CN110479210A - A kind of activated carbon containing iron in situ and its preparation method and application removing hydrogen sulfide - Google Patents
A kind of activated carbon containing iron in situ and its preparation method and application removing hydrogen sulfide Download PDFInfo
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- CN110479210A CN110479210A CN201910831684.2A CN201910831684A CN110479210A CN 110479210 A CN110479210 A CN 110479210A CN 201910831684 A CN201910831684 A CN 201910831684A CN 110479210 A CN110479210 A CN 110479210A
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- iron
- hydrogen sulfide
- coal
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- heat treatment
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 60
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 6
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003245 coal Substances 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000002817 coal dust Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 159000000014 iron salts Chemical class 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 235000000396 iron Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000012778 molding material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000002386 leaching Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000003077 lignite Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 timber Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention belongs to exhaust gas adsorption technology fields, specifically disclose a kind of activated carbon containing iron in situ for removing hydrogen sulfide, including active carbon and the source of iron in situ being supported in active carbon；The source of iron is at least one of fe, cementite.Adsorption applications the invention also discloses the preparation method of the active carbon and its in hydrogen sulfide.The present invention, which innovatively provides the completely new load in situ of one kind, the active carbon of fe, cementite, and innovatively finds that the completely new active carbon has excellent hydrogen sulfide catalytic adsorption effect.
Description
Technical field
The present invention relates to a kind of methods for preparing removal hydrogen sulfide active carbon using low rank coal, belong to active carbon preparation
Field.
Background technique
H2S is mainly derived from natural gas, Biohazard Waste Disposal, sewage treatment plant, biogas production, paper mill, petroleum refining factory
Deng production or treatment process in, be a kind of gas with rotten-egg odour, can from respiratory system invade human body, cause people poisoning,
It makes one eyes stung to shed tears, vomit, or even goes into a coma.Therefore H2The removal of S gas is of great significance.
The removal methods of existing hydrogen sulfide gas mainly have lye absorption, adsorbent absorption, precipitating etc., wherein adsorbent
Absorption method is most widely used.In numerous adsorbent processing methods, active carbon adsorption is since activated carbon pore structure is flourishing, compares table
Area is big, absorption property is excellent, and simple process, it is high-efficient, easy to operate the advantages that and by favor.
Theoretically the substance of all carbon elements may be used to prepare active carbon, but due to raw material supply and prepared work
The reasons such as property charcoal product quality, can be used in industrializing, commercially produce at present active carbon raw material mainly have coal, timber,
Shell (coconut husk, almond) and a small amount of petroleum coke, other carbonaceous materials (such as chemical industry and domestic refuse prepare active carbon) are common
In experimental study and specific use.With the raw material such as sawdust, shell class and petroleum coke preparation active carbon compared with, coal be it is cheap and
The Activated Carbon Production raw material of steady sources has both the advantages that easily regenerating, is wear-resistant by the active carbon that raw material produces of coal.
Root is it was found that anthracite is the raw material for being most suitable for preparation removal hydrogen sulfide active carbon.However although China is coal
Big country, but smokeless coal reserves only accounts for 1/10th or so of coal in China reserves, and demand is big, at high price.And it goes vulcanisation
The extensive market of hydrogen, it is big to the demand of active carbon, if using anthracite prepare active carbon removal hydrogen sulfide, it will increase at
This, is unfavorable for the construction of conservation culture.Therefore, the preparation that the cheap raw material of one kind carries out vulcanisation hydrogen activity charcoal need to be found, is mentioned
The efficiency of height removal hydrogen sulfide, saves activated carbon dosage, reduces cost.
In addition, merely using active carbon it is limited to the removal effect of hydrogen sulfide, for this purpose, the prior art also reported it is some
Supported catalyst ingredient in active carbon, to promoted hydrogen sulfide degradation effect technology.For example, Kong Yupu et al. [1] is in work
Direct impregnation metal nitrate studies desulphurizing activated influence on property charcoal.Research is pointed out, is born on activated carbon substrates
Iron oxide bearing can improve the effect of desulfurizing agent removing hydrogen sulfide, still, when amount of metal and the quality of activated carbon ratio of load reach
When 1%, as the increase desulfurization effect of the load capacity of iron is decreased obviously instead.The reason is that the iron oxide of load is gathered in activity
Carbon surface is easy the micropore of blocking active carbon, reduces the activated adoption position of hydrogen sulfide.
