CN108786877A - A kind of no metal H2S selective oxidation catalysts and preparation method - Google Patents
A kind of no metal H2S selective oxidation catalysts and preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
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- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
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- 229920001661 Chitosan Polymers 0.000 claims description 4
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 8
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 235000013311 vegetables Nutrition 0.000 description 1
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Classifications
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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
- 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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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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- 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
- B01J35/618—Surface area more than 1000 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
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- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of no metal H2S selective oxidation catalysts and preparation method thereof.The catalyst is pre-processed using the carbohydrate of green non-pollution as primary carbon source using simple mechanical mixing, and then mixture is placed in in the tube furnace of inert atmosphere roasting at a slow speed can be obtained final catalyst.And the catalyst is in H2Show high activity in S selective catalytic oxidation performance tests, the characteristics of high stability, method for preparing catalyst of the present invention is simple, at low cost, and raw material is easy to get, easy to operate, has a extensive future.
Description
Technical field
The present invention relates to a kind of using carbohydrate as the porous nano carbon materials preparation method for material of raw material, and in particular to a kind of novel nothing
Metal H2H can be achieved at the same time in the preparation of S catalyst for selective oxidation and its application process, this method2The removal of S gases and sulphur
Recycling.
Background technology
H2Major pollutants one of of the S as air are a kind of high irritation severe toxicity gas, in aerobic and wet heat condition
Under, it can not only cause equipment and corrosion of piping, catalyst poisoning, but also personal safety can be seriously threatened.With the development of economy,
The desulphurization problem of the enhancing of people's environmental consciousness, tail gas has been to be concerned by more and more people.Country has also formulated corresponding simultaneously
Law, regulation, to H2S discharge capacitys have made stringent limitation.Hydrogen sulfide is the by-product in many industrial productions.Currently, having 70
A variety of occupations can touch hydrogen sulfide.These occupation include mining, oil exploitation synthesized with refinement, leather manufacture, rubber, coal gas
Produce, staple fibre, papermaking, dyestuff, printing and dyeing, sugaring, food processing etc..In addition, also there is hydrogen sulfide production in organic matter corruption place
It is raw, and easily accumulate in urban sewage pipe, Jiao Jing, septic tank, cesspool, paper pulp pond and the other kinds fermentation of improper ventilation
Pond and vegetables pickling pool etc. are closed and semi-enclosed facility, container and pipeline in or low-lying place therefore when clearing up these places,
Hydrogen sulfide can be contacted.In addition, hydrogen sulfide is water-soluble and methanol, ethyl alcohol, explosive mixture can be formed by being mixed with air；It meets bright
Fire, high temperature can cause combustion explosion.Currently, industrially H2The removing of S mainly uses Crouse (Claus methods) technique.It should
Technique need to first absorb H2Concentrate after S, then elemental sulfur is produced by further catalytic treatment.Removing H can be reached2The purpose of S gases,
The recycling of wherein element sulphur can be realized again.But since thermodynamics limits, the also vulcanization containing 3%-5% in Claus tail gases
Object fails to be converted to elemental sulfur.As environmental legislation is increasingly strict, searching one kind is needed not limited by thermodynamical equilibrium, it can be efficient
Remove H2S simultaneously realizes the processing method that sulphur simple substance recycles.
In recent years, selective catalytic oxidation H2The method of S attracts widespread attention, and reacts as shown in formula (1).H2S is selected
Selecting property catalytic oxidation is not limited by thermodynamical equilibrium, theoretical H2S conversion ratios can reach 100 %.And the reaction process
Advanced, process is simple.Because reaction is exothermic reaction, H20.3 % or more of S contents can not need heat credit, and low energy consumption.Cause
This, which has a good application prospect, and realizes that the key of this process is to develop with efficient catalytic activity and choosing
The catalyst of selecting property.
