CN114602420A - Demercuration adsorbent and preparation method and application thereof - Google Patents
Demercuration adsorbent and preparation method and application thereof Download PDFInfo
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- CN114602420A CN114602420A CN202210078350.4A CN202210078350A CN114602420A CN 114602420 A CN114602420 A CN 114602420A CN 202210078350 A CN202210078350 A CN 202210078350A CN 114602420 A CN114602420 A CN 114602420A
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- demercuration
- raffinate
- adsorbent
- coal liquefaction
- oil residue
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003245 coal Substances 0.000 claims abstract description 56
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012190 activator Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 230000003213 activating effect Effects 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 230000004913 activation Effects 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 17
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002594 sorbent Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052753 mercury Inorganic materials 0.000 abstract description 35
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000001035 drying Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 229920005596 polymer binder Polymers 0.000 description 10
- 239000002491 polymer binding agent Substances 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000007605 air drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- -1 so that on one hand Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000013078 crystal 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
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000003795 desorption Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052952 pyrrhotite Inorganic materials 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-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
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 239000000843 powder 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
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 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
- 239000011280 coal tar Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- 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
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- 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
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of coal chemical industry, in particular to a demercuration adsorbent and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) in the presence of inert gas, performing activation treatment on the coal liquefaction oil residue raffinate and an activating agent to obtain an activated substance; (2) stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the adhesive is obtained by carrying out polymerization reaction on halogenated alkane and imidazole at the temperature of 50-120 ℃ for 5-15 h; (3) and roasting the precursor in the presence of inert gas to obtain the demercuration adsorbent. The mercury removal adsorbent with excellent mercury removal performance is obtained by bonding an activator obtained by activating the powdered coal liquefaction oil residue raffinate with a specific binder, and the preparation method is simple and low in cost.
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) The special physicochemical characteristics, such as strong volatility, stable chemical properties, significant bioaccumulation, high pollution and toxicity, etc., have become a global pollutant of great concern. At present, corresponding policy and regulations are adopted by various countries to control Hg in the atmosphere0Discharge against Hg0The treatment removal technology of (1) has been studied in large numbers. Hg is a mercury vapor0The control technology mainly comprises the technologies of desulfurization, denitrification and dust removal synergetic removal, an adsorption method, photocatalytic oxidation, plasma treatment and the like; wherein, the activated carbon adsorption method has wide raw material source, low price, larger specific surface area and good regeneration performance in Hg0Has good application prospect in the field of adsorption and desorption.
The coal liquefaction oil residue (CLR) is a byproduct in the coal liquefaction process, and compared with combustion, gasification and other modes, the CLR can be extracted to realize the grading efficient utilization. However, the raffinate retains the characteristics of high carbon and high ash of CLR, is powdery and has not been researched and utilized effectively and reasonably. Therefore, the disposal of large amounts of raffinate has become a problem to be solved urgently. If the industrial waste raffinate can be used for preparing the demercuration adsorbent with low cost and excellent performance, the method is expected to provide guiding significance for the utilization of the industrial raffinate and the control of mercury pollution.
However, since the CLR raffinate is in powder form, the prepared carbon material is easily polluted by dust which is harmful when being transported, and the bed pressure drop and the air resistance of the fixed bed reactor are large, thereby further limiting the direct application of the powder carbon material.
Disclosure of Invention
The invention provides a demercuration adsorbent, and a preparation method and application thereof, aiming at the problems that in the prior art, the treatment and the disposal of coal liquefaction oil residue raffinate are difficult, the application of powdery coal liquefaction oil residue raffinate in a fixed bed reactor is limited, and the preparation process of the conventional demercuration adsorbent is complex and high in cost.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a demercuration adsorbent, the method comprising:
(1) in the presence of inert gas, carrying out activation treatment on the raffinate of the coal liquefaction oil residue and an activating agent to obtain an activated substance;
(2) stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the adhesive is obtained by carrying out polymerization reaction on halogenated alkane and imidazole at the temperature of 50-120 ℃ for 5-15 h;
(3) and roasting the precursor in the presence of inert gas to obtain the demercuration adsorbent.
