CN104098123A - Preparation method for zinc oxide desulfurizer - Google Patents
Preparation method for zinc oxide desulfurizer Download PDFInfo
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- CN104098123A CN104098123A CN201410356116.9A CN201410356116A CN104098123A CN 104098123 A CN104098123 A CN 104098123A CN 201410356116 A CN201410356116 A CN 201410356116A CN 104098123 A CN104098123 A CN 104098123A
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Abstract
The invention discloses a preparation method for a zinc oxide desulfurizer. The preparation method comprises the following steps: (1) the mixing liquor of ammonium bicarbonate and ammonium carbonate is prepared; (2) a zinc salt solution is mixed with the mixed liquor prepared from the step (1) to be subjected to coprecipitation reaction at the normal temperature, the pH value is controlled to be 5-8, and a basic zinc carbonate precursor is obtained; (3) the obtained basic zinc carbonate precursor is washed and dried to obtain a drying product; (4) the drying product is calcinated to obtain the needed zinc oxide desulfurizer, and the molar ratio of the ammonium bicarbonate and the ammonium carbonate is (1:1)-(6:1). According to the invention, the difference of the hydrolysis rate of the ammonium bicarbonate and the ammonium carbonate is fully used, so that ZN<2+> is slow and sequential to react with the ammonium bicarbonate and the ammonium carbonate, therefore, the prepared basic zinc carbonate precursor is regular in structure and distributed in a plate manner; the reaction can be conducted at the normal temperature, the precursor with good desulfurizing performance can be obtained, and the zinc oxide desulfurizer with good desulfurizing performance can be obtained in the following calcinating process.
Description
Technical field
The present invention relates to a kind of preparation method of sweetening agent, be specifically related to the preparation method of a zinc oxide desulfurizer, belong to catalyst preparation technical field.
Background technology
Zinc oxide desulfurizer is a kind of medium and high temperature sweetening agent that is widely used in the industries such as synthetic ammonia, hydrogen manufacturing, methyl alcohol processed, Coal Chemical Industry, refining of petroleum, have that desulfurization precision is high, easy to use, steady performance, at the smart desulfuration field of industry in occupation of critical role.At present, chemical industry both domestic and external is just towards future development large-scale, environmental protection, therefore the desulfurization performance of sweetening agent is also had higher requirement, wherein nano zine oxide sweetening agent is because its particle diameter is little, specific surface area is large, pore volume is high, be conducive to the carrying out of diffusion and the surface reaction of sulfocompound thereby increased reaction site, and then greatly improved the sweetening effectiveness of ZnO.According to pertinent literature, granularity is at nano level ZnO sweetening agent, and its sweetening effectiveness is 40 times of the pure ZnO of general analysis.
In prior art, nano-ZnO sweetening agent adopts coprecipitation method preparation mostly, it provides a kind of solution that contains soluble zinc salt, add precipitation agent to carry out coprecipitation reaction, by the precipitation generating through separating, washing, dry and roasting, thereby make the sweetening agent of excellent performance, preparing in the coprecipitation method of nano-ZnO sweetening agent, the precipitation agent difference adding, reaction mechanism is not identical yet, the throw out composition, the structure that obtain also have larger difference, thereby make the performance of the Zinc oxide desulfurizer obtaining after roasting and sweetening effectiveness have obvious difference.
Chinese patent literature CN101455966A discloses a kind of methanol synthesis gas desulfurizer, and its component of living comprises CuO, 40% the ZnO of 5-30% and the Cr of 20-50%
2o
3or Al
2o
3the preparation method of this sweetening agent is, first by the soluble salt solution of copper, zinc and chromium or aluminium, carry out coprecipitation reaction as precipitation agent with acid carbonate solution, then by the precipitation obtaining through washing, dry, granulation, beat sheet and roasting process finally makes above-mentioned methanol synthesis gas desulfurizer.But applicant studies discovery, prepare taking bicarbonate of ammonia as precipitation agent in the process of Zinc oxide desulfurizer, only at the temperature higher than 60 DEG C, carry out precipitin reaction, could obtain the zinc subcarbonate presoma of sheet structure, and then after roasting, obtain the little and uniform nano-oxide particles of particle diameter, thereby make it have higher sweetening effectiveness, if and in above-mentioned document, record lower than carrying out precipitin reaction at the temperature of 50 DEG C, the zinc subcarbonate presoma obtaining is irregular closelypacked structure, thereby has reduced sweetening effectiveness.
