CN106518024B - The method for preparing activated alumina using aluminum i ndustry surface treatment solid waste - Google Patents

The method for preparing activated alumina using aluminum i ndustry surface treatment solid waste Download PDF

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CN106518024B
CN106518024B CN201610828245.2A CN201610828245A CN106518024B CN 106518024 B CN106518024 B CN 106518024B CN 201610828245 A CN201610828245 A CN 201610828245A CN 106518024 B CN106518024 B CN 106518024B
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solid waste
activated alumina
aluminum
ndustry
aluminium
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CN106518024A (en
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陈东初
叶秀芳
张敏
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Guangdong Jiadele Technology Co ltd
Guangzhou Huanglong Biotechnology Co ltd
Foshan University
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Abstract

It the present invention relates to the use of the method that aluminum i ndustry surface treatment solid waste prepares activated alumina.1) preparation method of the activated alumina is the following steps are included: wash aluminium solid waste, removing impurity;2) dilute hydrochloric acid solution and triethanolamine solution is added toward aluminium solid waste, adjusts pH value, recrystallizes alumina particle;3) aluminium solid waste dry, pulverize, surfactant is added, is ground to micron order using colloid mill, obtains material A;4) material A and cellulose acetate, expanding agent are mixed, is placed in disk bowling machine and prepares spheric granules;5) spheric granules is subjected to hydro-thermal process, reuses low molecule alcohol washing, obtains material B;6) material B is placed in baking oven dry, then is placed in Muffle furnace calcining, cooled to room temperature to get.Activated alumina obtained not only has biggish specific surface area and Kong Rong, and the aperture of reasonable layout also has good crushing strength and catalytic activity.

