CN112642413A - Preparation method and product of mercury removal adsorbent based on active coke - Google Patents

Preparation method and product of mercury removal adsorbent based on active coke Download PDF

Info

Publication number
CN112642413A
CN112642413A CN202011454134.2A CN202011454134A CN112642413A CN 112642413 A CN112642413 A CN 112642413A CN 202011454134 A CN202011454134 A CN 202011454134A CN 112642413 A CN112642413 A CN 112642413A
Authority
CN
China
Prior art keywords
sulfur
preset
active coke
adsorbent
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011454134.2A
Other languages
Chinese (zh)
Inventor
昌健
龚得喜
吕小玲
严铭
魏艳立
左文华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing SPC Environment Protection Tech Co Ltd
Original Assignee
Beijing SPC Environment Protection Tech Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing SPC Environment Protection Tech Co Ltd filed Critical Beijing SPC Environment Protection Tech Co Ltd
Priority to CN202011454134.2A priority Critical patent/CN112642413A/en
Publication of CN112642413A publication Critical patent/CN112642413A/en
Pending legal-status Critical Current

Links

Images

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
    • B01J20/28—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a preparation method and a product of a mercury removal adsorbent based on active coke, wherein the method comprises the following steps: mixing active coke with a preset index and sulfur with a preset granularity according to a preset proportion to obtain a mixture; and placing the obtained mixture in a closed reactor, and carrying out rotary type co-thermal reaction under preset process conditions to obtain the sulfur-carrying mercury removal adsorbent. The basic carbon material adopted by the invention has specific porosity and granularity, can better adsorb and load sulfur element, and improves the sulfur load rate; and a closed reactor is adopted in the process, so that the waste of sulfur resources is prevented; the rotary dynamic co-heating reaction is adopted, so that the sulfur element loading uniformity is better, and the product consistency is higher. Simple operation, high efficiency and suitability for industrial production. Thereby solving the technical problems of low sulfur loading rate, uneven loading and poor product quality consistency of the existing preparation method of the demercuration adsorbent.

