CN106076380A - The preparation method of modified coal activated carbon base catalyst - Google Patents
The preparation method of modified coal activated carbon base catalyst Download PDFInfo
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- CN106076380A CN106076380A CN201610565832.7A CN201610565832A CN106076380A CN 106076380 A CN106076380 A CN 106076380A CN 201610565832 A CN201610565832 A CN 201610565832A CN 106076380 A CN106076380 A CN 106076380A
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- activated carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000003245 coal Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- -1 Nitric Acid Modified activated carbon Chemical class 0.000 claims description 2
- 229930013930 alkaloid Natural products 0.000 claims description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 claims description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N mercury(II) nitrate Inorganic materials [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead(II) nitrate Inorganic materials [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/755—Nickel
-
- 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
-
- 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
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Abstract
The present invention relates to the preparation method of a kind of modified coal activated carbon base catalyst, preparation process is as follows: (1) carries out pretreatment and modification to coal mass active carbon: washed by activated carbon, and with nitric acid, activated carbon is modified, increase its hydrophilic functional group, it is washed with deionized water again to neutrality, drying for standby；(2) the coal mass active carbon evacuation that will process, uses Double solvent method dipping soluble metal salt solution, after drying roasting；(3) coal mass active carbon after roasting is put in alkaline solution impregnate at a certain temperature, obtain modified coal activated carbon base catalyst after drying.The present invention is interacted by hydrophobe, impregnation liquid penetrates in carrier duct, this method overcomes catalytic active component skewness that tradition infusion process causes, easily rests on outer surface and the shortcoming for big crystal grain of easily reuniting, it is mainly used in the cos in removing unstripped gas, this catalyst is applicable to low temperature environment, active good, low cost and other advantages.
Description
Technical field
The present invention relates to catalyst technical field, be specifically related to the preparation side of a kind of modified coal activated carbon base catalyst
Method.
Background technology
Material gas with coal, coke, natural gas and oil etc. as raw material production all contains organic sulfur, but has
The existence of machine sulfur especially COS not only results in the corrosion of environmental pollution, pipeline and equipment, also results in downstream catalyst
Poison, thus affect the production of a series of chemical products.The most treated COS being discharged in air can form SO2, promote photochemistry
Reaction, changes into sulfate aerosol, brings serious environmental problem.Owing to acidity and the polarity of COS are all weaker than H2S, typically
For removing H2The method of S is the most fully effective for COS, and therefore, removing COS is the key realizing gas fine de-sulfur, only
Solve this problem in that and it is possible to make the total sulfur content of industrial gases to be down to use requirement.Removing sulfuldioxide currently mainly has absorption
Method, absorption method, light solution, reducing process, Hydrolyze method etc..What recently research was relatively more is Hydrolyze method, its research be concentrated mainly on by
Transition metal or metal oxide supported to activated carbon, molecular sieve, γ-AI2O3Deng on carrier.
Chinese patent CN101108339A discloses a kind of middle temperature hydrolytic catalyst of carbonyl sulfur and preparation method thereof and purposes,
It is with γ-AI2O3For carrier, by adding V2O5Change catalyst composition and improve the sulfate resistance under catalyst medium temperature condition
Changing performance, the use temperature of this catalyst is the highest (200-400 DEG C).
United States Patent (USP) USP 4,455,446 discloses a kind of at γ-AI2O3The COS hydrolyst of upper load platinum sulfide,
Weak point is that catalyst cost is high, and needs regular regeneration.
Chinese patent CN103506071A discloses a kind of hydrogen sulfide and cos clean in absorbed natural gas tail gas
Net agent, it is with activated carbon as carrier, and the zinc salt of solubility and the mantoquita of solubility are active component, and it is disadvantageous in that this is clear
, there is mechanical strength and the defect of comprcssive strength deficiency in clean dose of convection drying molding after dipping active component.
