CN108295806B - A kind of method and application preparing desulfuration adsorbent using Industrial Solid Waste - Google Patents
A kind of method and application preparing desulfuration adsorbent using Industrial Solid Waste Download PDFInfo
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- CN108295806B CN108295806B CN201711274219.0A CN201711274219A CN108295806B CN 108295806 B CN108295806 B CN 108295806B CN 201711274219 A CN201711274219 A CN 201711274219A CN 108295806 B CN108295806 B CN 108295806B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01D15/08—Selective adsorption, e.g. chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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Abstract
The invention discloses a kind of method for preparing desulfuration adsorbent using Industrial Solid Waste, includes the following steps: that a solution is added in a kettle, add Ni (NO3)2Solution is stirred, and then adsorbing agent carrier is added in reaction kettle again, and heating is reacted；Then sodium bicarbonate solution is added dropwise into reaction kettle with constant pressure buret, improves revolving speed and continues to stir, obtain mixed liquor a after stopping stirring；Claim excessive anhydrous Na2CO3It pours into mixed liquor a, b solution is then added dropwise into reaction kettle with constant pressure buret, continues to stir after being added dropwise to complete, obtain mixed liquor b after stopping stirring；Mixed liquor b is filtered, during suction filtration and filter cake to filtrate is washed with deionized is in neutrality；It takes filter cake to be dried, calcination, when being cooled to room temperature, obtains desulfuration adsorbent.The present invention uses Industrial Solid Waste, enhances the intensity of desulfuration adsorbent, improves wearability, and large specific surface area, good to the selectivity of sulphur, adsorption effect is more preferable.
Description
Technical field
The invention belongs to adsorbent material technical field, relate particularly to a kind of prepare desulfuration adsorbent using Industrial Solid Waste
Method, and the application of desulfuration adsorbent being prepared.
Background technique
As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly stringent, and reduces the sulphur of gasoline and diesel oil
Content is considered as improving one of the most important measure of air quality, because the sulphur in fuel can be to the property of vehicle catalytic converter
It can have adverse effect on.Sulfur oxide present in automobile engine tail gas can inhibit the noble metal catalyst in converter
And it can be allowed to occur irreversibly to be poisoned.The gas being discharged from inefficient or poisoning converter contains unburned non-methane hydrocarbon
With nitrogen oxide and carbon monoxide, and these discharge gas are by hydrophilic dye then photochemical fog easy to form.
Most of sulphur is from hot-working petroleum, predominantly catalytically cracked gasoline in China's gasoline, therefore cracking vapour
The reduction of sulfur content helps to reduce the sulfur content of these gasoline in oil.The existing gasoline products standard in China contains sulfur in gasoline
Amount further restricts.In this case, catalytically cracked gasoline, which has to pass through deep desulfuration just, can meet the requirement of environmental protection.
Traditional gasoline desulfurization technology generally adsorbs desulfurization, and there is also hydrodesulfurizations.It is existing more common or de-
Sulfur absorbent, most of is activated carbon desulphurization agent, ZSM-5 desulfurizing agent.But existing desulfuration adsorbent has the following disadvantages: 1, ratio
Surface area is small, reduces adsorptive value；2, service life is short, it is difficult to recycling and reusing；3, the cost is relatively high.
The presence of industrial waste not only causes huge economic loss, also exacerbates problem of environmental pollution, therefore find one
Kind rationally effectively carries out Industrial Solid Waste to recycle production extremely urgent.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing desulfuration adsorbent using Industrial Solid Waste, prepared desulfurization is inhaled
Attached dose using simple and reusable；It joined Industrial Solid Waste in raw material due to preparing, significantly reduce desulfuration adsorbent
Production cost solves the problems, such as Industrial Solid Waste pollution environment and results in waste of resources.
To achieve the above object, the technical scheme is that
A method of desulfuration adsorbent being prepared using Industrial Solid Waste, is included the following steps:
(1) a solution is prepared using industrial waste steel dreg；
(2) b solution is obtained using Industry Waste glass preparation；
(3) above-mentioned a solution is added in a kettle, adds Ni (NO3)2Solution is stirred, then again by adsorbent
Carrier is added in reaction kettle, and heating is reacted；Then sodium bicarbonate solution is added dropwise into reaction kettle with constant pressure buret, improves
Revolving speed continues to stir, and obtains mixed liquor a after stopping stirring；
(4) claim excessive anhydrous Na2CO3It pours into mixed liquor a, it is molten that above-mentioned b is then added dropwise into reaction kettle with constant pressure buret
Liquid continues to stir after being added dropwise to complete, and obtains mixed liquor b after stopping stirring；
(5) mixed liquor b is filtered, during suction filtration and filter cake to filtrate is washed with deionized is in neutrality；
(6) it takes filter cake to be dried, calcination, when being cooled to room temperature, obtains desulfuration adsorbent.
