CN114602420B - Mercury-removing adsorbent and preparation method and application thereof - Google Patents
Mercury-removing adsorbent and preparation method and application thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title abstract description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 108
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003245 coal Substances 0.000 claims abstract description 54
- 239000012190 activator Substances 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 230000003213 activating effect Effects 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 104
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000002594 sorbent Substances 0.000 claims description 23
- 230000004913 activation Effects 0.000 claims description 20
- 238000010304 firing Methods 0.000 claims description 17
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 17
- 239000003921 oil Substances 0.000 description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 28
- 238000001035 drying Methods 0.000 description 20
- 238000005406 washing Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000284 extract Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229920005596 polymer binder Polymers 0.000 description 12
- 239000002491 polymer binding agent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- -1 on the one hand Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
Abstract
The invention relates to the technical field of coal chemical industry, in particular to a mercury removal adsorbent, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Activating the raffinate of the coal liquefaction oil residue and an activating agent in the presence of inert gas to obtain an activator; (2) Stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the binder is obtained by carrying out polymerization reaction on halogenated alkane and imidazole for 5-15h at 50-120 ℃; (3) Roasting the precursor in the presence of inert gas to obtain the mercury-removing adsorbent. The activated substance obtained by activating the powdered coal liquefied oil residue raffinate is bonded with a specific binder, so that the mercury-removing adsorbent with excellent mercury-removing performance is obtained, and the preparation method is simple and the cost is low.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a mercury removal adsorbent and a preparation method and application thereof.
Background
Due to elemental mercury (Hg) 0 ) Special physicochemical properties, e.g. high volatility, chemical propertiesStable, remarkable bioaccumulation, greater pollution and toxicity, etc., have become a global contaminant of great concern. At present, corresponding policy and regulation are adopted for controlling Hg in the atmosphere in each country 0 Is directed to Hg emissions 0 Is subjected to a great deal of research on the treatment and removal technology. Hg of Hg 0 The control technology of the device mainly comprises the technologies of desulfurization, denitrification, dedusting, co-removal, adsorption, photocatalytic oxidation, plasma treatment and the like; wherein, the active carbon adsorption method has wide raw material sources, low price, larger specific surface area and good regeneration performance in Hg 0 Has good application prospect in the field of adsorption removal.
The coal liquefaction oil residue (CLR) is a byproduct in the coal liquefaction process, and compared with modes such as combustion, gasification and the like, the CLR can be effectively utilized in a grading manner by extracting. However, the raffinate maintains the characteristics of high carbon and high ash of the CLR, is in a powdery state and has not been effectively and reasonably researched and utilized. Thus, the disposal of large amounts of raffinate has become a matter to be solved urgently. If the industrial waste raffinate is used for preparing the mercury-removing adsorbent with low cost and excellent performance, the mercury-removing adsorbent is expected to provide guiding significance for the utilization of the industrial raffinate and the control of mercury pollution.
However, since CLR raffinate is in powder form, the prepared carbon material is easy to cause dust pollution with larger harm during transportation, and the bed pressure drop and air resistance of the fixed bed reactor are larger, so that the direct application of the powder carbon material is further limited.
Disclosure of Invention
Aiming at the problems that the treatment and disposal of the coal liquefied oil residue raffinate are difficult, the application of the powdery coal liquefied oil residue raffinate in a fixed bed reactor is limited, and the existing mercury removal adsorbent is complex in preparation flow and high in cost, the invention provides a mercury removal adsorbent and a preparation method and application thereof.
To achieve the above object, a first aspect of the present invention provides a method for preparing a mercury removal adsorbent, the method comprising:
(1) Activating the raffinate of the coal liquefaction oil residue and an activating agent in the presence of inert gas to obtain an activator;
(2) Stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the binder is obtained by carrying out polymerization reaction on halogenated alkane and imidazole for 5-15h at 50-120 ℃;
(3) Roasting the precursor in the presence of inert gas to obtain the mercury-removing adsorbent.
In a second aspect, the present invention provides a mercury removal sorbent prepared according to the method of the first aspect.
A third aspect of the invention provides the use of the mercury removal sorbent of the second aspect described above in flue gas mercury removal.
Through the technical scheme, the activated substance obtained by activating the powdered coal liquefied oil residue raffinate is bonded with the specific binder, so that the mercury-removing adsorbent with excellent mercury-removing performance is obtained, and the preparation method is simple and low in cost.