Summary of the invention
In preparation process, need the problem of higher precipitation temperature for solving Zinc oxide desulfurizer in prior art, and then a kind of Zinc oxide desulfurizer that can carry out at normal temperatures precipitin reaction and just can obtain good sweetening effectiveness is provided.
For this reason, the technical scheme that the present invention takes is:
The preparation method of one zinc oxide desulfurizer, comprises,
(1) prepare the mixed solution of bicarbonate of ammonia and volatile salt, for subsequent use;
(2) zinc solution is mixed with the described mixed solution that step (1) prepares, carry out at normal temperatures coprecipitation reaction, the pH value of controlling reaction is 5-8, obtains zinc subcarbonate presoma;
(3) by the described zinc subcarbonate presoma washing obtaining, dry, obtain desciccate;
(4) roasting at 250-550 DEG C of described desciccate is obtained to required Zinc oxide desulfurizer.
In the preparation method of above-mentioned Zinc oxide desulfurizer, in the mixed solution of described step (1), the mol ratio of bicarbonate of ammonia and volatile salt is 1:1-6:1.
In the preparation method of above-mentioned Zinc oxide desulfurizer, in ammonium bicarbonate soln, add ammoniacal liquor to prepare bicarbonate of ammonia in described step (1) and the mixed solution of volatile salt.
In the preparation method of above-mentioned Zinc oxide desulfurizer, the concentration of described zinc solution is 0.5-1.55mol/L.
In the preparation method of above-mentioned Zinc oxide desulfurizer, described zinc salt is one or more in zinc sulfate, zinc chloride, zinc acetate, zinc oxalate or zinc nitrate.
In the preparation method of above-mentioned Zinc oxide desulfurizer, in described step (4), the roasting at 350-450 DEG C of described desciccate obtains required Zinc oxide desulfurizer.
In the preparation method of above-mentioned Zinc oxide desulfurizer, in described step (4), described desciccate roasting time is 2-4h.
In the preparation method of above-mentioned Zinc oxide desulfurizer, be 20-50 DEG C in the temperature of reaction of coprecipitation reaction described in described step (2).
In the preparation method of above-mentioned Zinc oxide desulfurizer, be 20-40 DEG C in the temperature of reaction of coprecipitation reaction described in described step (2).
In the preparation method of above-mentioned Zinc oxide desulfurizer, the reaction times of coprecipitation reaction described in described step (2) is 1-10 hour,
The pH value of described coprecipitation reaction is 6.5-7.5.
In the preparation method of above-mentioned Zinc oxide desulfurizer, coprecipitation reaction described in described step (2) is single current or co-precipitation reaction, and in reaction process, also comprises the step stirring.
Compared with prior art, tool of the present invention has the following advantages:
(1) in the preparation method of the application's Zinc oxide desulfurizer, adopt the mixed solution of bicarbonate of ammonia and volatile salt as precipitation agent, in coprecipitation reaction process, first volatile salt starts hydrolysis, along with the hydrolysis of volatile salt, and itself and Zn
2+effect produces a large amount of nucleus, and in the process being slowly hydrolyzed at bicarbonate of ammonia subsequently, nucleus is grown up gradually, and the application's applicant makes full use of the otherness of bicarbonate of ammonia and volatile salt hydrolysis rate, makes Zn
2+slowly orderly reacting with it, thereby the zinc subcarbonate precursor construction that makes generation is regular, distribution in the form of sheets, only need react at normal temperatures, can obtain the presoma of good desulfurization performance, be conducive to form the ZnO particle of small particle size, thereby form more avtive spot, improved the desulfurization performance of sweetening agent, and and then in follow-up roasting process, obtain the Zinc oxide desulfurizer of good desulfurization performance.
