CN110280235A - A kind of loaded catalyst and its preparation method and application - Google Patents
A kind of loaded catalyst and its preparation method and application Download PDFInfo
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- CN110280235A CN110280235A CN201910728785.7A CN201910728785A CN110280235A CN 110280235 A CN110280235 A CN 110280235A CN 201910728785 A CN201910728785 A CN 201910728785A CN 110280235 A CN110280235 A CN 110280235A
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- loaded catalyst
- activated carbon
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- activated sludge
- methyl mercaptan
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000010802 sludge Substances 0.000 claims abstract description 44
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 19
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000084 colloidal system Substances 0.000 claims description 26
- 239000005539 carbonized material Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012620 biological material Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 6
- 244000060011 Cocos nucifera Species 0.000 claims description 6
- 235000009496 Juglans regia Nutrition 0.000 claims description 6
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 6
- 239000010903 husk Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 235000020234 walnut Nutrition 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 240000007049 Juglans regia Species 0.000 claims 1
- 244000061176 Nicotiana tabacum Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000003292 glue Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 241000758789 Juglans Species 0.000 description 5
- 241000208125 Nicotiana Species 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- -1 methyl mercaptan Compound Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming 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
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000012855 volatile organic compound Substances 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
- B01D53/34—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
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalyst technical field, in particular to a kind of loaded catalyst and its preparation method and application.The present invention provides a kind of loaded catalysts, including activated carbon from activated sludge and the ceria being supported on activated carbon from activated sludge.Object generation without secondary pollution after methyl mercaptan mild condition and catalytic decomposition methyl mercaptan is catalytically decomposed in the active feature high, stability is strong, the service life is long of loaded catalyst provided by the invention.When experimental data shows loaded catalyst provided by the invention for catalytic eliminating methyl mercaptan, reaction condition is mild；After loaded catalyst catalytic eliminating methyl mercaptan provided by the invention, remaining methyl mercaptan concentration only 0.0035~0.0037mg/m3, there is good removing methyl mercaptan effect.
Description
Technical field
The invention belongs to catalyst technical field, in particular to a kind of loaded catalyst and its preparation method and application.
Background technique
Methyl mercaptan is a kind of special organic matter, is mainly derived from natural gas and petroleum industry, and main component is alkane, this
Outer is one kind of organic sulfur there are also impurity such as a small amount of organic sulfurs, has fetor smell, and be insoluble in water, in air
Easily conversion forms Organic aerosol, and Atmospheric Photochemical Smog and haze etc. is caused seriously to pollute, and it is strong to seriously endanger environment and human body
Health, so the efficient removal of methyl mercaptan has important meaning to sulphur pollution, realization sulphur and volatile organic compounds emission reduction is reduced
Justice.
Currently, the method for removing methyl mercaptan has very much, mainly there are absorption method, alkali absorption method, direct combustion method, biology drop
Solution and catalytic decomposition.Wherein catalytic decomposition has the advantages such as efficient, low power consuming, by extensive in thiol treatment research
Concern.
From the point of view of current research, metal hydroxides, metal oxygen are broadly divided into applied to the catalyst for sloughing methyl mercaptan
Compound solid solution and load-type solid.It has also been developed in succession with MgO/Al at present2O3、NiO/Al2O3And NiO/MgO/Al2O3
The solid base of equal metal oxide solid solutions form, these solid alkali materials have strong oxidation performance, thermal stability high and compare table
The features such as area is big, but these catalyst preparation process are cumbersome, and the decomposition product of methyl mercaptan is complicated, decompose removal methyl mercaptan meeting
The new pollutant of thioether class is generated, secondary pollution, such as MgO/Al are caused2O3Equal metal oxides and load sulfonated phthalocyanine cobalt etc.
After catalysis material catalytic decomposition removal methyl mercaptan, new organic sulphur pollution such as dimethyl sulfide and dimethyl disulfide can be generated
Object；Or have the defects that severe reaction conditions；Or have the defects that catalyst life is short.(solid base is to oil by Xiang Yuzhi etc.