Drawings
FIG. 1 is an XRD pattern of a coal liquefaction oil residue raffinate of the present invention and each of the mercury removal adsorbents of examples 1-2 and comparative examples 1-4; wherein 1-2 represents the XRD patterns of the mercury-free adsorbents prepared in examples 1-2, 3-6 represents the XRD patterns of the mercury-free adsorbents prepared in comparative examples 1-4, and 7 represents the XRD patterns of the coal liquefaction oil residue raffinate, respectively;
fig. 2 is a Hg-TPD curve for the mercury removal adsorbent of example 2 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a method of preparing a mercury removal sorbent, the method comprising:
(1) Activating the raffinate of the coal liquefaction oil residue and an activating agent in the presence of inert gas to obtain an activator;
(2) Stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the binder is obtained by carrying out polymerization reaction on halogenated alkane and imidazole for 5-15h at 50-120 ℃;
(3) Roasting the precursor in the presence of inert gas to obtain the mercury-removing adsorbent.
In the present invention, the activator obtained by the activation treatment is subjected to the binding treatment with the binder, on the one hand, dust pollution caused by the powdery activator can be reduced, and on the other hand, the activator can be allowed to react in the fixed bed reactor. The mercury-removing adsorbent prepared by the binder and the activator has good mercury-removing performance.
In the present invention, the coal liquefaction oil residue raffinate is a raffinate obtained by extracting coal liquefaction oil residue generated in a coal liquefaction process, and further preferably, the method for obtaining the coal liquefaction oil residue raffinate comprises: extracting coal tar washing oil, toluene or tetrahydrofuran and the like as an extractant under an inert atmosphere, wherein the weight ratio of the coal tar washing oil to the extractant is 1 (1-8), the extraction is carried out at the temperature of normal temperature to 200 ℃ and the pressure of 0.01-1MPa, and the obtained raffinate product is the coal tar residue raffinate.
In the invention, the raffinate obtained by extracting the coal liquefied oil residue is in a powder form, and under the preferable condition, the average particle size of the coal liquefied oil residue raffinate is 150-180 meshes.
According to the invention, preferably, siO is contained in the coal liquefaction oil residue raffinate based on the total amount of the coal liquefaction oil residue raffinate 2 The content of CaCO is 3-5 wt% 3 The content of (C) is 4-8 wt%, fe 1-x The content of S is 2-10 wt%, so that the mercury removal performance of the mercury removal adsorbent can be improved.
In the invention, the Fe 1-x S is pyrrhotite, wherein x has a value ranging from 0 to 0.2.
In the present invention, step (1) of the method further comprises: and drying the coal liquefaction oil residue raffinate for 12-48 hours at 100-120 ℃ before the activation treatment.
In some preferred embodiments of the present invention, the activator activates the raffinate to a porous material by reacting with carbon in the raffinate, thereby significantly improving the mercury removal performance of the mercury removal adsorbent, and in step (1), the weight ratio of the coal liquefaction oil residue raffinate to the activator is 5: (2.5-4), preferably 5: (3-4). In order to further optimize the mercury removal performance of the mercury removal adsorbent, preferably, the activator is selected from at least one of potassium hydroxide, potassium acetate, potassium carbonate, and potassium bicarbonate; further preferably, the activator is potassium acetate.
According to the present invention, in order to further increase the mercury removal activity of the mercury removal adsorbent, preferably, in the step (1), the conditions of the activation treatment include: the temperature is 750-900 ℃ and the time is 1-4h; preferably at 800-850 deg.C for 1.5-2h.
In the present invention, in order to remove the alkaline activator which is not completely reacted in the activator, preferably, the method further comprises: after step (1), the activator is washed to neutrality and then dried at 70-100 ℃ for 8-24h.
In the invention, the kind of the binder affects the physical and chemical properties (such as specific surface area) of the activator and the mercury removal performance, and only the specific binder is adopted to obtain the mercury removal performance of the mercury removal adsorbent; preferably, in step (2), the molar ratio of haloalkane to imidazole is 1: (0.2-1), preferably 1: (0.3-0.5); further preferably, the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
In the present invention, preferably, the chlorinated alkane used for synthesizing the binder is methylene chloride.
According to the invention, in step (2), in order to further preferably select the mercury removal performance of the mercury removal adsorbent, the weight ratio of the activator to the binder is preferably 1: (0.5-1.5).
According to the present invention, in the step (2), the mixing method of the activator and the binder may be known to those skilled in the art as long as uniform mixing of the both can be achieved. In a preferred embodiment of the present invention, the method of agitation mixing comprises: heating the binder to be in a viscous state at 40-70 ℃, adding the activator, stirring and mixing, and grinding to be in a plasticine state to obtain the precursor.