(2) in the preparation method of the application's Zinc oxide desulfurizer, adopt the mixed solution of bicarbonate of ammonia and volatile salt as precipitation agent, wherein the mol ratio of bicarbonate of ammonia and volatile salt is controlled at the scope of 1:1-6:1, under normal temperature, can make the ZnO nano particle of sheet accumulation, size homogeneous, be rich in-OH of particle surface functional group, particle interphase interaction is stronger, without adding auxiliary agent, can obtain the good ZnO sweetening agent of intensity.
(3) in the preparation method of the application's Zinc oxide desulfurizer, only need react at normal temperatures, thereby greatly reduce the energy expenditure of preparing in Zinc oxide desulfurizer process, reduce the preparation cost of sweetening agent.
Brief description of the drawings
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the thermogravimetric curve figure of zinc subcarbonate presoma in embodiment 1;
Fig. 2 is the scanning electron microscope picture that adopts the Zinc oxide desulfurizer product that the method for embodiment 2 prepares.
Embodiment
Embodiment 1
(1) get the NH of 1mol/L
4hCO
3solution 300ml, and to add wherein 4.48ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 4:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the ZnSO of 1mol/L
4solution 75ml, adopts and is just adding single current coprecipitation method, under agitation condition, to ZnSO
4in solution, drip described mixed solution, control 20 DEG C of temperature of reaction, pH is 7.0, is added dropwise to complete rear continuation stirring reaction 2h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S1.
Zinc subcarbonate presoma in the present embodiment is carried out to thermogravimetric analysis, draw the thermogravimetric curve figure shown in Fig. 1, as seen from the figure, prepared presoma is decomposed into ZnO completely 250 DEG C of left and right.
Embodiment 2
(1) get the NH of 1mol/L
4hCO
3solution 200ml, and to add wherein 3.73ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 3:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the ZnSO of 1mol/L
4solution 75ml, adopts and is just adding single current coprecipitation method, under agitation condition, to ZnSO
4in solution, drip described mixed solution, control 20 DEG C of temperature of reaction, pH is 7.0, is added dropwise to complete rear continuation stirring reaction 2h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S2.
Adopt the S-4800 type Electronic Speculum that Japanese Hitachi provides to analyze the Zinc oxide desulfurizer S2 of the present embodiment, obtain the scanning electron microscope (SEM) photograph shown in Fig. 2, as can be seen from the figure, preparation-obtained ZnO uniform particles, the about 20-30nm of size, can find out that part small-particle is agglomerated into sheet structure, kept the constitutional features of its zinc subcarbonate presoma simultaneously.
Embodiment 3
(1) get the NH of 1mol/L
4hCO
3solution 200ml, and to add wherein 4.98ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 2:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the ZnSO of 1mol/L
4solution 75ml, adopts and is just adding single current coprecipitation method, under agitation condition, to ZnSO
4in solution, drip described mixed solution, control 20 DEG C of temperature of reaction, pH is 7.0, is added dropwise to complete rear continuation stirring reaction 2h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S3.
Embodiment 4
(1) get the NH of 1mol/L
4hCO
3solution 300ml, and to add wherein 7.47ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 1:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the ZnSO of 1mol/L
4solution 75ml, adopts and is just adding single current coprecipitation method, under agitation condition, to ZnSO
4in solution, drip described mixed solution, control 20 DEG C of temperature of reaction, pH is 7.0, is added dropwise to complete rear continuation stirring reaction 2h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S4.
