CN106621797B - A kind of preparation method of high efficiency composition oxide desulfurizing agent - Google Patents
A kind of preparation method of high efficiency composition oxide desulfurizing agent Download PDFInfo
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- CN106621797B CN106621797B CN201611127642.3A CN201611127642A CN106621797B CN 106621797 B CN106621797 B CN 106621797B CN 201611127642 A CN201611127642 A CN 201611127642A CN 106621797 B CN106621797 B CN 106621797B
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Abstract
The present invention provides a kind of preparation methods of high efficiency composition oxide desulfurizing agent.This method selects Fe2+Source of iron as main active component, the soluble-salt of the metals such as a certain proportion of Zn, Mn, Cu, Co is added as co-catalyst, using hydramine as precipitating reagent, complex hydroxide precipitating is obtained using the method for co-precipitation, under certain reaction condition, with alkanolamine solution precipitate A l3+Obtain Aluminum sol, the complex hydroxide system then obtained with coprecipitation mixes according to a certain percentage, it is washed, dry, aoxidize, pulverize after to be added a certain amount of binder kneaded and formed, that is, obtain composite oxide desulfurizing agent.The present invention has creatively used alcamines organic base as the precipitating reagent for preparing complex hydroxide, and desulfurizing agent obtained has higher working sulfur capacity in an oxygen-free atmosphere；Simultaneously the invention proposes method of the Aluminum sol as the duct carrier of composite oxide desulfurizing agent is prepared using hydramine, the pore structure of composite oxide desulfurizing agent is improved.
Description
Technical field
The present invention relates to environmental protection and chemical technology fields, are related specifically to a kind of system of high efficiency composition oxide desulfurizing agent
Preparation Method.
Background technique
Usually all containing a certain amount of inorganic in the process gas such as the combustion gas such as coal gas, natural gas, liquefied gas and lower carbon number hydrocarbons
Sulphur (H2) and organic sulfur (COS, CS S2, RSH etc.) ingredient.Because desulfurization plays the guarantor for checking on to environment and processing to downstream product
Shield effect, so in occupation of very important position in gas purification.Iron-base desulfurizer since its feeding is cheap, Sulfur capacity it is high and
It is widely used in normal-temperature dry desulfurization.Currently, the raw material that iron-base desulfurizer in the market uses mainly has natural iron ore, industry
Waste material and artificial synthesized iron oxide three classes.The above two cause prepared desulfurizing agent property unstable since raw material sources are indefinite
It is fixed, so artificial synthesized iron oxide is the main path for preparing highly active desulfurization agent.
According to the specific form of the basic principle of desulfurization and iron oxide it is known that preparing with specific crystal phase or form
Iron oxide, make its loose porous, large specific surface area, activated centre high degree of dispersion be improve ferric oxide desulfurizer service efficiency
Where core, and these are often depending on the factors such as the condition of molding of concrete technology and desulfurizing agent for preparing iron oxide.Due to mistake
It crosses metal oxide and is usually present the problems such as form is unstable, skeleton easily collapses, and be difficult to that urging for high-ratio surface high activity is made
Agent.Then people start to avoid the deficiency of itself using complex carrier to play respective advantage.Chinese patent literature
CN201410598020.3, which is disclosed, a kind of by magnesia, cobalt oxide, copper oxide isoreactivity component loads to tool using infusion process
Have on the porous carrier of dispersion performance, the method for preparing the composite desulfurizing agent of removing hydrogen sulfide and part organic sulfur.This method
It is middle to select the solution of soluble cobalt and magnesium salts as the first maceration extract, select the solution of soluble copper salt as the second dipping
Liquid in two steps loads to active component on porous carrier, and selected porous carrier is that specific surface is greater than 800m2The activity of/g
The mixture of one or more of charcoal, aluminium oxide, silica gel；Then desulfurizing agent is obtained after drying, roasting.Above-mentioned desulfurizing agent exists
In preparation process, by impregnating twice, program is complicated, and secondary dipping may destroy the effect of preceding single-steeping, make
Obtaining load factor not can fully ensure that；Although infusion process makes used work in addition, porous carrier has biggish pore structure
Property component duct is blocked, greatly reduce the specific surface and pore volume of desulfurizing agent, the utilization rate decline of carrier.Therefore infusion process exists
Preparing the desulfurizing agent aspect with flourishing cellular structure and high desulfurization activity, there are certain operating barriers and technology drawback.