In some preferred embodiments of the present invention, in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h; preferably at a temperature of 650-750 ℃ for a time of 1-1.5 hours. Under the above preferable conditions, the active sites in the mercury removal adsorbent can be more fully exposed, and the mercury removal capacity of the mercury removal adsorbent is improved.
In some preferred embodiments of the invention, the method further comprises: after the step (3), washing the demercuration adsorbent, and removing soluble impurities in the demercuration adsorbent by washing the demercuration adsorbent, thereby eliminating the influence of chloride ions in the binder on demercuration performance and improving the specific surface area and demercuration performance of the demercuration adsorbent.
In the present invention, the inert gas may be nitrogen, helium, argon, or the like, and is preferably nitrogen.
In the present invention, the normal temperature is not particularly limited, and may be, for example, 10 to 30℃according to the conventional understanding in the art.
In a second aspect, the present invention provides a mercury removal sorbent prepared according to the method of the first aspect.
Preferably, the specific surface area of the mercury removal adsorbent is 30-100m 2 /g; the micropore area is 10-70m 2 /g; preferably, in the mercury removal adsorbent, fe 2 O 3 The content of (C) is 5-9 wt%, siO 2 The content of (C) is 3-5 wt%.
A third aspect of the invention provides the use of the mercury removal sorbent of the second aspect described above in flue gas mercury removal.
The present invention will be described in detail by examples. In the following examples, X-ray diffraction (XRD) pattern measurements were performed on a Miniflex 600X-ray diffractometer with a Cu K alpha tube voltage of 40kV, a tube current of 15mA, a scan speed of 8/min, a scan range of 2 θ=15° -80 °;
the micropore area and specific surface area were both measured for N of the sample at liquid nitrogen temperature using an ASAP2460 nitrogen adsorber from Micromeritics 2 After the adsorption and desorption curves, performing BET fitting on the adsorption curves to obtain;
fe in mercury-removing adsorbent 2 O 3 、SiO 2 And CaO content were measured by an Epsilon type 1X-ray fluorescence spectrometer (XRF).
In the following examples, the raffinate of the coal liquefaction oil residue is obtained from the oil-making company of Erdos coal, a chemical industry Co., ltd. Of Shenhua coal oil production, and is powdery solid with an average particle size of 150-180 meshes; siO in the extract 2 The content of CaCO was 4% by weight 3 The content of (C) is 6 wt%, fe 1-x The S content was 7% by weight.
Example 1
Placing the coal liquefied oil residue extract in a 110 ℃ blast drying oven for drying for 24 hours;
5g of raffinate and 3g of CH 3 Uniformly stirring and mixing COOK, placing in a tube furnace, and activating at 850 ℃ for 2 hours under the protection of nitrogen to obtain an activated substance;
repeatedly washing the activated substance with distilled water until the filtrate is neutral, and drying the filter cake at 80 ℃ for 12 hours to obtain a powdery mercury removal adsorbent A850;
64mL of dichloromethane (1 mol) and 27.23g of imidazole (0.4 mol) are taken and placed in a polytetrafluoroethylene reaction kettle, and fully and uniformly stirred; placing the reaction kettle in a homogeneous phase reactor, and polymerizing for 8 hours at 100 ℃ to obtain a polymer binder which is solid at normal temperature;
heating 3g of polymer binder to be in a viscous liquid state at 50 ℃, uniformly adding 3g of powdery mercury removal adsorbent A850, uniformly stirring and grinding to obtain a precursor;
and (3) placing the precursor in a tube furnace, and pyrolyzing for 1h at 700 ℃ under the protection of nitrogen to obtain the bonded mercury-removing adsorbent A850P700.
Example 2
The method according to embodiment 1, except that further comprising: repeatedly washing the bonded mercury-removing adsorbent A850P700 with distilled water until the sample is free of Cl - Exists. Other conditions were the same as in example 1. The bonded mercury removal adsorbent A850P700-Xi is prepared.
Example 3
The procedure of example 1 is followed, except that in the activation treatment, the weight of the raffinate is measured to be 5g, CH 3 COOK weight was 2.5g (i.e. coal liquefaction oil residue raffinate and CH 3 The weight ratio of COOK is 5: 2.5). Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-1.
Example 4
The procedure of example 1 is followed, except that in the activation treatment, the weight of the raffinate is measured to be 5g, CH 3 COOK has a weight of 4g (i.e. coal liquefaction oil residue extract and CH 3 The weight ratio of COOK is 5: 4). Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-2.