Summary of the invention
For overcoming defect present in existing catalyst, the present invention provides the system of a kind of modified coal activated carbon base catalyst
Preparation Method, is interacted by hydrophobe, and impregnation liquid penetrates in carrier duct, and this method overcomes tradition urging of causing of infusion process
Change Active components distribution is uneven, easily rest on outer surface and the shortcoming for big crystal grain of easily reuniting, and is mainly used in removing raw material
Cos in gas, this catalyst is applicable to low temperature environment, active good, low cost and other advantages.
The preparation method of the present invention a kind of modified coal activated carbon base catalyst, preparation process is as follows:
(1) coal mass active carbon is carried out pretreatment and modification: washed by activated carbon, and with nitric acid, activated carbon is changed
Property, increase its hydrophilic functional group, then be washed with deionized water to neutrality, drying for standby；
(2) the coal mass active carbon evacuation that will process, uses Double solvent method dipping soluble metal salt solution, drying
Rear roasting；
(3) coal mass active carbon after roasting is put in alkaline solution impregnate at a certain temperature, obtain after drying
Modified coal activated carbon base catalyst.
In described step (1), baking temperature is 50 DEG C-120 DEG C, and drying time is 4-24h, the Nitric Acid Modified activated carbon time
For 2-24h.
Hydrophobic solvent is added to by described step (2) in the activated carbon after evacuation, make activated carbon be distributed to hydrophobic
Property solvent in, dropwise drip metal salt solution after stirring certain time, the clarification outwelling upper strata after continuing stirring certain time is molten
Liquid, puts into drying baker and is dried, roasting.
In described step (2), hydrophobic solvent is hexamethylene, carbon tetrachloride, dichloromethane, and mixing time is 15-60min,
Metal salt solution is Fe (NO3)3、Cu(NO3)2、Ni(NO3)2、Co(NO3)2、Mg(NO3)2、(NH4)6Mo7O24、Hg(NO3)2、Pb
(NO3)2In one or more mixture, the mass ratio of described slaine and activated carbon is 3-30%, and baking temperature is 50
DEG C-120 DEG C, sintering temperature is 200-700 DEG C, and roasting time is 2-8h, and vacuum ranges is 0.02-0.08MPa.
Alkaline solution in described step (3) is NaOH, KOH, K2CO3、NaHCO3、Na2CO3、NH3·H2O、Ba(OH)2In
One or more mixture, the mass ratio of alkaloid substance and activated carbon is 3-25%, and dipping temperature 20-60 DEG C, dip time is
2-24h, baking temperature is 50 DEG C-120 DEG C, and drying time is 4-24h.
Evaluating catalyst condition: COS concentration 100-1500ppm, reaction temperature 30-150 DEG C.
The active testing of catalyst is carried out in fixed bed reactors, and condition is reactor diameter 8-15mm, and catalyst is high
Degree is 4-8cm.Activity represents with COS hydrolysis clearance.Catalytic reaction condition is: COS concentration 100-1500ppm, temperature 30-
150℃。
Compared with prior art, the present invention has following technical effect that
(1) preparation method of the present invention is simple to operate, and metal salt solution and aqueous slkali are cheap and easy to get, and easily realizing industrialization should
With, can be used for the removing of COS in the material gas with coal, coke, natural gas and oil etc. as raw material production, be applied to take off
Except the cos in unstripped gas, H hydrolysis produced simultaneously2S removes in the lump.
(2) present invention is interacted by hydrophobe, is penetrated into by impregnation liquid in carrier duct, and this method overcomes tradition leaching
Catalytic active component skewness that stain method causes, easily rest on outer surface and the shortcoming for big crystal grain of easily reuniting.