Summary of the invention
High, pore structure prosperity that it is an object of the present invention to provide a kind of working sulfur capacities, desulfurization stability are high, are main with iron oxide
The preparation method of the high efficiency composition oxide desulfurizing agent of active component.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of preparation method of high efficiency composition oxide desulfurizing agent, it is characterised in that: the method comprises the following steps:
1, Fe is selected2+As the source of iron of main active component, be added relative to main active component ratio be mass fraction be 5% ~
The mixed solution that one of 35% Zn, Mn, Cu, Co metal or any several soluble-salts are configured to, using hydramine as precipitating
Agent obtains complex hydroxide sediment A using the method for co-precipitation；
2, under defined reaction condition, with alkanolamine solution precipitate A l3+Aluminum sol B is obtained, then by A and B and step (1)
The middle ratio for obtaining complex hydroxide sediment A coprecipitation by complex hydroxide system and Aluminum sol according to 1:0.1 ~ 1
Example mixing, obtains mixed sediment C after the reaction was continued 1-3 hours；
3, by step (2) obtain mixed sediment C through autoxidation in centrifuge washing, cold air drying, air, pulverize
It is kneaded and formed that the binder that mass fraction is 0% ~ 10% is added afterwards, is answered after aerobic drying at being 80 DEG C ~ 120 DEG C in temperature
Close oxide desulfurizing agent S.
Source of iron Fe described in step 12+For FeSO4、FeCl2, Fe(NO3)2One of molysite, mass fraction 50%
~80%。
Zn, Mn, Cu, Co metal soluble-salt described in step 1 are the chloride or sulfate of the metal.
Precipitating reagent hydramine described in step 1 is any one in MEA, DEA, TEA, DIPA, MDEA organic amine.
Aluminum sol described in step 2 is obtained after being reacted by the soluble-salt of aluminium with any one hydramine in power 4, aluminium
The mass fraction of sol vehicle is 10% ~ 25%, the preparation condition of Aluminum sol are as follows: Al3+Concentration be 0.5-1.5mol/L, precipitating
The mass concentration of agent is 5% ~ 15%, saline and alkaline than being 1:2.5 ~ 4.5, and mode is added dropwise using the positive drop method of alkali drop salt, mixing speed
300-600r/min, reaction temperature are 50-80 DEG C, reaction time 1-3h, and ageing 24 hours spare；The soluble-salt of the aluminium
For AlCl3Or Al2(SO4)3。
The concentration of the molysite is 0.5-2.0mol/L；The mass concentration control of precipitating reagent in 10-35%, precipitating reagent with
The molar ratio of metal salt is 1.8 ~ 3:1, and mode is added dropwise using the positive drop method of alkali drop salt, mixing speed 300-600r/min, reaction
Temperature is 30-80 DEG C, reaction time 1-3h.
The binder is one or both of calcium oxide, bentonite, kaolin.
Its working sulfur capacity of prepared composite oxide desulfurizing agent is up to 40.1%, and duct is 3-10nm slit-type Jie
Hole, BET specific surface are greater than 150.0m2/ g, pore volume are greater than 0.20cm3/g。
The positive effect of the present invention are as follows:
1, the present invention selects alcamines organic base as precipitating reagent, compares and uses sodium hydroxide, ammonium hydroxide, sodium carbonate, carbonic acid
The inorganic bases such as hydrogen sodium, ammonium hydrogen carbonate have a clear superiority as precipitating reagent:
(1) alkalinity of hydramine is so big not as good as ammonium hydroxide and sodium hydroxide, so that the pH of system has controllability and wide scope
Adjustability, hydramine belongs to weak base, in aqueous solution slowly ionization so that precipitation reaction orderly occurs, effectively evaded by
The systematic error caused by rate of addition and concentration of lye and human error；In addition, ammonium hydroxide or ammonium salt class alkali is there are volatility,
Alkali number is not easy to control, unstable product quality；
(2) organic amine often can be miscible with arbitrary proportion with water, and solubility is very big, this had both improved the throwing of unit time
Doses also facilitates the washing and post-processing of product, reduces costs, improve work efficiency;And sodium hydroxide or alkalinity
The solubility of sodium salt is limited, and the washing to feed intake with subsequent products exists tired；
(3) organic amine plays multiple action in the reaction, is both precipitating reagent and dispersing agent or template, so that
Have with iron oxide prepared by organic amine it is excellent desulphurizing activated, this be prepare flourishing cellular structure, higher specific surface,
The porous highly active desulfurization agent in the activated centre of relatively narrow pore-size distribution, high degree of dispersion provides the foundation；
2, the present invention is co-precipitated preparation using one or more of soluble-salts of the metals such as divalent iron salt and Zn, Mn, Cu, Co
Composite oxides, the composite oxides obtained compared to conventional impregnation want more uniform, and active site is richer, and activated centre is more
Dispersion, the synergistic effect between main active component and co-catalyst is more obvious, and adsoption catalysis activity is higher；
3, the present invention is using the Al in alkanolamine solution precipitating aluminum salt solution3+Aluminum sol is obtained as composite oxide desulfurizing agent
Porous carrier, for infusion process, active component can be well dispersed in the duct of porous carrier this method, so that living
The utilization rate of property component is higher.In addition, not by Al in the present invention3+Directly there is special meaning with other metal salt coprecipitations
Justice: the preparation of carrier and the preparation of active composite oxides individually carry out, and advantageously ensure that the property and carrier of active component
Duct it is complete because the environment pH that environment pH and active composite oxides that aluminium glue is formed are formed is in the same range,
By Al3+Directly it can make alumina supporter and active component that optimum performance state be not achieved with other metal salt coprecipitations.