Description

The method for preparing activated alumina using aluminum i ndustry surface treatment solid waste
Technical field
The invention belongs to the preparation fields of inorganic material, and in particular to be prepared using aluminum i ndustry surface treatment solid waste The method of activated alumina.
Background technique
Aluminium alloy be dosage be only second to steel and occupy second structural metallic materials, since aluminum alloy chemically property is living It sprinkles, in order to improve its corrosion resistance and decorative performance, aluminium alloy extrusions often needs to be surface-treated.In aluminium shape surface processing Master operation includes the processes such as degreasing, alkaline etching, pickling, oxidation, sealing of hole and coloring, in these processes, about 1~2% aluminium Alloy is dissolved in tank liquor in the form of an ion.Big quantity of fluid can be taken away from each treatment trough in aluminum profile treatment process simultaneously, need It is cleaned with a large amount of water, handles every square metre of aluminum profile according to statistics and about consume 65~180L water, 1 100,000 tons of annual output of aluminium profiles Material enterprise, the year water consumption for aluminium material surface processing each process cleaning is about 2,000,000 m3, containing a large amount of in these industrial wastewaters Aluminium ion and the metal ions such as a small amount of zinc, nickel, copper.It is general to be adjusted using neutralization to avoid direct emission from causing environmental pollution Section and coagulant sedimentation technique are handled, and wastewater sludge is obtained, and sludge is further dehydrated as Aluminiferous waste slag.Aluminum profile is useless The content of scale slag very high purity, the oxide of aluminium, hydroxide and its hydrate reaches 90% or more.Calculation shows that only one Item produces 20000 tons of aluminum profile of heat-tinting production line per year, annual to generate about 4000 tons of waste residue, high number.Currently, China's aluminium The waste water alkaline residue millions of tons that profile factory generates every year, if taking the processing mode directly filled, cause resources of production with The waste of land resource also brings secondary pollution, therefore, carries out resource utilization with important to aluminum section industrial wastewater alkaline residues Meaning.
Activated alumina is the solid matter of a kind of porosity, high degree of dispersion, has large specific surface area, excellent adsorption, table The characteristics of face acidity, good thermal stability, it is widely used in chemical industry as catalyst, carrier and adsorbent.Active oxidation Aluminium not only requires the aperture of biggish specific surface area and Kong Rong and reasonable layout when applying as catalyst or carrier, It should also have good mechanical strength and heat resistance, especially pore-size distribution, i.e., effective Kong Rong influences most catalytic perfomance Greatly, but domestic existing active alumina product can reach the seldom of requirement, and from catalytic industries requirement, there is also big gaps.Benefit It is rich in oxide, hydroxide and its hydrate of aluminium with section aluminum waste water alkaline residue, prepares activated alumina using it as raw material, Realize that the comprehensive utilization of solid waste is of great significance.Chinese patent application 200410014031.9, which discloses, utilizes aluminium The method that profile factory industrial silt prepares activated alumina, this method utilize nitric acid using aluminium section bar plant industrial silt as raw material Method carries out mixing pugging, and spherical walk is made, and dries, and sintering obtains γ-Al2O3For the activated alumina of crystal phase, but using should The activated alumina specific surface area of method preparation is 180~450mm2/ g, average pore size be 3~7nm and Kong Rongwei 0.15~ 0.8cm3/ g, range fluctuation is larger, influences its catalytic activity, additionally due to formed with nitric acid, when drying activated alumina, meeting A large amount of nitrogen oxides is generated, environment is seriously polluted.Separately there is Chinese patent application 201310336464.5 to disclose a kind of from containing The method that aluminium oxide is extracted in waste slag of aluminum, this method are by gangue and/or flyash and a certain amount of red mud (gangue, powder Coal ash and red mud are Aluminiferous waste slag) and sodium carbonate mixing after be sintered, hydrochloric acid acidleach, concentrated hydrochloric acid crystal aluminum chloride, ammonium hydroxide Precipitation aluminium hydroxide, calcining obtain aluminium oxide, but in hydrochloric acid acidleach, the impurity such as Fe, Ca, Mg in Aluminiferous waste slag can be with Al dissolve out together, influence the preparation of aluminium oxide, need complicated dedoping step.
Summary of the invention
The purpose of the present invention is to provide a kind of simple process, at low cost, product purity is high, does not generate pollution to environment Activated alumina preparation method, this method are surface-treated solid waste as raw material using aluminum i ndustry, realize aluminium solid waste The regeneration of object, preparation-obtained activated alumina not only catalytic activity and selectivity with higher also have larger Specific surface area and Kong Rong and reasonable layout aperture, while there is good mechanical strength and heat resistance.
The present invention is by following technical solution to be attained in that