Description

Preparation method and product of mercury removal adsorbent based on active coke
Technical Field
The invention relates to the technical field of preparation of mercury removal adsorbents, and particularly relates to a preparation method and a product of a mercury removal adsorbent based on active coke.
Background
Mercury has strong toxicity, enrichment, durability and long-distance migration, and is always the key point and difficult point of environmental management. According to the United nations environmental planning agency '2018 annual global mercury assessment report', the current global mercury emission amount is about 2220 tons every year, Asia accounts for about 40% of the whole mercury emission amount, and China is the world with the largest mercury production, use and emission countries. In the 10 th year 2013, China officially signed "water guarantee official treaty on mercury, and the regulations take effect globally in the 8 th month 2017, which means that the requirements of China on standards related to mercury pollution such as flue gas treatment, environmental monitoring and the like are gradually increased. At present, the best method for treating mercury-containing flue gas is known as a modified activated carbon injection method or a fixed bed adsorption method, and high-quality demercuration adsorbents are required to be used as supports.
At present, domestic research on the activated coke/carbon demercuration adsorbent mainly focuses on the aspect of load modification, and the aim of modification is achieved by heating or dipping the activated coke and loading sulfur, halogen or other metal elements and the like. For example, in one prior art, the sulfur-loaded activated carbon with the sulfur loading rate of 18-30% is obtained by a preparation method of thermal precipitation by using activated carbon with 20-40 meshes. In another existing process, 2-20 meshes of activated carbon and a certain proportion of sulfur powder are mixed, stirred, sealed and heated at 300-400 ℃ for 2-4 hours to obtain the activated carbon composite mercury removing agent. Or, impregnating and modifying coconut shell activated carbon with the diameter of 4-8 mm by using a 2% sodium sulfide aqueous solution, then carrying out microwave heating for 10-15 min, uniformly mixing with sulfur in a certain mass ratio, and carrying out microwave heating to 500 ℃ to obtain the flue gas demercuration adsorbent. However, the demercuration adsorbent obtained by the existing preparation method or a fixed bed co-heating mode causes sulfur element to escape along with protective gas in the sulfur-carrying process, thereby causing waste of sulfur resources and reducing the load rate; or only under closed heating conditions, resulting in uneven sulfur loading and poor product quality consistency.
Disclosure of Invention
Therefore, the invention provides a preparation method and a product of the mercury removal adsorbent based on active coke, and aims to at least partially solve the technical problems of low sulfur loading rate, uneven loading and poor product quality consistency of the existing preparation method of the mercury removal adsorbent.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
a preparation method of a mercury removal adsorbent based on activated coke comprises the following steps:
mixing active coke with a preset index and sulfur with a preset granularity according to a preset proportion to obtain a mixture;
and placing the obtained mixture in a closed reactor, and carrying out rotary type co-thermal reaction under preset process conditions to obtain the sulfur-carrying mercury removal adsorbent.
Furthermore, the active coke is unshaped granular coal active coke, the preset index is 3-8 mm of granularity, the specific surface area is 300-600 m-2/g-2/g, and the ignition point is more than or equal to 420 ℃.
Further, the preset granularity of the sulfur is 40-200 meshes.
Further, the preset mixing ratio of the active coke and the sulfur in the mixture is a preset mass ratio, and the preset mass ratio is that the active coke: the sulfur is 100: 3-100: 20.
Further, blending the active coke with a preset index and sulfur with a preset granularity according to a preset proportion to obtain a mixture, which specifically comprises the following steps:
manually mixing active coke and sulfur in a preset proportion in a container to obtain a primary mixed material;
placing the primary mixed material in a closed reactor, and mixing for the second time to obtain a mixed material;
and putting the closed reactor filled with the mixture into a rotating system of a tubular resistance furnace, and rotating at the frequency of 5 Hz-30 Hz.
Further, the reaction conditions of the rotary type co-thermal reaction are that the heating rate is 3 ℃/min to 15 ℃/min, the reaction temperature is 200 ℃ to 600 ℃, and the reaction time is 2h to 5 h.
Further, still include:
stopping heating, taking out the sealed reactor, cooling to normal temperature, taking out the demercuration adsorbent, and sealing for storage.
The invention also provides a mercury removal adsorbent which is prepared by applying the method, the mercury removal adsorbent is in an amorphous granular shape, the granularity of the mercury removal adsorbent is 3-8 mm, the specific surface area is 200-600 square meters per gram, the sulfur loading rate is 3-15%, and the mercury capacity is more than or equal to 1 mg/g.
