CN109107374A - A kind of metal composite oxide desulfurizing agent and preparation method thereof - Google Patents
A kind of metal composite oxide desulfurizing agent and preparation method thereof Download PDFInfo
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- CN109107374A CN109107374A CN201811138794.2A CN201811138794A CN109107374A CN 109107374 A CN109107374 A CN 109107374A CN 201811138794 A CN201811138794 A CN 201811138794A CN 109107374 A CN109107374 A CN 109107374A
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- 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
- B01D53/81—Solid phase processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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Abstract
The invention discloses a kind of metal composite oxide desulfurizing agents and preparation method thereof, belong to environmental protection and chemical technology field field, desulfurizing agent of the invention is made after precipitating active component and carrier by precipitating reagent through kneading method, active component is divided into main active component and third active component, and main active component is Cu2+, third active component is Mn2+, Zn2+,Ca2+,Fe3+Carrier is Al3+,Precipitating reagent is organic amine.The present invention utilizes the mixing of multicomponent metal, utilization rate is performed into maximum, active component is well dispersed in the carrier duct with certain specific surface and pore structure using the method for co-precipitation, so that active component and sulfide sufficiently combine, greatly improve utilization rate, and using the doping between different metal oxides, desulfurization precision is improved.
Description
Technical field
The invention belongs to environmental protection and chemical technology field more particularly to a kind of metal composite oxide desulfurizing agent and its preparations
Method.
Background technique
China is that the country that rich coal oil starvation lacks gas mentions under the higher and higher situation of energy security and environmental protection requirement
High coal utilization efficiency and strictly controlled environment pollution are the important subjects faced at present.Therefore, coal liquid is developed
Changing product and clean fuel using technology is to solve the inevitable choice of China's oil energy shortage, and ICL for Indirect Coal Liquefaction technology is exactly will
The gasification gas that coal is generated by gasification furnace is converted to synthesis gas, and is basic raw material with synthesis gas, is converted using Fischer-Tropsch Synthesis
For hydrocarbon compound, and liquid fuel and various chemicals are produced by rectifying.Sulfurous gas present in synthesis gas is (main
Have H2S, COS) subsequent synthetic catalyst poisoning, the decline of instrument and equipment burn into product quality and ecological environment destruction can be caused, most
Coal gas green is interfered eventually, cleaning, is efficiently develop and useedd.Therefore, the desulfurizing and purifying of synthesis gas is very necessary.
Relative to H2S, COS property are relatively stable, are difficult to be removed with conventional method, and COS is frequently with reduction method, hydrolysis at present
Method, absorption process and absorption method, reduction method mainly utilize H2It restores COS and generates H2A kind of method of S, the catalyst generally used
Carrier is γ-Al2O3, the metal oxides such as load C o, Mn, but hydrogenation reaction by-product is more, and reaction process need to additionally add hydrogen
It is relatively complicated, higher cost.Hydrolyze method mainly uses COS and H2O reaction generates CO2And H2The process of S, Hydrolyze method high conversion rate,
Low energy consumption, but Hydrolyze method is difficult that COS one-step removal is clean, and reaction rate is lower.Absorption process mainly uses ethanol amine, MDEA etc.
Organic amine compound absorbs COS, and this method can remove completely COS, but since organic amine is volatile, easily become in gas source
A kind of new impurity prevents absorption process from being widely applied.Photodissociation method is to be irradiated to resolve into it to COS using ultraviolet light
A kind of method of other substances, but do not industrialized even since its controllability is not high.
Patent CN101031350A provides a kind of from containing H2The method that COS is removed in the synthesis air-flow of S and COS, should
Method first converts H for COS by COS hydrolytic reagent for synthesis gas in hydrolysis area2S, after by the synthesis gas and solid after conversion
Adsorbent contact is to remove H2S, to obtain synthesis gas after purification of the COS content lower than 5ppbv.