In a second aspect, the invention provides a demercuration adsorbent prepared according to the method of the first aspect.
A third aspect of the present invention provides the use of the demercuration adsorbent described in the second aspect in the demercuration of flue gas.
Through the technical scheme, the activated substance obtained by activating the powdered coal liquefaction oil residue raffinate is bonded with the specific binder, so that the demercuration adsorbent with excellent demercuration performance is obtained, and the preparation method is simple and low in cost.
Drawings
FIG. 1 is an XRD pattern of coal liquefaction bottoms raffinate of the present invention and each of the demercuration sorbents of examples 1-2 and comparative examples 1-4; wherein, 1-2 respectively represent XRD patterns of the demercuration adsorbent prepared in the embodiment 1-2, 3-6 respectively represent XRD patterns of the demercuration adsorbent prepared in the comparative example 1-4, and 7 represents an XRD pattern of raffinate of coal liquefaction oil residue;
figure 2 is a Hg-TPD curve for the demercuration adsorbent of example 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, a first aspect of the invention provides a method of preparing a demercuration sorbent, the method comprising:
(1) in the presence of inert gas, performing activation treatment on the coal liquefaction oil residue raffinate and an activating agent to obtain an activated substance;
(2) stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the adhesive is obtained by carrying out polymerization reaction on halogenated alkane and imidazole at the temperature of 50-120 ℃ for 5-15 h;
(3) and roasting the precursor in the presence of inert gas to obtain the demercuration adsorbent.
In the invention, the activating substance obtained by the activating treatment is bonded by the adhesive, so that on one hand, dust pollution caused by the powdery activating substance can be reduced, and on the other hand, the activating substance can react in a fixed bed reactor. The demercuration adsorbent prepared by the binder and the activator has good demercuration performance.
In the present invention, the raffinate of the coal liquefaction oil residue is raffinate obtained by extracting coal liquefaction oil residue generated in a coal liquefaction process, and further preferably, the method for obtaining the raffinate of the coal liquefaction oil residue comprises: extracting the coal liquefaction oil residue by using coal tar wash oil, toluene or tetrahydrofuran and the like as extracting agents under an inert atmosphere, wherein the weight ratio of the coal liquefaction oil residue to the extracting agents is 1 (1-8), the extraction is carried out under the conditions that the temperature is from normal temperature to 200 ℃ and the pressure is 0.01-1MPa, and the obtained raffinate is the coal liquefaction oil residue raffinate.
In the invention, raffinate obtained by extracting the coal liquefaction oil residue is powdery, and under the preferable condition, the average particle size of the raffinate of the coal liquefaction oil residue is 150-180 meshes.
According to the invention, under the preferable conditions, SiO is contained in the raffinate of the coal liquefaction oil residue based on the total amount of the raffinate of the coal liquefaction oil residue2The content of (C) is 3-5 wt.% CaCO3In an amount of 4-8 wt.%, Fe1-xThe content of S is 2-10 wt%, so that the demercuration performance of the demercuration adsorbent can be improved.
In the present invention, the Fe1-xS refers to pyrrhotite, wherein x has a value in the range of 0 to 0.2.
In the present invention, step (1) of the method further comprises: and before the activation treatment, drying the coal liquefaction oil residue raffinate at the temperature of 100-120 ℃ for 12-48 h.
In some preferred embodiments of the present invention, the activating agent activates the raffinate into a porous substance by reacting with carbon in the raffinate, so that the mercury removal performance of the mercury removal adsorbent can be significantly improved, and in the step (1), the weight ratio of the coal liquefaction oil residue raffinate to the activating agent is 5: (2.5-4), preferably 5: (3-4). In order to further optimize the demercuration performance of the demercuration 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 improve the demercuration activity of the demercuration adsorbent, it is preferable that in the step (1), the activation treatment conditions include: the temperature is 750 ℃ and 900 ℃, and the time is 1-4 h; preferably 800-850 ℃ and 1.5-2 h.
In the present invention, in order to remove the incompletely reacted alkaline activator from the activator, it is preferable that the method further comprises: after the step (1), washing the activator to be neutral, and then drying the activator for 8-24h at 70-100 ℃.