The removal performance of organic sulfur compound and analysis [J] Xiang Yuzhi, Xia Daohong, Duan Yongfeng chemistry of fuel journal in product, 2006,34
(5): 633-636.) using active carbon as carrier, alkaline-earth metal (Ca, Ba and Mg etc.) and its mixture are supported on by infusion process
On active carbon, and its performance for removing the organic sulfur compounds such as mercaptan, thioether, curing, object carbonyl sulfur and thiophene-based is studied, these
When catalyst degradation mercaptan, the new organic sulfur contaminant such as dimethyl sulfide and dimethyl disulfide can be also generated；It is external
There is scholar (Conversion ofpoisonous methanethiol to hydrogen rich gas by
chemisorption/reforming over nano-scale CeO2:The use of CeO2 as catalyst
coating material.Laosiripojana N,Assabumrungrat,S.Applied Catalysis B:
Environmental, 2011,102,267-275.) carry out utilization nano particle CeO2The research work of methyl mercaptan is catalytically decomposed
Make, however, the reaction need to carry out under 900 DEG C or more hot conditions, reaction condition and its harshness；Methyl mercaptan is in HZSM-5 molecule
Temperature is that 100% conversion of methyl mercaptan can be achieved at 550 DEG C, but the service life of HZSM-5 molecular sieve catalyst is very short on sieve,
After line reacts 6h, catalyst begins to inactivate.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of loaded catalysts.Supported catalyst provided by the invention
Nothing after methyl mercaptan mild condition and catalytic decomposition methyl mercaptan is catalytically decomposed in the active feature high, stability is strong, the service life is long of agent
Secondary pollution generates.
In order to realize the purpose of foregoing invention, the present invention the following technical schemes are provided:
The present invention provides a kind of loaded catalyst, including activated carbon from activated sludge and it is supported on the activated carbon from activated sludge
On ceria.
Preferably, the mass ratio of the activated carbon from activated sludge and ceria is 1:(0.03~0.15)；The support type
The granularity of catalyst is 30~50 mesh.
The present invention also provides the preparation methods of loaded catalyst described in above-mentioned technical proposal, comprising the following steps:
(1) activated carbon from activated sludge is provided；
(2) by Na2CO3、Ce(NO3)3·6H2O and deionized water mixing, form colloid；
(3) activated carbon from activated sludge is mixed with the colloid, successively carries out the first dry, roasting, aqueous slkali dipping
It is dried with second, obtains loaded catalyst；
The step (1) and (2) do not have chronological order.
Preferably, the preparation method of activated carbon from activated sludge includes the following steps: in the step (1)
Biological material is subjected to charing process, obtains carbonized material；
The carbonized material is mixed with NaOH, successively activated, washed, dried and microwave treatment, it is living to obtain biomass
Property charcoal.
Preferably, the biological material includes one of walnut shell, coconut husk and tobacco rod or a variety of；The carbonized material with
The mass ratio of NaOH is 1:(1~4).
Preferably, the temperature of the activation is 500~700 DEG C, and the time is 1~2h, and atmosphere is nitrogen atmosphere；The microwave
The microwave frequency of processing is 2000~3000MHz, and microwave power is 600~800W, and the time is 2~4min, vapor flow 4
~5mL/min.
Preferably, the mass ratio of activated carbon from activated sludge and colloid is 1:(1~6 in the step (3)).
Preferably, the temperature roasted in the step (3) is 300~700 DEG C, time 3h.
Preferably, the solute of aqueous slkali dipping aqueous slkali is NaOH or KOH in the step (3)；The aqueous slkali
Mass concentration is 5~20%；The time of the aqueous slkali dipping is 30min.
The present invention also provides preparation methods described in loaded catalyst described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the loaded catalyst being prepared in removing methyl mercaptan.
The present invention provides a kind of loaded catalyst, including activated carbon from activated sludge and it is supported on the activated carbon from activated sludge
On ceria.
Ceria has the function of stronger catalysis oxidation methyl mercaptan in loaded catalyst provided by the invention；Biology
Activated carbon has excellent suction-operated and power of regeneration, can efficient absorption and carrying active ingredients ceria, collaboration
Ceria catalysis oxidation ability, while the physical absorption ability that activated carbon from activated sludge itself has are improved, first sulphur can be adsorbed
Alcohol decomposes removing product and methyl mercaptan itself, has significant deodorizing effect.
When experimental data shows loaded catalyst provided by the invention for catalytic eliminating methyl mercaptan, reaction condition temperature
With；After removing methyl mercaptan using catalyst provided by the invention, remaining methyl mercaptan concentration only 0.0035~0.0037mg/
m3, there is good removing methyl mercaptan effect.