Patent CN104667926A provides a kind of preparation method of low temperature hydrolytic catalyst of carbonyl sulfur, and this method will be ferrous
Salt is uniformly mixed to form solution with modifying agent, and precipitating reagent is added dropwise under stirring condition into solution, passes through after adjusting pH to a certain range
Ageing is crossed, forming agent is added in centrifugation, washing, and binder kneading obtains product after molding drying.COS is first under hydrolytic reagent effect
It is reacted with water and generates H2Then S falls H by desulfurizing agent removing again2S。
Patent CN101280227B provides a kind of preparation method of high temperature gas desulfurizer, and this method is by red mud and nothing
Machine binder is ground up, sieved respectively after drying at a certain temperature, then with a certain amount of magnesia, titanium dioxide, lanthana, five
V 2 O, lithia and organic binder after being thoroughly mixed, then plus suitable quantity of water it is kneaded and formed, it is dry, it is cooling after roasting
Desulfurizing agent is made.Advantage: raw material is cheap and easy to get, simple process, mechanicalness not dusting by force.Disadvantage: COS tail gas content is higher, takes off
Except being not thorough.
Patent CN101455966B discloses a kind of preparation method of methanol synthesis gas desulfurizer, and this method is by copper, zinc,
Chromium, the soluble-salt of aluminium is dissolved in water and is occasionally made into mixed solution, then is co-precipitated with acid carbonate as precipitating reagent, after to precipitating
Object is filtered, and is washed, dry, and pore creating material is added after being broken into particle, obtains having certain specific surface and hole after tabletting roasting
The desulfurizing agent of diameter.
Patent CN101462063B is provided a kind of can remove carbonyl sulfur, the catalytic oxidation desulfurization of mercaptan and hydrogen sulfide simultaneously
Soluble in water be made of a certain amount of metal oxide or metal salt is impregnated in liquid by the preparation method of agent, this method, at
The coaly activated carbon of reason impregnated after by being dried to obtain former granularity desulfurizing agent.Advantage: can remove carbonyl sulfur simultaneously, mercaptan and
Hydrogen sulfide, it is not necessary to which several workshop sections are set, and simplification of flowsheet saves equipment investment expense.Disadvantage: it due to catalytic mechanism, needs to mend
A certain amount of oxygen is filled, brings difficulty to operation, and is due to oxygen content unstable, experimental repeatability is poor, and effect is unstable.
Patent CN104415652B discloses a kind of method for removing hydrogen sulfide and carbonyl sulfur in gas, and this method, which uses, to be contained
Hydrogen sulfide in gas is transformed into sulphur hydrogen radical ion in absorption process by the Complexing Iron absorbing liquid of heterocyclic amine, in urging for heterocyclic amine
Change acts on lower carbonyl sulfur and is transformed into hydrogen sulfide and carbon dioxide, and the rich solution for absorbing hydrogen sulfide is regenerated by air oxidation by sulphur hydrogen
It is recycled after root solution regeneration elemental sulfur.The inventive method is simple, and removing amount is big, is recycled to harmful substance, but
It is that 80% is only reached for the removal efficiency of carbonyl sulfur.
The deficiency that above desulfurizing agent and preparation method thereof is primarily present:
(1) there are a certain amount of vapor and some organic solvents in existing liquid desulfuration method requirement unstripped gas, can make
Catalyst process for using is complex, increased costs.
(2) existing desulfurizing agent technology of preparing is by will obtain after active ingredient precipitation and drying with auxiliary agent mixed-forming
Desulfurizing agent, this method have a defect that auxiliary agent and active group by mechanical mixture, and part material is still located in mixed process
Disperse in graininess not complete enough；Therefore raw material mixing is not uniform enough in mixed process, and active component dispersion degree is not high, finally
Influence desulfurization effect
(3) there are also catalyst is made using infusion process in existing desulfurizing agent technology of preparing, this method is had a defect that
Active component can not sufficiently achieve the inner surface of carrier in dipping process, and the higher active component of concentration can be poly- in outer surface
Collection influences the diffusion of active component inner surface, and the solution where active component can not will cause big completely by carrier absorption
The material waste of amount.