Further, in step (1) a solution the preparation method comprises the following steps: industrial waste steel dreg is crushed, then take crushing
Steel slag powder afterwards is added in reactor, and hydrochloric acid solution is added drop-wise in reactor, after complete reaction, solution was carried out
Filter takes filtrate that distilled water, ZnCl is added2·6H2After O after mixing evenly, a solution is obtained.
Further, in step (2) b solution the preparation method comprises the following steps: by Industry Waste glass cleaning it is clean after crush,
Then it takes smashed powder to be added in reactor, sodium hydroxide solution is added drop-wise in reactor, control reaction temperature carries out
Reaction, after complete reaction, solution is filtered, and is stirred evenly after taking filtrate that distilled water, sodium carbonate is added, is obtained b solution.
Further, a solution, Ni (NO in step (3)3)2Solution, adsorbing agent carrier, sodium bicarbonate solution additional amount point
It Wei not be 100-120 parts, 80-100 parts, 30-50 parts, 80-120 parts；Ni(NO3)2The mass fraction point of solution, sodium bicarbonate solution
It Wei not 16-23%, 27-35%；Mixing speed is 100-200rpm, and improving the speed stirred after revolving speed is 300-400rpm；It rises
Temperature arrives 40-60 DEG C, reacts 3-4h；Rate of addition is 2-3 drop/minute；Continue to stir 1-2h after improving revolving speed.
Further, b solution additional amount is 80-120 parts in step (4)；Rate of addition is 2-5 drop/minute；Stirring speed
Degree is 300-400rpm, mixing time 1-2h.
Further, drying temperature is 100-120 DEG C in step (6), and calcination temperature is 600-800 DEG C, calcination time
For 3-4h；When being cooled to room temperature, carry out being ground to partial size being 80-100 mesh.
Further, the preparation method of the adsorbing agent carrier in step (3) includes the following steps:
A at room temperature, weighs 100-200 parts of a solution and is added in reaction kettle, controls mixing speed as 200-300rpm progress
Then stirring 80-120 parts of b solution is added dropwise into reaction kettle with 2-5 drop/minute speed with constant pressure buret, is being added dropwise to complete
Afterwards, revolving speed is improved to 300-400rpm, continues to stir 1-2h, obtains mixed liquor after stopping stirring；
B is still aging at room temperature by mixed liquor, when solution clarification, takes and deionized water is added after supernatant liquor to original
Scale, then carry out after being slowly stirred 1-2min, repeat aforesaid operations, until ageing total time be 8-10h；
After drawing supernatant liquor after C ageing, is filtered, during suction filtration and filter cake is washed with deionized to filtrate
It is in neutrality；
D takes filter cake to be dried at a temperature of 100-120 DEG C, after drying by it at a temperature of 600-800 DEG C calcination 3-4h,
When being cooled to room temperature, carries out being ground to partial size being 100-150 mesh, obtain adsorbing agent carrier.
Further, partial size is 100-200 mesh after industrial waste steel dreg crushes；Steel slag powder, dilute hydrochloric acid, distilled water,
ZnCl2·6H2The additional amount of O is respectively 100-120 parts, 40-80 parts, 40-60 parts, 30-40 parts；The mass fraction of dilute hydrochloric acid is
14-23%.
Further, partial size is 50-100 mesh after industrial waste glass crushing；Powder, sodium hydroxide solution, distilled water, carbon
The additional amount of sour sodium is respectively 100-150 powder, 60-100 parts, 60-80 parts, 60-80 parts；The mass fraction of sodium hydroxide solution is
37-46%；Reaction temperature is 60-70 DEG C.
The application in desulfurization for the desulfuration adsorbent being prepared by the above method, which is characterized in that desulfurization absorption
Agent is put into the both ends that diameter is 3-5mm steel pipe, and is sealed with ventilative steel mesh, obtains single desulfurization adsorption tube；More desulfurization are inhaled
Attached pipe, which combines, to be put into the liquid or gas of sulfur-bearing, and desulfurization is carried out.
Compared with prior art, the invention has the advantages that
1, Industrial Solid Waste has been used in desulfuration adsorbent raw material prepared by the present invention, so that the intensity of desulfuration adsorbent increases
By force, wearability improves, and can not only prolong its service life, acceptable good recycling and reusing, and then reduces cost.