According to the preparation method of the mercury removal adsorbent based on the activated coke, the basic carbon material is low-cost small-particle activated coke, and wood activated carbon and coal columnar activated carbon which are commonly used in the prior art are abandoned, so that the production cost is greatly reduced, and the preparation method is economical and practical; the basic carbon material adopted by the invention has specific porosity and granularity, can better adsorb and load sulfur element, and improves the sulfur load rate; and a closed reactor is adopted in the process, so that the waste of sulfur resources is prevented; the rotary dynamic co-heating reaction is adopted, so that the sulfur element loading uniformity is better, and the product consistency is higher. Simple operation, high efficiency and suitability for industrial production. Thereby solving the technical problems of low sulfur loading rate, uneven loading and poor product quality consistency of the existing preparation method of the demercuration adsorbent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
Fig. 1 is a flow chart of a method for preparing an activated coke-based demercuration adsorbent provided by the invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a specific embodiment, the preparation method of the mercury removal adsorbent based on active coke provided by the invention is to use small-particle active coke as a raw material and a certain proportion of sulfur as an auxiliary material, and adopts a closed reactor to rotate and heat. As shown in fig. 1, the method specifically comprises the following steps:
s1: mixing active coke with a preset index and sulfur with a preset granularity according to a preset proportion to obtain a mixture; specifically, the active coke is amorphous granular coal active coke, the preset index is 3-8 mm in granularity, the specific surface area is 300m 2/g-600 m2/g, the ignition point is not less than 420 ℃, the preset granularity of the sulfur is 40-200 meshes, the preset proportion of the active coke mixed with the sulfur in the mixture is a preset mass proportion, and the preset mass proportion is as follows: the sulfur is 100: 3-100: 20.
That is, in the preparation stage of the raw and auxiliary materials, selecting unshaped granular coal active coke, wherein the indexes are that the granularity is 3 mm-8 mm, the specific surface area is 300m 2/g-600 m2/g, the ignition point is more than or equal to 420 ℃, and drying for later use; crushing the sulfur to the granularity of 40-200 meshes; in the proportioning stage, the active coke and the sulfur are proportioned according to the following weight: 3-20 parts of sulfur powder per 100 parts of active coke.
S2: and placing the obtained mixture in a closed reactor, and carrying out rotary type co-thermal reaction under preset process conditions to obtain the sulfur-carrying mercury removal adsorbent. Wherein the reaction conditions of the rotary type co-thermal reaction are that the heating rate is 3 ℃/min-15 ℃/min, the reaction temperature is 200-600 ℃, and the reaction time is 2-5 h.
In the stage of heat supply reaction, setting various reaction parameters, determining the final reaction temperature to be 200-600 ℃ at the heating rate of 3-15 ℃/min, ensuring the rotation frequency of the reactor to be 5-30 Hz, keeping the co-heating reaction time to be 2-5 h after the tubular resistance furnace reaches the final reaction temperature, and stopping the test.
In order to improve the mixing uniformity and improve the reaction performance, the active coke with preset indexes and the sulfur with preset granularity are mixed according to a preset proportion to obtain a mixture, and the method specifically comprises the following steps:
manually mixing active coke and sulfur in a preset proportion in a container to obtain a primary mixed material;
placing the primary mixed material in a closed reactor, and mixing for the second time to obtain a mixed material;
and putting the closed reactor filled with the mixture into a rotating system of a tubular resistance furnace, and rotating at the frequency of 5 Hz-30 Hz.
That is, in the mixing stage, the active coke and sulfur which are proportioned and finished are firstly manually mixed in a container and then are placed in a special closed reactor for secondary mixing. And (3) putting the closed reactor into a rotating system of the tubular resistance furnace, and starting a co-heating reaction after the installation is finished.
S3: stopping heating, taking out the sealed reactor, cooling to normal temperature, taking out the demercuration adsorbent, and sealing for storage.
In the above specific embodiment, the preparation method of the mercury removal adsorbent based on activated coke provided by the invention utilizes the base carbon material of the low-cost small-particle activated coke, abandons the commonly used wood activated carbon and coal columnar activated carbon in the prior art, greatly reduces the production cost, and is economical and practical; the basic carbon material adopted by the invention has specific porosity and granularity, can better adsorb and load sulfur element, and improves the sulfur load rate; and a closed reactor is adopted in the process, so that the waste of sulfur resources is prevented; the rotary dynamic co-heating reaction is adopted, so that the sulfur element loading uniformity is better, and the product consistency is higher. Simple operation, high efficiency and suitability for industrial production. Thereby solving the technical problems of low sulfur loading rate, uneven loading and poor product quality consistency of the existing preparation method of the demercuration adsorbent.
The following examples 1-5 are given as examples to briefly describe the implementation of the method provided by the present invention, and it is obvious that the described examples are some, but not all, examples of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, the granularity of the coal indefinite form particle active coke selected in the test is 2 mm-3 mm, the specific surface area is 550m2/g, the ignition point is 440 ℃, and the coal indefinite form particle active coke is dried for 2 hours at 105 ℃ for standby; the sulfur is crushed to 60-160 meshes. 100 g of the screened active coke is weighed according to the proportion, 10 g of sulfur (the sulfur-carbon ratio is 10 percent) is weighed, and the active coke is manually mixed and stirred in a glass container.