[1] Kong Yupu, Li Chunhu, Wang Liang, Feng Lijuan；Method of modifying is to hydrogen sulfide in active carbon removing analog synthesis gas
It influences；Chemical industry progress, the 508-511 pages of of the supplementary issue of volume 29 in 2010
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of activated carbon containing irons in situ for removing hydrogen sulfide, it is intended to mention
Rise the removal effect of hydrogen sulfide.
Second purpose of the invention is, provides the preparation method of activated carbon containing iron in situ described in one kind, it is intended to using bad
The low rank coal of matter is raw material, and the activated carbon containing iron in situ for having excellent absorption property to hydrogen sulfide is made.
Third purpose of the present invention is, provides application of the activated carbon containing iron in situ in hydrogen sulfide stripping.
Relative to other pernicious gases, hydrogen sulfide is a kind of super hypertoxic gas, even if the hydrogen sulfide gas of very low concentrations
(being less than 1ppm) also can be to respiratory tract and the irritating effect of eyes, and causes to have a headache and be poisoned.So the removing of hydrogen sulfide is necessary
Thoroughly.But the technique (wet process and bioanalysis) of current removing hydrogen sulfide is extremely difficult to this purpose, usually must be de- at these
Increase dry method abjection technique after sulphur technique, that is, utilizes the absorption method of the adsorbents such as active carbon removing hydrogen sulfide.So being directed to this
Difficult point and demand, the adsorbent for developing the removing hydrogen sulfide of high efficiency low cost is exactly resolving ideas provided by the invention and scheme.
A kind of activated carbon containing iron in situ removing hydrogen sulfide, including active carbon and the iron in situ being supported in active carbon
Source；The source of iron is at least one of fe, cementite.
The present invention innovatively provides the active carbon that the completely new load in situ of one kind has fe, cementite, and innovatively
It was found that the completely new active carbon has excellent hydrogen sulfide catalytic adsorption effect.
In the present invention, the fe is α-Fe.
Compared with the active carbon that existing ferriferous oxide supports, the iron that the present invention supports is with reduction-state (α-Fe, Fe of iron3C)
Nanoparticle high dispersive in active carbon, have higher hydrogen sulfide stripping than the active carbon that existing ferriferous oxide supports
Energy.
Preferably, the partial size of the source of iron is 5~50 nanometers.Content is 0.5~15.0%.
Preferably, the specific surface area of the active carbon is 300~1500 meters squared per grams.
The present invention also provides a kind of preparation methods of activated carbon containing iron in situ for removing hydrogen sulfide, comprising the following steps:
Step (1): by low rank coal, water-soluble iron salts and binder mixed-forming；
Step (2): by step (1) molding material in protective atmosphere, 500~700 DEG C of at a temperature of progress first segment heat
Processing；
Step (3): by first segment heat treatment product again protective atmosphere, higher than first segment heat treatment at a temperature of carry out
Second segment heat treatment；Then washed, drying is to get the activated carbon containing iron in situ.
The present invention innovatively has found, uses low rank coal for raw material, it is mixed with water-soluble iron salts contact in advance, then
Innovatively by two sections of heat treatment process at the temperature, can unexpectedly obtain with good porosity, load in situ
It is loaded with the active carbon of iron simple substance and/or cementite, the study found that the active carbon obtained has excellent hydrogen sulfide adsorption
Energy.
Preparation method of the present invention, key are the use of the low rank coal, low rank coal and water-soluble
Property molysite mixing after be heat-treated；And the Collaborative Control of two sections of heat treatment process and heat treatment temperature.
In the present invention, using low rank coal as raw material, not only raw material sources are wide, at low cost, but also made from it
Activated carbon containing iron in situ unexpectedly has more preferably hydrogen sulfide adsorption performance.
Preferably, the low rank coal is at least one of mud coal, jet coal, lignite etc..