(3) application conditions of catalyst is gentle, and removal efficiency is high, and the operating temperature of catalyst is 30-150 DEG C, and COS removes
Rate >=98%.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 1；
Fig. 2 is the XRD figure of embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) take coal mass active carbon distillation washing 4 times, then use nitric acid treatment 2h, then be washed till pH=7 with distilled water, put
120 DEG C of drying baker dry for standby；
(2) by the Fe (NO of mass fraction 17%3)3Add in 10mL distilled water, hexamethylene is added to the work after evacuation
Property charcoal in, make activated carbon disperse wherein, vacuum is 0.02Mpa, stirs 15min, then by Fe (NO3)3It is added drop-wise in hexamethylene,
Continue stirring 15min, filter hexamethylene, activated carbon is dried in 120 DEG C of thermostatic drying chambers 4h, is then placed in Muffle furnace,
2h is activated at 450 DEG C；
(3) by the K of mass fraction 3%2CO3Add in 10mL distilled water, the activated carbon after roasting impregnated at 40 DEG C,
In thermostatic drying chamber, at 120 DEG C, it is dried 4h, obtains absorbent charcoal based catalyst.
Evaluating catalyst condition is: reaction temperature 90 DEG C, reactor inlet air speed 1000h-1, reactor inlet COS concentration
It is not detected by H for reaction outlet in 100ppm, 750min2S。
Embodiment 2
(1) take coal mass active carbon distillation washing 4 times, then use nitric acid treatment 14h, then be washed till pH ≈ 7 with distilled water, put
85 DEG C of drying baker dry for standby；
(2) by the Cu (NO of mass fraction 3%3)2Add in 10mL distilled water, after adding carbon tetrachloride to evacuation
In activated carbon, making activated carbon disperse wherein, vacuum is 0.08Mpa, stirs 38min, then by Cu (NO3)2Solution is slowly dropped to
In carbon tetrachloride, continue stirring 38min, filter carbon tetrachloride, activated carbon is dried in 85 DEG C of thermostatic drying chambers 14h, then
Put in Muffle furnace, at 200 DEG C, activate 8h；
(3) KOH of mass fraction 25% is added in 10mL distilled water, the activated carbon after roasting is impregnated at 20 DEG C,
In thermostatic drying chamber, at 85 DEG C, it is dried 14h, obtains absorbent charcoal based catalyst.
Evaluating catalyst condition is: reaction temperature 30 DEG C, reactor inlet air speed 1000h-1, reactor inlet COS concentration
It is not detected by H for reaction outlet in 800ppm, 600min2S。
Embodiment 3
(1) take coal mass active carbon distillation washing 4 times, then use nitric acid treatment 24h, then be washed till pH ≈ 7 with distilled water, put
85 DEG C of drying baker dry for standby；
(2) by the Ni (NO of mass fraction 30%3)2Add in 10mL distilled water, after adding dichloromethane to evacuation
In activated carbon, making activated carbon disperse wherein, vacuum is 0.05Mpa, stirs 60min, then by Ni (NO3)2Solution is slowly dropped to
In dichloromethane, continue stirring 60min, filter dichloromethane, activated carbon is dried in 50 DEG C of thermostatic drying chambers 24h, then
Put in Muffle furnace, at 700 DEG C, activate 5h；
(3) NaOH of mass fraction 14% is added in 10mL distilled water, the activated carbon after roasting is impregnated at 60 DEG C,
In thermostatic drying chamber, at 50 DEG C, it is dried 24h, obtains absorbent charcoal based catalyst.
Evaluating catalyst condition is: reaction temperature 150 DEG C, reactor inlet air speed 1000h-1, reactor inlet COS concentration
It is not detected by H for reaction outlet in 1500ppm, 550min2S。
Embodiment 4
According to the method for embodiment 1, change Fe (NO3)3For Co (NO3)2, change K2CO3For NaHCO3, reaction in 500min
Outlet is not detected by H2S。
Embodiment 5
According to the method for embodiment 2, change Cu (NO3)2For Mg (NO3)2, change KOH is Na2CO3.Reflect in 400min
Mouth is not detected by H2S。
Embodiment 6
According to the method for embodiment 3, change Ni (NO3)2For (NH4)6Mo7O24, change NaOH is NH3·H2O.In 650min
Reaction outlet is not detected by H2S。
Embodiment 7
According to the method for embodiment 1, change Fe (NO3)3For Hg (NO3)2, change K2CO3For Ba (OH)2.In 450min instead
Should export and be not detected by H2S。
Embodiment 8
According to the method for embodiment 2, change Cu (NO3)2For Pb (NO3)2。
Evaluating catalyst condition is: temperature 40 DEG C, air speed 1000h-1, COS concentration is reaction outlet in 700ppm, 500min
It is not detected by H2S。
Fig. 1 is the SEM figure of embodiment 1；Fig. 2 is the XRD figure of embodiment 1.