Detailed description of the invention
1 desulfurizing agent evaluation rubric figure of attached drawing；
1 is unstripped gas (H in figure2S+N2), 2 be flow control system, 3 be the micro- anti-system of fixed bed, 4 be tail gas absorption system
System；
The BET isothermal of 2 desulfurizing agent of attached drawing inhales (de-) attached curve graph；
3 desulfurizing agent BJH method pore size distribution curve figure of attached drawing.
Specific embodiment:
Clear, complete description further is carried out to technical solution of the present invention below with reference to embodiment.If without spy
The conventional means bright, technological means as used in the following examples is well known to the skilled person are not mentionleted alone.
Embodiment 1
1, the FeSO4 of 0.3mol, 0.02molZn (NO are weighed3)2, 0.04molCu (NO3)2, 0.03molCoCl2, it is added
250mL water is configured to mixing salt solution M, pours into spare in 1L three-necked flask;
2, the diethanol amine DEA for weighing 0.80mol is configured to the lye D that mass fraction is 10%, spare；
3, the three-necked flask equipped with salting liquid M is placed in 40 DEG C of water-bath, opens stirring 400r/min, is added dropwise
Lye D, time for adding control are added dropwise to complete subsequent continuous insulated and stirred 1.5h in 1h or so, obtain mixed hydroxides A；
4,0.03molAlCl is weighed3, it is configured to mass fraction and is 10% salting liquid N, while weighs the diethyl of 0.12mol
Hydramine DEA, be configured to 5% lye E it is spare；
5, lye E is added in salting liquid N dropwise under conditions of 80 DEG C of water-bath, mixing speed 600r/min, is added dropwise
It finishes and continues insulated and stirred 1h, be then shut off stirring and heating, ageing for 24 hours, obtains Aluminum sol B；
6, Aluminum sol B being poured slowly into mixed hydroxides A, 400r/min stirs 1h under 40 DEG C of water-baths, stop reaction,
It filters, clear water washing spontaneously dries, pulverizes after oxidation completely, obtains desulfurizing agent original powder S；
7,20g catalyst raw powder S is weighed, 1gCaO is added as adhesive, is added after suitable quantity of water reconciles to mix and mediate, use
Single-screw extruder extruded moulding is dried in 120 DEG C of driers to get composite oxide desulfurizing agent S is arrivedA。
Embodiment 2
1, the FeCl of 0.3mol is weighed2, 0.03molZnSO4, 0.02molCoCl2, 0.04molMnSO4, 250mL water is added
It is configured to mixing salt solution M, is poured into spare in 1L three-necked flask;
2, the triethanolamine TEA for weighing 0.85mol is configured to the lye D that mass fraction is 10%, spare；
3, the three-necked flask equipped with salting liquid M is placed in 60 DEG C of water-bath, opens stirring 400r/min, is added dropwise
Lye D, time for adding control are added dropwise to complete subsequent continuous insulated and stirred 1.5h in 1h or so, obtain mixed hydroxides A；
4,0.045molAlCl is weighed3, it is configured to mass fraction and is 5% salting liquid N, while weighs three second of 0.18mol
Hydramine TEA, be configured to 5% lye E it is spare；
5, lye E is added in salting liquid N dropwise under conditions of 80 DEG C of water-bath, mixing speed 600r/min, is added dropwise
It finishes and continues insulated and stirred 1h, be then shut off stirring and heating, ageing for 24 hours, obtains Aluminum sol B；
6, Aluminum sol B being poured slowly into mixed hydroxides A, 400r/min stirs 1h under 80 DEG C of water-baths, stop reaction,
It filters, clear water washing spontaneously dries, pulverizes after oxidation completely, obtains desulfurizing agent original powder S；
7,20g catalyst raw powder S is weighed, 1g bentonite is added as adhesive, is added after suitable quantity of water reconciles to mix and mediate,
With single-screw extruder extruded moulding, dried in 120 DEG C of driers to get composite oxide desulfurizing agent S is arrivedB。
Embodiment 3