2, the present invention is prepared into a solution and b solution using industrial waste steel dreg and industrial cullet respectively, is prepared using the two
Adsorbing agent carrier, then by a solution and b solution loadings on adsorbing agent carrier, the specific surface area for the desulfuration adsorbent being prepared
Greatly, good to the selectivity of sulphur, and then the adsorptive value to sulphur can be increased, the effect for adsorbing sulphur is more preferable.
3, since primary raw material of the invention is Industrial Solid Waste, i.e. industrial waste steel dreg and industrial cullet, system of the invention
It is standby low in cost, while Industrial Solid Waste can also rationally be recycled, its pollution to environment is reduced, economic effect is also increased
Benefit.
Specific embodiment
Below by the technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiment obtained without making creative work, belong to guarantor of the invention
Protect range.
Embodiment 1
A method of desulfuration adsorbent being prepared using Industrial Solid Waste, is included the following steps:
(1) preparation of a solution:
Industrial waste steel dreg is added in pulverizer and is crushed, smashed partial size is 100 mesh；Take 100 parts it is smashed
Steel slag powder is added in reactor, 55 parts of 20% hydrochloric acid solution is added drop-wise in reactor, after complete reaction, by solution
It is filtered, removes insoluble impurities, take filtrate that 60 parts of distilled water, 30 parts of ZnCl is added2·6H2After O after mixing evenly,
Obtain a solution.
(2) it the preparation of b solution: after industrial cullet is cleaned up, is added in pulverizer and is crushed, after crushing
Partial size be 50 mesh；It weighs 150 parts of smashed powder to be added in reactor, the hydroxide for being 40% by 70 parts of mass fraction
Sodium solution is added drop-wise in reactor, and control reaction temperature is 65 DEG C, and after complete reaction, solution is filtered, and is removed insoluble
Property impurity, take filtrate be added 60 parts of distilled water, 78 parts of sodium carbonate after mixing evenly, obtain b solution.
(3) preparation of adsorbing agent carrier: at room temperature, 120 parts of a solution is weighed and are added in reaction kettle, mixing speed is controlled
It is stirred for 200rpm, 90 parts of b solution is then added dropwise into reaction kettle with 2 drops/minute speed with constant pressure buret, are dripping
After the completion of adding, revolving speed is improved to 300rpm, continues to stir 1h, obtains mixed liquor after stopping stirring；Mixed liquor is stood at room temperature
Ageing is added deionized water to original scale after taking supernatant liquor, then carries out being slowly stirred 2min when solution clarification
Afterwards, aforesaid operations are repeated, until the total time of ageing is 8h；It after drawing supernatant liquor after ageing, is filtered, in the process of suction filtration
In and filter cake to filtrate be washed with deionized be in neutrality；Take filter cake to be dried at a temperature of 100 DEG C, after drying by its
Calcination 3h at a temperature of 750 DEG C when being cooled to room temperature, carries out being ground to partial size being 100 mesh, obtains adsorbing agent carrier.
(4) preparation of desulfuration adsorbent: being added 110 parts of a solution in a kettle, and the mass fraction for adding 85 parts is
20% Ni (NO3)2Solution is opened blender and is stirred, mixing speed 100rpm, then again by 30 parts of adsorbent
Carrier is added in reaction kettle, increases the temperature to 55 DEG C, reacts 3.3h；After forming unit for uniform suspension, with constant pressure buret to reaction
The sodium bicarbonate solution that 80 parts of mass fractions are 30% is added dropwise in kettle, control rate of addition is to be added dropwise 2 drops/minute, at this time
Solution starts to become cloudy, and has a large amount of precipitatings to be formed, and after being added dropwise to complete, improves revolving speed to 300rpm, continues after stirring 1h, stop stirring
Mixed liquor a is obtained after mixing；Claim excessive anhydrous Na2CO3It pours into mixed liquor a, 100 is then added dropwise into reaction kettle with constant pressure buret
The b solution of part, control rate of addition are to be added dropwise 5 drops/minute, and solution starts to become cloudy at this time, has a large amount of precipitatings to be formed, drips
After the completion of adding, continue after stirring 1.5h, mixing speed 300rpm, obtains mixed liquor b after stopping stirring；Mixed liquor b is taken out
Filter during suction filtration and is washed with deionized filter cake to filtrate and is in neutrality, takes filter cake to be put into baking oven and dried, and dries
Temperature is 110 DEG C, after drying, puts it into progress calcination 3h in high temperature furnace, and calcination temperature is 800 DEG C, when being cooled to room temperature, will
It is 80 mesh that it, which is added in ball mill and carries out grinding partial size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends that diameter is 3mm steel pipe, and close with ventilative steel mesh
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined in the liquid or gas that are put into sulfur-bearing, are taken off
Sulphur.