In the invention, the physical and chemical properties (such as specific surface area) and demercuration performance of the activator are influenced by the type of the binder, and the demercuration performance of the demercuration adsorbent can be obtained only by using a specific binder; preferably, in step (2), the molar ratio of said 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 7-9 h.
In the present invention, preferably, the chloroalkane used for synthesizing the binder is dichloromethane.
According to the invention, in step (2), in order to further preferably optimize the demercuration performance of the demercuration 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 method of mixing the activator and the binder may be known to those skilled in the art as long as uniform mixing of the two can be achieved. In a preferred embodiment of the present invention, the method of agitating and mixing comprises: heating the binder to be viscous at 40-70 ℃, adding the activator, stirring and mixing, and grinding to be plasticine-like to obtain the precursor.
In some preferred embodiments of the present invention, in the step (3), the roasting conditions include: the temperature is 500 ℃ and 800 ℃, and the time is 0.5-2 h; preferably at 650-750 ℃ for 1-1.5 h. Under the preferable conditions, the active sites in the demercuration adsorbent can be more fully exposed, and the demercuration capacity of the demercuration adsorbent is improved.
In some preferred embodiments of the invention, the method further comprises: after the step (3), the demercuration adsorbent is washed, and soluble impurities in the demercuration adsorbent can be removed by washing the demercuration adsorbent, so that the influence of chloride ions in the binder on the demercuration performance is eliminated, and the specific surface area and the demercuration performance of the demercuration adsorbent are improved.
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 ℃ as conventionally understood in the art.
In a second aspect, the invention provides a demercuration adsorbent prepared according to the method of the first aspect.
Preferably, the specific surface area of the demercuration adsorbent is 30-100m2(ii)/g; the area of the micropores is 10-70m2(ii)/g; preferably, in the demercuration adsorbent, Fe2O3Is 5-9 wt% SiO2Is contained in an amount of 3 to 5 wt%.
In a third aspect, the invention provides the use of the demercuration adsorbent of the second aspect in the demercuration of flue gas.
The present invention will be described in detail below by way of examples. In the following examples, X-ray diffraction (XRD) crystallographic phase diagram measurements were performed on a Miniflex 600X-ray diffractometer with a Cu ka tube voltage of 40kV, a tube current of 15mA, a scanning speed of 8 °/min, and a scanning range of 2 θ of 15 ° -80 °;
both the micropore area and the specific surface area were measured as N of a sample at a liquid nitrogen temperature using an ASAP2460 nitrogen adsorption apparatus from Micromeritics2After the adsorption and desorption curve, performing BET fitting on the adsorption curve to obtain the adsorption curve;
fe in demercuration adsorbent2O3、SiO2And CaO content were measured by an X-ray fluorescence spectrometer (XRF) model Epsilon 1.
In the following examples, the raffinate of the coal liquefaction oil residue is from Eldos coal oil production division of Shenhua coal oil production chemical Limited, and is a powdery solid with an average particle size of 150-; SiO in the extract2Content of (C) 4 wt.% CaCO3Is 6 wt.% Fe1-xThe S content was 7% by weight.
Example 1
Putting the raffinate of the coal liquefaction oil residue into a 110 ℃ forced air drying oven for drying for 24 hours;
5g of raffinate and 3g of CH3COOK is stirred and mixed evenly and then placed in a tubular furnace, and under the protection of nitrogen, activation treatment is carried out for 2 hours at 850 ℃ to obtain an activated substance;
repeatedly washing the activator with distilled water until the filtrate is neutral, and drying the filter cake at 80 deg.C for 12h to obtain powdered demercuration adsorbent A850;
putting 64mL of dichloromethane (1mol) and 27.23g of imidazole (0.4mol) into a polytetrafluoroethylene reaction kettle, and fully and uniformly stirring; placing the reaction kettle in a homogeneous 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 a viscous state at 50 ℃, uniformly adding 3g of powdered mercury removal adsorbent A850, uniformly stirring and grinding to obtain a precursor;
and (3) putting the precursor into a tube furnace, and pyrolyzing the precursor for 1h at 700 ℃ under the protection of nitrogen to obtain the adhesive demercuration adsorbent A850P 700.