And transferring the preliminarily mixed active coke and a sulfur sample into a closed reactor specially made for a test, slightly shaking for secondary mixing after completely screwing, then placing the closed reactor into a tubular resistance furnace, and connecting two ends of the closed reactor with a rotating system.
Setting the test parameters related to the co-thermal modification load, setting the temperature rise rate to 10 ℃/min in the embodiment, keeping the temperature for 2h at the final reaction temperature of 550 ℃, setting the rotation frequency of the reactor to 15Hz, and stopping the test after the reaction time is up. Cooling, taking out the demercuration adsorbent, and sealing for storage.
The sulfur loading rate of the demercuration adsorbent prepared in the example is 8.5%, the specific surface area is 498m2/g, and the mercury capacity is 5.2 mg/g.
Example 2
Firstly, the granularity of the coal indefinite form particle active coke selected in the test is 5 mm-6 mm, the specific surface area is 535m2/g, the ignition point is 440 ℃, and the coal indefinite form particle active coke is dried for 2 hours at 105 ℃ for standby; the sulfur is crushed to 60-160 meshes. 100 g of the screened active coke is weighed according to the proportion, 5 g of sulfur (the sulfur-carbon ratio is 5 percent) is weighed, and the active coke is manually mixed and stirred in a glass container.
And transferring the preliminarily mixed active coke and a sulfur sample into a closed reactor specially made for a test, slightly shaking for secondary mixing after completely screwing, then placing the closed reactor into a tubular resistance furnace, and connecting two ends of the closed reactor with a rotating system.
Setting the test parameters related to the co-thermal modification load, setting the temperature rise rate to be 5 ℃/min in the embodiment, keeping the temperature for 4h under the condition of the reaction final temperature of 400 ℃, setting the rotation frequency of the reactor to be 10Hz, and stopping the test after the reaction time is up. Cooling, taking out the demercuration adsorbent, and sealing for storage.
The sulfur loading rate of the demercuration adsorbent prepared in the example is 3.8%, the specific surface area is 502m2/g, and the mercury capacity is 1.7 mg/g.
Example 3
Firstly, the granularity of the coal indefinite form particle active coke selected in the test is 4 mm-6 mm, the specific surface area is 550m2/g, the ignition point is 437 ℃, and the active coke is dried for 2 hours at 105 ℃ for standby; the sulfur is crushed to 60-160 meshes. 100 g of the screened active coke is weighed according to the proportion, 15 g of sulfur (the sulfur-carbon ratio is 15 percent) is weighed, and the mixture is manually mixed and stirred in a glass container.
And transferring the preliminarily mixed active coke and a sulfur sample into a closed reactor specially made for a test, slightly shaking for secondary mixing after completely screwing, then placing the closed reactor into a tubular resistance furnace, and connecting two ends of the closed reactor with a rotating system.
Setting the test parameters related to the co-thermal modification load, setting the temperature rise rate to be 8 ℃/min in the embodiment, keeping the temperature for 3h under the condition that the reaction final temperature is 500 ℃, setting the rotation frequency of the reactor to be 10Hz, and stopping the test after the reaction time is up. Cooling, taking out the demercuration adsorbent, and sealing for storage.
The sulfur loading rate of the demercuration adsorbent prepared in the example is 12.3%, the specific surface area is 461m2/g, and the mercury capacity is 8.4 mg/g.
Example 4
Firstly, the granularity of the coal indefinite form particle active coke selected in the test is 2 mm-4 mm, the specific surface area is 544m2/g, the ignition point is 440 ℃, and the coal indefinite form particle active coke is dried for 2 hours at 105 ℃ for standby; the sulfur is crushed to 60-160 meshes. 100 g of the screened active coke is weighed according to the proportion, 10 g of sulfur (the sulfur-carbon ratio is 10 percent) is weighed, and the active coke is manually mixed and stirred in a glass container.
And transferring the preliminarily mixed active coke and a sulfur sample into a closed reactor specially made for a test, slightly shaking for secondary mixing after completely screwing, then placing the closed reactor into a tubular resistance furnace, and connecting two ends of the closed reactor with a rotating system.
Setting the test parameters related to the co-thermal modification load, setting the temperature rise rate to be 5 ℃/min in the embodiment, keeping the temperature for 4h under the condition that the reaction final temperature is 350 ℃, setting the rotation frequency of the reactor to be 5Hz, and stopping the test after the reaction time is up. Cooling, taking out the demercuration adsorbent, and sealing for storage.
The sulfur loading rate of the demercuration adsorbent prepared in the example is 6.8%, the specific surface area is 477m2/g, and the mercury capacity is 4.6 mg/g.
Example 5
Firstly, the granularity of the coal indefinite form particle active coke selected in the test is 2 mm-8 mm, the specific surface area is 528m2/g, the ignition point is 430 ℃, and the coal indefinite form particle active coke is dried for 2 hours at 105 ℃ for standby; the sulfur is crushed to 60-160 meshes. 100 g of the screened active coke is weighed according to the proportion, 8 g of sulfur (the sulfur-carbon ratio is 8 percent) is weighed, and the active coke is manually mixed and stirred in a glass container.