Embodiment 2
A method of desulfuration adsorbent being prepared using Industrial Solid Waste, is included the following steps:
(1) preparation of a solution:
Industrial waste steel dreg is added in pulverizer and is crushed, smashed partial size is 140 mesh；Take 115 parts it is smashed
Steel slag powder is added in reactor, 70 parts of 18% hydrochloric acid solution is added drop-wise in reactor, after complete reaction, by solution
It is filtered, removes insoluble impurities, take filtrate that 54 parts of distilled water, 33 parts of ZnCl is added2·6H2After O after mixing evenly,
Obtain a solution.
(2) it the preparation of b solution: after industrial cullet is cleaned up, is added in pulverizer and is crushed, after crushing
Partial size be 80 mesh；It weighs 133 parts of smashed powder to be added in reactor, the hydroxide for being 37% by 85 parts of mass fraction
Sodium solution is added drop-wise in reactor, and control reaction temperature is 68 DEG C, and after complete reaction, solution is filtered, and is removed insoluble
Property impurity, take filtrate be added 65 parts of distilled water, 80 parts of sodium carbonate after mixing evenly, obtain b solution.
(3) preparation of adsorbing agent carrier: at room temperature, 150 parts of a solution is weighed and are added in reaction kettle, mixing speed is controlled
It is stirred for 230rpm, 80 parts of b solution is then added dropwise into reaction kettle with 3 drops/minute speed with constant pressure buret, are dripping
After the completion of adding, revolving speed is improved to 320rpm, continues to stir 1h, obtains mixed liquor after stopping stirring；Mixed liquor is stood at room temperature
Ageing is added deionized water to original scale after taking supernatant liquor, then carries out being slowly stirred 1.5min when solution clarification
Afterwards, aforesaid operations are repeated, until the total time of ageing is 9h；It after drawing supernatant liquor after ageing, is filtered, in the process of suction filtration
In and filter cake to filtrate be washed with deionized be in neutrality；Take filter cake to be dried at a temperature of 115 DEG C, after drying by its
Calcination 3.3h at a temperature of 800 DEG C when being cooled to room temperature, carries out being ground to partial size being 110 mesh, obtains adsorbing agent carrier.
(4) preparation of desulfuration adsorbent: 105 parts of a solution is added in a kettle, adds 100 parts of mass fraction
For 18% Ni (NO3)2Solution is opened blender and is stirred, mixing speed 120rpm, then again by 35 parts of absorption
Agent carrier is added in reaction kettle, increases the temperature to 60 DEG C, reacts 3h；After forming unit for uniform suspension, with constant pressure buret to reaction
The sodium bicarbonate solution that 90 parts of mass fractions are 27% is added dropwise in kettle, control rate of addition is to be added dropwise 3 drops/minute, at this time
Solution starts to become cloudy, and has a large amount of precipitatings to be formed, and after being added dropwise to complete, improves revolving speed to 350rpm, continues after stirring 1.2h, stop
Mixed liquor a is obtained after stirring；Claim excessive anhydrous Na2CO3It pours into mixed liquor a, 90 is then added dropwise into reaction kettle with constant pressure buret
The b solution of part, control rate of addition are to be added dropwise 3 drops/minute, and solution starts to become cloudy at this time, has a large amount of precipitatings to be formed, drips
After the completion of adding, continue after stirring 1.5h, mixing speed 400rpm, obtains mixed liquor b after stopping stirring；Mixed liquor b is taken out
Filter during suction filtration and is washed with deionized filter cake to filtrate and is in neutrality, takes filter cake to be put into baking oven and dried, and dries
Temperature is 120 DEG C, after drying, puts it into progress calcination 4h in high temperature furnace, and calcination temperature is 700 DEG C, when being cooled to room temperature, will
It is 90 mesh that it, which is added in ball mill and carries out grinding partial size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends that diameter is 4mm steel pipe, and close with ventilative steel mesh
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined in the liquid or gas that are put into sulfur-bearing, are taken off
Sulphur.
Embodiment 3
A method of desulfuration adsorbent being prepared using Industrial Solid Waste, is included the following steps:
(1) preparation of a solution:
Industrial waste steel dreg is added in pulverizer and is crushed, smashed partial size is 170 mesh；Take 108 parts it is smashed
Steel slag powder is added in reactor, 80 parts of 14% hydrochloric acid solution is added drop-wise in reactor, after complete reaction, by solution
It is filtered, removes insoluble impurities, take filtrate that 40 parts of distilled water, 40 parts of ZnCl is added2·6H2After O after mixing evenly,
Obtain a solution.