Preferably, the ingredient of low rank coal is 40%≤C≤80%, ash content accounting is between 0.5%-35%.Make
To be preferred, in step (1), comprising the following steps:
Low rank coal is crushed, is sieved by step (1-a), sieves to obtain coal dust；
Step (1-b) impregnates coal dust in the aqueous solution of the water-soluble iron salts, then so dry that soak iron coal
Powder；
Step (1-c) will be soaked iron coal dust and is uniformly mixed with binder, compression moulding.
Preferably, coal particle size is not more than 1mm in step (1-a).
Preferably, water-soluble iron salts be iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate and ferric nitrate one kind or
It is several；Further preferably ferric nitrate.The study found that using the preferred ferric nitrate, technical solution through the invention can be with
Unexpectedly further improve absorptive capacity.
Wherein, the mass ratio of water-soluble iron salts and coal dust is 0.1~2.0.
In step (1-b), impregnates and place under the conditions of 20-80 DEG C, dip time 6-18h, then in 80-120 DEG C of drying
12-24h。
Preferably, the mass ratio of binder selection polyvinyl alcohol, polyvinyl alcohol and coal dust is 4%-25%.
Preferably, polyvinyl alcohol is added in coal dust, it is uniformly mixed, then feeds the mixture into molding machine and suppressed
Molding, forming shape are column, honeycomb, any one in graininess.
In the present invention, innovatively water-soluble iron salts are loaded in low rank coal in advance, followed by described
One section of heat treatment.The study found that, by the temperature of control first segment heat treatment, it is former to obtain iron simple substance, ferrous-carbide in the present invention
The disordering heat-treated products that position supports, and control the order degree of material.Further cooperate the heat treatment of subsequent second segment with
And the control of temperature, it can further improve pore structure, promote material obtained to the adsorption effect of hydrogen sulfide.
Preferably, the temperature of first segment heat treatment is 600~700 DEG C.
The atmosphere of first segment heat treatment is protective atmosphere, preferably nitrogen, inert gas.
Preferably, the time of first segment heat treatment is 10-60min.
Preferably, the temperature of second segment heat treatment is not higher than 1000 DEG C, further preferably 700~1000 DEG C；More into
One step is preferably 800~1000 DEG C.
The atmosphere of second segment heat treatment is that can choose vapor, CO2And one of nitrogen and air gas mixture.
The time of second segment heat treatment is 10-60min.
After second segment heat treatment, product after cooling is washed to pH value neutrality by water washing device, after then washing
The active carbon of acquisition obtains removal hydrogen sulfide activated carbon product after 60-100 DEG C of at least dry 12h.
Compared with the existing technology, beneficial outcomes of the invention:
(1) the present invention provides a kind of in-situ impregnation iron simple substance, the active carbon of ferrous-carbide, the active carbon is to vulcanization
Hydrogen has the effects that absorption, catalysis, oxidation simultaneously, high to the removal efficiency of hydrogen sulfide, can achieve environment protection emission requirement；In addition
Active carbon from coal of different shapes can be also prepared as needed, it is easy to operate, it is only necessary to replace press-forming machine outlet die.
The study found that active carbon of the present invention has better than hydrogen sulfide compared to existing adsorbent material
Effect；
(2) present invention innovatively provide it is a kind of by after low rank coal, water-soluble iron salts mixing through two sections of heat
The active carbon of in-situ impregnation iron simple substance, ferrous-carbide can be made in the preparation method of processing.It is carried on a shoulder pole compared to common active carbon
Iron technology is carried, entirely different material can be obtained, and finds that the completely new material obtained is imitated with more preferably hydrogen sulfide stripping
Fruit.
(3) present invention prepares active carbon from coal by raw material of low rank coal, and raw material rich reserves are cheap, can be big
Width reduces preparation cost, turns waste into wealth simultaneously, improves the utility value of low rank coal；Moreover, using low rank coal
There is more preferably hydrogen sulfide stripping effect through active carbon made from the preparation method.
Detailed description of the invention
Fig. 1 is the process flow chart of preparation method of the invention.
Fig. 2 is the XRD diagram of the removal hydrogen sulfide activated carbon product obtained of embodiment 2.