H2S + 1/2O2 → (1/n) Sn + H2O (1)
It is applied to H at present2The catalyst in S selective catalytic oxidations field mainly has traditional carbon material, molecular sieve and metal oxidation
Object.But from document, there are still shortcomings for the above catalyst.For example, activated carbon, molecular screen material are because of its specific surface area
Greatly, duct is abundant makes its mass transport process and the product sulfur desorption rate accelerate, but the material autocatalysis center is few, needs to load
Active component just has catalytic performance after being modified, thus cumbersome there are preparation process and active component easily flows in the reaction
The problems such as mistake；Carbon nanotube has unique one-dimentional structure, and degree of graphitization is higher, under certain humidity, H2The HS of S dissociation-From
Son is easy to, in its surface fast transferring, have preferable oxidation sweetening performance；But it is small to be limited its specific surface area, is saturated Sulfur capacity highest
Only reach 1.86g H2S/g catalyst.Mesoporous carbon has larger mesoporous hole, is conducive to the storage of sulphur；It is mixed simultaneously by nitrogen
The miscellaneous surface alkalinty that material can be improved increases the quantity of carbon margin location and defective bit, strengthens H2The absorption of S is dissociated, and is enhanced it and is urged
Change ability.The working sulfur capacity of N doping mesoporous carbon can be improved to 2.77g H2S/g catalyst.But the preparation method of meso-porous carbon material
Complexity, synthetic technology require height, are not easy to realize industrialized production.Metal oxide itself has active site, and stablizes
Property is relatively high, but specific surface area is smaller, limits it to H2The absorption of S, and it is easy to happen sulphur covering activity in the reaction
Center makes catalyst performance be greatly reduced.Therefore, other than modified on original carrier, the efficient H of Development of Novel2S selectivity
Catalyst for catalytic oxidation is current the only way which must be passed for realizing hydrogen sulfide stripping technological break-through.
It has been investigated that with abundant pore passage structure, big specific surface area and a large amount of evenly dispersed active sites
Catalyst is conducive to H2The absorption of S and the generation of redox reaction.In view of catalyst such as traditional carbon materials, there are specific surfaces
Product is small and active site waits many deficiencies less, it is proposed that a kind of preparation method of the polysaccharide series carbon material of simplicity, and
Compared with the similar material of other documents and patent report, it is proposed that preparation method it is environmentally protective, operating method is simple, and
And the catalyst prepared has the characteristics that high Sulfur capacity, high specific surface area, abundant pore passage structure and active site, this is also
The material is applied to the key of hydrogen sulfide selective catalytic oxidation.
Invention content
It is an object of the invention to solve existing H2S selective oxidation catalysts there are the problem of, be dedicated to developing
A kind of preparation method is easy, the excellent catalyst of catalytic performance.Raw material is uniformly mixed by the mechanical lapping of simple green,
In inert atmosphere after high-temperature roasting is handled, obtain a kind of efficient H2S selective catalytic oxidation non-metal catalysts.Pass through
Regulate and control rotating speed and the calcination temperature of ball mill to obtain the porous carbon materials of different nitrogen contents and grain size aperture.Prepared by this method
Porous carbon materials catalyst in H2Excellent catalytic performance is shown in S selective catalytic oxidations.The invention is also for the first time will
Porous carbon materials prepared by this method are used for H2In the reaction of S selective catalytic oxidations, while being exploitation green high-efficient, Yi Jifang
The H of method simplicity2S selective oxidation catalysts provide new approaches.
In order to realize that the purpose of above-mentioned design catalyst, the present invention will adopt the following technical scheme that：
A kind of no metal H2The preparation of S selective oxidation catalysts, with carbohydrate for main carbon source, with dicyandiamide etc. for nitrogen
Source, mechanical lapping first pass through the grinding of mortar, are sized to certain mesh number, are then uniformly mixed in the ball mill, ball milling obtains
Micron-sized mixture, by roasting to obtain sample in inert gas high temperature.