(2) it the preparation of b solution: after industrial cullet is cleaned up, is added in pulverizer and is crushed, after crushing
Partial size be 75 mesh；It weighs 127 parts of smashed powder to be added in reactor, the hydrogen-oxygen for being 43% by 100 parts of mass fraction
Change sodium solution to be added drop-wise in reactor, control reaction temperature is 60 DEG C, and after complete reaction, solution is filtered, and is removed not
Solubility impurity takes filtrate that 70 parts of distilled water, 60 parts of sodium carbonate is added after mixing evenly, obtains b solution.
(3) preparation of adsorbing agent carrier: at room temperature, 200 parts of a solution is weighed and are added in reaction kettle, mixing speed is controlled
It is stirred for 260rpm, 100 parts of b solution, In is then added dropwise into reaction kettle with 4 drops/minute speed with constant pressure buret
After being added dropwise to complete, revolving speed is improved to 350rpm, continues to stir 1.5h, obtains mixed liquor after stopping stirring；At room temperature by mixed liquor
It is still aging, when solution clarification, deionized water is added to original scale after taking supernatant liquor, is then slowly stirred
After 1min, aforesaid operations are repeated, until the total time of ageing is 9h；After drawing supernatant liquor after ageing, is filtered, filtered
In the process and filter cake to filtrate is washed with deionized it is in neutrality；Filter cake is taken to be dried at a temperature of 108 DEG C, by it after drying
Calcination 4h at a temperature of 640 DEG C when being cooled to room temperature, carries out being ground to partial size being 130 mesh, obtains adsorbing agent carrier.
(4) preparation of desulfuration adsorbent: being added 100 parts of a solution in a kettle, and the mass fraction for adding 80 parts is
23% Ni (NO3)2Solution is opened blender and is stirred, mixing speed 160rpm, then again by 40 parts of adsorbent
Carrier is added in reaction kettle, increases the temperature to 40 DEG C, reacts 4h；After forming unit for uniform suspension, with constant pressure buret to reaction kettle
The middle sodium bicarbonate solution that 100 parts of mass fractions are added dropwise and are 35%, control rate of addition is to be added dropwise 2 drops/minute, molten at this time
Liquid starts to become cloudy, and has a large amount of precipitatings to be formed, and after being added dropwise to complete, improves revolving speed to 400rpm, continues after stirring 1.5h, stop stirring
Mixed liquor a is obtained after mixing；Claim excessive anhydrous Na2CO3It pours into mixed liquor a, 120 is then added dropwise into reaction kettle with constant pressure buret
The b solution of part, control rate of addition are to be added dropwise 2 drops/minute, and solution starts to become cloudy at this time, has a large amount of precipitatings to be formed, drips
After the completion of adding, continue after stirring 1h, mixing speed 380rpm, obtains mixed liquor b after stopping stirring；Mixed liquor b is filtered,
It during suction filtration and filter cake to filtrate is washed with deionized is in neutrality, take filter cake to be put into baking oven and dried, drying temperature
Degree is 106 DEG C, after drying, puts it into progress calcination 3.6h in high temperature furnace, and calcination temperature is 600 DEG C, when being cooled to room temperature, will
It is 90 mesh that it, which is added in ball mill and carries out grinding partial size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends that diameter is 5mm steel pipe, and close with ventilative steel mesh
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined in the liquid or gas that are put into sulfur-bearing, are taken off
Sulphur.
Embodiment 4
A method of desulfuration adsorbent being prepared using Industrial Solid Waste, is included the following steps:
(1) preparation of a solution:
Industrial waste steel dreg is added in pulverizer and is crushed, smashed partial size is 200 mesh；Take 120 parts it is smashed
Steel slag powder is added in reactor, 40 parts of 23% hydrochloric acid solution is added drop-wise in reactor, after complete reaction, by solution
It is filtered, removes insoluble impurities, take filtrate that 47 parts of distilled water, 38 parts of ZnCl is added2·6H2After O after mixing evenly,
Obtain a solution.
(2) it the preparation of b solution: after industrial cullet is cleaned up, is added in pulverizer and is crushed, after crushing
Partial size be 100 mesh；It weighs 100 parts of smashed powder to be added in reactor, the hydrogen-oxygen for being 46% by 60 parts of mass fraction
Change sodium solution to be added drop-wise in reactor, control reaction temperature is 70 DEG C, and after complete reaction, solution is filtered, and is removed not
Solubility impurity takes filtrate that 80 parts of distilled water, 64 parts of sodium carbonate is added after mixing evenly, obtains b solution.