(4) oxide is made using the method for co-precipitation in copper and aluminium by existing copper base desulfurizer, in the effect of removing hydrogen sulfide
More obvious on fruit, removing precision can reach 5ppb, but effect is not obvious in terms of removing COS.
Summary of the invention
The present invention provides a kind of metal composite oxide desulfurizing agent and preparation method thereof to solve Problems Existing, and use is coprecipitated
Active component is well dispersed in the carrier duct with certain specific surface and pore structure by the method in shallow lake so that active component and
Sulfide sufficiently combines, and greatly improves utilization rate, can remove H simultaneously2S and COS, and utilize mixing between different metal oxides
It is miscellaneous, desulfurization precision solid desulfurating agent small toxicity itself is improved, property is stablized, and it is not volatile, it is nonflammable, life life can be effectively ensured
Safety.
The technical solution adopted by the present invention to solve the technical problems are as follows:
On the one hand, the present invention provides a kind of metal composite oxide desulfurizing agents, in which: the desulfurizing agent is by active component
It is made after being precipitated with carrier by precipitating reagent through mediating method；
The active component is divided into main active component and third active component, and the main active component is Cu2+, the third
Active component is Mn2+, Zn2+, Ca2+, Fe3+；
The carrier is Al3+；
The precipitating reagent is organic amine.
It is further preferred that the Cu2+Active component source is one of copper chloride, copper nitrate, copper sulphate, copper acetate
Or it is several, mantoquita mass concentration is 5%~25%.
It is further preferred that the third active component Mn2+, Zn2+, Ca2+, Fe3+For Zn, Mn, Ca, the solubility gold of Fe
Belong to salt, including metal chloride or sulfate.The preferred Mn of third active component2+.The content of the third active component
Relative to 30%~70% that main active component ratio is mass fraction.
It is further preferred that the carrier Al3+Source is aluminum soluble salt, mainly includes aluminium chloride, aluminum nitrate, aluminum sulfate
One or more of mixture, aluminium salt mass concentration be 3%~20%.
It is further preferred that the organic amine precipitation agent be hydramine (MEA, DEA, TEA, MDEA), enamine (DETA, TETA,
TEPA) any one or a few the mixture in organic amine, preferably DEA, MEA, DETA, TETA, concentration are 5~30%.Machine
Amine wiring solution-forming point, which is added dropwise to, has fully ensured that the metal salts such as aluminium salt and mantoquita react the dispersion for generating hydroxide with organic amine
Property, so that active component is evenly distributed in the inside and surface of carrier, to make the benefit of active component oxide in final product
It is maximized with rate.And organic amine plays multiple action in the reaction, is both precipitating reagent and dispersing agent or template, this
For prepare flourishing cellular structure, higher specific surface, relatively narrow pore-size distribution, high degree of dispersion activated centre desulfurizing agent
Basis is provided.
On the other hand, the present invention also provides the preparation methods of any metal composite oxide desulfurizing agent, specific to walk
Suddenly are as follows:
(1) active component and bearer configuration are placed in container at mixed solution, stir simultaneously heating water bath, it is molten to mixing
Precipitating reagent is added dropwise in liquid, complex hydroxide precipitating is obtained using the method for co-precipitation；
(2) gained complex hydroxide is deposited under step (1) reaction temperature after ageing to stable state, duct is added
Auxiliary agent and dispersing agent, mechanical stirring after ultrasonic water bath heating, obtain mixed sediment；
(3) mixed sediment will be obtained and is ground into powder after centrifuge washing, drying, roasting, binder is added, mixing is equal
It is kneaded and formed after even to obtain molding；
(4) it will dry, roast after molding, metal composite oxide desulfurizing agent is made.
