CN106629796B - A kind of method of discarded industrial activated alumina activating and regenerating - Google Patents
A kind of method of discarded industrial activated alumina activating and regenerating Download PDFInfo
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- CN106629796B CN106629796B CN201611146633.9A CN201611146633A CN106629796B CN 106629796 B CN106629796 B CN 106629796B CN 201611146633 A CN201611146633 A CN 201611146633A CN 106629796 B CN106629796 B CN 106629796B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention discloses a kind of method of discarded industrial activated alumina activating and regenerating, including pretreatment, cleaning solution impregnation and regeneration treatment；The cleaning solution of use is selected from least one of acid solution, lye, surfactant solution；Regeneration treatment includes regenerated liquid dipping and calcination processing, and the regenerated liquid of use is selected from containing aluminum solutions；Calcination processing carries out in air atmosphere, and air intake is 300~800m3/(h·t).The present invention provides a kind of methods of discarded industrial activated alumina activation reuse, and original pore structure passage is dredged by physics and chemical method, and new pore structure is regenerated on the basis of existing pore structure, obtain the activated alumina of the high pore volume of high-specific surface area.
Description
Technical field
The present invention relates to the regeneration fields of industrial solid wastes, and in particular to a kind of discarded industrial activated alumina activation is again
Raw method.
Background technology
Activated alumina is a kind of high degree of dispersion, porous solid material, and there is hole gap to enrich, thermal stability is good,
It is wear-resistant, crushing strength is high, specific surface area is high, attraction performance is good, surface acidity, the characteristics of aperture and hole are adjustable, therefore
It is widely used as adsorbent, catalyst, catalyst carrier, drier, defluorinating agent etc..With the fast development of industry, activity
The demand of aluminium oxide is also constantly increasing.After certain time use, since a large amount of impurity are adsorbed on surface and internal pore structure
(by taking discarded space division drier as an example, alumina balls are in khaki, and the impurity of absorption is mainly dust and mineral quasi-grease), causes
It loses original activity and throws aside.After largely discarded activated alumina is abandoned as solid waste, the wave of resource is not only caused
Take, while environment can also be caused seriously to pollute, therefore the recycling to discarding aluminium oxide has great importance.
Discarded industrial activated alumina regeneration regenerates and in foramen primum structure using discarded oxidation aluminum for aluminium powder
On the basis of regenerate.The former is primarily referred to as discarded alumina powder is broken, then carries out sour molten or alkali fusion and obtains, containing aluminum solutions, passing through
It filters, be recrystallized to give high-purity solid containing aluminium, then carry out high-temperature roasting and obtain activated alumina.Xu Zhi soldier et al. will discard
Aluminium oxide is calcined at high temperature together with sodium carbonate, and cooled and filtered goes out sodium metaaluminate filtrate, then adds into sodium aluminate solution
Enter acid solution and be passed through CO simultaneously2Control pH is settled out aluminium hydroxide, and finally roasting obtains active oxidation at a certain temperature again
Aluminium (Xu Zhibing etc., the Primary Study of Studying of Recycling Aluminum from waste catalyst, Anqing Teachers College's journal (natural science edition),
2004,10 (1)：57-58).This process is complicated, and activated alumina needs to be molded again, relatively complicated.
Regeneration is primarily referred to as to adsorb and be removed in the impurity of oxidation aluminium surface and internal pore structure on foramen primum architecture basics,
Duct is dredged, recovers original pore structure.Renovation process is mainly solution dipping-roasting method, common maceration extract include nitric acid,
Sulfuric acid, sodium acid carbonate, sodium carbonate, sodium hydroxide, sodium metaaluminate and aluminum sulfate solution etc..Master operation is by discarded active oxidation
Aluminium is impregnated with solution, and then dry, calcining determines suitable impregnation concentration according to the species of discarded alumina impurities and content
With the time, and then the parameters such as suitable drying temperature and time, calcining heat and time are determined.
The researchs of section grain husk etc. find using low-concentration sulfuric acid aluminium (0.5%, by Al2O30.06%) and ferric sulfate (0.2%) it is calculated as
Its absorption property to fluorine in water can be significantly improved to activated alumina modification.(section grain husk etc., two kinds of composite modified active oxygens of salt
Change aluminium to the characterization of adsorption of fluorine in water, Environmental Chemistry, 2014,33 (11)：1950-1956) Chou Fuguo et al. is by the work after fluorine removal
Property aluminium oxide and various concentration aluminum sulfate solution press volume 1:It fully washs, can be aoxidized with activity recovery after 1 proportioning dipping
The adsorption capacity of aluminium, the solution optium concentration of aluminum sulfate (press Al for 1-2%2O3It is calculated as 0.12-0.24%).(Chou Fu states etc., it is living
Property aluminium oxide and bone black fluorine removal research, Xi'an University of Architecture and Technology's journal, 2001,33 (1)：56-60) Zheng Yunhong etc. uses 6-
20% nitric acid carries out dipping regeneration to discarded regenerative agent aluminium oxide (hydrogen dioxide solution production by anthraquinone process with aluminium oxide), finds in 8% nitre
10min is impregnated in acid solution and then 2h is calcined under the conditions of 500 DEG C can obtain maximum specific surface area 251.97m2/ g, but compared with
High acidity can make alumina particle intensity be badly damaged.(Zheng Yunhong etc., hydrogen nitrate dipping method regenerating waste active alumina it is microcosmic
Structural research, silicate circular, 2007,26 (4)：821-825).
Pore property is the important parameter for determining aluminium oxide performance (including specific surface area and aperture).Aluminium oxide first should
Contact area as big as possible is provided；Its is secondary suitable aperture, and aperture is excessive, and the specific surface area of carrier will reduce, hole
Footpath is too small, is adversely affected to adsorbate diffusion zone.The discarded activated alumina key that is recycled is by physically or chemically
Again expansion of the method to its pore structure, activity recovery.By taking discarded space division special drying agent as an example, surface and internal pore structure
It is blocked by mud stain and grease, loses original absorption property.Ultrasonic cavitation can effectively go mechanical fitting and vessel surface
Oil stain, but using fresh herb is cleaned in porous material, by adjust supersonic frequency and power or can remove mud stain inside duct and
Grease.Acid, the acidifying of alkaline cleaner and saponification can remove the organic matter mixed in duct, dredging duct, make original
Alumina pore structure is exposed again.But aluminium oxide is amphoteric oxide, and excessive concentration can destroy original pore structure, cause
Intensity and specific surface area decline；Concentration is too low and without cleaning performance.Surfactant can have by lipophilic group effect
Effect removes the grease in duct, but larger molecular weight and space structure can hinder it in aluminium oxide micropore diffusion inside.By multiple
Complex acid, alkali and surfactant washing liquid by ultrasonication or can effectively remove discarded oxidation aluminium surface and internal gutter
Impurity.Aluminium oxide inevitably generates internal pore structure certain damage using process and impregnation process, leads to
Crossing molten aluminum dipping can be such that aluminium ion remains to inside duct, then repaired the pore structure of damage by calcining and generated
New pore structure increases specific surface area, while improves alumina balls intensity.
Heat treatment plays key effect to recovering aluminium oxide active, is divided into two processes of drying and calcination.Drying is often referred to
Using thermal energy hygroscopic water in material is made to gasify, and the steam of generation is taken away by inert gas, so as to the process for removing hygroscopic water.Oxidation
Aluminium hydrate belongs to porous material, and structure mesoporous road interconnects, and the opening in duct and the size in section are irregular.It is dry
When, moisture is initially moved from capillarity and to surface, and maintains surface complete wetting, and the moisture in macropore is due to steaming
Vapour pressure is larger and is first begin to evaporate, when moisture evaporation in smaller hole, due to capillarity, the moisture of reduction can be from
It adsorbs and is supplemented in larger hole.If using higher temperature rapid draing, can often cause granule strength reduce and
Generate crack.
The physicochemical change of calcination can be attributed to three thermal decomposition, recrystallization and sintering processes, and effect is respectively：
(1) gone out by pyrolysis the volatile components and chemical bonding water of aluminium scrap oxygen material, aluminium scrap oxygen is made to be converted into needs
Chemical constituent forms stable structure；(2) pass through the recrystallization process occurred during calcination, carrier is made to obtain certain crystal form, crystalline substance
Grain size, pore structure and specific surface；(3) it is sintered by crystallite, improves mechanical strength.Thermal decomposition can make moisture in material and
Volatile component constantly escapes, and increased internal surface area, tiny microcellular structure occurs, but this process inner surface product
It contributes and little.Recrystallization can greatly improve the crystallite number in product, so that specific surface area dramatically increases.Sintering is
When finger solid is heated to the temperature less than its fusing point, solid microcrystalline particle is bonded to aggregation, is closed duct, densification, Gu
The specific surface area of body is reduced, but intensity increases.
The content of the invention
The present invention provides a kind of methods of discarded industrial activated alumina activation reuse, are dredged by physics and chemical method
Logical original pore structure passage, and new pore structure is regenerated on the basis of existing pore structure, obtain the high pore volume of high-specific surface area
Activated alumina.Discarded industrial activated alumina recycling is the method achieve, while solves the ring thrown aside and brought
Border pollution problem.
Specific technical solution is as follows：
A kind of method of discarded industrial activated alumina activating and regenerating, includes the following steps：
(1) pre-process：The impurity on the discarded industrial activated alumina surface of removal；
(2) cleaning solution impregnates：The impurity of the discarded industrial activated alumina internal gutter of removal；
The cleaning solution is selected from least one of acid solution, lye, surfactant solution；
(3) regenerate：Step (2) treated aluminium oxide is immersed in regenerated liquid, then through drying, calcination processing, is lived
Property aluminium oxide；
The regenerated liquid is selected from containing aluminum solutions；
The calcination processing carries out in air atmosphere, and the calcination processing carries out in air atmosphere, and air leads to
Enter amount for 300~800m3/(h·t)。
The key of the process for activating and regenerating of the present invention is：It is clear using acid, alkali and surfactant compound under ultrasonication
Washing lotion can effectively remove the impurity of alumina adsorption, dredge original duct, expose the pore structure with absorption property again, should
Cleaning solution is small to the damage of original pore structure, and alumina balls is made to be able to maintain that certain intensity, reduce the energy consumption of calcining link；Both
Have and revived structure grafting is carried out on the basis of pore structure, carry out effective pore structure modification, obtain the active oxygen of high-specific surface area
Change aluminium, and improve product strength；According to the content of total organic carbon in aluminium oxide suitable oxygen-supplying amount is controlled to prevent in calcining link
The generation of carbon distribution, while avoid energy waste.Discarded industrial activated alumina can be become by high added value by the technique
Industrial products, turn waste into wealth, efficiently solve the problem of environmental pollution thrown aside and brought.
The discarded industrial activated alumina derives from《Industrial activated alumina》(HJ/T3927-2007) it is used to adsorb
Agent, regenerative agent, the discarded activated alumina of space division drier.Preferably, space division special drying agent activated alumina is selected from,
Impurities are stablized, and relatively single.
Preferably, in step (1), using water-bath mechanical friction cleaning, ultrasonic cleaning or the two Combined Treatment, removal
The impurity such as the mud stain of adsorption and grease.
Further preferably, the frequency of ultrasonic cleaning be 15~60kHz, solid-to-liquid ratio 1:1~10.
Preferably, pretreatment mode is handled using water-bath mechanical friction.
Preferably, in step (1), raw material after pretreatment also needs to enter back into after separation of solid and liquid and drying process
Step (2), preferred drying temperature are 80~150 DEG C, and the time is 1.0~5.0h.It is discarded when dry wet in aluminium oxide duct
Divide since capillarity is to surface movement, then evaporate, this process is tied for the hole of the activated alumina after activating and regenerating
Structure and granule strength have a major impact.Further preferably, drying temperature is 100~150 DEG C.
Further, the washings reusable edible used in preprocessing process.
In step (2), cleaning solution impregnates the impurity for being mainly used for alumina internal gutter, preferably, cleaning solution
It is aided with ultrasonication during dipping, ultrasonic frequency is 40~100kHz.
Preferably, the acid solution include hydrochloric acid solution, salpeter solution, sulfuric acid solution, phosphoric acid solution, boric acid solution,
At least one of oxalic acid solution；
The lye includes sodium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution, sodium silicate solution, trimerization phosphorus
At least one of acid sodium solution；
The surfactant solution includes induced by alkyl hydroxybenzene polyether solutions, 13 carbon alcohol ethereal solution of isomery, fatty acid methyl
At least one of ester ethoxylate solution.
Cleaning solution can expand duct section and pore volume, increase specific surface area, increase duct number, improve surface property.
Too low concentration of lotion or shorter dip time are poor to the activation effect for discarding aluminium oxide, excessively high impregnation concentration or
Dip time too long can generate ill effect to pore structure and granule strength.It is when ultrasonic with solid-liquid simultaneously to impregnate cleaning performance
Wave frequency rate is related.
Preferably, the concentration of the cleaning solution is 1.0~20.0wt%.When cleaning solution is one-component, then clean
The concentration of liquid is the mass percent concentration of the one-component；When cleaning solution is multicomponent, then each component in cleaning solution
Concentration all be respectively 1.0~20.0wt%.
Preferably, the time of cleaning solution dipping is 5~120min, solid-to-liquid ratio is 1 in cleaning solution:1~10；It is further excellent
It selects, solid-to-liquid ratio is 1 in cleaning solution:1~3, ultrasonic frequency is 40~80kHz.
Further preferably, the cleaning solution is bi-component, is mixed by acid solution or lye, then with surfactant solution
It arrives；
When using the cleaning solution of bi-component, can select to be separately configured acid solution or lye, then with surfactant solution
The mode of mixing, at this point, the acid solution or the concentration range of lye that are separately configured are 1.0~20.0wt%.
Acid after calculating or solid base can also be directly added into surfactant solution, ensure acid solution or alkali in solution
The concentration range of liquid is in 1.0~20.0wt%.
Further preferably, in the cleaning solution of bi-component, the acid solution is selected from boric acid solution；
The lye is selected from sodium carbonate liquor or sodium hydroxide solution；
The surfactant solution be selected from nonylphenol polyoxyethylene ether solution, octyl phenol polyoxyethylene ethereal solution or
Ethoxylated dodecyl alcohol solution.
Preferably, after cleaned liquid impregnation, also need to enter back into step (3) after separation of solid and liquid and drying process,
Preferred drying temperature is 80~150 DEG C, and the time is 1.0~5.0h.
The dipping regeneration containing aluminum solutions described in step (3) is mainly used for reparation cleaning solution dipping and original pore structure is caused
Destruction, and new pore structure is grafted on the basis of existing pore structure, improves alumina ratio surface area.It is preferably, described
Aluminum nitrate solution, aluminum sulfate solution, liquor alumini chloridi or sodium aluminate solution are selected from containing aluminum solutions, with Al2O3Meter, it is described to contain aluminium
The mass concentration of solution is 1.0~12.0wt%；The time of regenerated liquid dipping is 30~120min.
Further preferably, the regenerated liquid is aluminum sulfate solution.
In step (3), the calcination processing after regenerated liquid impregnates can make the low melting point in aluminium oxide volatile substances and
Moisture evaporation removes impurity, dredges duct, obtains certain crystal form, pore structure and specific surface area.
Calcining heat is too low, and the organic matter in aluminium oxide duct cannot normally volatilize, for aluminium oxide regeneration effect compared with
Difference.Calcining heat is excessively high, and the crystal form of aluminium oxide can change, and converts Viability relatively low α-Al2O3。
Too long, adsorbent melting is bonded to agglomerate, porous structure caves in, duct number to calcination time under agglomeration
Mesh is reduced, and specific surface area reduces.It is too fast to calcine heating rate, the pore structure of aluminium oxide can be destroyed, comparison surface area has certain
It influences.
Oxygen-supplying amount during calcining determines that discarded activated alumina adsorbs carbonization and the degree of decomposition of organic matter, to activation
The final performance of rear oxidation aluminium has more critical influence, by taking discarded space division drier and adsorbent as an example, in impurity
Grease occupies larger proportion, if oxygen-supplying amount deficiency can cause organic carbon in calcination process, forms carbon distribution obstruction duct
Or oxidation aluminium surface is attached to, adsorption capacity is caused to decline；If oxygen-supplying amount crosses conference energy consumption is caused to increase.
Preferably, the calcine technology condition is：
Heating rate is 5~20K/min；
Calcining heat is 300~600 DEG C, and the time is 30~300min.
Preferably, in step (3), dry temperature is 80~150 DEG C, and the time is 1.0~5.0h.
Unless otherwise specified, the concentration of all raw materials is mass percent concentration in the present invention.
Compared with prior art, the present invention has the following advantages：
(1) compounding cleaning agent can effectively remove the impurity in aluminium oxide duct under ultrasonication, while reduce to original
There is pore structure destruction, certain granule strength is able to maintain that on the basis of the original activated adoption structure of exposure, when reducing calcining
Energy consumption.
(2) using pore structure reparation and grafting regeneration techniques, activate the activated alumina intensity obtained after reuse and carried
Height, and specific surface area is significantly higher than the aluminium oxide of commercially available equal product rank, reaches as high as 326m2/g。
(3) suitable oxygen-supplying amount is determined according to the content of total organic carbon, prevent carbon distribution from generating and reduces energy waste.
(4) realize discarded industrial activated alumina secondary use, reach recycling purpose.
Description of the drawings
Fig. 1 is the process flow chart that industrial activated alumina activating and regenerating is discarded in the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but the invention is not restricted to following embodiments.
Embodiment 1
Discarded space division special aluminium oxide drier and water are pressed 1:5 dippings make alumina balls suspend, rub using mechanical agitation
It wipes, separation of solid and liquid after 40min, liquid reuse, solid phase is put into 105 DEG C of air dry ovens dry 3h；By pretreated oxidation
Aluminium is according to volume ratio 1:1 is immersed in the nonylphenol polyoxyethylene ether for the sodium carbonate+5.0wt% that mass percent is 4.0wt%
(TX) in mixed solution, 1h is kept, then with 40kHz ultrasonication 30min, separation of solid and liquid, liquid phase reuse, solid phase is put into
Dry 3h in 105 DEG C of air dry ovens；By the aluminium oxide after cleaning according to 1:1 volume ratio is immersed in 4.0% (by Al2O3Meter)
60min in aluminum sulfate solution, separation of solid and liquid, liquid phase reuse, solid phase are put into 150 DEG C of air dry ovens dry 1h, are then put
500 DEG C are warming up to using 17K/min rates in calcining furnace, 0.5h is kept, 500m is pressed in calcination process3/ (ht) rates are led to
Enter air capacity, obtain specific surface area as 312.4m2/ g, the white alumina product that intensity is 153.4N/.
Embodiment 2
Discarded space division special aluminium oxide drier and water are pressed 1:5 dippings make alumina balls suspend, rub using mechanical agitation
It wipes, separation of solid and liquid after 60min, liquid reuse, solid phase is put into 105 DEG C of air dry ovens dry 3h；By pretreated oxidation
Aluminium is according to volume ratio 1:3 are immersed in the nonylphenol polyoxyethylene ether for the sodium carbonate+10.0wt% that mass percent is 4.0wt%
(TX) in mixed solution, 2h is kept, then with 40kHz ultrasonication 60min, separation of solid and liquid, liquid phase reuse, phase solid phase is put into
Dry 3h in 105 DEG C of air dry ovens；By the aluminium oxide after cleaning according to 1:3 volume ratio is immersed in 4.0% (by Al2O3Meter)
30min in aluminum sulfate solution, separation of solid and liquid, liquid phase reuse, solid phase are put into 105 DEG C of air dry ovens dry 3h, are then put
500 DEG C are warming up to using 10K/min rates in calcining furnace, 0.5h is kept, 500m is pressed in calcination process3/ (ht) rates are led to
Enter air capacity, obtain specific surface area as 326.6m2/ g, the white alumina product that intensity is 160.3N/.
Embodiment 3
Discarded space division special aluminium oxide drier and water are pressed 1:1 dipping is cleaned by ultrasonic 20min, solid-liquid point using 25kHz
From liquid reuse, solid is put into 90 DEG C of air dry ovens dry 4h；By pretreated aluminium oxide according to volume ratio 1:3 leachings
Enter into the salpeter solution of 8.0wt%, keep 1h, then with 50kHz ultrasonication 10min, separation of solid and liquid, liquid phase reuse,
Phase solid phase is put into 105 DEG C of air dry ovens dry 3h；By the aluminium oxide after cleaning according to 1:1 volume ratio is immersed in 5.0%
(press Al2O3Meter) 30min in aluminum sulfate solution, separation of solid and liquid, liquid phase reuse, solid phase is put into 105 DEG C of air dry ovens dry
3h is subsequently placed in calcining furnace and is warming up to 500 DEG C using 10K/min rates, keeps 2.0h, 500m is pressed in calcination process3/(h·
T) rate is passed through air capacity, obtains specific surface area 285.1m2/ g, the white alumina product that intensity is 132.7N/.
Comparative example 1
Discarded space division special aluminium oxide drier and water are pressed 1:1 dipping is cleaned by ultrasonic 20min, solid-liquid point using 25kHz
From liquid reuse, solid is put into 90 DEG C of air dry ovens dry 4h；By pretreated aluminium oxide according to volume ratio 1:3 leachings
Enter into the salpeter solution of 8.0wt%, keep 1.h, then with 50kHz ultrasonication 10min, separation of solid and liquid, liquid phase reuse,
Phase solid phase is put into 105 DEG C of air dry ovens dry 3h；It is subsequently placed in calcining furnace and is warming up to 500 DEG C using 10K/min rates,
2h is kept, 500m is pressed in calcination process3/ (ht) rates are passed through air capacity, obtain specific surface area 285.6m2/ g, intensity are
The white alumina product of 53.2N/.
Comparative example 2
Discarded space division special aluminium oxide drier and water are pressed 1:1 dipping is cleaned by ultrasonic 20min, solid-liquid point using 25kHz
From liquid reuse, solid is put into 90 DEG C of air dry ovens dry 4h；By pretreated aluminium oxide according to volume ratio 1:3 leachings
Enter into the salpeter solution of 8.0wt%, keep 1.h, then with 50kHz ultrasonication 10min, separation of solid and liquid, liquid phase reuse,
Phase solid phase is put into 105 DEG C of air dry ovens dry 3h；It is subsequently placed in calcining furnace and is warming up to 500 DEG C using 10K/min rates,
2h is kept, 100m is pressed in calcination process3/ (ht) rates are passed through air capacity and obtain specific surface area 232.6m2/ g, intensity are
The gray oxide aluminium product of 63.2N/.
Comparative example 3
Discarded space division special aluminium oxide drier and water are pressed 1:1 dipping is cleaned by ultrasonic 20min, solid-liquid point using 25kHz
From liquid reuse, solid is put into 90 DEG C of air dry ovens dry 4h；By pretreated aluminium oxide according to volume ratio 1:3 leachings
Enter into the salpeter solution of 8.0wt%, keep 1.h, then with 50kHz ultrasonication 10min, separation of solid and liquid, liquid phase reuse,
Phase solid phase is put into 105 DEG C of air dry ovens dry 3h；It is subsequently placed in calcining furnace and is warming up to 500 DEG C using 10K/min rates,
2h is kept, air is not passed through in calcination process, obtains specific surface area 212.6m2/ g, the black alumina that intensity is 55.8N/
Product.
Comparative example 4
Discarded space division special aluminium oxide drier and water are pressed 1:1 dipping is cleaned by ultrasonic 40min, solid-liquid point using 20kHz
From liquid reuse, solid is put into 120 DEG C of air dry ovens dry 2.5h；By pretreated aluminium oxide according to volume ratio 1:1
It is immersed in the salpeter solution of 4.0wt%, keeps 2.0h, then with 60kHz ultrasonication 10min, separation of solid and liquid, liquid phase time
With phase solid phase is put into 120 DEG C of air dry ovens dry 2.5h；It is subsequently placed in calcining furnace and is warming up to using 10K/min rates
600 DEG C, 1.0h is kept, 600m is pressed in calcination process3/ (ht) rates are passed through air capacity, obtain specific surface area 254.4m2It is/g, strong
Spend the aluminium oxide for 80.8N/.
Embodiment 4
Discarded alumina adsorbant and water are pressed 1:1 dipping is cleaned by ultrasonic 40min, separation of solid and liquid, liquid using 30kHz
Reuse, solid are put into 120 DEG C of air dry ovens dry 2.5h；By pretreated aluminium oxide according to volume ratio 1:1 is immersed in
In the sulfuric acid solution of mass percent 10.0wt%, 1.0h is kept, then with 60kHz ultrasonication 20min, separation of solid and liquid,
Liquid phase reuse, phase solid phase are put into 120 DEG C of air dry ovens dry 2.5h；By the aluminium oxide after cleaning according to 1:1 volume ratio
8.0wt% is immersed in (by Al2O3Meter) 60min in aluminum sulfate solution, separation of solid and liquid, liquid phase reuse, solid phase is put into 120 DEG C of drums
Dry 2.5h, is subsequently placed in calcining furnace and is warming up to 450 DEG C using 5K/min rates in wind drying box, keeps 4.0h, calcined
400m is pressed in journey3/ (ht) rates are passed through air capacity, obtain specific surface area 278.2m2/ g, the aluminium oxide that intensity is 124.3N/
Product.
Embodiment 5
Discarded alumina adsorbant and water are pressed 1:4 dippings make aluminium oxide suspend, friction using mechanical agitation, after 40min
Separation of solid and liquid, liquid reuse are carried out, solid is put into 80 DEG C of air dry ovens dry 5h；By pretreated aluminium oxide according to body
Product ratio 1:1 is immersed in the hydrochloric acid solution of 8.0wt%, keeps 2.0h, then with 80kHz ultrasonication 20min, solid-liquid point
From liquid phase reuse, phase solid phase is put into 120 DEG C of air dry ovens dry 2.5h；By the aluminium oxide after cleaning according to 1:1 volume
Than being immersed in 8.0wt% (by Al2O3Meter) 60min in liquor alumini chloridi, separation of solid and liquid, liquid phase reuse, solid phase is put into 120 DEG C
Dry 2.5h, is subsequently placed in calcining furnace and is warming up to 500 DEG C using 20K/min rates in air dry oven, keeps 1h, calcined
700m is pressed in journey3/ (ht) rates are passed through air capacity, obtain specific surface area 285.3m2/ g, the activation oxygen that intensity is 103.6N/
Change aluminium.
Embodiment 6
Discarded alumina adsorbant and water are pressed 1:5 dippings make aluminium oxide suspend, friction using mechanical agitation, after 60min
Separation of solid and liquid, liquid reuse are carried out, solid is put into 105 DEG C of air dry ovens dry 3h；By pretreated aluminium oxide according to
Volume ratio 1:1 is immersed in the boric acid+2.0wt% octyl phenol polyoxyethylene ether solution of 4.0wt%, keeps 2h, then uses 80kHz
Ultrasonication 20min, separation of solid and liquid, liquid phase reuse, phase solid phase are put into 105 DEG C of air dry ovens dry 3h；After cleaning
Aluminium oxide according to 1:1 volume ratio is immersed in 8.0wt% (by Al2O3Meter) 60min in aluminum nitrate solution, separation of solid and liquid, liquid phase
Reuse, solid phase are put into 105 DEG C of air dry ovens dry 3h, are subsequently placed in calcining furnace and are warming up to using 15K/min rates
500 DEG C, 1h is kept, 800m is pressed in calcination process3/ (ht) rates are passed through air capacity, obtain specific surface area 292.3m2/ g, intensity
For the alumina product of 166.5N/.
Embodiment 7
Discarded adsorbent aluminium oxide and water are pressed 1:5 dippings make aluminium oxide suspend, friction using mechanical agitation, after 60min
Separation of solid and liquid, liquid reuse are carried out, solid is put into 105 DEG C of air dry ovens dry 3h；By pretreated aluminium oxide according to
Volume ratio 1:1 is immersed in the sodium hydroxide+5.0wt% ethoxylated dodecyl alcohol solution of 1.0wt%, keeps 4h, Ran Houyong
60kHz ultrasonication 30min, separation of solid and liquid, liquid phase reuse, phase solid phase are put into 120 DEG C of air dry ovens dry 2.5h；It will
Aluminium oxide after cleaning is according to 1:1 volume ratio is immersed in 7.0wt% (by Al2O3Meter) 60min in aluminum sulfate solution, solid-liquid point
From liquid phase reuse, solid phase is put into 120 DEG C of air dry ovens dry 2.5h, is subsequently placed in calcining furnace using 10K/min speed
Rate is warming up to 450 DEG C, keeps 2.0h, 750m is pressed in calcination process3/ (ht) rates are passed through air capacity, obtain specific surface area
280.4m2/ g, the alumina product that intensity is 150.1N/.
Embodiment 8
Discarded regenerative agent aluminium oxide and water are pressed 1:5 dippings are cleaned by ultrasonic 30min, separation of solid and liquid, liquid using 20kHz
Reuse, solid are put into 140 DEG C of air dry ovens dry 2h；By pretreated aluminium oxide according to volume ratio 1:1 is immersed in
In the sodium carbonate+6.0wt% ethoxylated dodecyl alcohol solution of 4.0wt%, 4h is kept, then with 80kHz ultrasonications
30min, separation of solid and liquid, liquid phase reuse, phase solid phase are put into 140 DEG C of air dry ovens dry 2h；Aluminium oxide after cleaning is pressed
According to 1:1 volume ratio is immersed in 8.0wt% (by Al2O3Meter) 60min in sodium aluminate solution, separation of solid and liquid, liquid phase reuse, Gu
Dry 2.0h is mutually put into 140 DEG C of air dry ovens, is subsequently placed in calcining furnace and is warming up to 500 DEG C using 15K/min rates,
2.0h is kept, 300m is pressed in calcination process3/ (ht) rates are passed through air capacity, obtain specific surface area 315.0m2/ g, intensity are
146.7N/ alumina product.
Claims (9)
- A kind of 1. method of discarded industrial activated alumina activating and regenerating, which is characterized in that include the following steps：(1) pre-process：The impurity on the discarded industrial activated alumina surface of removal；The discarded industrial activated alumina derives from the discarded active oxidation for adsorbent, regenerative agent, space division drier Aluminium；(2) cleaning solution impregnates：The impurity of the discarded industrial activated alumina internal gutter of removal；The cleaning solution is bi-component, is mixed to get by acid solution or lye, then with surfactant solution；The cleaning solution Concentration for 1.0~20.0wt%, the acid solution or the concentration range of lye being separately configured are 1.0~8.0wt%；Cleaning solution impregnates When be aided with ultrasonication, ultrasonic frequency is 40~100kHz；(3) regenerate：Step (2) treated aluminium oxide is immersed again In raw liquid, then through drying, calcination processing, obtain activated alumina；The regenerated liquid is selected from containing aluminum solutions；The calcination processing carries out in air atmosphere, and air intake is 300~800m3/(h·t)。
- 2. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that step (1) In, pretreating process includes water-bath mechanical friction cleaning, ultrasonic cleaning or the two Combined Treatment, washs water circulation use；The frequency of the ultrasonic cleaning is 15~60kHz, and solid-liquid volume ratio is 1:1~10.
- 3. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that step (2) In, the acid solution is included in hydrochloric acid solution, salpeter solution, sulfuric acid solution, phosphoric acid solution, boric acid solution, oxalic acid solution at least It is a kind of；The lye includes sodium hydroxide solution, sodium carbonate liquor, sodium bicarbonate solution, sodium silicate solution, sodium tripolyphosphate At least one of solution；The surfactant solution includes induced by alkyl hydroxybenzene polyether solutions, 13 carbon alcohol ethereal solution of isomery, fatty acid methyl ester second At least one of oxygroup compound solution；The induced by alkyl hydroxybenzene polyether solutions are selected from nonylphenol polyoxyethylene ether solution or octyl phenol polyoxyethylene ether solution.
- 4. the method for discarded industrial activated alumina activating and regenerating according to claim 3, which is characterized in that step (2) In, the dip time of the cleaning solution is 5~120min, and solid-liquid volume ratio is 1:1~10.
- 5. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that the acid Liquid is selected from boric acid solution；The lye is selected from sodium carbonate liquor or sodium hydroxide solution；The surfactant solution is selected from nonylphenol polyoxyethylene ether solution, octyl phenol polyoxyethylene ether solution or laruyl alcohol Polyoxyethylene ethereal solution.
- 6. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that step (3) In, described is selected from aluminum nitrate solution, aluminum sulfate solution, liquor alumini chloridi, sodium aluminate solution containing aluminum solutions, with Al2O3Meter, The concentration containing aluminum solutions is 1.0~12.0wt%；The time of regenerated liquid dipping is 30~120min.
- 7. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that step (3) In, the calcine technology condition is：Heating rate is 5~20K/min；Calcining heat is 300~600 DEG C, and the time is 30~300min.
- 8. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that step (1) In, after pretreatment, also need to enter back into next step treatment process after separation of solid and liquid and drying process；In step (2), after cleaned liquid impregnation, also need to enter back into processing work in next step after separation of solid and liquid and drying process Skill；In step (1)~step (2), drying temperature independently selected from 80~150 DEG C, drying time independently selected from 1.0~ 5.0h。
- 9. the method for discarded industrial activated alumina activating and regenerating according to claim 1, which is characterized in that step (3) In, dry temperature is 80~150 DEG C, and the time is 1.0~5.0h.
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| CN107528435B (en) * | 2017-08-30 | 2018-11-30 | 界首永恩机电科技有限公司 | A kind of surface treatment method of washing machine motor shell |
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| CN109734110A (en) * | 2019-02-28 | 2019-05-10 | 潍坊工商职业学院 | A kind of alumina powder preparation method |
| US11554366B2 (en) * | 2019-03-20 | 2023-01-17 | 9449710 Canada Inc. | Process for recovering and reusing depolymerization catalyst |
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| CN109956489A (en) * | 2019-04-30 | 2019-07-02 | 刘�文 | The recovery method of waste activated alumina during process for prepairng hydrogen peroxide by anthraquinone |
| CN110980654B (en) * | 2019-12-30 | 2023-04-14 | 广西田东达盛化工科技有限公司 | Method for cleaning active alumina balls in hydrogen peroxide production |
| CN111282557B (en) * | 2020-03-03 | 2021-03-16 | 王晶晶 | Regeneration method of waste alumina in hydrogen peroxide production |
| CN112169782A (en) * | 2020-10-08 | 2021-01-05 | 潍坊中凯新能源有限公司 | Treatment method for regenerating active alumina with high specific surface area by using efficient impurity removing agent |
| CN112221479A (en) * | 2020-10-13 | 2021-01-15 | 河北冀研能源科学技术研究院有限公司 | Active regeneration treatment method of desulfurization wastewater defluorination adsorbent |
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| CN114887669A (en) * | 2022-03-10 | 2022-08-12 | 中国平煤神马集团尼龙科技有限公司 | Regeneration method of catalyst for producing hydrogen peroxide by anthraquinone process |
| CN115254077A (en) * | 2022-08-05 | 2022-11-01 | 安徽国泰化工有限公司 | Recovery process and system for raw materials in waste alumina |
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| Title |
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