(3) preparation of adsorbing agent carrier: at room temperature, 100 parts of a solution is weighed and are added in reaction kettle, mixing speed is controlled
It is stirred for 300rpm, 120 parts of b solution, In is then added dropwise into reaction kettle with 5 drops/minute speed with constant pressure buret
After being added dropwise to complete, revolving speed is improved to 400rpm, continues to stir 2h, obtains mixed liquor after stopping stirring；Mixed liquor is quiet at room temperature
Ageing is set, when solution clarification, deionized water is added to original scale after taking supernatant liquor, is then slowly stirred
After 1.5min, aforesaid operations are repeated, until the total time of ageing is 10h；After drawing supernatant liquor after ageing, filtered, In
During suction filtration and filter cake to filtrate is washed with deionized it is in neutrality；Filter cake is taken to be dried at a temperature of 120 DEG C, after drying
By it at a temperature of 600 DEG C calcination 3.7h, when being cooled to room temperature, be ground to partial size is 150 mesh, obtains adsorbing agent carrier.
(4) preparation of desulfuration adsorbent: being added 120 parts of a solution in a kettle, and the mass fraction for adding 90 parts is
16% Ni (NO3)2Solution is opened blender and is stirred, mixing speed 200rpm, then again by 50 parts of adsorbent
Carrier is added in reaction kettle, increases the temperature to 50 DEG C, reacts 3.8h；After forming unit for uniform suspension, with constant pressure buret to reaction
The sodium bicarbonate solution that 120 parts of mass fractions are 32% is added dropwise in kettle, control rate of addition is to be added dropwise 3 drops/minute, at this time
Solution starts to become cloudy, and has a large amount of precipitatings to be formed, and after being added dropwise to complete, improves revolving speed to 340rpm, continues after stirring 2h, stop stirring
Mixed liquor a is obtained after mixing；Claim excessive anhydrous Na2CO3It pours into mixed liquor a, 80 parts is then added dropwise into reaction kettle with constant pressure buret
B solution, control rate of addition is to be added dropwise 4 drops/minute, and solution starts to become cloudy at this time, has a large amount of precipitatings to be formed, is added dropwise
After the completion, continue after stirring 2h, mixing speed 310rpm, obtain mixed liquor b after stopping stirring；Mixed liquor b is filtered, In
It during suction filtration and filter cake to filtrate is washed with deionized is in neutrality, take filter cake to be put into baking oven and dried, drying temperature
It is 100 DEG C, after drying, puts it into progress calcination 3.5h in high temperature furnace, calcination temperature is 750 DEG C, when being cooled to room temperature, by it
Being added in ball mill and carrying out grinding partial size is 100 mesh, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends that diameter is 4mm steel pipe, and close with ventilative steel mesh
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined in the liquid or gas that are put into sulfur-bearing, are taken off
Sulphur.
Comparative example 1
A kind of desulfuration adsorbent is made of the raw material below according to parts by weight: 37 parts of nanometer concavo-convex rod soil, methyl ketone hexamethylene
3 parts of ester, 11 parts of acrylic acid, 15 parts of ammonium metavanadate.Ammonium metavanadate is mixed with 6.1 times of its quality of deionized water, inclined vanadium is made
Acid ammonium solution；Acrylic acid is mixed with 2.7 times of its quality of dehydrated alcohol, acrylic acid solution is made.By nanometer concavo-convex rod soil with
Methyl ketone cyclohexyl mixed grinding crosses 120 meshes, and ammonium metavanadate solution is then added, and is warming up to 72 DEG C and close at such a temperature
Stir process 2.1h is sealed, acrylic acid solution is then added, is warming up to 89 DEG C and at such a temperature heating stirring processing 15min, so
Be ultrasonically treated 33min, ultrasonic power 900W at such a temperature afterwards, then 100 DEG C at a temperature of stirring to dry, then 450
DEG C Muffle furnace in calcine 4.3h up to desulfuration adsorbent.
The desulfuration adsorbent difference that the desulfuration adsorbent being prepared by embodiment 1-4 and comparative example 1 are prepared
It is tested for the property, obtains following test result:
1, using BET specific surface area method of testing to the ratio table of embodiment 1-4 and comparative example 1 desulfuration adsorbent being prepared
Area is tested, and test result is as follows shown in table:
BET specific surface area test result:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Specific surface area (m2/g) | 426.7 | 395.8 | 419.2 | 400.3 | 269.2 |
By upper table it is found that the specific surface area by the embodiment 1-4 desulfuration adsorbent being prepared is much larger than comparative example 1
In desulfuration adsorbent, illustrate the large specific surface area of desulfuration adsorbent that the present invention is prepared, and then the suction to sulphur can be increased
Assignments, the effect for adsorbing sulphur are more preferable.