1, the Fe (NO of 0.4mol is weighed3)2, 0.04molZn (NO3)2, 0.032molCuCl2, 0.025molMnCl2, add
250mL water is configured to mixing salt solution M, pours into spare in 1L three-necked flask;
2, the MEA for weighing 9.2mol is configured to the lye D that mass fraction is 15%, spare；
3, the three-necked flask equipped with salting liquid M is placed in 40 DEG C of water-bath, opens stirring 400r/min, is added dropwise
Lye D, time for adding control are added dropwise to complete subsequent continuous insulated and stirred 1.5h in 1h or so, obtain mixed hydroxides A；
4,0.025molAl is weighed2(SO4)3, it is configured to mass fraction and is 10% salting liquid N, while weighs 0.1mol's
Diethanol amine DEA, be configured to 8% lye E it is spare；
5, lye E is added in salting liquid N dropwise under conditions of 80 DEG C of water-bath, mixing speed 600r/min, is added dropwise
It finishes and continues insulated and stirred 1h, be then shut off stirring and heating, ageing for 24 hours, obtains Aluminum sol B；
6, Aluminum sol B being poured slowly into mixed hydroxides A, 400r/min stirs 1h under 60 DEG C of water-baths, stop reaction,
It filters, clear water washing spontaneously dries, pulverizes after oxidation completely, obtains desulfurizing agent original powder S；
7,25g catalyst raw powder S is weighed, 1g bentonite and 1g kaolin is added as adhesive, suitable quantity of water is added and reconciles
It mixes and mediates afterwards, with single-screw extruder extruded moulding, dried in 120 DEG C of driers to get composite oxide desulfurizing agent is arrived
SC。
Embodiment 4
1, the FeSO4 of 0.35mol, 0.02molCu (NO are weighed3)2, 0.03molCoCl2, 0.015molMnCl2, add
300mL water is configured to mixing salt solution M, pours into spare in 1L three-necked flask;
2, the methyl diethanolamine MDEA for weighing 1mol is configured to the lye D that mass fraction is 20%, spare；
3, the three-necked flask equipped with salting liquid M is placed in 40 DEG C of water-bath, opens stirring 400r/min, is added dropwise
Lye D, time for adding control are added dropwise to complete subsequent continuous insulated and stirred 1.5h in 1h or so, obtain mixed hydroxides A；
4,0.015molAlCl is weighed3, it is configured to mass fraction and is 10% salting liquid N, while weighs the three of 0.08mol
Ethanol amine TEA, be configured to 5% lye E it is spare；
5, lye E is added in salting liquid N dropwise under conditions of 80 DEG C of water-bath, mixing speed 600r/min, is added dropwise
It finishes and continues insulated and stirred 1h, be then shut off stirring and heating, ageing for 24 hours, obtains Aluminum sol B；
6, Aluminum sol B being poured slowly into mixed hydroxides A, 600r/min stirs 1h under 60 DEG C of water-baths, stop reaction,
It filters, clear water washing spontaneously dries, pulverizes after oxidation completely, obtains desulfurizing agent original powder S；
7,25g catalyst raw powder S is weighed, 1gCaO is added, 1g kaolin is added after suitable quantity of water reconciles and mixes as adhesive
Even kneading is dried in 120 DEG C of driers with single-screw extruder extruded moulding to get composite oxide desulfurizing agent S is arrivedD。
Embodiment 5
1, the FeCl of 0.4mol is weighed2, 0.025molZn (NO3)2, 0.01molCuCl2, 0.02molCoSO4,
0.03molMnCl2, 300mL water is added and is configured to mixing salt solution M, pours into spare in 1L three-necked flask;
2,1.07molDIPA is weighed, the lye D that mass fraction is 25% is configured to, it is spare；
3, the three-necked flask equipped with salting liquid M is placed in 40 DEG C of water-bath, opens stirring 400r/min, is added dropwise
Lye D, time for adding control are added dropwise to complete subsequent continuous insulated and stirred 1.5h in 1h or so, obtain mixed hydroxides A；
4,0.05molAl is weighed2(SO4)3, it is configured to mass fraction and is 10% salting liquid N, while weighs 0.15mol's
Methyl diethanolamine MDEA, be configured to 10% lye E it is spare；