Embodiment 5
(1) get the NH of 1mol/L
4hCO
3solution 300ml, and to add wherein 3.78ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 5:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the ZnCl of 1mol/L
2solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, control reaction and carry out at normal temperatures, pH value of reaction system is 5.0, after dropping finishes, continue reaction 4h, being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 5h at 350 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S5.
Embodiment 6
(1) get the NH of 0.5mol/L
4hCO
3solution 600ml, and to add wherein 3.24ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 6:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the Zn (NO of 1mol/L
3)
2solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, controlling reaction carries out at normal temperatures, pH value of reaction system is 6.5, drips and finishes rear continuation reaction 6h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 8h at 250 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S6.
Embodiment 7
(1) get the NH of 1mol/L
4hCO
3solution 300ml, and to add wherein 5.67ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 3:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the zinc oxalate ZnC of 1mol/L
2o
4solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, controlling reaction carries out at normal temperatures, pH value of reaction system is 7.5, drips and finishes rear continuation reaction 8h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 1h at 550 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S7.
Embodiment 8
(1) get the NH of 0.5mol/L
4hCO
3solution 400ml, and to add wherein 4.98ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 2:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the zinc acetate Zn (CH of 1mol/L
3cOO)
2solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, controlling reaction carries out at normal temperatures, pH value of reaction system is 8.0, drips and finishes rear continuation reaction 10h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 6h at 300 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S8.
Embodiment 9
(1) get the NH of 1mol/L
4hCO
3solution 300ml, and to add wherein 4.48ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 4:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the Zn (NO of 1mol/L
3)
2solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, control reaction carries out at 25 DEG C, pH value of reaction system is 8.0, drips and finishes rear continuation reaction 5h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 4h at 450 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S2.
Embodiment 10
(1) get the NH of 1mol/L
4hCO
3solution 200ml, and to add wherein 3.73ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 3:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the zinc oxalate ZnC of 1mol/L
2o
4solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, control reaction carries out at 25 DEG C, pH value of reaction system is 6.0, drips and finishes rear continuation reaction 7h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 3h at 500 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S10.
Embodiment 11
(1) get the NH of 1mol/L
4hCO
3solution 200ml, and to add wherein 4.98ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 2:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the ZnCl of 1mol/L
2solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, control reaction carries out at 40 DEG C, pH value of reaction system is 7.0, drips and finishes rear continuation reaction 4h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 450 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S11.
Embodiment 12
(1) get the NH of 1mol/L
4hCO
3solution 300ml, and to add wherein 3.78ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 5:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the zinc acetate Zn (CH of 1mol/L
3cOO)
2solution 75ml, adopt co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, control reaction carries out at 40 DEG C, pH value of reaction system is 6.0, drips and finishes rear continuation reaction 5h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 300 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S12.
Embodiment 13
(1) measure the NH of 2mol/L
4hCO
3solution 400ml, and to add wherein 14.92ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 3:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) take the ZnO that 25g obtains after waste desulfurizing agent high-temperature roasting, be scattered in 141.7ml deionized water, slowly add 33.5ml sulphuric acid soln (1:1, ω), after fully stirring, filter, obtain the ZnSO that concentration is 0.93mol/L
4solution, for subsequent use;
(3) adopt and just adding single current coprecipitation method, the ZnSO preparing to described step (2)
4in solution, drip described mixed solution, 30 DEG C of bath temperatures, pH value is 7.0, drips and finishes rear continuation reaction 2h, being precipitated thing is zinc subcarbonate presoma;
(4) throw out centrifugal treating step (3) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(5) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S13.
Embodiment 14
(1) measure the NH of 2mol/L
4hCO
3solution 400ml, and to add wherein 14.92ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 3:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) take the ZnO that 25g obtains after waste desulfurizing agent high-temperature roasting, be scattered in 100.0ml deionized water, slowly add 33.5ml sulphuric acid soln (1:1, ω), after fully stirring, filter, obtain the ZnSO that concentration is 1.24mol/L
4solution, for subsequent use;
(3) adopt and just adding single current coprecipitation method, the ZnSO preparing to described step (2)
4in solution, drip described mixed solution and mix, 30 DEG C of bath temperatures, pH value is within 7.0 o'clock, to stop dripping, and then continues reaction 2h, being precipitated thing is zinc subcarbonate presoma;
(4) throw out centrifugal treating step (3) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(5) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S14.