Example 5
The procedure of example 1 was followed, except that the activation treatment was carried out at 750℃for 4 hours. Other conditions were the same as in example 1. To obtain the bonded mercury removal adsorbent A750P700.
Example 6
The procedure of example 1 was followed, except that the temperature of the activation treatment was 900℃and the time was 1h. Other conditions were the same as in example 1. And (3) obtaining the bonded mercury removal adsorbent A900P700.
Example 7
The procedure of example 1 was followed except that 64mL of methylene chloride (1 mol) and 13.615g of imidazole (0.2 mol) (i.e., a molar ratio of methylene chloride to imidazole of 1:0.2) were measured in the step of synthesizing the binder. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-3.
Example 8
The procedure of example 1 was followed except that in the step of synthesizing the binder, 64mL of methylene chloride (1 mol) and 68.075g of imidazole (1 mol) were measured (i.e., the molar ratio of methylene chloride to the imidazole was 1:1). Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-4.
Example 9
The procedure of example 1 was followed except that in the step of preparing the precursor, 1.5g of the polymer binder and 3g of powdered mercury-free adsorbent A850 (i.e., activator to binder weight ratio of 1:0.5) were measured. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-5.
Example 10
The procedure of example 1 was followed except that in the step of preparing the precursor, 4.5g of the polymer binder and 3g of powdered mercury-free sorbent A850 (i.e., activator to binder weight ratio of 1:1.5) were measured. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-6.
Example 11
The procedure of example 1 was followed except that in the step of synthesizing the binder, the polymerization conditions included: the temperature was 90℃and the time was 9 hours. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-7.
Example 12
The procedure of example 1 was followed, except that: the polymerization conditions include: the temperature was 110℃and the time was 7 hours. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P700-8.
Example 13
The procedure of example 1 was followed, except that: the temperature of the precursor roasting is 500 ℃ and the time is 2 hours. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P500.
Example 14
The procedure of example 1 was followed, except that: the temperature of the precursor roasting is 800 ℃ and the time is 1h. Other conditions were the same as in example 1. And obtaining the bonded mercury removal adsorbent A850P800.
Comparative example 1
The procedure of example 1 is followed, except that the powder isThe raffinate of the coal liquefied oil residue is not subjected to CH 3 COOK activation, direct bonding, the method is as follows:
placing the coal liquefied oil residue extract in a 110 ℃ blast drying oven for drying for 24 hours;
64mL of dichloromethane and 27.23g of imidazole are taken and placed in a polytetrafluoroethylene reaction kettle, and fully and uniformly stirred; placing the reaction kettle in a homogeneous phase reactor, and polymerizing for 8 hours at 100 ℃ to obtain a polymer binder which is solid at normal temperature;
heating 3g of polymer binder to be in a mucilage state at 50 ℃, uniformly adding 3g of powdery coal liquefied oil residue extract, uniformly stirring and grinding to obtain a precursor;
and (3) placing the precursor in a tube furnace, and pyrolyzing for 1h at 700 ℃ under the protection of nitrogen to obtain the bonded mercury-removing adsorbent P700.
Comparative example 2
The procedure of example 1 was followed except that the powdered coal liquefaction oil residue raffinate was first bound and then passed through CH 3 COOK activation is carried out by the following steps:
a bonded mercury removal adsorbent P700 was prepared as in comparative example 1;
5g of bound mercury removal adsorbent P700 and 3g of CH 3 Uniformly stirring and mixing COOK, placing in a tube furnace, and activating at 850 ℃ for 2 hours under the protection of nitrogen to obtain an activated substance;
repeatedly washing the activated substance with distilled water until the filtrate is neutral, and drying the filter cake at 80 ℃ for 12 hours to obtain the bonded mercury-removing adsorbent P700A850.