It is further preferred that water bath heating temperature described in the step (1) is 20~100 DEG C, mechanical stirring speed is
200~600r/min, the molal weight of metal salt and precipitating reagent ratio is 1:1.2~2 in mixed solution, and rate of addition is 1~3
Drop/S, time for adding are 1~2h, are added dropwise and continue 0.5~1h of stirring, pH control range 8-10.Step (1) co-precipitation
Active component is well dispersed in the carrier duct with certain specific surface and pore structure by method, so that active component and vulcanization
Object sufficiently combines, and greatly improves utilization rate, and using the doping between different metal oxides, improves desulfurization precision.
It is further preferred that the molecular sieve selects one of 4X, 5X or 13X, the dispersing agent selects polyethylene glycol
200 or polyethylene glycol 400.
It is further preferred that digestion time is 18~36h in the step (2), water bath sonicator heating temperature is 20~100
DEG C, mechanical stirring speed is 200~600r/min.
It is further preferred that centrifugal washing times described in the step (3) are to wash three times, alcohol is washed three times, when washing
The range 7-10 of pH is controlled, drying temperature is 80~120 DEG C, is roasted through 400~700 DEG C of Muffle furnace, diameter of particle is less than 200
Mesh.
It is further preferred that the humidity of the kneaded and formed condition 30~60%, it is kneaded and formed after using 80~120
It dries at DEG C, then is roasted through 400~700 DEG C of Muffle furnace.
It is further preferred that the binder is one or more of bentonite, kaolin, additional amount accounts for sample quality
1~30%.
Molding composite oxide desulfurizing agent prepared by the present invention removes H2S precision can reach 10ppb hereinafter, COS is same
Reach 10ppb hereinafter, desulfurizing agent specific surface is in 30~60m2Between/g, average pore size is between 7~13nm, and 50% or more
All be it is mesoporous, contain a small amount of macropore in part and minimal amount of micropore.
In conclusion compared with prior art, the invention has the benefit that
(1) metal composite oxide desulfurizing agent is the development trend of the following desulfurizing agent, in the active component of certain content,
Using the mixing of multicomponent metal, utilization rate is performed into maximum, is well dispersed in active component using the method for co-precipitation
In carrier duct with certain specific surface and pore structure, so that active component and sulfide sufficiently combine, utilization is greatly improved
Rate, and using the doping between different metal oxides, improve desulfurization precision.
(2) present invention prepares metal composite oxide in removing H2The COS more stable for property removing on the basis of S
Effect is also more obvious, is different from traditional " sandwich " formula removal methods bring troublesome operation process, which can one
Step removing H2S and COS, the key solved the problems, such as are during the preparation process, using organic amine as precipitating reagent, since organic amine has
There is larger solubility, inventory can be increased within the unit time, improves reaction efficiency；And organic amine delays in the solution as weak base
Slow ionization makes to precipitate orderly progress, and reaction is more slow and reaction condition is more mild, in this way can be by active component and carrier point
It is scattered to molecule rank, preferably guarantees the dispersion of active component, so that active component utilization rate, which reaches, does bigization.To guarantee de-
Except H2COS can be made to come into full contact with desulfurizing agent on the basis of S, improve COS and remove precision.
(3) present invention makees precipitating reagent using organic amine, and organic amine wiring solution-forming point, which is added dropwise to, has fully ensured that aluminium salt and copper
The metal salts such as salt reacted with organic amine generate hydroxide dispersibility, make active component be evenly distributed in carrier inside and
Surface, so that the utilization rate of active component oxide in final product be made to maximize.And organic amine play in the reaction it is multiple
Effect, is both precipitating reagent and dispersing agent or template, this be prepare flourishing cellular structure, higher specific surface,
The desulfurizing agent in the activated centre of relatively narrow pore-size distribution, high degree of dispersion provides basis.
(4) desulfurizing agent prepared being capable of one-step removal H2S and COS, it is not necessary to water therein is removed as wet desulphurization
Vapour, and eliminate coal gas heat exchange and save energy consumption, and degree of purification is high, reduces process and equipment investment, operating cost is reduced, and
Removing precision greatly promotes.