Example 2
The method according to embodiment 1, except that it further comprises: repeatedly washing the bonded demercuration adsorbent A850P700 with distilled water until no Cl exists in the sample-Are present. The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-Xi is prepared.
Example 3
The procedure is as in example 1, except that, in the activation treatment, the raffinate is weighed 5g and CH is added3COOK 2.5g (i.e. coal liquefaction oil residue raffinate and CH)3COOK in a weight ratio of 5: 2.5). The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-1 is obtained.
Example 4
The procedure is as in example 1, except that, in the activation treatment, the raffinate is weighed 5g and CH is added3COOK weighing 4g (i.e. coal liquefaction oil residue raffinate and CH)3COOK in a weight ratio of 5: 4). The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-2 is obtained.
Example 5
The procedure is as in example 1, except that the temperature of the activation treatment is 750 ℃ and the time is 4 h. The other conditions were the same as in example 1. The bonded demercuration adsorbent A750P700 is obtained.
Example 6
The procedure of example 1 was followed except that the temperature of the activation treatment was 900 ℃ and the time was 1 hour. The other conditions were the same as in example 1. The bonded demercuration adsorbent A900P700 is obtained.
Example 7
The procedure of example 1 was followed except that in the step of synthesizing the binder, 64mL of methylene chloride (1mol) and 13.615g of imidazole (0.2mol) were measured (i.e., the molar ratio of methylene chloride to imidazole was 1: 0.2). The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-3 is obtained.
Example 8
The procedure of example 1 was followed except that in the step of synthesizing the binder, 64mL of methylene chloride (1mol) and 68.075g of imidazole (1mol) were measured (i.e., the molar ratio of methylene chloride to the imidazole was 1: 1). The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-4 is obtained.
Example 9
The procedure of example 1 was followed except that in the step of preparing the precursor, 1.5g of the polymeric binder and 3g of the powdered mercury removal sorbent a850 were measured (i.e., the activator to binder weight ratio was 1: 0.5). The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-5 is obtained.
Example 10
The procedure of example 1 was followed except that in the step of preparing the precursor, 4.5g of the polymeric binder and 3g of the powdered mercury removal sorbent a850 were measured (i.e., the activator to binder weight ratio was 1: 1.5). The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-6 is obtained.
Example 11
The method of example 1 was followed except that, in the step of synthesizing the binder, the conditions of the polymerization reaction included: the temperature is 90 ℃ and the time is 9 h. The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-7 is obtained.
Example 12
The process of example 1 was followed except that: the conditions of the polymerization reaction include: the temperature is 110 ℃ and the time is 7 h. The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P700-8 is obtained.
Example 13
The process of example 1 was followed except that: the temperature for roasting the precursor is 500 ℃ and the time is 2 h. The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P500 is obtained.
Example 14
The process of example 1 was followed except that: the temperature for roasting the precursor is 800 ℃ and the time is 1 h. The other conditions were the same as in example 1. The bonded demercuration adsorbent A850P800 is obtained.
Comparative example 1
The process of example 1 was followed except that the powdered coal liquefaction bottoms raffinate was not CH processed3COOK activation, direct bonding, the method is as follows:
putting the coal liquefaction oil residue raffinate in a 110 ℃ forced air drying oven for drying for 24 hours;
putting 64mL of dichloromethane and 27.23g of imidazole into a polytetrafluoroethylene reaction kettle, and fully and uniformly stirring; placing the reaction kettle in a homogeneous 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 a viscous state at 50 ℃, uniformly adding 3g of powdered coal liquefaction oil residue raffinate, uniformly stirring and grinding to obtain a precursor;
and (3) putting the precursor into a tube furnace, and pyrolyzing the precursor for 1h at 700 ℃ under the protection of nitrogen to obtain the adhesive demercuration adsorbent P700.