Detailed description of the invention
Fig. 1 is remaining methyl mercaptan volumetric concentration content after application examples 1~3 of the present invention and the removing of 1 mercaptan catalyst of comparative example
Figure.
Specific embodiment
The present invention provides a kind of loaded catalyst, including activated carbon from activated sludge and it is supported on the activated carbon from activated sludge
On ceria.
In the present invention, the mass ratio of the activated carbon from activated sludge and ceria is preferably 1:(0.03~0.15), more
Preferably 1:(0.04~0.13), be further preferably 1:(0.04~0.10).In the present invention, the granularity of the loaded catalyst
Preferably 30~50 mesh, more preferably 33~45 mesh are further preferably 35~42 mesh.
The present invention also provides the preparation methods of loaded catalyst described in above-mentioned technical proposal, comprising the following steps:
(1) activated carbon from activated sludge is provided；
(2) by Na2CO3、Ce(NO3)3·6H2O and deionized water mixing, form colloid；
(3) activated carbon from activated sludge is mixed with the colloid, successively carries out the first dry, roasting, aqueous slkali dipping
It is dried with second, obtains loaded catalyst；
The step (1) and (2) do not have chronological order.
In the present invention, the preparation method of the activated carbon from activated sludge preferably includes following steps:
Biological material is subjected to charing process, obtains carbonized material；
The carbonized material is mixed with NaOH, successively activated, washed, dried and microwave treatment, it is living to obtain biomass
Property charcoal.
Biological material is preferably carried out charing process by the present invention, obtains carbonized material.In the present invention, the biological material
Material preferably includes one of walnut shell, coconut husk and tobacco rod or a variety of.In the present invention, the temperature of the charing process is preferably
400~700 DEG C, more preferably 450~650 DEG C are further preferably 500~650 DEG C；Time is preferably 1~2h, and more preferably 1.2
~2h is further preferably 1.5~2h.In the present invention, the atmosphere of the charing is preferably nitrogen atmosphere.The present invention is to the charing
Equipment be not particularly limited, using carbonization device well known to those skilled in the art, specifically, such as tube furnace.
After obtaining carbonized material, the present invention mixes the carbonized material with NaOH, is successively activated, is washed, dried and is micro-
Wave processing, obtains activated carbon from activated sludge.
In the present invention, the mass ratio of the carbonized material and NaOH are preferably 1:(1~4), more preferably 1:(1.5~
It 3.5) is further preferably, 1:(1.8~3).The present invention is not particularly limited the hybrid mode of the carbonized material and NaOH, using this
Hybrid mode known to the technical staff of field.In the present invention, the temperature of the activation is preferably 500~700 DEG C, more excellent
530~650 DEG C are selected as, is further preferably 540~600 DEG C；Time is preferably 1~2h, more preferably 1.2~1.8h, further preferably for
1.5~1.8h.In the present invention, the atmosphere of the activation is preferably nitrogen atmosphere.The present invention does not have the equipment of the activation
Particular determination, using carbonization device well known to those skilled in the art, specifically, such as tube furnace.The present invention passes through activation,
Obtain activated material.The present invention is not particularly limited the technique of the washing, is in neutrality with that can wash activated material to pH value
?.In the present invention, the temperature of the drying is preferably 100~150 DEG C, and more preferably 110~140 DEG C, be further preferably 120
~140 DEG C；Time is preferably 5~6h, more preferably 5.3~6h, is further preferably 5.5~6h.The present invention is to the microwave treatment
Equipment be not particularly limited, using microwave equipment well known to those skilled in the art.The present invention is in the same of microwave treatment
Shi Youxuan passes to vapor into microwave equipment.In the present invention, the microwave frequency of the microwave treatment be preferably 2000~
3000MHz, more preferably 2200~2800MHz are further preferably 2400~2600MHz, and microwave power is preferably 600~800W,
More preferably 650~780W is further preferably 700~770W；Time is preferably 2~4min, more preferably 2~3min, further preferably
For 2.2~2.7min；Vapor flow is preferably 4~5mL/min, more preferably 4.2~4.8mL/min, further preferably for 4.4~
4.6mL/min。
The present invention is by Na2CO3、Ce(NO3)3·6H2O and deionized water mixing, form colloid.