(5) method that the present invention uses ultrasonic water bath, by gained precipitating after ageing with pore creating material and dispersing agent in certain temperature
Degree is lower by water bath with thermostatic control ultrasound, so that obtained desulfurizing agent presoma has pore structure abundant and good dispersion performance.
And solid desulfurating agent itself small toxicity that the preparation method of metal composite oxide desulfurizing agent provided by the invention is produced, property
Stablize, it is not volatile, it is nonflammable, people's life security can be effectively ensured.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of metal composite oxide desulfurizing agent provided in an embodiment of the present invention；
Fig. 2 is that the BET isothermal of desulfurizing agent provided in an embodiment of the present invention inhales (de-) attached curve graph；
Fig. 3 is desulfurizing agent BJH method pore size distribution curve figure provided in an embodiment of the present invention.
Specific embodiment
The application is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is used only for explaining related invention, rather than the restriction to the invention.It also should be noted that in order to
Convenient for description, part relevant to invention is illustrated only in attached drawing.
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
Embodiment 1
1 weighs the AlCl of 0.08mol3.6H2Cu (the NO of O, 0.04mol3)2, the MnCl of 0.04mol2It is configured to Cu (NO3)2
The total solution A that mass fraction is 10%, is poured into 500mL three-necked flask, spare.
2. weigh 0.13mol diethylenetriamine (EDTA) again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of the total solution A of equal salt is placed in 70 DEG C of water-bath, opens stirring
Lye B is added dropwise into total solution A with constant pressure funnel in 400r/min, and rate of addition is 1 drop/S, time for adding control
In 1.5h, it is added dropwise and continues to stir 0.5h, control pH=10；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
18h。
5. completion to be aged, rear that the 13X molecular sieve relative to precipitating quality 5% is added as duct auxiliary agent, relative to heavy
The polyethylene glycol 200 of deposit amount 5% is as dispersing agent, and ultrasound 1h, first uses ethyl alcohol for gained sediment under the conditions of 70 DEG C of water-bath
Continuous washing uses deionized water centrifuge washing three times again three times, keeps pH=7, is centrifugally separating to obtain mixed sediment C.
6. the mixed sediment C after washing is placed in 80 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. composite hydrous oxide D is passed through 400 DEG C of roasting 2h of Muffle furnace, after be ground into the powder of 150 mesh of partial size, acquisition
Desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 0.2g is added, after mixing under 30% damp condition
It is kneaded and formed, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SA。
Embodiment 2
1. weighing the AlCl of 0.08mol3.6H2Cu (the NO of O, 0.04mol3)2, the ZnCl of 0.04mol2It is configured to Cu
(NO3)2The total solution A that mass fraction is 10%, is poured into 500mL three-necked flask, spare.
2. weigh 0.13molDEA again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of the total solution A of equal salt is placed in 20 DEG C of water-bath, opens stirring
Lye B is added dropwise into total solution A with constant pressure funnel in 600r/min, and rate of addition is 3 drops/S, time for adding control
In 1h, it is added dropwise and continues to stir 1h, control pH=8；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
36h。
5. completion to be aged, rear that the 4X molecular sieve relative to precipitating quality 5% is added as duct auxiliary agent, relative to precipitating
The polyethylene glycol 200 of quality 5% is as dispersing agent, and ultrasound 1h, gained sediment is first connected with ethyl alcohol under the conditions of 70 DEG C of water-bath
Continuous washing uses deionized water centrifuge washing three times again three times, keeps pH=10, is centrifugally separating to obtain mixed sediment C.
6. the mixed sediment C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. composite hydrous oxide D is passed through 600 DEG C of roasting 2h of Muffle furnace, after be ground into the powder of 150 mesh of partial size, acquisition
Desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the Kaolin binder of 2g is added, is pinched under 30% damp condition after mixing
Synthesis type, after by drying at 80 DEG C, then through 700 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SB。
Embodiment 3
1. weighing the AlCl of 0.08mol3.6H2Cu (the NO of O, 0.04mol3)2, the FeCl of 0.04mol3It is configured to Cu
(NO3)2The total solution A that mass fraction is 10%, is poured into 500mL three-necked flask, spare.