5, lye E is added in salting liquid N dropwise under conditions of 60 DEG C of water-bath, mixing speed 600r/min, is added dropwise
It finishes and continues insulated and stirred 1h, be then shut off stirring and heating, ageing for 24 hours, obtains Aluminum sol B；
6, Aluminum sol B being poured slowly into mixed hydroxides A, 400r/min stirs 1h under 60 DEG C of water-baths, stop reaction,
It filters, clear water washing spontaneously dries, pulverizes after oxidation completely, obtains desulfurizing agent original powder S；
7,25g catalyst raw powder S is weighed, 1gCaO is added, 1.5g bentonite is as adhesive, after suitable quantity of water reconciliation is added
It mixes and mediates, with single-screw extruder extruded moulding, dried in 120 DEG C of driers to get composite oxide desulfurizing agent S is arrivedE。
Activity rating example:
Desulfurization performance test is carried out to the composite oxide desulfurizing agent that specific example 1-5 above-mentioned in the present invention is prepared.
Test condition is as follows:
In this test, evaluation unstripped gas (H2S/N2) import hydrogen sulfide content control in 15000ppm or so, air speed 400-
1000h-1, 35 DEG C of desulfurization environment temperature.Desulfurizing agent obtained is smashed and is sieved, the little particle of 16-40 mesh is obtained, according to a set pattern
It is then uniformly fitted into homemade fixed-bed micro-reactor, control catalyst bed ratio of height to diameter is 5 ~ 8.Desulfurizing agent evaluation rubric figure is detailed
See attached drawing 1.The analysis into and out of H2S content in implication is analyzed using mercurimetry in evaluation procedure.Reactor tail gas is used
Gas-chromatography GC-2060 detection outlet hydrogen sulfide content, detection are limited to 0.02ppm.By to inlet and outlet hydrogen sulfide content CInto、
COut, the real-time air speed S of unstripped gasy, sulphur soak time t, the parameters such as desulfurizing agent bed layer heap density d measurement, carry out overall merit oxidation
The desulfurization performance of iron desulfurizing agent.As the H for just starting to detect 0.02ppm in reactor tail gas2When S, default desulfurizing agent is
Inactivation, Sulfur capacity at this time are referred to as working sulfur capacity, and Sulfur capacity size is 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.
Example evaluation result:
Under the test conditions above, composite oxide desulfurizing agent S example 1-5 being preparedA-EIn Fig. 2 evaluation rubric
Under its desulfurization performance is evaluated, while according to HG/T2782-2011 to the radial crush strength of obtained desulfurizing agent
It is tested, test result is as shown in table 1:
1 example 1-5 composite oxide desulfurizing agent S of tableA-EEvaluation result
Using the desulfurizing agent of the preparation method preparation of the iron-base desulfurizer in the present invention it can be seen from 1 test result of table
Highest penetration Sulfur capacity can achieve 40.10%, and radial crush strength is in 70N/cm or more.
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 1-5 composite oxide desulfurizing agent S of tableA-EPore 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 150m2/ g or more, pore volume is in 0.20cm3/ g or more, average pore size is between 5-9nm.Meanwhile it tying
The isothermal for closing 2 desulfurizing agent of attached drawing inhales the desulfurizing agent pore size distribution curve of (de-) attached curve and attached drawing 3, can from which further follow that, institute
The composite oxide desulfurizing agent of preparation belongs to slit-type meso-hole structure, and pore-size distribution is narrow, and mean pore size is hydrogen sulfide molecule
15-25 times of diameter 3.6A is able to satisfy hydrogen sulfide molecule and has disengaging by oneself in desulfurizing agent duct, and reactivity is higher.