Specific embodiment
The purpose of the present invention, process flow, preparation method reaches purpose and effect is easy to understand in order to make, and below will
Preparation method of the present invention is described further in conjunction with attached drawing.
A kind of active carbon from coal and preparation method thereof removing hydrogen sulfide, the specific steps are as follows:
(1) lignite is crushed, sieved, screen out the coal dust of suitable particle diameter；
(2) coal dust is impregnated in soluble iron salting liquid, is then dried；
(3) dry coal dust is uniformly mixed with binder, compression moulding；
(4) shaped article is completely cut off to air at 500-700 DEG C and carries out first segment heat treatment；
(5) by the material of first segment heat treatment in 700-1000 DEG C of progress second segment heat treatment；Then carry out cooling, water
It washes, dry, obtain required product.
Embodiment 1
A kind of active carbon from coal and preparation method thereof removing hydrogen sulfide, comprising the following steps:
(1) lignite that C under dry ash free basis is 70%, ash content accounting is 3% is crushed, sieved, screen out partial size
Coal dust less than 0.1mm；
(2) coal dust is impregnated in ferric chloride solution, the mass ratio of iron chloride and coal dust is 1, at 20 °C
18h is impregnated, is then dried for 24 hours at 80 DEG C；
(3) selecting polyvinyl alcohol is binder, and dry iron chloride load coal dust is mixed with polyvinyl alcohol by 10:1, is squeezed
It is pressed into column；
(4) columnar product is completely cut off to air at 600 DEG C and carries out first segment heat treatment 30min；
(5) first segment heat-treated products are heat-treated 40min in 800 DEG C of progress second segments；
(6) second segment heat-treated products are cooled down, pH value is then washed to as neutrality by water washing device, then will
Active carbon after washing obtains removal hydrogen sulfide activated carbon product at 80 DEG C after dry 18h.
Ingredient, specific surface area, removing experiment and the experimental data of test product, as a result see attached list 1.
Embodiment 2
A kind of active carbon from coal and preparation method thereof removing hydrogen sulfide, comprising the following steps:
(1) lignite that C under dry ash free basis is 60%, ash content accounting is 10% is crushed, sieved, screen out partial size
Coal dust less than 1mm；
(2) coal dust is impregnated in iron nitrate solution, the mass ratio of ferric nitrate and coal dust is 2, under the conditions of 80 DEG C
6h is impregnated, then in 120 DEG C of dry 12h；
(3) selecting polyvinyl alcohol is binder, and coal dust is mixed with polyvinyl alcohol by 5:1, suppresses column；
(4) columnar product is completely cut off to air at 700 DEG C and carries out first segment heat treatment 10min, obtains carbonized material；
(5) material of first segment heat treatment is heat-treated 10min in 1000 DEG C of progress second segments；
(6) material that second segment is heat-treated is cooled down, then for neutrality, then pH value is washed to by water washing device
By the active carbon after washing, dry obtain afterwards for 24 hours removes hydrogen sulfide activated carbon product at 60 DEG C.
Composition information, iron content, specific surface area and removing experiment and experimental data see attached list 1.
Embodiment 3
A kind of active carbon from coal and preparation method thereof removing hydrogen sulfide, comprising the following steps:
(1) lignite that C under dry ash free basis is 50%, ash content accounting is 20% is crushed, sieved, screen out partial size
Coal dust less than 0.01mm；
(2) coal dust is impregnated in solution of ferrous chloride, the mass ratio of frerrous chloride and coal dust is 0.5, at 40 DEG C
Under the conditions of impregnate 12h, then in 100 DEG C of dry 18h；
(3) selecting polyvinyl alcohol is binder, coal dust is mixed with polyvinyl alcohol by 5:1, compressed granulate shape；
(4) granular product is completely cut off to air at 500 DEG C and carries out first segment heat treatment 60min；
(5) material of first segment heat treatment is heat-treated 60min in 700 DEG C of progress second segments；
(6) material that second segment is heat-treated is cooled down, then for neutrality, then pH value is washed to by water washing device
Active carbon after washing is obtained into removal hydrogen sulfide activated carbon product at 100 DEG C after dry 12h.Product characteristic and absorption effect
Fruit sees attached list 1.