Comparative example 3
The procedure of example 1 was followed except that the powdered coal liquefaction oil residue raffinate was subjected to HCl and HF deashing and demineralization followed by cementing as follows:
placing the powdered coal liquefied oil residue extract in a blast drying oven at 110 ℃ for drying for 24 hours;
100g of the powdered raffinate was added to 600mL of HCl solution (6 mol/L) and stirred at room temperature for 12h, after which it was repeatedly washed with distilled water until the filtrate was neutral and Cl-free - Drying the filter cake at 60deg.C for 12 hr to obtain HCl washWashing the sample;
50g of HCl wash was added to 375mL of aqueous hydrofluoric acid (40 wt.%) and stirred at room temperature for 12h, followed by repeated washing with distilled water until the filtrate was neutral and F-free - Drying the filter cake at 60 ℃ for 12 hours in the presence of the catalyst to obtain an HCl-HF washing sample;
64mL of dichloromethane and 27.23g of imidazole are taken and placed in a polytetrafluoroethylene reaction kettle, and fully and uniformly stirred; placing the reaction kettle in a homogeneous phase reactor, and polymerizing for 8 hours at 100 ℃ to obtain a polymer binder which is solid at normal temperature;
heating 3g of polymer binder to be in a viscous liquid state at 50 ℃, uniformly adding 3g of HCl-HF washing sample, uniformly stirring and grinding to obtain a precursor;
and (3) placing the precursor in a tube furnace, and pyrolyzing for 1H at 700 ℃ under the protection of nitrogen to obtain the bonded mercury-removing adsorbent H-P700.
Comparative example 4
The procedure of example 1 was followed except that the powdered coal liquefaction oil residue raffinate was subjected to HCl and HF deashing and demineralization followed by CH 3 COOK activation and bonding is carried out as follows:
HCl-HF washes were prepared as in comparative example 3;
taking 5g of HCl-HF wash sample and 3g of CH 3 Uniformly stirring and mixing COOK, placing in a tube furnace, and activating at 850 ℃ for 2 hours under the protection of nitrogen to obtain an activated substance;
repeatedly washing the activated substance with distilled water until the filtrate is neutral, and drying the filter cake at 80 ℃ for 12 hours to obtain a powdery mercury removal adsorbent H-A850;
taking 64mL of dichloromethane and 27.23g of imidazole, and placing the dichloromethane and the 27.23g of imidazole into a polytetrafluoroethylene reaction kettle to be fully and uniformly stirred; placing the reaction kettle in a homogeneous phase reactor, and polymerizing for 8 hours at 100 ℃ to obtain a polymer binder which is solid at normal temperature;
heating 3g of polymer binder to be in a viscous liquid state at 50 ℃, uniformly adding 3g of powdery mercury-removing adsorbent H-A850, uniformly stirring and grinding to obtain a precursor;
and (3) placing the precursor in a tube furnace, and pyrolyzing for 1H at 700 ℃ under the protection of nitrogen to obtain the bonded mercury-removing adsorbent H-A850P700.
Comparative example 5
The procedure of example 1 was followed except that the binder used was starch, as follows:
placing the coal liquefied oil residue extract in a 110 ℃ blast drying oven for drying for 24 hours;
5g of raffinate, 3g of CH 3 Grinding COOK and 5g of starch, mixing uniformly, adding distilled water, stirring, drying the mixture in a blast drying oven at 80 ℃ for 12 hours, placing in a tube furnace, and activating at 850 ℃ for 2 hours under the protection of nitrogen to obtain an activated product;
repeatedly washing the activated substance with distilled water until the filtrate is neutral, and drying the filter cake at 80 ℃ for 12 hours to obtain the mercury-removing adsorbents A850-D.
Comparative example 6
The procedure of example 1 was followed except that the haloalkane used was chloroform, as follows:
placing the coal liquefied oil residue extract in a 110 ℃ blast drying oven for drying for 24 hours;
5g of raffinate and 3g of CH 3 Uniformly stirring and mixing COOK, placing in a tube furnace, and activating at 850 ℃ for 2 hours under the protection of nitrogen to obtain an activated substance;
repeatedly washing the activated substance with distilled water until the filtrate is neutral, and drying the filter cake at 80 ℃ for 12 hours to obtain a powdery mercury removal adsorbent A850;
81mL of chloroform (1 mol) and 27.23g of imidazole (0.4 mol) are taken and placed in a polytetrafluoroethylene reaction kettle, and fully and uniformly stirred; placing the reaction kettle in a homogeneous phase reactor, and polymerizing for 8 hours at 100 ℃ to obtain a polymer binder which is solid at normal temperature;
heating 3g of polymer binder to be in a viscous liquid state at 50 ℃, uniformly adding 3g of powdery mercury removal adsorbent A850, uniformly stirring and grinding to obtain a precursor;
and (3) placing the precursor in a tube furnace, and pyrolyzing for 1h at 700 ℃ under the protection of nitrogen to obtain the bonded mercury-removing adsorbent A850P700-9.
Experimental example 1
The mercury removal performance of the mercury removal adsorbents prepared in examples 1 to 14 and comparative examples 1 to 6 was evaluated, and the evaluation experiment was performed in a fixed bed reactor under the following reaction conditions: the temperature is 150 ℃, and the simulated smoke is 40+/-2 mug/m 3 Hg 0 4 vol% O 2 And N 2 Composition, total flow rate of 1000mL/min, airspeed of 1.5X10 5 h -1 The mercury removal adsorbent is sieved to 40-60 meshes.