Embodiment 15
(1) measure the NH of 2mol/L
4hCO
3solution 400ml, and to add wherein 14.92ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 3:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) take the ZnO that 25g obtains after waste desulfurizing agent high-temperature roasting, be scattered in 75ml deionized water, slowly add 33.5ml sulphuric acid soln (1:1, ω), after fully stirring, filter, obtain the ZnSO that concentration is 1.55mo/L
4solution, for subsequent use;
(3) adopt and just adding single current coprecipitation method, the ZnSO preparing to described step (2)
4in solution, drip described mixed solution and mix, 30 DEG C of bath temperatures, controlling pH value is within 7.0 o'clock, to stop dripping, and then continues reaction 2h, being precipitated thing is zinc subcarbonate presoma;
(4) throw out centrifugal treating step (3) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(5) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S15.
Embodiment 16
(1) get the NH of 2mol/L
4hCO
3solution 150ml, and to add wherein 7.47ml massfraction be the NH of 25wt%
3h
2o prepares the NH that mol ratio is 1:1
4hCO
3(NH
4)
2cO
3mixed solution, for subsequent use;
(2) measure the Zn (NO of 1mol/L
3)
2solution 75ml, with employing co-precipitation method, under agitation condition, prepare mixed solution with step (1) is added drop-wise in reaction vessel simultaneously, control reaction carries out at 50 DEG C, pH value of reaction system 8.0, drips and finishes rear continuation reaction 3h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 550 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer S16.
Comparative example 1
(1) get the NH of 1mol/L
4hCO
3solution 400ml, for subsequent use;
(2) measure the ZnSO of 1mol/L
4solution 75ml, with the NH of step (1)
4hCO
3solution mixes, and adopts and is just adding single current coprecipitation method, and vigorous stirring, controls 20 DEG C of temperature of reaction, and pH value 7.0 drips and finishes rear continuation reaction 2h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be Zinc oxide desulfurizer D1.
Comparative example 2
(1) get the NH of 2mol/L
4hCO
3solution 150ml, for subsequent use;
(2) measure the Zn (NO of 1mol/L
3)
2solution 75ml, with the NH of step (1)
4hCO
3solution mixes, and adopts co-precipitation method, and vigorous stirring is controlled 50 DEG C of temperature of reaction, and pH value 8.0 drips and finishes rear continuation reaction 3h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 550 DEG C in still air atmosphere, obtain white powder sample, be Zinc oxide desulfurizer D2.
Comparative example 3
(1) get the NH of 0.5mol/L
4hCO
3solution 600ml, for subsequent use;
(2) measure the Zn (NO of 1mol/L
3)
2solution 75ml, the described NH preparing with step (1)
4hCO
3solution mixes, and adopts co-precipitation method, vigorous stirring, and reaction is carried out at normal temperatures, controls pH value 6.5, drips and finishes rear continuation reaction 6h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 8h at 250 DEG C in still air atmosphere, obtain white powder sample, be required Zinc oxide desulfurizer D3.
Comparative example 4
(1) get (NH of 2mol/L
4)
2cO
3solution 150ml, for subsequent use;
(2) measure the Zn (NO of 1mol/L
3)
2solution 75ml, with (the NH of step (1)
4)
2cO
3solution mixes, and adopts co-precipitation method, and vigorous stirring is controlled 25 DEG C of temperature of reaction, and pH value 8.0 drips and finishes rear continuation reaction 3h, and being precipitated thing is zinc subcarbonate presoma;
(3) throw out centrifugal treating step (2) being obtained, wash 8 times, obtain drying products through 110 DEG C of dry 12h.