In the present invention, the Na2CO3With Ce (NO3)3·6H2The molar ratio of O is preferably 3:2.The present invention passes through design
Na2CO3With Ce (NO3)3·6H2O is the ratio reacted completely, and the colloidal substance type guaranteed is consistent, and then is conducive to protect
The purity of catalyst active component is demonstrate,proved, catalyst efficiency is improved.In the present invention, the Na2CO3With the use of deionized water
Magnitude relation is preferably 1:2.In the present invention, the preparation method of the colloid is preferably by the Na2CO3、Ce(NO3)3·6H2O
With deionized water mix, obtain mixing salt solution, will after the mixing salt solution deionized water centrifuge washing to neutrality redissolve in
In deionized water, crystallization and washing are successively carried out, colloid is obtained；The temperature of the crystallization is preferably 90~100 DEG C, and the time is preferred
For 15~20h；The washing is preferably deionized water centrifuge washing, and the number of the washing is preferably 3~4 times.
After obtaining activated carbon from activated sludge and colloid, the present invention mixes the activated carbon from activated sludge with the colloid, obtains
Mixed glue solution.In the present invention, the mass ratio of the activated carbon from activated sludge and the colloid is preferably 1:(1~6), more preferably
1:(2~5), be further preferably 1:(3~4).The no spy of the hybrid mode that the present invention mixes the activated carbon from activated sludge with colloid
It is different to limit, with hybrid mode well known to those skilled in the art.In the present invention, the mixed mode is preferably ultrasound
Stirring；The time of the ultrasonic agitation is preferably 30min.In the present invention, frequency ultrasonic in the ultrasonic agitation is preferably
40kHz；The revolving speed stirred in the ultrasonic agitation is preferably 250rpm.
After obtaining mixed glue solution, the present invention mixed glue solution is successively carried out first dry, roasting, aqueous slkali dipping and
Second is dried, and obtains loaded catalyst.
In the present invention, the described first dry temperature is preferably 120 DEG C, and the time is preferably 3~4h, and more preferably 3.5
~4h.In the present invention, the described first dry equipment is preferably air dry oven.In the present invention, the temperature of the roasting
Preferably 300~700 DEG C, more preferably 400~650 DEG C are further preferably 500~650 DEG C；Time is preferably 3h.The present invention is logical
Crossing the first drying and roasting makes mixed glue solution obtain dry activation.In the present invention, the aqueous slkali dipping aqueous slkali is molten
It is of fine quality to be selected as NaOH or KOH；The mass concentration of the aqueous slkali is preferably 5~20%, more preferably 10~18%, further preferably for
10~15%.In the present invention, the time that the aqueous slkali leaching is set is preferably 30min.In the present invention, the aqueous slkali leaching is set
It is preferred that being carried out under conditions of ultrasound.The present invention is not particularly limited the frequency of the ultrasound, using those skilled in the art
Well known supersonic frequency.In the present invention, the described second dry temperature is preferably 120 DEG C, and the time is preferably 3~4h,
More preferably 3.5~4h.
The present invention also provides preparation methods described in loaded catalyst described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the loaded catalyst being prepared in removing methyl mercaptan.Loaded catalyst of the present invention can be urged in mild
Change efficient removal methyl mercaptan in environment.
After the loaded catalyst removes methyl mercaptan, the present invention is preferably activated by used loaded catalyst
It is recycled after processing.The present invention is not particularly limited the mode of the activation processing, using known to those skilled in the art
Activation method, specifically, preferably include washing regeneration treatment, nitrogen purging regeneration treatment and aqueous slkali dipping regeneration at
One or more of reason is mixed, is more preferably combined using nitrogen purging regeneration treatment and aqueous slkali dipping regeneration treatment.At this
In invention, the temperature of nitrogen purging regeneration treatment is preferably 300~500 DEG C, more preferably 350~450 DEG C, further preferably for
380~420 DEG C, the present invention purges regeneration treatment by nitrogen, can remove the thioether impurity that surface is attached to after reacting.At this
In invention, the aqueous slkali dipping regeneration treatment is preferably NaOH solution with aqueous slkali, and the mass concentration of the NaOH solution is excellent
12~18%, more preferably 13~17% are selected as, is further preferably 14~16%, the present invention impregnates regeneration treatment by aqueous slkali,
The catalytic capability of catalyst can largely be restored.