It is as follows：
（1）It weighs at least one of carbohydrates such as a certain amount of glucose, chitosan, sucrose and is used as carbon source, place it in mortar
In and fully it is finely ground, the raw material A of 120 ~ 140 mesh is obtained after standard screen sieves；
（2）It weighs at least one of drugs such as a certain amount of dicyandiamide, melamine, urea and is used as nitrogen source, place it in and grind
It is in alms bowl and fully finely ground, the raw material B of 120 ~ 140 mesh is obtained after standard screen sieves；
（3）By obtained raw material A, B by certain mass ratio（A:B=0.02~0.1：1）Mixing, is packed into after mixing
In the ball grinder of 100ml, agate abrading-ball accounts for 20%, middle ball by big ball and accounts for the mass ratio loading ball grinder that 50%, bead accounts for 30%
In, with 180 ~ 240 revs/min of rotating speed, ball milling 30 ~ 60 minutes in the direction of the clock, then ball milling 30 ~ 60 counterclockwise again
Minute；
（4）After waiting for ball milling, the mixture in ball grinder is placed in ceramic Noah's ark, and is put into quartz tube furnace, then
It opens vacuum pumping 30 ~ 60 minutes, then nitrogen is passed through in tube furnace, and by room temperature by temperature programming in 4 ~ 6 hours to 400
~ 600 DEG C, temperature programming in 1 ~ 4 hour is then passed through to final carburizing temperature（700~900℃）It carries out high temperature cabonization 1 ~ 4 hour, waits for
It is cooled to room temperature to collect to obtain catalyst, and can be used for H2In the reaction of S selective catalytic oxidations.
The application of non-metal catalyst：It is applied to selective catalytic oxidation H2S is the catalysis reaction of sulphur simple substance and water
In, reaction temperature is 100 DEG C ~ 200 DEG C, and unstripped gas is 5000 ppm H2S, 2500 ppm O2, N2For three components of Balance Air
Gas, feed gas flow rates V are 20 mLmin-1, tube inner diameter is 5 mm.
Catalyst described in step is used in H2In the reaction of S selective catalytic oxidations, performance evaluation formula is as follows：
Due to current H2There is many in S selective catalytic oxidations, such as preparation method very complicated is difficult to industrialize, and urges
Agent is easy permanent deactivation etc..The present invention provides a kind of H thus2The simple preparation method of S selective oxidation catalysts,
With carbohydrate for most important carbon source, dicyandiamide, urea and melamine etc. are main nitrogen source, by simply sieving and mechanical ball
Mill mixing, can be obtained catalyst in the high-temperature tubular kiln roasting of inert atmosphere.
The above technical solution of the present invention has the following advantages over the prior art：
（1）Non-metal catalyst preparation method of the present invention is simple, and the synthetic raw material of selection is easy to get, at low cost, green
Color is pollution-free, is conducive to industrialized large-scale production, and have universality, has a extensive future；
（2）The present invention is without metal H2S selective oxidation catalysts have a large amount of active site, abundant pore passage structure
With larger specific surface area；
（3）No metal H of the present invention2S selective oxidation catalysts are without load or add other active components,
While high conversion and selectivity, also there is preferable catalytic stability；
（4）No metal H of the present invention2S selective oxidation catalysts are selected with environmentally protective carbohydrate as main carbon
Source, the raw material that the nitrogen content of dicyandiamide, urea and melamine is high is main nitrogen source, can reduce the production cost of catalyst,
Simultaneously synthesizing catalyst can obtain the pyridine nitrogen content of 15 ~ 45 wt %, current research shows that pyridine nitrogen can conduct
H2Active site during S selective catalytic oxidations, compared with common N doping, containing high level pyridine nitrogen without gold
Metal catalyst catalytic performance has obtained significant raising；
（5）No metal H of the present invention2S selective oxidation catalysts, using the preparation method roasted at a slow speed, the party
Catalyst prepared by method can generate more pore passage structures, while also increasing and urging compared with the method quickly roasted
The specific surface area of agent.