The mercury removal efficiency (η) of the mercury removal sorbent is calculated by the following formula: η (%) = (1-C 0 /C 1 ) X 100%, where C 0 And C 1 Respectively the Hg at the outlet and inlet of the fixed bed reactor as measured by a LUMEX 915M mercury meter 0 Concentration (. Mu.g/m) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The evaluation results are shown in Table 1.
TABLE 1
As can be seen from table 1, the mercury removal adsorbent a850P700 prepared in example 1 showed better mercury removal performance, and the mercury removal efficiency was reduced from 93% to 85% in 2h.
As can be seen from comparison of the example 1 and the example 2, the mercury removal performance of the mercury removal adsorbent A850P700-Xi prepared by washing the mercury removal adsorbent A850P700 with water is more stable, and the mercury removal efficiency of the adsorbent within 2 hours is more than 92%.
As can be seen from comparison of example 1 and comparative example 1, the demercuration performance of the demercuration adsorbent P700 is poor, and the demercuration efficiency is reduced from 27% to 24% within 2 hours, which indicates that the activation of the activator has a great influence on the demercuration performance of the demercuration adsorbent.
As can be seen by comparing example 1 with comparative example 2, the sequence of activation and bonding also affects the mercury removal performance of the mercury removal adsorbent, and the mercury removal efficiency 2h of the mercury removal adsorbent P700A850 prepared in comparative example 2 is reduced from 67% to 51%.
As can be seen by comparing example 1 with comparative examples 3-4, the ash content of the coal liquefaction oil residue raffinate has a greater impact on the mercury removal performance of the mercury removal sorbent.
As can be seen from a comparison of example 1 with comparative examples 5-6, binders prepared with methylene chloride and imidazole allow the demercuration adsorbent to exhibit better demercuration performance.
Experimental example 2
N was conducted on the demercuration adsorbents prepared in examples 1 to 14 and comparative examples 1 to 6 2 Adsorption-desorption characterization, characterization results are shown in table 2. And elemental content determination was performed by XRF on the mercury free sorbents prepared in example 1 and example 2.
TABLE 2
As can be seen from Table 2, the demercuration adsorbent A850P700 prepared in example 1 has a BET specific surface area of 50.99m 2 /g; in example 2, the specific surface area of the mercury-free adsorbent A850P700-Xi after washing with water was increased to 90.25m 2 And/g, showing that the specific surface area and the micropore area of the mercury-free adsorbent obtained by roasting can be improved by washing.
In addition, XRF tests showed that the mercury removal sorbent A850P700 prepared in example 1 was SiO 2 The content of (2) is 4 wt%, fe 2 O 3 Is 7% by weight; in example 2, siO in the bound mercury removal adsorbent A850P700-Xi after washing with water 2 The content of (2) is 4 wt%, fe 2 O 3 The content of (2) was 8% by weight.
The specific surface area of the mercury removal adsorbent P700 prepared in comparative example 1 is only 4.36m 2 /g, which may be responsible for its high mercury removal efficiencyThe reason for the difference shows that the activation of the activator can significantly improve the specific surface area of the coal liquefaction oil residue raffinate.
The mercury removal adsorbent P700A850 prepared in comparative example 2 has a larger specific surface area (181.87 m 2 And/g), but the mercury removal performance of the mercury-free liquid-phase coal-liquefied oil residue extract is poorer than that of A850P700 in the example 1, which shows that the mercury removal performance of the mercury-free liquid-phase coal-liquefied oil residue extract is influenced by chemical active sites in the mercury absorption process of the mercury-free liquid-phase coal-liquefied oil residue extract, and the activation and bonding sequence of the coal-liquefied oil residue extract have larger influence on the mercury removal performance of the mercury-free adsorbent.
In comparative examples 3 and 4, the specific surface areas of H-P700 and H-A850P700 after deashing treatment of the coal liquefaction oil residue raffinate with HCl and HF were 68.05 and 120.32m, respectively 2 And/g, but the mercury removal efficiency is lower than 50% in 2h, which shows that ash in the coal liquefaction oil residue raffinate has a great influence on the mercury removal performance of the prepared mercury removal adsorbent.