2. weigh 0.146mol diethylenetriamine (EDTA) again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of the total solution A of equal salt is placed in 70 DEG C of water-bath, opens stirring
Lye B is added dropwise into total solution A with constant pressure funnel in 200r/min, and rate of addition is 3 drops/S, time for adding control
In 1.5h, it is added dropwise and continues to stir 0.5h, control pH=9；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
36h。
5. completion to be aged, rear that the 13X molecular sieve relative to precipitating quality 5% is added as duct auxiliary agent, relative to heavy
The polyethylene glycol of deposit amount 5% is as dispersing agent, and ultrasound 1h, gained sediment is first connected with ethyl alcohol under the conditions of 100 DEG C of water-bath
Continuous washing uses deionized water centrifuge washing three times again three times, keeps pH=8, is centrifugally separating to obtain mixed sediment C.
6. the mixed sediment C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. composite hydrous oxide D is passed through 600 DEG C of roasting 2h of Muffle furnace, after be ground into the powder of 150 mesh of partial size, acquisition
Desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 6g is added, is pinched under 40% damp condition after mixing
Synthesis type, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent Sc.
Embodiment 4
1. weighing the AlCl of 0.08mol3.6H2Cu (the NO of O, 0.04mol3)2, the CaCl of 0.04mol2It is configured to Cu
(NO3)2The total solution A that mass fraction is 10%, is poured into 500mL three-necked flask, spare.
2. weigh 0.13mol diethylenetriamine (EDTA) again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of the total solution A of equal salt is placed in 70 DEG C of water-bath, opens stirring
Lye B is added dropwise into total solution A with constant pressure funnel in 400r/min, and rate of addition is 2 drops/S, time for adding control
In 1.5h, pH=8 is controlled；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
20h。
5. completion to be aged, rear that the 13X molecular sieve relative to precipitating quality 5% is added as duct auxiliary agent, relative to heavy
The polyethylene glycol of deposit amount 5% is as dispersing agent, and ultrasound 1h, first continuous with ethyl alcohol by gained sediment under the conditions of 70 DEG C of water-bath
Washing uses deionized water centrifuge washing three times again three times, keeps pH=7, is centrifugally separating to obtain mixed sediment C.
6. the mixed sediment C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. composite hydrous oxide D is passed through 600 DEG C of roasting 2h of Muffle furnace, after be ground into the powder of 100 mesh of partial size, acquisition
Desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 2g is added, is pinched under 40% damp condition after mixing
Synthesis type, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SD。
Below with reference to activity rating example, the invention will be further described.
Activity rating example:
Desulfurization performance test is carried out to the composite oxide desulfurizing agent that specific example 1~4 above-mentioned in the present invention is prepared.
In this test, evaluation unstripped gas (H2S, COS/N2) import H2S content is controlled in 6000-8000ppm or so, COS
Content control is controlled in 30-40ppm or so, air speed in 400-1000h-1, 100 DEG C of desulfurization environment temperature.By desulfurizing agent obtained
Sieving is smashed, the little particle of 16-40 mesh is obtained, is fitted into homemade fixed-bed micro-reactor according to certain regular uniform, upper layer
It is respectively charged into quartz sand with lower layer to fix, control catalyst bed ratio of height to diameter is 5~8.