Comparative example 2
The procedure of example 1 was followed except that the raffinate of the pulverized coal-to-liquid residue was first bound and then passed through CH3COOK activation, as follows:
preparing a bonded demercuration adsorbent P700 according to the method of comparative example 1;
5g of the bound demercuration adsorbent P700 and 3g of CH3COOK is stirred and mixed evenly and is placed in a tube furnaceUnder the protection of nitrogen, activating at 850 ℃ for 2h to obtain an activator;
repeatedly washing the activator with distilled water until the filtrate is neutral, and drying the filter cake at 80 deg.C for 12h to obtain the bonded demercuration adsorbent P700A 850.
Comparative example 3
The method of example 1 was followed except that the raffinate of the pulverized coal liquefaction bottoms was first delimed and demineralized with HCl and HF, and then bound as follows:
putting the powdered coal liquefaction oil residue raffinate in a 110 ℃ forced air drying oven for drying for 24 hours;
100g of the powdery raffinate was added to 600mL of HCl solution (6mol/L), stirred at room temperature for 12 hours, and then washed repeatedly with distilled water until the filtrate was neutral and free of Cl-When the HCl exists, the filter cake is dried for 12 hours at 60 ℃ to obtain an HCl washing sample;
50g of the HCl-washed sample was added to 375mL of aqueous hydrofluoric acid (40 wt%), stirred at room temperature for 12 hours, and washed repeatedly with distilled water until the filtrate was neutral and free of F-Drying the filter cake at 60 ℃ for 12h to obtain an HCl-HF washing sample;
putting 64mL of dichloromethane and 27.23g of imidazole into a polytetrafluoroethylene reaction kettle, and fully and uniformly stirring; placing the reaction kettle in a homogeneous 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 a viscous state at 50 ℃, uniformly adding 3g of HCl-HF washing sample, uniformly stirring and grinding to obtain a precursor;
and (3) putting the precursor into a tube furnace, and pyrolyzing the precursor for 1H at 700 ℃ under the protection of nitrogen to prepare the bonding demercuration adsorbent H-P700.
Comparative example 4
The method of example 1 was followed except that the raffinate of the pulverized coal liquefaction bottoms was subjected to deliming and demineralization treatment with HCl and HF, and then to CH3COOK activation and bonding, the method is as follows:
preparing an HCl-HF washed sample according to the method of comparative example 3;
taking 5gHCl-HF wash sample and 3g of CH3COOK, stirring and mixing uniformly, placing in a tubular furnace, and activating at 850 ℃ for 2h under the protection of nitrogen to obtain an activator;
repeatedly washing the activator with distilled water until the filtrate is neutral, and drying the filter cake at 80 deg.C for 12H to obtain powdered demercuration adsorbent H-A850;
putting 64mL of dichloromethane and 27.23g of imidazole into a polytetrafluoroethylene reaction kettle, and fully and uniformly stirring; placing the reaction kettle in a homogeneous 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 a viscous state at 50 ℃, uniformly adding 3g of powdery demercuration adsorbent H-A850, uniformly stirring and grinding to obtain a precursor;
and (3) putting the precursor into a tube furnace, and pyrolyzing the precursor for 1H at 700 ℃ under the protection of nitrogen to prepare the bonding demercuration adsorbent H-A850P 700.
Comparative example 5
The procedure of example 1 was followed, except that the binder used was starch, as follows:
putting the coal liquefaction oil residue raffinate in a 110 ℃ forced air drying oven for drying for 24 hours;
5g of raffinate, 3g of CH3Grinding and uniformly mixing COOK and 5g of starch, adding distilled water, stirring, drying the mixture in a forced air drying oven at 80 ℃ for 12 hours, placing in a tubular furnace, and activating at 850 ℃ for 2 hours under the protection of nitrogen to obtain an activated substance;
repeatedly washing the activator with distilled water until the filtrate is neutral, and drying the filter cake at 80 deg.C for 12h to obtain demercuration adsorbent A850-D.