It will be seen from figure 1 that active component is evenly distributed on activated carbon, the slaine after roasting is with the shape of oxide
State exists.
Figure it is seen that stronger diffraction maximum peak value occurs in 2 θ=30.33 °, 35.74 °, 43.41 °, 53.78 °,
57.39 ° and 63.06 °, Fe is described2O3Characteristic peak exist.
Table 1 is pH and the surface chemical structure Boehm titration data of embodiment 1.
The pH of table 1 embodiment 1 and surface chemical structure Boehm titration data
From table 1 it follows that contrast activated carbon, the quantity of the hydrolyst surface alkalinty group being prepared from is significantly
Increase.
Claims (7)
1. the preparation method of a modified coal activated carbon base catalyst, it is characterised in that preparation process is as follows:
(1) coal mass active carbon is carried out pretreatment and modification: washed by activated carbon, and with nitric acid, activated carbon is modified, increase
Add its hydrophilic functional group, then be washed with deionized water to neutrality, drying for standby；
(2) the coal mass active carbon evacuation that will process, uses Double solvent method dipping soluble metal salt solution, roasts after drying
Burn；
(3) coal mass active carbon after roasting is put in alkaline solution impregnate at a certain temperature, obtain modification after drying
Coal mass active carbon base catalyst.
The preparation method of modified coal activated carbon base catalyst the most according to claim 1, it is characterised in that described step
(1) in, baking temperature is 50 DEG C-120 DEG C, and drying time is 4-24h, and the Nitric Acid Modified activated carbon time is 2-24h.
The preparation method of modified coal activated carbon base catalyst the most according to claim 1, it is characterised in that described step
(2) being added to by hydrophobic solvent in the activated carbon after evacuation, make activated carbon be distributed in hydrophobic solvent, stirring is certain
Dropwise drip metal salt solution after time, outwell the settled solution on upper strata after continuing stirring certain time, put into drying baker and be dried,
Roasting.
The preparation method of modified coal activated carbon base catalyst the most according to claim 3, it is characterised in that described step
(2) in, hydrophobic solvent is hexamethylene, carbon tetrachloride, dichloromethane, and mixing time is 15-60min, and metal salt solution is Fe
(NO3)3、Cu(NO3)2、Ni(NO3)2、Co(NO3)2、Mg(NO3)2、(NH4)6Mo7O24、Hg(NO3)2、Pb(NO3)2In one or
Multiple mixture, described slaine is 3-30% with the mass ratio of activated carbon, and baking temperature is 50 DEG C-120 DEG C, sintering temperature
For 200-700 DEG C, roasting time is 2-8h, and vacuum ranges is 0.02-0.08MPa.
The preparation method of modified coal activated carbon base catalyst the most according to claim 1, it is characterised in that described step
(3) alkaline solution in is NaOH, KOH, K2CO3、NaHCO3、Na2CO3、NH3·H2O、Ba(OH)2In one or more mixing
Thing, alkaloid substance is 3-25% with the mass ratio of activated carbon, and dipping temperature 20-60 DEG C, dip time is 2-24h, and baking temperature is
50 DEG C-120 DEG C, drying time is 4-24h.
The preparation method of modified coal activated carbon base catalyst the most according to claim 1, it is characterised in that catalyst is commented
Valency condition is: COS concentration 100-1500ppm, reaction temperature 30-150 DEG C.
The preparation method of modified coal activated carbon base catalyst the most according to claim 1, it is characterised in that catalyst
Active testing is carried out in fixed bed reactors, and condition is reactor diameter 8-15mm, and catalyst height is 4-8cm.
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