Above-mentioned Activity evaluation is combined by above-mentioned specific embodiment, it can be seen that composite oxides are de- in the present invention
In the preparation method of sulphur agent, system is co-precipitated using one or more of soluble-salts of the metals such as divalent iron salt and Zn, Mn, Cu, Co
Standby composite oxides, active site is abundant, and activated centre is uniformly dispersed, the synergistic effect between main active component and co-catalyst
Obviously, adsoption catalysis activity is higher；Secondly, the present invention prepares Aluminum sol as the porous of composite oxide desulfurizing agent using hydramine
Carrier, active component can be well dispersed in the duct of porous carrier, the preparation of the preparation of carrier and active composite oxides
It individually carries out, advantageously ensures that the complete of the property of active component and the duct of carrier.In addition, the present invention is using calcium oxide, swollen
Profit soil and kaolin mixing are used as binder, and more preferable compared to one-component binder effect, calcium system binder can only improve merely
Intensity, excessive be added can reduce desulfurization performance, and clay system binder has viscosity and hole structural property, and it is viscous to be used in mixed way both
Knot agent can reach the double effects for improving intensity and hole structural property.
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.Disclosed in this specification (including claim, abstract)
Any feature can be replaced by other alternative features that are equivalent or have similar purpose unless specifically stated.It is i.e. unless special
It does not describe, each feature is an example in a series of equivalent or similar characteristics.
Described above is only the non-limiting embodiment of invention, a large amount of embodiment can also be derived, for this field
Those of ordinary skill for, not departing from the invention design and under the premise of do not make creative work, can also do
The embodiment of several modifications and improvements out, these are all within the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of high efficiency composition oxide desulfurizing agent, it is characterised in that: the method comprises the following steps:
(1) Fe is selected2+As the source of iron of main active component, be added relative to the Zn that main active component mass fraction is 5%-35%,
The mixed solution that one of Mn, Cu, Co metal or any several soluble-salts are configured to is used using hydramine as precipitating reagent
The method of co-precipitation obtains complex hydroxide sediment A；
(2) under defined reaction condition, with alkanolamine solution precipitate A l3+Aluminum sol B is obtained, then with coprecipitation by compound hydrogen
Oxide precipitation object A and Aluminum sol B is mixed according to the ratio of 1:0.1-1, and mixed sediment C is obtained after the reaction was continued 1-3 hours；
(3) by step (2) obtain mixed sediment C through autoxidation in centrifuge washing, cold air drying, air, pulverize after
It is kneaded and formed that the binder that mass fraction is 0%-10% is added, is obtained after aerobic drying at being 80 DEG C -120 DEG C in temperature compound
Oxide desulfurizing agent S.
2. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 1, it is characterised in that: in step (1)
The source of iron Fe2+For FeSO4、FeCl2, Fe(NO3)2One of molysite, mass fraction 50%-80%.
3. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 1, it is characterised in that: in step (1)
Zn, Mn, Cu, Co metal soluble-salt is the chloride or sulfate of the metal.
4. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 1, it is characterised in that: in step (1)
The precipitating reagent hydramine is any one in MEA, DEA, TEA, DIPA, MDEA organic amine.
5. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 1, it is characterised in that: in step (2)
The Aluminum sol is obtained after being reacted by the soluble-salt of aluminium with any one hydramine in claim 4, Aluminum sol carrier
Mass fraction be 10%-25%, the preparation condition of Aluminum sol are as follows: Al3+Concentration be 0.5-1.5mol/L, the quality of precipitating reagent
Concentration is 5%-15%, saline and alkaline than being 1:2.5-4.5, and mode is added dropwise using the positive drop method of alkali drop salt, mixing speed 300-600r/
Min, reaction temperature are 50-80 DEG C, and in reaction time 1-3 hour, ageing 24 hours spare；The soluble-salt of the aluminium is AlCl3
Or Al2(SO4)3。
6. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 2, it is characterised in that: in step (1)
The Fe2+The concentration of molysite is 0.5-2.0mol/L；The mass concentration control of precipitating reagent in 10-35%, precipitating reagent and metal salt
Molar ratio is 1.8-3:1, and mode is added dropwise using the positive drop method of alkali drop salt, mixing speed 300-600r/min, reaction temperature 30-
80 DEG C, reaction time 1-3 hour.
7. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 1, it is characterised in that: the bonding
Agent is one or both of calcium oxide, bentonite, kaolin.
8. the preparation method of high efficiency composition oxide desulfurizing agent according to claim 1, it is characterised in that: prepared answers
It closes its working sulfur capacity of oxide desulfurizing agent and is up to 40.1%, duct is that 3-10nm slit-type is mesoporous, and BET specific surface is greater than
150.0m2/ g, pore volume are greater than 0.20cm3/g。
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| CN109107374A (en) * | 2018-09-28 | 2019-01-01 | 武汉纺织大学 | A kind of metal composite oxide desulfurizing agent and preparation method thereof |
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