In order to further illustrate the present invention, below with reference to embodiment to loaded catalyst provided by the invention and its preparation
Methods and applications are described in detail, but they cannot be interpreted as limiting the scope of the present invention.Obviously, described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
Embodiment 1
Coconut husk is carbonized into 2h under nitrogen protection in 650 DEG C of tube furnace, obtains carbonized material, then carbonized material and NaOH are pressed
The ratio of mass ratio 1:2 is uniformly mixed, and activates 1.5h under nitrogen atmosphere in 550 DEG C of tube furnace, obtains activated material, is taken out and is lived
Material is simultaneously washed to pH value and is in neutrality with distillation, is ground and is sieved after dry 6h under the conditions of 100 DEG C, chooses under 10 mesh mesh screens
Material is washed to supernatant and suspends without muddy object, uses the side of microwave heating after dry 6h in air dry oven at 140 DEG C
Formula, without being heated to furnace body itself, microwave frequency 2500MHz, microwave power 750W, activation time 2.5min, vapor
Activated carbon from activated sludge is made in flow 4.5ml/min.
By Na2CO3With Ce (NO3)3·6H2The ratio of O 3:2 in molar ratio is mixed in deionized water and forms colloid.
It according to the mass ratio of activated carbon from activated sludge and the colloid is 1:4 (metal by gained activated carbon from activated sludge and colloid
Cerium active component quality accounts for the 5% of the quality of carbon) mixing, mixed glue solution is obtained, mixed glue solution is stirred under ultrasound condition
Mixed glue solution is placed in air dry oven at 120 DEG C dry 4h, the solid matter after drying is then placed in horse by 30min
Not in furnace, 3h is roasted under 600 DEG C and condition of normal pressure, the material after roasting is impregnated in the aqueous slkali that mass concentration is 15%
Sample is finally placed in air dry oven at 120 DEG C dry 4h, it is living to obtain coconut husk biomass by middle ultrasonic immersing 30min
Property charcoal load ceria loaded catalyst.
Embodiment 2
Walnut shell is carbonized into 2h under nitrogen protection in 650 DEG C of tube furnace, obtains carbonized material, then by carbonized material and NaOH
The ratio of 1:2 is uniformly mixed in mass ratio, is activated 1.5h under nitrogen atmosphere in 550 DEG C of tube furnace, is obtained activated material, is taken out
Activated material is simultaneously washed to pH value and is in neutrality with distillation, is ground and is sieved after dry 6h under the conditions of 100 DEG C, chooses 10 mesh mesh screens
Lower material is washed to supernatant and suspends without muddy object, uses microwave heating after dry 6h in air dry oven at 140 DEG C
Mode, without being heated to furnace body itself, microwave frequency 2500MHz, microwave power 750W, activation time 2.5min, water steaming
Activated carbon from activated sludge is made in throughput 4.5ml/min.
By Na2CO3With Ce (NO3)3·6H2O is that the ratio of 3:2 is mixed in deionized water formation colloid in molar ratio.
It according to the mass ratio of activated carbon from activated sludge and the colloid is 1:4 (metal by gained activated carbon from activated sludge and colloid
Cerium active component quality accounts for the 5% of the quality of carbon) mixing, mixed glue solution is obtained, mixed glue solution is stirred under ultrasound condition
Mixed glue solution is placed in air dry oven at 120 DEG C dry 4h, the solid matter after drying is then placed in horse by 30min
Not in furnace, 3h is roasted under 600 DEG C and condition of normal pressure, the material after roasting is impregnated in the aqueous slkali that mass concentration is 15%
Sample is finally placed in air dry oven at 120 DEG C dry 4h, obtains walnut shell biomass by middle ultrasonic immersing 30min
The loaded catalyst of activated carbon supported ceria.
Embodiment 3
Tobacco rod is carbonized into 2h under nitrogen protection in 650 DEG C of tube furnace, obtains carbonized material, then carbonized material and NaOH are pressed
The ratio of mass ratio 1:2 is uniformly mixed, and activates 1.5h under nitrogen atmosphere in 550 DEG C of tube furnace, obtains activated material, is taken out and is lived
Material is simultaneously washed to pH value and is in neutrality with distillation, is ground and is sieved after dry 6h under the conditions of 100 DEG C, chooses under 10 mesh mesh screens
Material is washed to supernatant and suspends without muddy object, uses the side of microwave heating after dry 6h in air dry oven at 140 DEG C
Formula, without being heated to furnace body itself, microwave frequency 2500MHz, microwave power 750W, activation time 2.5min, vapor
Activated carbon from activated sludge is made in flow 4.5ml/min.
