the mixed material, silica sol and starch according to a weight ratio of 85:15:3, forming, and roasting at 550 ℃ and 10% RH (25 ℃) humidity air for 2h to obtain the adsorbent ninc.
Example 10
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component (sodium formate: ferric nitrate: calcium carbonate: 1:1) and trace moisture according to the weight ratio of 40:40:30:2, fully grinding, and carrying out 1200W microwave irradiation treatment for 5min under the condition of 2450 MHz. Mixing the above mixture, alumina sol and cellulose at a weight ratio of 80:20:2, molding, and roasting at 650 deg.C and 20% RH (25 deg.C) in humidity air for 1h to obtain adsorbent.
Example 11
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component (basic zinc carbonate: calcium acetate: ferric nitrate: 1:0.8:0.2) and trace water according to the weight ratio of 40:30:40:4, fully grinding, and carrying out 800W microwave irradiation treatment for 15min under the condition of 2450 MHz. Mixing the mixed material, attapulgite and starch at a weight ratio of 85:15:1, molding, and roasting at 350 deg.C and 10% RH (25 deg.C) in humid air for 2 hr to obtain adsorbent
Crushing the adsorbent to 20-40 meshes, filling 3mL of adsorbent into a fixed bed reactor, wherein the size of the reactor bed is 1cm (ID) × 20cm (H), placing quartz sand at the bottom of the bed layer during filling, then placing glass wool, then placing the adsorbent, vibrating to fill the adsorbent, placing the quartz sand at the top to fill the whole adsorbent bed layer, and filling the adsorbent bed layer for about 500h-1A stream of high purity nitrogen at GHSV was purged over the bed for 10 min. Pure nitrogen gas at a space velocity of 1000h-1The simulated working condition of (2) is introduced into hydrochloric acid solution and then introducedRemoving water vapor by using concentrated sulfuric acid, absorbing the tail gas by using an absorption bottle filled with 500.0mL of deionized water for 15min (the absorption bottle is replaced every 15 min) after the absorption by using a fixed bed reactor, and finally absorbing the tail gas by using the absorption bottle filled with 10% sodium hydroxide solution; detecting the chlorine content of the solution in the deionized water absorption bottle by using a microcoulomb meter, and converting the chlorine content into the chlorine content in the gas exceeding 5mg/m3I.e. penetration.
The results of testing the adsorbents prepared in examples 8-11 are shown in Table 2.
TABLE 2
Example 12
Uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component (sodium formate: sodium acetate: 1) and trace moisture according to the weight ratio of 40:30:50:1, fully grinding, and performing 600W microwave irradiation treatment for 15min at 2450 MHz. The mixed material, inorganic binder (kaolin: attapulgite 5:10) and organic pore former (lignin: starch: 2:1) are mixed and molded according to the weight ratio of 85:15:3, and the mixture is roasted for 1.5h at 600 ℃ and 30% RH (25 ℃) in humidity air to obtain the adsorbent.
Example 13
This example is substantially the same as example 1 except that the active component in this example is copper nitrate.
Example 14
This example is substantially the same as example 1 except that the microwave irradiation treatment time in this example was 5 min.
Example 15
This example is substantially the same as example 1 except that in this example the final blend-molded mixture was calcined at 650 deg.C in a humidity atmosphere of 15% RH (25 deg.C) for 30 minutes to obtain an adsorbent.
The type X molecular sieve in each of the above examples is at least one of a 13X molecular sieve, a 10X molecular sieve, and a NaLSX molecular sieve.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of an adsorbent for removing chlorinated pollutants is characterized by comprising the following steps:
(1) uniformly mixing a ZSM-5 molecular sieve, an X-type molecular sieve, an active component and trace moisture, and fully grinding;
(2) carrying out microwave irradiation treatment on the material obtained in the step (1);
(3) uniformly mixing the material obtained in the step (2), an organic pore-forming agent and an inorganic binder, and forming to prepare a granular adsorbent;
(4) activating the granular adsorbent obtained in the step (3) in a low-humidity air atmosphere to obtain the adsorbent for removing chlorinated pollutants;
the weight ratio of the ZSM-5 molecular sieve, the X-type molecular sieve, the active component and the trace moisture in the step (1) is (20-60): 20-50): 0.5-5);
the active component is metal salt selected from at least one of nitrate, formate, acetate, carbonate, bicarbonate and alkali carbonate of metal elements, and the metal elements are selected from at least one of zinc, sodium, potassium, calcium, iron, copper, nickel and magnesium;
the low-humidity air in the step (4) is low-humidity air with relative humidity of 10-30% RH at 25 ℃.
2. The method of claim 1, wherein the type X molecular sieve is at least one of a 13X molecular sieve, a 10X molecular sieve and a NaLSX molecular sieve.
3. The method for preparing the adsorbent for removing chlorinated pollutants according to claim 1, wherein the microwave irradiation frequency in the step (2) is 2450MHz, the power is 600W-1200W, and the treatment time is 3 min-20 min.
4. The method for preparing an adsorbent for removing chlorinated pollutants according to claim 1, wherein:
the organic pore-forming agent in the step (3) is selected from at least one of starch, dextrin, lignin and cellulose;
the inorganic binder in the step (3) is at least one selected from kaolin, attapulgite, bentonite, water glass, alumina sol and silica sol.
5. The method as claimed in claim 1 or 4, wherein in the step (3), the weight ratio of the material obtained in the step (2), the inorganic binder and the organic pore-forming agent is (80-90): 10-20): 1-3.