And transferring the preliminarily mixed active coke and a sulfur sample into a closed reactor specially made for a test, slightly shaking for secondary mixing after completely screwing, then placing the closed reactor into a tubular resistance furnace, and connecting two ends of the closed reactor with a rotating system.
Setting the test parameters related to the co-thermal modification load, setting the temperature rise rate to 10 ℃/min in the embodiment, keeping the temperature for 3h at the reaction final temperature of 450 ℃, setting the rotation frequency of the reactor to 15Hz, and stopping the test after the reaction time is up. Cooling, taking out the demercuration adsorbent, and sealing for storage.
The sulfur loading rate of the demercuration adsorbent prepared in the example is 6.0%, the specific surface area is 439m2/g, and the mercury capacity is 4.2 mg/g.
The product index of the shaped carbon-based material prepared by the above 5 examples. In the above 5 examples, the results were averaged by performing 2 parallel replicates. The demercuration adsorbent prepared by the technical scheme provided by the invention has the characteristics of high sulfur carrying rate, large mercury capacity and the like, and both indexes are superior to demercuration carbon materials in the current market; the selected basic carbon material is small-particle active coke, the modifier is common sulfur, and the production cost is low; the preparation is carried out by adopting a closed reactor dynamic heating mode, the sulfur loading uniformity is higher, and the consistency is better; the proper granularity is selected, the disadvantage that the powdery demercuration adsorbent is difficult to regenerate is avoided, and the utilization rate is improved.
For the performance indexes of the mercury removal adsorbent prepared by the invention, the determination of the sulfur carrying rate is based on a determination method of total sulfur in GB/T214-2007 coal, and the determination of the mercury capacity is based on a detection method in GB/T35254-2017 special carbon-based products for integrated purification of flue gas.
In addition to the method, the invention also provides a mercury removal adsorbent which is prepared by applying the method, wherein the mercury removal adsorbent is in an amorphous granular shape, the granularity of the mercury removal adsorbent is 3-8 mm, the specific surface area is 200-600 square meters per gram, the sulfur loading rate is 3-15%, and the mercury capacity is more than or equal to 1 mg/g. The product of the mercury removal adsorbent prepared by the low-cost small-particle activated coke has high sulfur carrying rate and higher flue gas mercury removal capacity; the particle size is moderate, and the method is suitable for subsequent regeneration operation and achieves the aim of recycling.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A preparation method of a mercury removal adsorbent based on activated coke is characterized by comprising the following steps:
mixing active coke with a preset index and sulfur with a preset granularity according to a preset proportion to obtain a mixture;
and placing the obtained mixture in a closed reactor, and carrying out rotary type co-thermal reaction under preset process conditions to obtain the sulfur-carrying mercury removal adsorbent.
2. The preparation method of the mercury-removing adsorbent according to claim 1, wherein the active coke is amorphous granular coal active coke, the preset index is 3 mm-8 mm of granularity, the specific surface area is 300m 2/g-600 m2/g, and the ignition point is not less than 420 ℃.
3. The method for preparing the demercuration adsorbent according to claim 1, wherein the preset particle size of the sulfur is 40-200 meshes.
4. The preparation method of the demercuration adsorbent according to claim 1, wherein the preset ratio of the active coke to the sulfur in the mixed material is a preset mass ratio, and the preset mass ratio is that the active coke: the sulfur is 100: 3-100: 20.
5. The preparation method of the demercuration adsorbent according to claim 1, wherein the active coke with a preset index and sulfur with a preset particle size are mixed according to a preset proportion to obtain a mixture, and the preparation method specifically comprises the following steps:
manually mixing active coke and sulfur in a preset proportion in a container to obtain a primary mixed material;
placing the primary mixed material in a closed reactor, and mixing for the second time to obtain a mixed material;
and putting the closed reactor filled with the mixture into a rotating system of a tubular resistance furnace, and rotating at the frequency of 5 Hz-30 Hz.
6. The method for preparing the mercury-removing adsorbent according to claim 1, wherein the reaction conditions of the rotary type co-thermal reaction are that the temperature rising rate is 3 ℃/min to 15 ℃/min, the reaction temperature is 200 ℃ to 600 ℃, and the reaction time is 2h to 5 h.
7. The method for preparing the demercuration adsorbent according to claim 1, further comprising:
stopping heating, taking out the sealed reactor, cooling to normal temperature, taking out the demercuration adsorbent, and sealing for storage.
8. A mercury removal adsorbent prepared by the method according to any one of claims 1 to 7, wherein the mercury removal adsorbent is an amorphous granular adsorbent, the particle size of the mercury removal adsorbent is 3mm to 8mm, the specific surface area of the mercury removal adsorbent is 200 square meters per gram to 600 square meters per gram, the sulfur loading rate is 3% to 15%, and the mercury capacity is more than or equal to 1 mg/g.
CN202011454134.2A 2020-12-10 2020-12-10 Preparation method and product of mercury removal adsorbent based on active coke Pending CN112642413A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011454134.2A CN112642413A (en) 2020-12-10 2020-12-10 Preparation method and product of mercury removal adsorbent based on active coke