Comparative example 6
The procedure of example 1 was followed, except that the haloalkane used was chloroform, as follows:
putting the coal liquefaction oil residue raffinate in a 110 ℃ forced air drying oven for drying for 24 hours;
5g of raffinate and 3g of CH3COOK is stirred and mixed evenly and then is put into a tube furnace under the protection of nitrogenThen, activating for 2 hours at 850 ℃ to obtain an activator;
repeatedly washing the activator with distilled water until the filtrate is neutral, and drying the filter cake at 80 deg.C for 12h to obtain powdered demercuration adsorbent A850;
putting 81mL of trichloromethane (1mol) and 27.23g of imidazole (0.4mol) into a polytetrafluoroethylene reaction kettle, and fully and uniformly stirring; placing the reaction kettle in a homogeneous 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 a viscous state at 50 ℃, uniformly adding 3g of powdered mercury removal adsorbent A850, uniformly stirring and grinding to obtain a precursor;
and (3) putting the precursor into a tube furnace, and pyrolyzing the precursor for 1h at 700 ℃ under the protection of nitrogen to obtain the adhesive demercuration adsorbent A850P 700-9.
Experimental example 1
The demercuration performance of the demercuration adsorbents prepared in examples 1-14 and comparative examples 1-6 was evaluated, and the evaluation experiment was carried out on a fixed bed reactor under the following reaction conditions: the temperature is 150 ℃, and the simulated smoke gas is 40 +/-2 mu g/m3 Hg04% by volume of O2And N2The total flow is 1000mL/min, and the space velocity is 1.5 multiplied by 105h-1And sieving the demercuration adsorbent to 40-60 meshes.
The demercuration efficiency (eta) of the demercuration adsorbent is calculated by the following formula: eta (%) ═ 1-C0/C1) X 100% where C0And C1Respectively, the Hg at the outlet and inlet of the fixed bed reactor as measured by a LUMEX 915M mercury calorimeter0Concentration (. mu.g/m)3) (ii) a The evaluation results are shown in table 1.
TABLE 1
As can be seen from table 1, the demercuration adsorbent a850P700 prepared in example 1 showed better demercuration performance, and the demercuration efficiency thereof decreased from 93% to 85% within 2 h.
Compared with the example 2, the mercury removal adsorbent A850P700-Xi prepared by washing the mercury removal adsorbent A850P700 with water has more stable mercury removal performance, and the mercury removal efficiency of the adsorbent within 2h is stabilized to be more than 92%.
As can be seen by comparing example 1 with comparative example 1, the demercuration performance of the demercuration adsorbent P700 is poor, and the demercuration efficiency is reduced from 27% to 24% within 2h, 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 demercuration performance of the demercuration adsorbent, and the demercuration efficiency of the demercuration adsorbent P700a850 prepared in comparative example 2 is reduced from 67% to 51% within 2 h.
As can be seen by comparing example 1 with comparative examples 3-4, the ash content of the raffinate of the coal liquefaction oil residue has a great influence on the mercury removal performance of the mercury removal adsorbent.
As can be seen by comparing example 1 with comparative examples 5-6, the binder prepared by dichloromethane and imidazole can make the demercuration adsorbent show better demercuration performance.
Experimental example 2
N runs on the mercury removal sorbents prepared in examples 1-14 and comparative examples 1-62And (5) performing adsorption-desorption characterization, wherein the characterization results are shown in table 2. And elemental content measurements were performed by XRF on the demercuration sorbents prepared in examples 1 and 2.
TABLE 2
From Table 2It is seen that the BET specific surface area of the demercuration adsorbent A850P700 prepared in example 1 is 50.99m2(ii)/g; in example 2, the specific surface area of the mercury removal adsorbent A850P700-Xi after water washing is increased to 90.25m2And g, showing that the specific surface area and the micropore area of the mercury-removing adsorbent obtained by roasting can be improved by washing.
In addition, XRF testing indicated that SiO in the demercuration adsorbent A850P700 prepared in example 12Is 4 wt.% Fe2O3The content of (B) is 7 wt%; in example 2, SiO in the bonded demercuration adsorbent A850P700-Xi after washing2Is 4 wt.% Fe2O3The content of (B) is 8% by weight.
The specific surface area of the demercuration adsorbent P700 prepared in the comparative example 1 is only 4.36m2The fact that the mercury removal efficiency is poor is probably caused by the fact that the activating agent is activated, and the specific surface area of the raffinate of the coal liquefaction oil residue can be remarkably increased.
The demercuration adsorbent P700A850 prepared in the comparative example 2 has larger specific surface area (181.87 m)2The mercury removal performance of the adsorbent is poorer than that of A850P700 of example 1, which shows that the adsorbent has chemical active sites influencing the mercury removal performance in the process of adsorbing mercury, and the activation and bonding sequence of the coal liquefied oil residue raffinate has a larger influence on the mercury removal performance of the mercury removal adsorbent.
In comparative examples 3 and 4, the specific surface areas of H-P700 and H-A850P700 after deashing the coal liquefaction oil residue raffinate with HCl and HF were 68.05 and 120.32m respectively2The demercuration efficiency is lower than 50% within 2h, which shows that ash content in raffinate of coal liquefaction oil residue has great influence on demercuration performance of the demercuration adsorbent.
In comparative example 5, the mercury removal adsorbent prepared by binding starch and activating with an activator had a specific surface area of 48.17m2(ii)/g, substantially equivalent to the specific surface area of the adsorbent prepared in example 1; the specific surface area of the demercuration adsorbent of comparative example 6 was significantly smaller than that of the adsorbent prepared in example 1. However, the demercuration performance of the demercuration adsorbents of comparative examples 5 and 6 is significantly lower than that of the demercuration adsorbent of example 1, which shows the ratioThe surface area is not the only factor influencing the demercuration activity of the adsorbent, and the property of the binder has a great influence on the demercuration activity of the prepared demercuration adsorbent.
Experimental example 3
XRD characterization of the raw material coal liquefaction oil residue raffinate (CYW) and the mercury removal adsorbents prepared in examples 1-2 and comparative examples 1-4 was performed to determine the crystal structures of the adsorbents, and the characterization results are shown in FIG. 1, wherein diamond-solid represents CaCO3The characteristic peak of (a) is,
represents Fe1-xThe characteristic peak of S is shown as,
represents SiO2The characteristic peak of (a) is obtained,
represents Fe2O3● represents the characteristic peak of KCl,
represents a characteristic peak of Fe, and o represents a characteristic peak of C.
As can be seen from FIG. 1, the crystal form in the coal liquefaction oil residue raffinate (CYW) is mainly SiO2、CaCO3And Fe1-xS, adsorbent P700 (comparative example 1) prepared by directly binding raffinate, in which SiO was the main crystal phase2And Fe2O3Showing CaCO3Decomposed by roasting.
The main crystalline phases of the adsorbent A850P700 (example 1) prepared by activating the coal liquefaction oil residue raffinate (CYW) with an activating agent and then bonding the activated CYW are KCl and Fe2O3(As can be seen from the XRF test in Experimental example 2, SiO in the demercuration adsorbent A850P700 prepared in example 12The content of (A) is 4 wt.%, probably due to SiO in A850P7002Due to the amorphous form, no SiO can be detected by XRD2Crystalline phase), the predominant crystalline phase in the adsorbent A850P700-Xi (example 2) prepared by washing with water was Fe2O3The KCl crystal phase disappeared, indicating that KCl on the surface of the demercuration adsorbent was washed away by distilled water, and Fe2O3Is the main active site for mercury removal.
The main crystalline phase of the adsorbent P700A850 (comparative example 2) prepared by bonding the residues (CYW) of the coal liquefaction oil residues and activating by an activating agent2、CaCO3And Fe; the main crystal phases of the adsorbents (comparative examples 3 and 4) prepared by directly bonding the coal liquefaction oil residue (CYW) after deashing by HCl and HF and activating by an activating agent and then bonding are carbon, and Fe does not appear2O3And SiO2Indicating that ash loss may be the reason for the poor mercury removal performance of the sorbent.
Experimental example 4
The mercury removal adsorbent A850P700-Xi prepared in example 2 was subjected to Hg-TPD (temperature programmed desorption) characterization by the following method: adsorbing the A850P700-Xi adsorbent after adsorbing mercury in N2The programmed temperature to 550 ℃ was increased at 5 ℃/min under the atmosphere to release mercury, and the results are shown in fig. 2.
As can be seen from FIG. 2, the peak of mercury release in the adsorbent of A850P700-Xi after adsorbing mercury is at 330 ℃ due to the release of HgO, while HgCl2The release peak is about 138 +/-4 ℃, and Cl in the adsorbent can be removed-Indicating Fe on the surface of the adsorbent2O3Is the main mercury removal active site.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of preparing a demercuration sorbent, the method comprising:
(1) in the presence of inert gas, performing activation treatment on the coal liquefaction oil residue raffinate and an activating agent to obtain an activated substance;
(2) stirring and mixing the activator and the binder at 40-70 ℃ to obtain a precursor; wherein the adhesive is obtained by performing polymerization reaction on chloralkane and imidazole at 50-120 ℃ for 5-15 h;
(3) and roasting the precursor in the presence of inert gas to obtain the demercuration adsorbent.
2. The method according to claim 1, wherein, in the step (1), the raffinate of the coal liquefaction oil residue is raffinate obtained by extracting the coal liquefaction oil residue generated in the coal liquefaction process;
preferably, the average particle size of the raffinate of the coal liquefaction oil residue is 150-180 meshes;
preferably, in the coal liquefaction oil residue raffinate, SiO is based on the total amount of the coal liquefaction oil residue raffinate2The content of (C) is 3-5 wt.% CaCO3In an amount of 4-8 wt.%, Fe1-xThe S content is 2-10 wt%.
3. The method of claim 1 or 2, wherein in step (1), the weight ratio of the coal liquefaction oil residue raffinate to the activating agent is 5: (2.5-4), preferably 5: (3-4);
preferably, the activator is selected from at least one of potassium hydroxide, potassium acetate, potassium carbonate and potassium bicarbonate, and further preferably potassium acetate.
4. The method according to any one of claims 1 to 3, wherein, in step (1), the conditions of the activation treatment include: the temperature is 750 ℃ and 900 ℃, and the time is 1-4 h; preferably 800-850 ℃ and 1.5-2 h.
5. The process according to any one of claims 1 to 4, wherein in step (2), the molar ratio of the haloalkane to imidazole is 1: (0.2-1), preferably 1: (0.3-0.5);
preferably, the weight ratio of the activator to the binder is 1: (0.5-1.5);
preferably, the chloroalkane is dichloromethane.
6. The process of any one of claims 1 to 5, wherein in step (2), the polymerization conditions comprise: the temperature is 90-110 ℃ and the time is 7-9 h.
7. The method of any one of claims 1-6, wherein in step (3), the firing conditions comprise: the temperature is 500 ℃ and 800 ℃, and the time is 0.5-2 h; preferably at 650-750 ℃ for 1-1.5 h.
8. The method according to any one of claims 1-7, wherein the method further comprises: after step (3), washing the demercuration adsorbent.
9. A demercuration adsorbent prepared by the method of any one of claims 1-8;
preferably, the specific surface area of the demercuration adsorbent is 30-100m2(ii)/g; the area of the micropores is 10-70m2/g；
Preferably, in the demercuration adsorbent, Fe2O3Is 5-9 wt% SiO2Is contained in an amount of 3 to 5 wt%.
10. Use of the demercuration adsorbent of claim 9 in the demercuration of flue gases.
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| CN113058574A (en) * | 2021-04-12 | 2021-07-02 | 贵州大学 | Preparation method of amino functionalized hydrogen sulfide porous polymer adsorbent |
| CN113499664A (en) * | 2021-06-28 | 2021-10-15 | 中国神华煤制油化工有限公司 | Mercury removal agent, preparation method thereof and method for removing elemental mercury in flue gas |
| CN114790281A (en) * | 2022-05-10 | 2022-07-26 | 沈阳工业大学 | Metal-based ionic liquid catalyst for preparing polyester through coupling reaction and preparation method and application thereof |
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