In comparative example 5, the specific surface area of the mercury-free adsorbent prepared by starch binding and activation with an activator was 48.17m 2 Per g, substantially equivalent to the specific surface area of the adsorbent prepared in example 1; the specific surface area of the mercury removal sorbent of comparative example 6 is significantly less than the sorbent prepared in example 1. However, the demercuration performance of each of the demercuration adsorbents of comparative example 5 and comparative example 6 was significantly lower than that of example 1, indicating that the specific surface area is not the only factor affecting the demercuration activity of the adsorbent, and that the properties of the binder have a greater influence on the demercuration activity of the prepared demercuration adsorbent.
Experimental example 3
XRD characterization of raw material coal liquefied oil residue raffinate (CYW) and mercury-removing adsorbents prepared in examples 1-2 and comparative examples 1-4 is carried out to determine the crystal form structure of the adsorbent, wherein the characterization result is shown in figure 1, and wherein the solid represents CaCO 3 Is characterized by the fact that,represents Fe 1-x Characteristic peak of S>Represents SiO 2 Characteristic peak of->Represents Fe 2 O 3 Is representative of the characteristic peak of KCl, +.>Represents the characteristic peak of Fe, and o represents the characteristic peak of C.
As can be seen from FIG. 1, the crystal form in the raffinate (CYW) of the coal liquefaction oil residue is mainly SiO 2 、CaCO 3 And Fe (Fe) 1-x S, the main crystal phase in the adsorbent P700 (comparative example 1) prepared by directly bonding the raffinate is SiO 2 And Fe (Fe) 2 O 3 Indicating CaCO 3 Is decomposed by roasting.
The main crystal phases in the adsorbent A850P700 (example 1) prepared by activating the coal liquefied oil residue raffinate (CYW) by an activating agent and then bonding are KCl and Fe 2 O 3 (As can be seen from XRF test in Experimental example 2, the mercury removal adsorbent A850P700 prepared in example 1 has SiO 2 The content of (2) is 4% by weight, possibly due to SiO in A850P700 2 Due to the presence of amorphous form, the XRD fails to detect SiO 2 Crystalline phase) of the adsorbent A850P700-Xi (example 2) prepared by washing with water, the main crystalline phase of the adsorbent A850P700-Xi is Fe 2 O 3 The KCl crystal phase disappeared, indicating that KCl on the surface of the demercuration adsorbent is washed off by distilled water, and Fe 2 O 3 Is the main active site for mercury removal.
The main crystal phase of the adsorbent P700A850 (comparative example 2) prepared by bonding the raffinate (CYW) of the liquefied petroleum residues and activating the bonded raffinate by an activating agent is SiO 2 、CaCO 3 And Fe; the main crystal phases of the adsorbents (comparative examples 3 and 4) prepared by directly bonding the coal liquefied oil residue (CYW) after deashing by HCl and HF and activating by an activating agent and then bonding are carbon, and Fe is not generated 2 O 3 And SiO 2 Indicating that ash loss may be responsible for the poor mercury removal performance of the sorbent.
Experimental example 4
The mercury-free adsorbent A850P700-Xi prepared in example 2 was subjected to mercury removalThe samples of (1) were characterized for Hg-TPD (temperature programmed desorption) by the following method: adsorbing mercury on A850P700-Xi adsorbent in N 2 The release of mercury by programming to 550 c at 5 c/min under an atmosphere is shown in fig. 2.
As can be seen from FIG. 2, the peak of mercury release in the adsorbent of A850P700-Xi after adsorption of mercury was 330℃due to the release of HgO, while HgCl 2 The release peak of (C) is about 138+ -4deg.C, and Cl in the adsorbent can be removed - Indicating the Fe on the surface of the adsorbent 2 O 3 Is the main mercury removal active site.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (59)
1. A method of making a mercury removal sorbent, the method comprising:
(1) Activating the raffinate of the coal liquefaction oil residue and an activating agent in the presence of inert gas to obtain an activator;
(2) Stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the binder is obtained by carrying out polymerization reaction on chloralkane and imidazole for 5-15h at 50-120 ℃;
(3) Roasting the precursor in the presence of inert gas to obtain a mercury-removing adsorbent;
the chlorinated alkane is dichloromethane;
SiO in the coal liquefied oil residue raffinate based on the total amount of the coal liquefied oil residue raffinate 2 The content of CaCO is 3-5 wt% 3 The content of (C) is 4-8 wt%, fe 1-x The S content is 2-10 wt%.
2. The method of claim 1, wherein in step (1), the coal liquefaction oil residue raffinate is a raffinate obtained by extracting coal liquefaction oil residue produced in a coal liquefaction process.