2, using the sulfur content in GB/T380-88 oil product sulphur content determination method measurement gasoline.Wherein, desulfurization degree meter
Calculation method are as follows:
Desulfurization degree=(1- sulfur-free gasoline content/feedstock oil sulfur content) × 100%
The calculation method of adsorption capacity are as follows:
Adsorption capacity=(feed gasoline sulfur content × desulfurization degree × feed gasoline quality)/adsorbent mass × 10-3
It is 0.10 by adsorbent and feedstock oil mass ratio, in 15.0020g (20ml) straight run that sulfur content is 628.6 μ g/g
Adsorbent is added in gasoline, Static Adsorption 2h at a temperature of 30 DEG C filters to isolate gasoline after absorption, obtains desulfurization vapour
Oil, the result for testing sulfur content, desulfurization degree and adsorption capacity in sulfur-free gasoline are as shown in the table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Sulfur content (μ g/g) in sulfur-free gasoline | 150.9 | 164.2 | 157.3 | 160.5 | 319.6 |
| Desulfurization degree | 76% | 73.88% | 74.98% | 74.47% | 49.2% |
| Adsorption capacity (mg/g) | 4.78 | 4.64 | 4.71 | 4.68 | 3.09 |
By upper table it is found that the desulfuration adsorbent adsorption capacity being prepared by embodiment 1-4 is big, to the selectivity of sulphur
Good, desulfurization effect is more preferably.
3, the desulfuration adsorbent after 2 test of test is subjected to strength character test, intensity wears method using straight tube
It is evaluated, method of the evaluation method with reference to IPP 29-90 in " petrochemical analysis method (RIPP) experimental method ", difference
Adsorbent attrition evaluation result is as shown in the table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Abrasion index | 1.6 | 2.2 | 2.0 | 1.8 | 4.9 |
By upper table it is found that abrasion of the desulfuration adsorbent being prepared by embodiment 1-4 after absorption sulphur compared with
Small, abrasion numerical value is smaller, shows that abrasion resistance properties are higher.Desulfuration adsorbent prepared by the present invention is due to having used work in raw material
Industry solid waste, therefore enhance the intensity of desulfuration adsorbent, improves its wearability, can not only prolong its service life, can be with
Good recycling and reusing, and then cost can be reduced.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (3)
1. a kind of method for preparing desulfuration adsorbent using Industrial Solid Waste, which comprises the steps of:
(1) a solution is prepared using industrial waste steel dreg；
(2) b solution is obtained using Industry Waste glass preparation；
(3) above-mentioned a solution is added in a kettle, adds Ni (NO3)2Solution is stirred, then again by adsorbing agent carrier
It is added in reaction kettle, heating is reacted；Then sodium bicarbonate solution is added dropwise into reaction kettle with constant pressure buret, improves revolving speed
Continue to stir, obtains mixed liquor a after stopping stirring；
(4) claim excessive anhydrous Na2CO3It pours into mixed liquor a, above-mentioned b solution is then added dropwise into reaction kettle with constant pressure buret,
Continue to stir after being added dropwise to complete, obtains mixed liquor b after stopping stirring；
(5) mixed liquor b is filtered, during suction filtration and filter cake to filtrate is washed with deionized is in neutrality；
(6) it takes filter cake to be dried, calcination, when being cooled to room temperature, obtains desulfuration adsorbent；
In the step (1) a solution the preparation method comprises the following steps: industrial waste steel dreg is crushed, then take smashed steel-making slag powder
End is added in reactor, and hydrochloric acid solution is added drop-wise in reactor, after complete reaction, solution is filtered, filtrate is taken to add
Enter distilled water, ZnCl2·6H2After O after mixing evenly, a solution is obtained；Partial size is 100-200 mesh after the industrial waste steel dreg crushes；
The steel slag powder, dilute hydrochloric acid, distilled water, ZnCl2·6H2The mass fraction of O is respectively 100-120 parts, 40-80 parts, 40-60
Part, 30-40 parts；The mass fraction of the dilute hydrochloric acid is 14-23%；
In the step (2) b solution the preparation method comprises the following steps: by Industry Waste glass cleaning it is clean after crush, then take crushing
Powder afterwards is added in reactor, and sodium hydroxide solution is added drop-wise in reactor, and control reaction temperature is reacted, wait react
After completely, solution is filtered, is stirred evenly after taking filtrate that distilled water, sodium carbonate is added, obtains b solution；The Industry Waste glass
Partial size is 50-100 mesh after glass crushes；The powder, sodium hydroxide solution, distilled water, sodium carbonate mass fraction be respectively