Description of the drawings
Fig. 1 is the nitrogen Adsorption and desorption isotherms of 1 ~ 3 sample of embodiment；
Fig. 2 is the pore size distribution curve of 1 ~ 3 sample of embodiment；
Fig. 3 is that embodiment 1 ~ 3 and 1 ~ 2 sample of comparative example carry out H2H in S catalysis oxidation catalytic performance tests2S conversion ratios
The curve graph varied with temperature；
Fig. 4 is that embodiment 1 ~ 3 and 1 ~ 2 sample of comparative example carry out H2In S catalysis oxidation catalytic performance tests S selectivity with
The curve graph of temperature change；
Fig. 5 is that embodiment 1 ~ 3 and 1 ~ 2 sample of comparative example carry out H2Sulphur yield in S catalysis oxidation catalytic performance tests with
The curve graph of temperature change；
Fig. 6 is 1 ~ 2 sample of embodiment 1 ~ 3 and comparative example, is reacted 25 hours at 180 DEG C, H2The catalysis of S catalysis oxidations is stablized
H in performance evaluation2The curve graph that S conversion ratios change with the reaction time.
Specific implementation mode
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail.
Embodiment 1：
It takes suitable glucose in mortar, after grinding 15 ~ 30 minutes, is sieved to obtain 120 mesh glucose below with standard screen,
It is denoted as raw material A；It takes suitable melamine in mortar, after grinding 15 ~ 30 minutes, is sieved to obtain 120 purposes three with standard screen
Poly cyanamid is denoted as raw material B.It is 1g to weigh raw material A with assay balance, and it is 35g to weigh raw material B, and raw material A and B are pressed 1:35 matter
Amount ratio is sufficiently mixed in mortar, and then uniformly mixed mixture is fitted into the ball grinder of 100ml, and agate abrading-ball presses big ball
It accounts for 20%, middle ball and accounts for 50%, bead and account for 30% mass ratio and be fitted into ball grinder, with 230 revs/min of rotating speed, in the direction of the clock
Ball milling 30 minutes, then ball milling 30 minutes counterclockwise.After waiting for ball milling, the mixture in ball grinder is placed in ceramics
It in Noah's ark, and is put into quartz tube furnace, then opens vacuum pumping 30 minutes, then nitrogen is passed through in tube furnace, by room
Temperature, to 400 DEG C, was then passed through temperature programming in 2 hours and carries out roasting 2 hours to 700 DEG C by temperature programming in 4 hours, to be cooled to arrive
Room temperature collects to obtain sample, is denoted as catalyst S1, and nitrogen content is 20 ~ 25wt%, and grain size is 2 ~ 5 μm.
Embodiment 2（Most preferred embodiment）：
It takes suitable chitosan in mortar, after grinding 15 ~ 30 minutes, is sieved to obtain 120 mesh chitosan below with standard screen,
It is denoted as raw material A；It takes suitable dicyanodiamine in mortar, after grinding 15 ~ 30 minutes, is sieved to obtain 130 purposes two with standard screen
Cyanogen diamines is denoted as raw material B.It is 1g to weigh raw material A with assay balance, and it is 35g to weigh raw material B, and raw material A and B are pressed 1:35 matter
Amount ratio is sufficiently mixed in mortar, and then uniformly mixed mixture is fitted into the ball grinder of 100ml, and agate abrading-ball presses big ball
It accounts for 20%, middle ball and accounts for 50%, bead and account for 30% mass ratio and be fitted into ball grinder, with 230 revs/min of rotating speed, in the direction of the clock
Ball milling 40 minutes, then ball milling 40 minutes counterclockwise.After waiting for ball milling, the mixture in ball grinder is placed in ceramics
It in Noah's ark, and is put into quartz tube furnace, then opens vacuum pumping 30 minutes, then nitrogen is passed through in tube furnace, by room
Temperature, to 500 DEG C, was then passed through temperature programming in 3 hours and carries out roasting 2 hours to 800 DEG C by temperature programming in 5 hours, to be cooled to arrive
Room temperature collects to obtain sample, is denoted as catalyst S2, and nitrogen content is 35 ~ 45wt%, and grain size is 500nm ~ 1 μm.