6. The preparation method of the adsorbent for removing chlorinated pollutants according to claim 1, wherein in the step (4), the temperature of the activation treatment is 350-650 ℃, and the activation time is 30 min-3 h.
7. An adsorbent for removing chlorinated pollutants, which is obtained by the preparation method of any one of claims 1 to 6.
8. Use of the adsorbent for removing chlorinated pollutants as claimed in claim 7, wherein it is applied to the removal of chlorinated pollutants including organic chlorides and hydrogen chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711046775.2A CN107876005B (en) | 2017-10-31 | 2017-10-31 | Adsorbent for removing chlorinated pollutants and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711046775.2A CN107876005B (en) | 2017-10-31 | 2017-10-31 | Adsorbent for removing chlorinated pollutants and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107876005A CN107876005A (en) | 2018-04-06 |
| CN107876005B true CN107876005B (en) | 2020-08-28 |
Family
ID=61783158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711046775.2A Active CN107876005B (en) | 2017-10-31 | 2017-10-31 | Adsorbent for removing chlorinated pollutants and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107876005B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110876922A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Naphtha dechlorination adsorbent and preparation method and application thereof |
| CN109482136A (en) * | 2018-12-27 | 2019-03-19 | 青岛华世洁环保科技有限公司 | A kind of adsorbent and preparation method thereof |
| CN111068613A (en) * | 2019-12-26 | 2020-04-28 | 四川润和催化新材料股份有限公司 | Organic chlorine remover and preparation method and application thereof |
| CN112316889B (en) * | 2020-10-22 | 2023-10-31 | 北京圣光环保工程股份有限公司 | Dechlorination composition and preparation method and application thereof |
| CN113185671B (en) * | 2021-05-27 | 2022-09-16 | 复旦大学 | Impurity removal and purification method for epoxy resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235508B2 (en) * | 2003-08-19 | 2007-06-26 | Korea Research Institute Of Chemical Technology | Metal-incorporated nanoporous nickel phosphate molecular sieve and its preparation method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037415C (en) * | 1994-01-29 | 1998-02-18 | 复旦大学 | Hydrophobic silicon zeolite adsorbent without cohesive agent and its preparation |
| CN101721972B (en) * | 2009-12-08 | 2011-11-09 | 华东理工大学 | Method for preparing spherical activated carbon with large CO2 absorption capacity |
| CN104689787A (en) * | 2013-12-09 | 2015-06-10 | 东营科尔特化工科技有限公司 | Liquefied petroleum gas dechlorination adsorbent and application method thereof |
| CN105498682B (en) * | 2015-12-07 | 2018-04-10 | 上海绿强新材料有限公司 | A kind of mesoporous chloride scavenger and preparation method thereof |
| CN105344130B (en) * | 2015-12-07 | 2017-07-14 | 上海绿强新材料有限公司 | A kind of method of heavy metal in utilization zeolite molecular sieve film removing Chinese medicine |
-
2017
- 2017-10-31 CN CN201711046775.2A patent/CN107876005B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235508B2 (en) * | 2003-08-19 | 2007-06-26 | Korea Research Institute Of Chemical Technology | Metal-incorporated nanoporous nickel phosphate molecular sieve and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107876005A (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107876005B (en) | Adsorbent for removing chlorinated pollutants and preparation method and application thereof | |
| US7288504B2 (en) | Method for producing spherical activation carbon | |
| Okunev et al. | Sorption of carbon dioxide from wet gases by K2CO3-in-porous matrix: influence of the matrix nature | |
| CN100560484C (en) | Absorbent charcoal special for adsorbing gasoline steam and preparation method thereof | |
| KR101400249B1 (en) | Method for preparing carbon dioxide absorbent based on natural biomass and carbon dioxide absorbent based on natural biomass prepared by the same | |
| CN104741000B (en) | A kind of application of composite bed low temperature SCR denitration catalyst | |
| CN107902655A (en) | A kind of method for preparing nitrating activated carbon using discarded activated carbon | |
| CN112619609B (en) | Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof | |
| CN103213984A (en) | Method for preparing high thermal conductivity active carbon taking waste cotton cloth as raw material | |
| CN103482624A (en) | Preparation method for active carbon with photocatalysis function | |
| KR101680610B1 (en) | Activated carbon adsorbent for acidic gas removal and manufacturing method the same | |
| CN101323794B (en) | Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof | |
| CN108607530B (en) | Desulfurizing agent, preparation method thereof and method for deeply removing sulfur dioxide | |
| CN103240059A (en) | Preparation method of active carbon for oil gas recovery | |
| CN107999020B (en) | Preparation method of porous alumina dealcoholization agent | |
| CN115888786A (en) | Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application | |
| CN111514849B (en) | Dechlorination adsorbent, preparation method thereof, regeneration method thereof and application of dechlorination adsorbent in removal of organic chlorine | |
| JP2002211911A (en) | Carbonized material containing hydroxyl group derived from hydrophilic polymer and method for producing the same | |
| CN109289508A (en) | A kind of preparation method of high hydrophobicity zeolitic material | |
| Yu et al. | Removal of indoor formaldehyde over CMK-8 adsorbents | |
| CN104645927A (en) | Method for preparing silver mercury removing agent | |
| CN113117639A (en) | Modified molecular sieve adsorbent and preparation method and application thereof | |
| CN106943864A (en) | A kind of method that carbon material selective absorbing purifies acetylene | |
| CN114307968A (en) | Adsorbent for adsorbing chlorine-containing volatile organic gas and application thereof | |
| CN102441317B (en) | Benzene chloride tail gas recovering and purifying method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |