CN108295806A - 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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- CN108295806A CN108295806A CN201711274219.0A CN201711274219A CN108295806A CN 108295806 A CN108295806 A CN 108295806A CN 201711274219 A CN201711274219 A CN 201711274219A CN 108295806 A CN108295806 A CN 108295806A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
Abstract
The invention discloses a kind of methods preparing desulfuration adsorbent using Industrial Solid Waste, include the following steps：A solution is added in a kettle, adds 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 rotating speed and continues to stir, mixed liquor a is obtained 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, mixed liquor b is obtained 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 sorbing material technical field, relate particularly to a kind of preparing desulfuration adsorbent using Industrial Solid Waste
Method, and the application of desulfuration adsorbent that is prepared.
Background technology
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 be then easy to form photochemical fog by hydrophilic dye.
Most of sulphur comes from hot-working petroleum, predominantly catalytically cracked gasoline, therefore cracking vapour in China's gasoline
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, it is most of for activated carbon desulphurization agent, ZSM-5 desulfurizing agents.But existing desulfuration adsorbent has the disadvantage that：1, compare
Surface area is small, reduces adsorptive value；2, service life is short, it is difficult to recycling；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.
Invention content
The object of the present invention is to provide a kind of method preparing desulfuration adsorbent using Industrial Solid Waste, prepared desulfurization is inhaled
Attached dose of use is simple, and repeatable utilization；Industrial Solid Waste is added in raw material due to preparing, and significantly reduces 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
Rotating speed continues to stir, and mixed liquor a is obtained 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 mixed liquor b is obtained 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, the preparation method of a solution is in step (1)：Industrial waste steel dreg is crushed, crushing is then taken
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 being stirred evenly after O, a solution is obtained.
Further, the preparation method of b solution is in step (2)：By Industry Waste glass cleaning it is clean after crush,
Then it takes the powder after crushing to be added in reactor, sodium hydroxide solution is added drop-wise in reactor, controlling 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 addition 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 it is 300-400rpm to improve the speed stirred after rotating speed；It rises
Temperature arrives 40-60 DEG C, reacts 3-4h；Rate of addition is 2-3 drops/minute；Continue to stir 1-2h after improving rotating speed.
Further, b solution additions are 80-120 parts in step (4)；Rate of addition is 2-5 drops/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, it is 80-100 mesh to be ground to grain size.
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, control mixing speed carries out for 200-300rpm
Stirring, 80-120 parts of b solution are then added dropwise into reaction kettle with the speed of 2-5 drops/minute with constant pressure buret, are being added dropwise to complete
Afterwards, rotating speed is improved to 300-400rpm, continues to stir 1-2h, and mixed liquor is obtained after stopping stirring；
B is still aging at room temperature by mixed liquor, when solution is clarified, 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 ageings, 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, it is 100-150 mesh to be ground to grain size, obtains adsorbing agent carrier.
Further, grain size is 100-200 mesh after industrial waste steel dreg crushes；Slag powder, dilute hydrochloric acid, distilled water,
ZnCl2·6H2The addition 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, grain size is 50-100 mesh after industrial waste glass crushing；Powder, sodium hydroxide solution, distilled water, carbon
The addition of sour sodium be 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 is adsorbed
Agent is put into the both ends of a diameter of 3-5mm steel pipes, and ventilative steel mesh sealing is used in combination, 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, it is an advantage of the invention 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 extend its service life, acceptable good recycling, and then reduces cost.
2, the present invention is prepared into a solution and b solution respectively using industrial waste steel dreg and industrial cullet, 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 the primary raw material of the present invention is Industrial Solid Waste, i.e. industrial waste steel dreg and industrial cullet, system of the invention
It is standby of low cost, while Industrial Solid Waste can also rationally be recycled, its pollution to environment is reduced, economic effect is also increased
Benefit.
Specific implementation mode
Technical solution in the embodiment of the present invention is subjected to clear, complete description below, 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
All other embodiment for being obtained without making creative work of technical staff, belong to the guarantor of the present 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, the grain size after crushing is 100 mesh；After taking 100 parts to crush
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 being stirred evenly after O,
Obtain a solution.
(2) preparation of b solution：After industrial cullet is cleaned up, it is added in pulverizer and crushes, after crushing
Grain size be 50 mesh；It weighs the powder after 150 parts of crushing 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 controlling reaction temperature is 65 DEG C, and after complete reaction, solution is filtered, and is removed insoluble
Property impurity, take filtrate to be added after 60 parts of distilled water, 78 parts of sodium carbonate stirs evenly, obtain b solution.
(3) preparation of adsorbing agent carrier：At room temperature, 120 parts of a solution are weighed to be added in reaction kettle, control mixing speed
It is stirred for 200rpm, 90 parts of b solution is then added dropwise into reaction kettle with the speed of 2 drops/minute with constant pressure buret, are dripping
After the completion of adding, rotating speed is improved to 300rpm, continues to stir 1h, and mixed liquor is obtained 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 is clarified
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, it is 100 mesh to be ground to grain size, obtains adsorbing agent carrier.
(4) preparation of desulfuration adsorbent：110 parts of a solution is added in a kettle, 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 precipitations to be formed, and after being added dropwise to complete, improves rotating 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 precipitations to be formed, drips
After the completion of adding, continue after stirring 1.5h, mixing speed 300rpm, mixed liquor b is obtained 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, will when being cooled to room temperature
It is 80 mesh that it, which is added in ball mill and is ground grain size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends of a diameter of 3mm steel pipes, is used in combination ventilative steel mesh close
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined and are put into the liquid or gas of 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, the grain size after crushing is 140 mesh；After taking 115 parts to crush
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 being stirred evenly after O,
Obtain a solution.
(2) preparation of b solution：After industrial cullet is cleaned up, it is added in pulverizer and crushes, after crushing
Grain size be 80 mesh；It weighs the powder after 133 parts of crushing 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 controlling reaction temperature is 68 DEG C, and after complete reaction, solution is filtered, and is removed insoluble
Property impurity, take filtrate to be added after 65 parts of distilled water, 80 parts of sodium carbonate stirs evenly, obtain b solution.
(3) preparation of adsorbing agent carrier：At room temperature, 150 parts of a solution are weighed to be added in reaction kettle, control mixing speed
It is stirred for 230rpm, 80 parts of b solution is then added dropwise into reaction kettle with the speed of 3 drops/minute with constant pressure buret, are dripping
After the completion of adding, rotating speed is improved to 320rpm, continues to stir 1h, and mixed liquor is obtained 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 is clarified
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, it is 110 mesh to be ground to grain size, 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 precipitations to be formed, and after being added dropwise to complete, improves rotating 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 precipitations to be formed, drips
After the completion of adding, continue after stirring 1.5h, mixing speed 400rpm, mixed liquor b is obtained 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, will when being cooled to room temperature
It is 90 mesh that it, which is added in ball mill and is ground grain size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends of a diameter of 4mm steel pipes, is used in combination ventilative steel mesh close
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined and are put into the liquid or gas of 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, the grain size after crushing is 170 mesh；After taking 108 parts to crush
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 being stirred evenly after O,
Obtain a solution.
(2) preparation of b solution：After industrial cullet is cleaned up, it is added in pulverizer and crushes, after crushing
Grain size be 75 mesh；It weighs the powder after 127 parts of crushing 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, controlling reaction temperature is 60 DEG C, and after complete reaction, solution is filtered, and is removed not
Solubility impurity obtains b solution after taking 70 parts of distilled water of filtrate addition, 60 parts of sodium carbonate to stir evenly.
(3) preparation of adsorbing agent carrier：At room temperature, 200 parts of a solution are weighed to be added in reaction kettle, control mixing speed
It is stirred for 260rpm, 100 parts of b solution is then added dropwise into reaction kettle with the speed of 4 drops/minute with constant pressure buret,
After being added dropwise to complete, rotating speed is improved to 350rpm, continues to stir 1.5h, and mixed liquor is obtained after stopping stirring；At room temperature by mixed liquor
It is still aging, when solution is clarified, 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, it is 130 mesh to be ground to grain size, obtains adsorbing agent carrier.
(4) preparation of desulfuration adsorbent：100 parts of a solution is added in a kettle, 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 precipitations to be formed, and after being added dropwise to complete, improves rotating 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 precipitations to be formed, drips
After the completion of adding, continue after stirring 1h, mixing speed 380rpm, mixed liquor b is obtained 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, will when being cooled to room temperature
It is 90 mesh that it, which is added in ball mill and is ground grain size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends of a diameter of 5mm steel pipes, is used in combination ventilative steel mesh close
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined and are put into the liquid or gas of 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, the grain size after crushing is 200 mesh；After taking 120 parts to crush
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 being stirred evenly after O,
Obtain a solution.
(2) preparation of b solution：After industrial cullet is cleaned up, it is added in pulverizer and crushes, after crushing
Grain size be 100 mesh；It weighs the powder after 100 parts of crushing 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, controlling reaction temperature is 70 DEG C, and after complete reaction, solution is filtered, and is removed not
Solubility impurity obtains b solution after taking 80 parts of distilled water of filtrate addition, 64 parts of sodium carbonate to stir evenly.
(3) preparation of adsorbing agent carrier：At room temperature, 100 parts of a solution are weighed to be added in reaction kettle, control mixing speed
It is stirred for 300rpm, 120 parts of b solution is then added dropwise into reaction kettle with the speed of 5 drops/minute with constant pressure buret,
After being added dropwise to complete, rotating speed is improved to 400rpm, continues to stir 2h, and mixed liquor is obtained after stopping stirring；Mixed liquor is quiet at room temperature
Ageing is set, when solution is clarified, 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,
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 grain size be 150 mesh, obtain adsorbing agent carrier.
(4) preparation of desulfuration adsorbent：120 parts of a solution is added in a kettle, 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 precipitations to be formed, and after being added dropwise to complete, improves rotating 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 precipitations to be formed, is added dropwise
After the completion, continue after stirring 2h, mixing speed 310rpm, mixed liquor b is obtained 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
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
It is 100 mesh to be added in ball mill and be ground grain size, obtains desulfuration adsorbent.
(5) the above-mentioned desulfuration adsorbent being prepared is put into the both ends of a diameter of 4mm steel pipes, is used in combination ventilative steel mesh close
Envelope, obtains single desulfurization adsorption tube；More desulfurization adsorption tubes are combined and are put into the liquid or gas of 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 concavo-convex rod soil of nanometer, methyl ketone hexamethylene
3 parts of ester, 11 parts of acrylic acid, 15 parts of ammonium metavanadate.6.1 times of deionized water of ammonium metavanadate and its quality is mixed, inclined vanadium is made
Acid ammonium solution；2.7 times of absolute ethyl alcohol of acrylic acid and its quality is mixed, acrylic acid solution is made.By nanometer concavo-convex rod soil with
Methyl ketone cyclohexyl mixed grinding crosses 120 mesh sieve, and ammonium metavanadate solution is then added, 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
33min, ultrasonic power 900W are ultrasonically treated at such a temperature afterwards, then stirring is to doing at a temperature of 100 DEG C, then 450
DEG C Muffle furnace in calcining 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 adsorbents 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, the sulfur content in gasoline is measured using GB/T380-88 oil product sulphur content determination methods.Wherein, desulfurization degree meter
Calculation method is：
Desulfurization degree=(1- sulfur-free gasolines content/feedstock oil sulfur content) × 100%
The computational methods of adsorption capacity are：
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, test sulfur-free gasoline in sulfur content, desulfurization degree and adsorption capacity the results are shown in table below：
| 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, evaluation method reference《Petrochemical analysis method (RIPP) experimental method》The method of middle IPP 29-90 is different
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 in raw material due to having used work
Industry solid waste, therefore enhance the intensity of desulfuration adsorbent, improves its wearability, can not only extend its service life, can be with
Good recycling, and then cost can be reduced.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every 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 (10)
1. a kind of method preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that include 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 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 rotating speed
Continue to stir, mixed liquor a is obtained after stopping stirring；
(4) claim excessive anhydrous Na 2CO3It 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, mixed liquor b is obtained 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.
2. the method according to claim 1 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the step
(1) preparation method of a solution is in：Industrial waste steel dreg is crushed, then takes the slag powder after crushing that reactor is added
In, hydrochloric acid solution is added drop-wise in reactor, after complete reaction, solution is filtered, take filtrate be added distilled water,
ZnCl2·6H2After being stirred evenly after O, a solution is obtained.
3. the method according to claim 1 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the step
(2) preparation method of b solution is in：By Industry Waste glass cleaning it is clean after crush, then take crush after powder be added
In reactor, sodium hydroxide solution is added drop-wise in reactor, controlling reaction temperature is reacted, after complete reaction, will be molten
Liquid is filtered, and is stirred evenly after taking filtrate that distilled water, sodium carbonate is added, is obtained b solution.
4. the method according to claim 1 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the step
(3) a solution, Ni (NO in3)2Solution, adsorbing agent carrier, sodium bicarbonate solution addition be respectively 100-120 parts, 80-100 parts,
30-50 parts, 80-120 parts；Ni (the NO3)2Solution, sodium bicarbonate solution mass fraction be respectively 16-23%, 27-35%；
Mixing speed is 100-200rpm, and it is 300-400rpm to improve the speed stirred after rotating speed；It is warming up to 40-60 DEG C, reacts 3-4h；
Rate of addition is 2-3 drops/minute；Continue to stir 1-2h after improving rotating speed.
5. the method according to claim 1 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the step
(4) b solution addition is 80-120 parts in；Rate of addition is 2-5 drops/minute；Mixing speed is 300-400rpm, mixing time
For 1-2h.
6. 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 is 3-4 h；When being cooled to room temperature, into
It is 80-100 mesh that row, which is ground to grain size,.
7. the method according to claim 1 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the step
(3) preparation method of the adsorbing agent carrier in includes the following steps：
A at room temperature, weighs 100-200 parts of a solution and is added in reaction kettle, and control mixing speed is that 200-300rpm is stirred
It mixes, 80-120 parts of b solution is then added dropwise into reaction kettle with the speed of 2-5 drops/minute with constant pressure buret, are being added dropwise to complete
Afterwards, rotating speed is improved to 300-400rpm, continues to stir 1-2 h, and mixed liquor is obtained after stopping stirring；
B is still aging at room temperature by mixed liquor, and when solution is clarified, deionized water is added to original quarter after taking supernatant liquor
Degree, then carries out after being slowly stirred 1-2min, repeats aforesaid operations, until the total time of ageing is 8-10 h；
It after drawing supernatant liquor after C ageings, is filtered, during suction filtration and is washed with deionized during filter cake is in filtrate
Property；
D takes filter cake to be dried at a temperature of 100-120 DEG C, calcination 3-4h, cooling at a temperature of 600-800 DEG C by it after drying
When to room temperature, it is 100-150 mesh to be ground to grain size, obtains adsorbing agent carrier.
8. the method according to claim 2 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the industry
Grain size is 100-200 mesh after steel slag crushes；The slag powder, dilute hydrochloric acid, distilled water, ZnCl2·6H2The addition of O is distinguished
It is 100-120 parts, 40-80 parts, 40-60 parts, 30-40 parts；The mass fraction of the dilute hydrochloric acid is 14-23%.
9. the method according to claim 3 for preparing desulfuration adsorbent using Industrial Solid Waste, which is characterized in that the industry
Grain size is 50-100 mesh after waste glass crushing；The powder, sodium hydroxide solution, distilled water, sodium carbonate addition be respectively
100-150 powder, 60-100 parts, 60-80 parts, 60-80 parts；The mass fraction of the sodium hydroxide solution is 37-46%；It is described anti-
It is 60-70 DEG C to answer temperature.
10. the application in desulfurization for the desulfuration adsorbent that a kind of any one of claim 1-9 the methods are prepared, special
Sign is that desulfuration adsorbent is put into the both ends of a diameter of 3-5mm steel pipes, and ventilative steel mesh sealing is used in combination, and obtains single desulfurization absorption
Pipe；More desulfurization adsorption tubes are combined and are put into the liquid or gas of sulfur-bearing, desulfurization is carried out.
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| 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 |
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