Embodiment 3：
It takes suitable sucrose in mortar, after grinding 15 ~ 30 minutes, is sieved to obtain 120 mesh sucrose below with standard screen, be denoted as
Raw material A；It takes suitable urea in mortar, after grinding 15 ~ 30 minutes, is sieved to obtain the urea of 140 mesh with standard screen, be denoted as original
Expect B.It is 1g to weigh raw material A with assay balance, and it is 35g to weigh raw material B, and raw material A and B are pressed 1:35 mass ratio fills in mortar
Divide mixing, then uniformly mixed mixture is fitted into the ball grinder of 100ml, agate abrading-ball accounts for 20%, middle ball by big ball and accounts for
50%, bead accounts for 30% mass ratio and is fitted into ball grinder, with 230 revs/min of rotating speed, ball milling 50 minutes in the direction of the clock,
Then ball milling 50 minutes counterclockwise.After waiting for ball milling, the mixture in ball grinder is placed in ceramic Noah's ark, and is put
Enter in quartz tube furnace, then open vacuum pumping 30 minutes, then nitrogen is passed through in tube furnace, is passed through 6 hours by room temperature
Temperature programming is then passed through temperature programming in 4 hours and carries out roasting 2 hours to 900 DEG C to 600 DEG C, to be cooled to be collected to room temperature
To sample, it is denoted as catalyst S3, nitrogen content is 25 ~ 30wt%, and grain size is 1 ~ 3 μm.
Comparative example 1：
3 ~ 5g starch and 1 ~ 2g glucose are dissolved in 60mL deionized waters, solution is moved to volume by magnetic agitation 30 minutes
In liner for the stainless steel cauldron of 100mL, finally it is placed in 180 DEG C of constant temperature oven and reacts 6 hours.After reaction,
After centrifuging and washing 3 times repeatedly with absolute ethyl alcohol, collects sample and be placed in drying 24 hours in 80 DEG C of vacuum drying chamber, obtain
Catalyst D1.
Comparative example 2：
3 ~ 5g glucose is dissolved in 60mL deionized waters, after stirring evenly, solution is moved into the stainless steel that volume is 50mL
In the liner of reaction kettle, it is finally placed in constant temperature 8h in 190 DEG C of electric heating constant-temperature blowing drying box.After reaction, solution is in mixed
Turbid black or rufous, slightly there is the smell of burning.After reaction, after centrifuging and washing 3 times repeatedly with absolute ethyl alcohol, sample is collected
Drying 24 hours in 80 DEG C of vacuum drying chamber are placed in, catalyst D2 is obtained.
Evaluate example
Table 1 is the branch structure parameter without metal sulphide selective oxidation catalyst of present example 1~3.It can from table 1
Know, the specific surface of three samples is in 700~1100 ranges, and average pore size is in 3nm or so.The sample obtained when 800 DEG C of roastings
Specific surface area is maximum, and pore volume is maximum.
The branch structure parameter of the characterization of 1 embodiment of table, 1 ~ 3 catalyst
As depicted in figs. 1 and 2, it is the N of 1~3 non-metal catalyst of present example2Physics Adsorption and desorption isotherms and aperture
Distribution map.It is seen that three prepared sample Adsorption and desorption isotherms are IV type curves, illustrate in these samples
There are meso-hole structures.Low-pressure area high starting point, nitrogen adsorption capacity is big, illustrates that there are a certain amount of micropores in sample.In addition, three samples
H is presented in the curve of product2Type hysteresis loop illustrates wherein there is body-centred cubic meso-hole structure.It can be seen that from graph of pore diameter distribution,
There is mesoporous (5-8nm) and micropore (1.8nm or so) in sample.
Fig. 3 is embodiment 1 ~ 3 and comparative example 1 ~ 2, the H in the catalyst performance evaluation2S conversion ratios vary with temperature
Curve graph.As can be seen from the figure the H of the catalyst prepared by the present invention2S conversion ratios are intended to than common carbon material catalyst
At 120 DEG C, the conversion ratio of hydrogen sulfide nearly reaches 100%, and with the liter of temperature for height, wherein most preferred embodiment S2 catalyst
Height, conversion ratio do not occur apparent decline.
Fig. 4 is embodiment 1 ~ 3 and comparative example 1 ~ 2, and the catalyst in the catalyst performance evaluation is to sulphur simple substance selectivity
The curve graph varied with temperature, as can be seen from the figure the present invention prepared by catalyst the selectivity of sulphur simple substance is intended to obviously
Better than common C catalyst, the selectivity of three samples prepared by embodiment is held in 90% or more.