3. The process of claim 2, wherein the coal liquefaction oil residue raffinate has an average particle size of 150-180 mesh.
4. A process according to claim 1, 2 or 3, wherein in step (1) the weight ratio of the coal liquefaction oil residue raffinate to the activator is 5: (2.5-4).
5. The process of claim 4, wherein in step (1), the weight ratio of the coal liquefaction oil residue raffinate to the activator is 5: (3-4).
6. The method of claim 4, wherein the activator is selected from at least one of potassium hydroxide, potassium acetate, potassium carbonate, and potassium bicarbonate.
7. The method of claim 5, wherein the activator is selected from at least one of potassium hydroxide, potassium acetate, potassium carbonate, and potassium bicarbonate.
8. The method of claim 6 or 7, wherein the activator is potassium acetate.
9. The method according to any one of claims 1, 2, 3, 5-7, wherein in step (1), the conditions of the activation treatment include: the temperature is 750-900 ℃ and the time is 1-4h.
10. The method according to claim 9, wherein in step (1), the conditions of the activation treatment include: the temperature is 800-850 ℃ and the time is 1.5-2h.
11. The method according to claim 4, wherein in step (1), the conditions of the activation treatment include: the temperature is 750-900 ℃ and the time is 1-4h.
12. The method according to claim 8, wherein in step (1), the conditions of the activation treatment include: the temperature is 750-900 ℃ and the time is 1-4h.
13. The method according to claim 11 or 12, wherein in step (1), the conditions of the activation treatment include: the temperature is 800-850 ℃ and the time is 1.5-2h.
14. The method of any one of claims 1, 2, 3, 5-7, 10-12, wherein in step (2) the molar ratio of chlorinated alkane to imidazole is 1: (0.2-1).
15. The method of claim 14, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.3-0.5).
16. The method of claim 4, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.2-1).
17. The method of claim 16, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.3-0.5).
18. The method of claim 8, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.2-1).
19. The method of claim 18, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.3-0.5).
20. The method of claim 9, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.2-1).
21. The method of claim 20, wherein in step (2), the molar ratio of chlorinated alkane to imidazole is 1: (0.3-0.5).
22. The method of claim 14, wherein the activator to binder weight ratio is 1: (0.5-1.5).
23. The method of any of claims 15-21, wherein the activator to binder weight ratio is 1: (0.5-1.5).
24. The method of any one of claims 1, 2, 3, 5-7, 10-12, 15-22, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
25. The method according to claim 4, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
26. The method of claim 8, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
27. The method of claim 9, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
28. The method of claim 13, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
29. The method of claim 14, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
30. The method of claim 23, wherein in step (2), the polymerization conditions include: the temperature is 90-110 ℃ and the time is 7-9h.
31. The method of any one of claims 1, 2, 3, 5-7, 10-12, 15-22, 25-30, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
32. The method of claim 31, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
33. The method of claim 4, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
34. The method of claim 33, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
35. The method of claim 8, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
36. The method of claim 35, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
37. The method of claim 9, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
38. The method of claim 37, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
39. The method of claim 13, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
40. The method of claim 39, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
41. The method of claim 14, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
42. The method of claim 41, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
43. The method of claim 23, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
44. The method of claim 43, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
45. The method of claim 24, wherein in step (3), the firing conditions include: the temperature is 500-800 ℃ and the time is 0.5-2h.
46. The method of claim 45, wherein in step (3), the firing conditions include: the temperature is 650-750 ℃ and the time is 1-1.5h.
47. The method of any one of claims 1, 2, 3, 5-7, 10-12, 15-22, 25-30, 32-46, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
48. The method of claim 4, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
49. The method of claim 8, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
50. The method of claim 9, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
51. The method of claim 13, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
52. The method of claim 14, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
53. The method of claim 23, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
54. The method of claim 24, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
55. The method of claim 31, wherein the method further comprises: after step (3), the mercury removal sorbent is washed.
56. A mercury removal adsorbent prepared by the method of any one of claims 1, 2, 3, 5-7, 10-12, 15-22, 25-30, 32-46, 48-55.
57. The demercuration adsorbent of claim 56, wherein the specific surface area of the demercuration adsorbent is from 30 to 100m 2 /g; the micropore area is 10-70m 2 /g。
58. The demercuration adsorbent of claim 57, wherein in the demercuration adsorbent, fe 2 O 3 The content of (C) is 5-9 wt%, siO 2 The content of (C) is 3-5 wt%.
59. The use of the mercury removal adsorbent of claim 56 in flue gas mercury removal.
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