For into and out of H in implication in evaluation procedure2The GC- of S and COS content Hui Fen Instrument Ltd. of BeiJing ZhongKe
The detection of 2060 analysis of sulfur content chromatographies.Reactor tail gas gas micro-analysis dedicated chromatography TY-2000 detection outlet hydrogen sulfide
Content, detection are limited to 5ppb.By to inlet and outlet hydrogen sulfide content CInto、COut, the real-time air speed S of unstripped gasy, it is sulphur soak time t, de-
The measurement of the parameters such as sulphur agent bed heap density d, carrys out the desulfurization performance of overall merit composite oxide desulfurizing agent.Work as reactor tail gas
In just start to detect the H of 10ppb2When S, default desulfurizing agent has been inactivated, and Sulfur capacity at this time is referred to as working sulfur capacity, and Sulfur capacity is big
It is small to be calculated by following formula:
Wherein, S --- working sulfur capacity；
ms--- the quality of Catalyst Adsorption sulfide in experimentation；
The quality of M --- loading catalyst；
CInto、COut--- experimental provision imports and exports sulfide content g/m3；
Sy--- experimentation gas space velocity, h-1；
T --- the time required to experiment penetrates, h；
D --- catalyst bulk density g/ml.
Under the test conditions above, composite oxide desulfurizing agent S example 1-4 being preparedA-DIt is right under evaluation rubric
Its desulfurization performance is evaluated, and test result is as shown in table 1:
1 composite oxide desulfurizing agent S of tableA-DEvaluation result
Held it can be seen from 1 test result of table using the composite oxide desulfurizing agent highest penetration of the preparation in the present invention
Amount can achieve 13.44, and desulfurization precision can reach H2S tail gas content is no more than 10ppb, and COS content is no more than 10ppb, even
Reach 0ppb.
For the internal pore structure situation for really reflecting desulfurizing agent, JW-BK112 type N2 adsorption specific surface and pore analysis are used
Instrument tests the pore structure of obtained desulfurizing agent, and test result is as shown in table 2:
2 example of table, 1~4 composite oxide desulfurizing agent SA-DPore structure analysis result
Using the preparation method preparation of the composite oxide desulfurizing agent in the present invention it can be seen from 2 test result of table
Desulfurizing agent specific surface is in 30~60m2Between/g, average pore size between 7~13nm, 50% or more be all it is mesoporous, contain
The a small amount of macropore in part and minimal amount of micropore.Meanwhile (de-) attached curve and attached drawing 3 are inhaled in conjunction with the isothermal of 2 desulfurizing agent of attached drawing
Desulfurizing agent pore size distribution curve can from which further follow that prepared composite oxide desulfurizing agent is 12.01nm in average pore size
When Sulfur capacity highest, this is because the characterization of pore size is spread condition of the hydrogen sulfide gas inside particle and for carbonyl sulfur
Molecule has certain suction-operated, can guarantee that shape is the gas cure hydrogen molecule of V-type when aperture is larger in a certain range
Enter inside catalyst pores with linear molecule carbonyl sulfur, and occurring on surface can be free after vulcanization reaction generates sulfide
Into catalytic inner, sufficiently reacted with desulfurizer active component.
The desulfurizing agent prepared it can be seen from 1 test result of table with currently available technology is being added to third active group
Divide Mn, Zn, Ca, different degrees of influence is all produced to the Sulfur capacity and precision of desulfurization after Fe.It is added to the catalyst of Mn component
Sulfur capacity can reach 12.13%, and obvious for the removal effect of COS, and tail gas COS content drops to 0ppb；It is added to Zn component
Catalyst Sulfur capacity is increased to 13.44%, tail gas COS content drops to 10ppb from 30ppb；It is added to the catalyst of Fe component
Sulfur capacity only has 10.12%, COS content that can drop to 9ppb, and Sulfur capacity is reduced to 8.23%, COS by the catalyst for being added to Ca component
Content drops to 9ppb.
Except for the technical features described in the specification, remaining technical characteristic is the known technology of those skilled in the art, is prominent
Innovative characteristics of the invention out, details are not described herein for remaining technical characteristic.To sum up, the foregoing is merely a prefered embodiment of the invention and
, it should not be limited the scope of the invention with this, i.e., all claims under this invention and present specification are made
Simple equivalent changes and modifications, should all still belong to the range that the invention patent covers.