100-150 parts, 60-100 parts, 60-80 parts, 60-80 parts；The mass fraction of the sodium hydroxide solution is 37-46%；It is described anti-
Answering temperature is 60-70 DEG C；
A solution, Ni (NO in the step (3)3)2Solution, adsorbing agent carrier, sodium bicarbonate solution mass fraction be respectively
100-120 parts, 80-100 parts, 30-50 parts, 80-120 parts；Ni (the NO3)2The mass fraction point of solution, sodium bicarbonate solution
It Wei not 16-23%, 27-35%；Mixing speed is 100-200rpm, and improving the speed stirred after revolving speed is 300-400rpm；It rises
Temperature arrives 40-60 DEG C, reacts 3-4h；Rate of addition is 2-3 drop/minute；Continue to stir 1-2h after improving revolving speed；
B solution additional amount is parts by weight 80-120 parts in the step (4)；Rate of addition is 2-5 drop/minute；Mixing speed is
300-400rpm, mixing time 1-2h；
The preparation method of adsorbing agent carrier in the step (3) includes the following steps:
A at room temperature, weighs 100-200 parts of a solution of parts by weight and is added in reaction kettle, control mixing speed is 200-300rpm
It is stirred, 80-120 parts of b solution of parts by weight is then added dropwise into reaction kettle with 2-5 drop/minute speed with constant pressure buret,
After being added dropwise to complete, revolving speed is improved to 300-400rpm, continues to stir 1-2h, obtains mixed liquor after stopping stirring；
B is still aging at room temperature by mixed liquor, when solution clarification, takes and deionized water is added after supernatant liquor to original
Then scale carries out after being slowly stirred 1-2min, repeat aforesaid operations, until the total time of ageing is 8-10h；
It after drawing supernatant liquor after C ageing, is filtered, during suction filtration and filter cake to filtrate is washed with deionized is in
It is neutral；
D takes filter cake to be dried at a temperature of 100-120 DEG C, after drying by it at a temperature of 600-800 DEG C calcination 3-4h, it is cold
When but to room temperature, carries out being ground to partial size being 100-150 mesh, obtain adsorbing agent carrier.
2. the method according to claim 1 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the step
(6) drying temperature is 100-120 DEG C in, and calcination temperature is 600-800 DEG C, calcination time 3-4h；When being cooled to room temperature, carry out
Being ground to partial size is 80-100 mesh.
3. application of the desulfuration adsorbent that a kind of any one of claim 1-2 the method is prepared in desulfurization, feature
It is, desulfuration adsorbent is put into the both ends that diameter is 3-5mm steel pipe, and is sealed with ventilative steel mesh, obtains single desulfurization adsorption tube；
More desulfurization adsorption tubes are combined in the liquid or gas that are put into sulfur-bearing, desulfurization is carried out.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264441A (en) * | 2008-05-09 | 2008-09-17 | 成都信息工程学院 | Modified steel scoria adsorbent and preparation thereof |
| CN101623619A (en) * | 2009-07-29 | 2010-01-13 | 东南大学 | Foaming-type industrial waste residue base compound dephosphorization material |
| CN103127902A (en) * | 2013-02-05 | 2013-06-05 | 浙江大学 | Preparation method, application method and purpose of poison control agent of cold waterlogged paddy field reduced sulfur |
| CN105854784A (en) * | 2015-01-19 | 2016-08-17 | 中国科学院过程工程研究所 | Method for preparing environmental protection material used for sewage treatment by reforming metallurgical dregs |
| CN106076257A (en) * | 2016-07-12 | 2016-11-09 | 成都信息工程大学 | One-step method prepares the method for slag municipal sludge magnetic adsorptive material |
| CN106311123A (en) * | 2016-11-08 | 2017-01-11 | 安徽工业大学 | Preparation method of water body molybdate adsorbent based on solid waste steel slag |
-
2017
- 2017-12-06 CN CN201711274219.0A patent/CN108295806B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264441A (en) * | 2008-05-09 | 2008-09-17 | 成都信息工程学院 | Modified steel scoria adsorbent and preparation thereof |
| CN101623619A (en) * | 2009-07-29 | 2010-01-13 | 东南大学 | Foaming-type industrial waste residue base compound dephosphorization material |
| CN103127902A (en) * | 2013-02-05 | 2013-06-05 | 浙江大学 | Preparation method, application method and purpose of poison control agent of cold waterlogged paddy field reduced sulfur |
| CN105854784A (en) * | 2015-01-19 | 2016-08-17 | 中国科学院过程工程研究所 | Method for preparing environmental protection material used for sewage treatment by reforming metallurgical dregs |
| CN106076257A (en) * | 2016-07-12 | 2016-11-09 | 成都信息工程大学 | One-step method prepares the method for slag municipal sludge magnetic adsorptive material |
| CN106311123A (en) * | 2016-11-08 | 2017-01-11 | 安徽工业大学 | Preparation method of water body molybdate adsorbent based on solid waste steel slag |
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