Fig. 5 is embodiment 1 ~ 3 and comparative example 1 ~ 2, the song that the Recovery ratio in the catalyst performance evaluation varies with temperature
Line chart, as can be seen from the figure the Recovery ratio of prepared catalyst of the present invention be better than common C catalyst.
Fig. 6 is embodiment 1 ~ 3 and comparative example 1 ~ 2, H in the catalyst stability2The conversion ratio of S becomes at any time
The curve graph of change, as can be seen from the figure the stable in catalytic performance of the non-metal catalyst prepared by the present invention is significantly excellent
In the stability of comparative example catalyst, after reaction carries out 25 hours, catalyst is not in the catalyst described in embodiment 1 ~ 3
Apparent deactivation phenomenom, this also shows that the superior H of prepared catalyst of the present invention2S selective catalytic oxidation performances.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (8)
1. a kind of no metal H2The preparation method of S selective oxidation catalysts, it is characterised in that：The H2S is selectively urged
Changing oxidation catalyst is mixed by simple mechanical lapping, then in inert atmosphere using carbohydrate as main raw material(s)
Carbonization obtains porous carbon materials catalyst in tube furnace.
2. preparation method as described in claim 1, it is characterised in that：The carbonization is carbonisation at a slow speed, is 700 in temperature
~ 900 DEG C of inert atmosphere high temperature is carbonized to obtain porous carbon materials catalyst.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：The mechanical lapping of raw material is to first pass through grinding for mortar
Mill, is sized to certain mesh number, is then uniformly mixed in the ball mill.
4. preparation method as claimed in claim 3, which is characterized in that comprise the following specific steps that：
（1）It weighs at least one of glucose, chitosan and sucrose and is used as carbon source, place it in mortar and fully finely ground,
The raw material A of 120 ~ 140 mesh is obtained after standard screen sieves；
（2）It weighs at least one of dicyandiamide, melamine and urea and is used as nitrogen source, place it in mortar and fully grind
Carefully, the raw material B of 120 ~ 140 mesh is obtained after standard screen sieves；
（3）Obtained raw material A, B are mixed according to a certain percentage, are fitted into the ball grinder of 100ml after mixing, agate abrading-ball
20%, middle ball is accounted for by big ball account for 50%, bead and account for 30% mass ratio and be fitted into ball grinder, with 180 ~ 240 revs/min of rotating speed, by suitable
Clockwise ball milling 30 ~ 60 minutes, then ball milling 30 ~ 60 minutes counterclockwise again；
（4）After waiting for ball milling, the mixture in ball grinder is placed in ceramic Noah's ark, and is put into quartz tube furnace, then
It opens vacuum pumping 30 ~ 60 minutes, then nitrogen is passed through in tube furnace, and by room temperature by temperature programming in 4 ~ 6 hours to 400
It ~ 600 DEG C, is then passed through temperature programming in 1 ~ 4 hour and carries out high temperature cabonization 1 ~ 4 hour to 700 ~ 900 DEG C, it is to be cooled to be collected to room temperature
Obtain sample.
5. preparation method as claimed in claim 4, which is characterized in that the preparation process（3）In, the matter of raw material A and raw material B
Amount is than being 0.02 ~ 0.1：1.
6. preparation method as claimed in claim 5 is obtained without metal H2S selective oxidation catalysts, which is characterized in that
The grain size of the catalyst is 500nm ~ 5 μm, and nitrogen content is 20 ~ 50wt%.
7. as claimed in claim 6 without metal H2The application of S selective oxidation catalysts, it is characterised in that：Described urges
Agent is used for H2The selective catalytic oxidation of S reacts.
8. the use as claimed in claim 7, it is characterised in that：Catalyst is used for selective catalytic oxidation H2S be sulphur simple substance and
In the catalysis reaction of water, reaction temperature is 100 DEG C ~ 200 DEG C, and unstripped gas is 5000 ppm H2S, 2500 ppm O2, N2It is flat
Three component gas of weighing apparatus gas, feed gas flow rates V are 20 mLmin-1, tube inner diameter is 5 mm.
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Application publication date: 20181113 |