The adsorpting data test method of hydrogen sulfide are as follows: the adsorption test of hydrogen sulfide using ADSORPTION IN A FIXED BED desulfurizer into
Row.It is packed into the desulfurizing agent (each embodiment is obtained to remove hydrogen sulfide activated carbon product) of 1-5g first in adsorptive reactor, takes off
The upper and lower side of sulphur agent is filled with a small amount of silica wool.Reaction start when with the gas velocity of 100ml/min to equipped with desulfurizing agent reactor from
It is passed through the calibrating gas containing 100-500ppm hydrogen sulfide on down, and continuously detects sulphur with concentration of hydrogen sulfide analyzer in outlet
Change the concentration of hydrogen.It is considered as when the concentration of hydrogen sulfide in purified gas reaches the 10% of its original concentration and penetrates.It will calculate at this time
Adsorption capacity of the working sulfur capacity arrived as hydrogen sulfide.
The performance of activated carbon containing iron property in situ prepared by 1 embodiment 1-3 of table and removing hydrogen sulfide
The above embodiment is a preferred embodiment of the present invention, but the embodiment of present aspect is not by above-described embodiment
Limitation, other any substitutions made without departing from the spirit and principles of the present invention, combination, change, are simplified modification
Deng should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of activated carbon containing iron in situ for removing hydrogen sulfide, which is characterized in that be supported on activity including active carbon and original position
Source of iron in charcoal；The source of iron is at least one of fe, cementite.
2. the activated carbon containing iron in situ of removal hydrogen sulfide as described in claim 1, which is characterized in that the partial size of the source of iron
It is 5~50 nanometers；Content is 0.5~15.0wt%；
The specific surface area of the active carbon is 300~1500m2/g。
3. a kind of preparation method for the activated carbon containing iron in situ for removing hydrogen sulfide, which comprises the following steps:
Step (1): by low rank coal, water-soluble iron salts and binder mixed-forming；
Step (2): by step (1) molding material in protective atmosphere, 500~700 DEG C of at a temperature of progress first segment heat treatment；
Step (3): by first segment heat treatment product again protective atmosphere, higher than first segment heat treatment at a temperature of carry out second
Section heat treatment；Then washed, drying is to get the activated carbon containing iron in situ.
4. preparation method as claimed in claim 3, which is characterized in that in step (1), comprising the following steps:
Low rank coal is crushed, is sieved by step (1-a), sieves to obtain coal dust；
Step (1-b) impregnates coal dust in the aqueous solution of the water-soluble iron salts, then the coal dust of dry leaching iron；
Step (1-c) will be soaked iron coal dust and is uniformly mixed with binder, compression moulding.
5. the preparation method according to claim 4, which is characterized in that the low rank coal is mud coal, jet coal, brown
At least one of coal；
The ingredient of low rank coal is 40%≤C≤80%, and ash content accounting is between 0.5%-35%；
In step (1-a), coal particle size is not more than 1mm.
6. the preparation method according to claim 4, which is characterized in that water-soluble iron salts are iron chloride, frerrous chloride, sulfuric acid
The one or more of iron, ferrous sulfate and ferric nitrate；
Wherein, the mass ratio of water-soluble iron salts and coal dust is 0.1~2.0.
7. the preparation method according to claim 4, which is characterized in that binder selects polyvinyl alcohol, polyvinyl alcohol and coal
The mass ratio of powder is 4%-25%.
8. the preparation method according to claim 4, which is characterized in that the atmosphere of first segment heat treatment is protective atmosphere, nitrogen
The inert gases such as gas or tiny structure；
The time of first segment heat treatment is 10-60min.
9. the preparation method according to claim 4, which is characterized in that the atmosphere of second segment heat treatment is vapor, CO2With
And one of nitrogen and air gas mixture.
The time of second segment heat treatment is 10-60min.
10. the preparation of any one of a kind of described in any item activated carbon containing irons in situ of claim 1~2 or claim 3~9
The application of original position activated carbon containing iron made from method, which is characterized in that the adsorbent as hydrogen sulfide；
Preferably, by itself and exhaust gas contact containing hydrogen sulfide, for removing hydrogen sulfide therein.
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