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011454134.2A CN112642413A (en) 2020-12-10 2020-12-10 Preparation method and product of mercury removal adsorbent based on active coke

Publications (1)

Publication Number Publication Date
CN112642413A true CN112642413A (en) 2021-04-13

Family

ID=75353572

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011454134.2A Pending CN112642413A (en) 2020-12-10 2020-12-10 Preparation method and product of mercury removal adsorbent based on active coke

Country Status (1)

Country Link
CN (1) CN112642413A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474551A (en) * 2008-12-22 2009-07-08 重庆大学 S-loaded activated carbon for mercury removal from flue gas and preparation method thereof
CN101492162A (en) * 2009-03-11 2009-07-29 煤炭科学研究总院 Modified active coke, production and uses thereof
CN101497029A (en) * 2009-01-08 2009-08-05 重庆大学 Sorbent for removing mercury from flue gas and preparation method thereof
CN101513605A (en) * 2009-02-27 2009-08-26 南京正森化工实业有限公司 Method of preparing sulfur leaching mercury control activated carbon
CN105921107A (en) * 2016-05-18 2016-09-07 天津普瑞特净化技术有限公司 Active-carbon composite mercury removing agent and preparing technology thereof
CN108993504A (en) * 2018-07-25 2018-12-14 北京市劳动保护科学研究所 A kind of modified active coke and preparation method thereof for sulfur-containing smoke gas demercuration

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101474551A (en) * 2008-12-22 2009-07-08 重庆大学 S-loaded activated carbon for mercury removal from flue gas and preparation method thereof
CN101497029A (en) * 2009-01-08 2009-08-05 重庆大学 Sorbent for removing mercury from flue gas and preparation method thereof
CN101513605A (en) * 2009-02-27 2009-08-26 南京正森化工实业有限公司 Method of preparing sulfur leaching mercury control activated carbon
CN101492162A (en) * 2009-03-11 2009-07-29 煤炭科学研究总院 Modified active coke, production and uses thereof
CN105921107A (en) * 2016-05-18 2016-09-07 天津普瑞特净化技术有限公司 Active-carbon composite mercury removing agent and preparing technology thereof
CN108993504A (en) * 2018-07-25 2018-12-14 北京市劳动保护科学研究所 A kind of modified active coke and preparation method thereof for sulfur-containing smoke gas demercuration

Similar Documents

Publication Publication Date Title
CN101474551B (en) S-loaded activated carbon for mercury removal from flue gas and preparation method thereof
CN107497399B (en) A kind of charcoal/bentonite composite material and its preparation method and application
CN112827468B (en) Preparation method and application of fly ash-based defluorination adsorbent
CN105195092A (en) Sludge-based charcoal and preparation method thereof
CN109621893A (en) A method of activated coke is prepared using chemical industry waste materials containing carbon
CN110698174A (en) Lightweight sludge ceramsite, and preparation method and application thereof
CN112320797B (en) Preparation method of activated carbon for desulfurization of tar hydrogenation product
CN109835899A (en) A kind of method that vapor activation prepares lignite base activated coke
CN110452703A (en) One heavy metal species normal temperature cure agent and the method for using heavy metal in its curing heavy metal pollutant
CN105858817A (en) Micro-electrolysis filler for treatment of hardly degraded waste water and preparation method of micro-electrolysis filler
CN102125786B (en) Method for preparing porous ceramsite filter material by using lepidolite extracted lithium slag
CN112642413A (en) Preparation method and product of mercury removal adsorbent based on active coke
CN101121515A (en) Method for preparing special-purpose active carbon for removing mercury and products thereof
CN106902764A (en) A kind of method for preparing acid and alkali-resistance mercury absorbing material and application
CN110255554A (en) A kind of novel desulphurization denitration activity charcoal
CN108144575B (en) Graphite sulfide, silica gel and lithium chloride curing composite dehumidifying agent and preparation method thereof
CN107583636A (en) A kind of activated carbon desulphurization agent of supported magnesium oxide and preparation method thereof
CN105771896A (en) Modified activated carbon compound adsorption treatment material for wastewater treatment
CN109205640A (en) A method of zeolitization granular materials is prepared by washing gangue
CN111992177B (en) Non-thermal activation red mud particle adsorbent and preparation method thereof
CN101538037B (en) Method for preparing desulphurizing activated coke
CN108865316A (en) The preparation method of biomass fuel applied to agglomeration for iron mine
CN107640771A (en) A kind of compound matrix activated carbon of sludge coal and preparation method thereof
CN110540364A (en) Method for performing gelation treatment on sulfate-containing electroplating wastewater and preparing foam glass ceramics from obtained gel and product
CN105056888A (en) Preparation method of composite coal-based adsorbing material

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