By Na2CO3With Ce (NO3)3·6H2O is that the ratio of 3:2 is mixed in deionized water formation colloid in molar ratio.
It according to the mass ratio of activated carbon from activated sludge and the colloid is 1:4 (metal by gained activated carbon from activated sludge and colloid
Cerium active component quality accounts for the 5% of the quality of carbon) mixing, mixed glue solution is obtained, mixed glue solution is stirred under ultrasound condition
Mixed glue solution is placed in air dry oven at 120 DEG C dry 4h, the solid matter after drying is then placed in horse by 30min
Not in furnace, 3h is roasted under 600 DEG C and condition of normal pressure, the material after roasting is impregnated in the aqueous slkali that mass concentration is 15%
Sample is finally placed in air dry oven at 120 DEG C dry 4h, it is living to obtain tobacco rod biomass by middle ultrasonic immersing 30min
Property charcoal load ceria loaded catalyst.
Application examples 1~3
Methyl mercaptan removing test is carried out using loaded catalyst obtained by Examples 1 to 3, specific test method is as follows:
Loaded catalyst grinding after drying is sized to 40 mesh, takes 0.3g to be put into tubular type roasting furnace and is reacted.
Methyl mercaptan feed rate is 500mL/min, air speed 20000h-1, 350 DEG C of reaction temperature, N2As Balance Air, it is passed through 5%
O2, the remaining methyl mercaptan concentration in test reaction outlet；Simultaneously measure catalyst activity hold time be followed successively by respectively 100h, 108h and
105h, length of holding time, methyl mercaptan removal effect are excellent.
After the removing methyl mercaptan of loaded catalyst obtained by Examples 1 to 3, remaining methyl mercaptan volumetric concentration is shown in Table 1.
Comparative example 1
By Na2CO3With Ce (NO3)3·6H2O is mixed in deionized water in the ratio reacted completely and forms colloid.
Gained colloid is stirred to 30min under ultrasound condition and is placed in air dry oven at 120 DEG C dry 4h, then
Solid matter after drying is placed in Muffle furnace, roasts 3h under 600 DEG C and condition of normal pressure, the material after roasting is impregnated
Sample, is finally placed in air dry oven at 120 DEG C by the ultrasonic immersing 30min in the aqueous slkali that mass concentration is 15%
Dry 4h obtains catalyst, and gained catalyst is free of activated carbon from activated sludge, and main component is ceria.
According to catalysis 1 gained catalyst of reaction test comparative example identical with application examples 1 to the removal effect of methyl mercaptan, survey
Test result is shown in Table 1.
Methyl mercaptan residual concentration after 1 application examples 1~3 of table and the reaction of 1 catalyst of comparative example
| Application examples 1 | Application examples 2 | Application examples 3 | Comparative example 1 | |
| Methyl mercaptan residual concentration/(mg/m3) | 0.0037 | 0.0035 | 0.0036 | 0.004 |
Remaining methyl mercaptan volumetric concentration contains spirogram after drawing application examples 1~3 and the removing of 1 mercaptan catalyst of comparative example by table 1,
See Fig. 1.By table 1 and Fig. 1 as it can be seen that after using loaded catalyst catalytic eliminating methyl mercaptan provided by the invention, remaining methyl mercaptan
Concentration only 0.0035~0.0037mg/m3, there is good removing methyl mercaptan effect；Without activated carbon from activated sludge of the present invention
Catalyst elimination reaction after, remaining methyl mercaptan concentration be 0.004mg/m3, illustrate provided by the invention containing biomass
Activated carbon from activated sludge and ceria have concerted catalysis effect in the loaded catalyst of active carbon.
Spent catalyst of the loaded catalyst obtained by Examples 1 to 3 after repeatedly reacting is re-started work by the present invention
Change processing, obtains quadric catalysis agent, activation processing method particularly includes: first by the catalyst after using in 400 DEG C of temperature conditions
Lower progress nitrogen purging, except the thioether impurity for being attached to surface after dereaction, then in the NaOH solution that mass fraction is 15%
Dipping largely restores the catalytic capability of catalyst.