(4) by described drying products roasting 2h at 400 DEG C in still air atmosphere, obtain white powder sample, be Zinc oxide desulfurizer D4.
Evaluation Example
Zinc subcarbonate presoma in zinc subcarbonate presoma in embodiment 1-16 and comparative example 1-4 is all carried out to thermogravimetric analysis, show that the zinc subcarbonate presoma in embodiment 1-16 can be decomposed into ZnO completely 250 DEG C of left and right.Adopt scanning electronic microscope characterizing method to carry out statistical study to the particle diameter of Zinc oxide desulfurizer and Zinc oxide desulfurizer D1-D4, adopt N simultaneously
2physics adsorption-desorption method is measured the BET specific surface area of the said products, with reference to " HG/T 2513-2006 Zinc oxide desulfurizer Sulfur capacity test method " standard, the sweetening effectiveness of above-mentioned sample is measured, and the data that obtain are as shown in table 1,
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (11)
1. the preparation method of a zinc oxide desulfurizer, comprises,
(1) prepare the mixed solution of bicarbonate of ammonia and volatile salt, for subsequent use;
(2) zinc solution is mixed with the described mixed solution that step (1) prepares, carry out at normal temperatures coprecipitation reaction, the pH value of controlling reaction is 5-8, obtains zinc subcarbonate presoma;
(3) by the described zinc subcarbonate presoma washing obtaining, dry, obtain desciccate;
(4) roasting at 250-550 DEG C of described desciccate is obtained to required Zinc oxide desulfurizer.
2. the preparation method of Zinc oxide desulfurizer according to claim 1, is characterized in that, in the mixed solution of described step (1), the mol ratio of bicarbonate of ammonia and volatile salt is 1:1-6:1.
3. the preparation method of Zinc oxide desulfurizer according to claim 1 and 2, is characterized in that, adds ammoniacal liquor to prepare bicarbonate of ammonia in described step (1) and the mixed solution of volatile salt in ammonium bicarbonate soln.
4. the preparation method of Zinc oxide desulfurizer according to claim 3, is characterized in that, the concentration of described zinc solution is 0.5-1.55mol/L.
5. the preparation method of Zinc oxide desulfurizer according to claim 4, is characterized in that, described zinc salt is one or more in zinc sulfate, zinc chloride, zinc acetate, zinc oxalate or zinc nitrate.
6. according to the preparation method of the arbitrary described Zinc oxide desulfurizer of claim 1-5, it is characterized in that, in described step (4), the roasting at 350-450 DEG C of described desciccate obtains required Zinc oxide desulfurizer.
7. the preparation method of Zinc oxide desulfurizer according to claim 6, is characterized in that, in described step (4), described desciccate roasting time is 2-4h.
8. according to the preparation method of the arbitrary described Zinc oxide desulfurizer of claim 1-5, it is characterized in that, is 20-50 DEG C in the temperature of reaction of coprecipitation reaction described in described step (2).
9. the preparation method of Zinc oxide desulfurizer according to claim 8, is characterized in that, is 20-40 DEG C in the temperature of reaction of coprecipitation reaction described in described step (2).
10. according to the preparation method of the arbitrary described Zinc oxide desulfurizer of claim 1-9, it is characterized in that, the reaction times of coprecipitation reaction described in described step (2) is 1-10 hour,
The pH value of described coprecipitation reaction is 6.5-7.5.
11. according to the preparation method of the Zinc oxide desulfurizer described in claim 1-10, it is characterized in that, coprecipitation reaction described in described step (2) is single current or co-precipitation reaction, and in reaction process, also comprises the step stirring.
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| CN106147886A (en) * | 2016-08-22 | 2016-11-23 | 沈阳三聚凯特催化剂有限公司 | One zinc oxide desulfurizer and preparation method thereof |
| CN111606352A (en) * | 2020-06-28 | 2020-09-01 | 孙美仙 | Preparation method of zinc oxide desulfurizer |
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