Claims (10)
1. a kind of metal composite oxide desulfurizing agent, which is characterized in that active component and carrier are passed through precipitating by the desulfurizing agent
Method is mediated after agent precipitating to be made；
The active component is divided into main active component and third active component, and the main active component is Cu2+, the third activity
Group is divided into Mn2+, Zn2+, Ca2+, Fe3+；
The carrier is Al3+；
The precipitating reagent is organic amine.
2. a kind of metal composite oxide desulfurizing agent according to claim 1, which is characterized in that the Cu2+Active component
Source is mantoquita: one or more of copper chloride, copper nitrate, copper sulphate, copper acetate, and mantoquita mass concentration is 5%~25%.
3. a kind of metal composite oxide desulfurizing agent according to claim 1, which is characterized in that the third active component
Mn2+, Zn2+, Ca2+, Fe3+Source is Zn, Mn, Ca, the soluble metallic salt of Fe.
4. a kind of multiple metal oxide desulfurizer according to claim 1, which is characterized in that the carrier Al3+Source is
Aluminum soluble salt: the mixture of one or more of aluminium chloride, aluminum nitrate, aluminum sulfate, aluminium salt mass concentration be 3%~
20%.
5. a kind of metal composite oxide desulfurizing agent according to claim 1, which is characterized in that the precipitating reagent organic amine
Source be hydramine, any one or a few the mixture in enamine, the concentration of the organic amine is 5~30%.
6. the preparation method of -5 any metal composite oxide desulfurizing agents appointed according to claim 1, which is characterized in that tool
Body step are as follows:
(1) active component and bearer configuration are placed in container at mixed solution, mechanical stirring and heating water bath are molten to mixing
Precipitating reagent is added dropwise in liquid, obtains complex hydroxide precipitating；
(2) after gained complex hydroxide being deposited under step (1) reaction temperature ageing to stable state, be added molecular sieve and
Dispersing agent, mechanical stirring after ultrasonic water bath heating, obtains mixed sediment；
(3) mixed sediment will be obtained and is ground into powder after centrifuge washing, drying, roasting, binder is added, after mixing
It is kneaded and formed to obtain molding；
(4) it will dry, roast after molding, metal composite oxide desulfurizing agent is made.
7. the preparation method of metal composite oxide desulfurizing agent according to claim 6, which is characterized in that in step (1)
The water bath heating temperature is 20~100 DEG C, and mechanical stirring speed is 200~600r/min, metal salt and heavy in mixed solution
The molal weight ratio of shallow lake agent is 1:1.2~2, and rate of addition is 1~3 drop/S, and time for adding is 1~2h, is added dropwise and continues to stir
0.5~1h is mixed, the range 8-10 of pH is controlled.
8. the preparation method of metal composite oxide desulfurizing agent according to claim 6, which is characterized in that the molecular sieve
One of 4X, 5X or 13X are selected, the dispersing agent selects polyethylene glycol 200 or polyethylene glycol 400.
9. the preparation method of metal composite oxide desulfurizing agent according to claim 6, which is characterized in that in step (2)
Digestion time is 18~36h, and water bath sonicator heating temperature is 20~100 DEG C, and mechanical stirring speed is 200~600r/min.
10. the preparation method of metal composite oxide desulfurizing agent according to claim 6, which is characterized in that in step (3)
The centrifuge washing after continuously washing three times continuous alcohol three times wash, when washing, controls the range 7-10 of pH, drying temperature is 80~
It 120 DEG C, roasts through 400~700 DEG C of Muffle furnace, diameter of particle is less than 200 mesh.
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| CN112552969A (en) * | 2020-11-20 | 2021-03-26 | 沈阳三聚凯特催化剂有限公司 | Desulfurizing agent and preparation method and application thereof |
| CN112760123A (en) * | 2020-12-19 | 2021-05-07 | 西安元创化工科技股份有限公司 | Heavy naphtha desulfurizer and preparation method thereof |
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