The quadric catalysis agent obtained after priming reaction is handled carries out catalysis survey under test condition identical with application examples 1
Examination, quadric catalysis agent catalytic efficiency reduced by only 30%, illustrate that loaded catalyst provided by the invention can reuse, urge
The service life of agent is extended.
Loaded catalyst provided by the invention takes full advantage of waste (coconut husk, walnut shell and tobacco rod), at low cost, easy
In obtain and it is pollution-free, realize waste recycling；The methyl mercaptan removal effect of gained loaded catalyst will be obvious, makes to urge
Methyl mercaptan concentration is in 0.004mg/m after changing removing3Hereinafter, reaching national " malodorant discharge standard " first discharge standard；Simultaneously
Activated carbon from activated sludge and loaded catalyst preparation process are simple, are suitable for industrialized production.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of loaded catalyst, which is characterized in that including activated carbon from activated sludge and be supported on the activated carbon from activated sludge
Ceria.
2. loaded catalyst according to claim 1, which is characterized in that the activated carbon from activated sludge and ceria
Mass ratio is 1:(0.03~0.15)；The granularity of the loaded catalyst is 30~50 mesh.
3. the preparation method of loaded catalyst as claimed in claim 1 or 2, which comprises the following steps:
(1) activated carbon from activated sludge is provided；
(2) by Na2CO3、Ce(NO3)3·6H2O and deionized water mixing, form colloid；
(3) activated carbon from activated sludge is mixed with the colloid, successively carries out first dry, roasting, aqueous slkali dipping and the
Two are dried, and obtain loaded catalyst；
The step (1) and (2) do not have chronological order.
4. preparation method according to claim 3, which is characterized in that the preparation of activated carbon from activated sludge in the step (1)
Method includes the following steps:
Biological material is subjected to charing process, obtains carbonized material；
The carbonized material is mixed with NaOH, successively activated, washed, dried and microwave treatment, activated carbon from activated sludge is obtained.
5. the preparation method according to claim 4, which is characterized in that the biological material include walnut shell, coconut husk and
One of tobacco rod is a variety of；The mass ratio of the carbonized material and NaOH are 1:(1~4).
6. the preparation method according to claim 4, which is characterized in that the temperature of the activation is 500~700 DEG C, the time
For 1~2h, atmosphere is nitrogen atmosphere；The microwave frequency of the microwave treatment be 2000~3000MHz, microwave power be 600~
800W, time are 2~4min, and vapor flow is 4~5mL/min.
7. preparation method according to claim 3, which is characterized in that activated carbon from activated sludge and colloid in the step (3)
Mass ratio be 1:(1~6).
8. preparation method according to claim 3, which is characterized in that the temperature roasted in the step (3) is 300~
700 DEG C, time 3h.
9. preparation method according to claim 3, which is characterized in that aqueous slkali dipping uses aqueous slkali in the step (3)
Solute be NaOH or KOH；The mass concentration of the aqueous slkali is 5~20%；The time of the aqueous slkali dipping is 30min.
What 10. any one of loaded catalyst as claimed in claim 1 or 2 or claim 3~9 preparation method were prepared
Application of the loaded catalyst in removing methyl mercaptan.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112354093A (en) * | 2020-11-02 | 2021-02-12 | 中国人民解放军陆军防化学院 | Multifunctional filtering tank for gas mask |
| CN113546644A (en) * | 2021-06-27 | 2021-10-26 | 昆明理工大学 | Preparation method and application of catalyst for deeply removing organic sulfur from coke oven gas |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
| CN116273022B (en) * | 2023-03-21 | 2024-06-07 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
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| CN108855108A (en) * | 2018-06-26 | 2018-11-23 | 天津工业大学 | Starch-based bio activated carbon loaded nano catalysis material and preparation method thereof |
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| CN108855108A (en) * | 2018-06-26 | 2018-11-23 | 天津工业大学 | Starch-based bio activated carbon loaded nano catalysis material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112354093A (en) * | 2020-11-02 | 2021-02-12 | 中国人民解放军陆军防化学院 | Multifunctional filtering tank for gas mask |
| CN113546644A (en) * | 2021-06-27 | 2021-10-26 | 昆明理工大学 | Preparation method and application of catalyst for deeply removing organic sulfur from coke oven gas |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
| CN116273022B (en) * | 2023-03-21 | 2024-06-07 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
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