The method for preparing activated alumina using aluminum i ndustry surface treatment solid waste, comprising the following steps:
(1) aluminum i ndustry is surface-treated solid waste 2~6 times wash with distilled water, it is useless that removing remains in aluminium solid Sodium ion and other soluble impurities in gurry;
(2) the aluminium solid waste addition dilute hydrochloric acid solution obtained toward step (1), adjusting pH value to 2~4, static 1~ 2min;Add triethanolamine solution, adjusting pH value to 10~12, static 1~2min;
(3) the aluminium solid waste handled through step (2) is placed in 60~80 DEG C of baking ovens and is dried, then powder Broken, the surfactant that aluminium solid waste weight 1~3% is added stirs evenly, using colloid mill by aluminium solid waste Composition granule is ground to 5~50 μm, obtains material A;
(4) material A for obtaining step (3) is mixed with cellulose acetate, expanding agent, is placed in disk bowling machine and is prepared ball Shape particle, the diameter of particle are 2~8mm;
(5) spheric granules for obtaining step (4), is placed in 4~6h of processing in hydrothermal treatment device, and temperature is 90~100 DEG C, then spheric granules is carried out washing 1~2 time using low molecule alcohol, obtains material B;
(6) material B is placed in baking oven and carries out temperature programming drying, be subsequently placed in 450~800 DEG C of Muffle furnaces and calcined 2~6h, cooled to room temperature is to get activated alumina.
Wherein, the surfactant of the step (3) is phosphate ester surfactant and fatty acid surfactant At least one of.
Further, the phosphate ester surfactant is single Tryfac 5573, laurel alcohol ether phosphate, palm One of stearyl alcohol phosphate, polyoxyethylene monoalkyl phosphoric acid esters and polyoxyethylene bisalkyl phosphate.
Further, the fatty acid surfactant is that fatty acyl amide or fatty acid ester non-ionic surface are living Property agent, such as: lauric acid amide of ethanol, ethoxylated fatty-acid methyl ester.
Further, the expanding agent of the step (4) is by galactomannans and tartaric acid with (1~3): 1 mass ratio Composition.
Preferably, the expanding agent of the step (4) is made of galactomannans and tartaric acid with the mass ratio of 2:1.
Further, the dosage of step (4) cellulose acetate is the 4~10% of aluminum profile waste residue weight, expanding agent Dosage be aluminium solid waste weight 10~30%.
Further, the cellulose acetate and expanding agent were the powder of 500~800 meshes.
Further, the low molecule alcohol of the step (5) is one of isopropanol, ethyl alcohol, n-butanol.
Further, the temperature programming of the step (6) is dry specifically: dry initial temperature is 60 DEG C, heating rate For 60 DEG C/h, drying time is 3~5h.
For the present invention using aluminum i ndustry surface treatment solid waste as raw material, the aluminium solid waste often contains sodium Ion and other soluble impurities, especially sodium ion are affected to the performance of aluminium oxide.Preparation of the sodium ion in aluminium oxide Exist mostly in the form of sodium oxide molybdena in the process, it is thicker that sodium oxide molybdena will lead to alumina grain, and specific surface area is reduced, and crystal form is not advised Then, the adverse effects such as refractoriness are reduced, therefore the present invention cleans aluminium solid waste using distilled water, to reduce sodium The interference that ion and other soluble impurities prepare aluminium oxide.
In addition, aluminium solid waste is rich in oxide, hydroxide and its hydrate of aluminium, wherein the hydrogen-oxygen of the aluminium For compound mostly with the presence of amorphous body structure, the specific surface and Kong Rongjun of these amorphous hydroted aluminas are smaller, will lead to pore size distribution Widthization, it is therefore necessary to remove.The present invention carries out pH value adjusting to aluminum profile waste residue respectively using dilute hydrochloric acid and triethanolamine, when When pH is lower, tiny amorphous hydroted alumina is very fast compared with alumina dissolution in acid environment, as pH higher, dissolution Aluminium hydroxide can be deposited on alumina particle, and alumina particle is promoted to recrystallize, and form that crystal grain is larger and uniform crystal.This Outside, triethanolamine can be used as pH poising agent, can also form complex compound with aluminium atom, change the coordination structure of aluminium atom, from And change interparticle accumulation mode, influence the distribution and size in aperture.
The present invention is mixed with phosphoric acid ester or fatty acid surfactant and aluminium solid waste, is ground, institute The oxygen atom in surfactant structure and γ-AlOOH, the Al (OH) in aluminium solid waste stated3In-OH pass through hydrogen Bond is combined, and advantageously reduces the stress of capillary wall, avoids collapsing and part that interlayer occurs in high-temperature burning process The sintering of micropore, with the hole for forming uniform pore diameter and being reasonably distributed.In addition, surfactant is opened by reducing the surface of material Power makes powder be not easy to assemble, and is conducive to grind.
Preferably, using phosphoric acid ester as surfactant, the phosphate ester surfactant is by introducing non-gold Belong to element phosphor, there is adjustment effect to activated alumina surface acidity, is conducive to the anti-caking power for improving activated alumina, promotees Hold larger, pore-size distribution concentration, even-grained activated alumina into formation specific surface area and hole.
The present invention promotes powder to prepare spherolite using cellulose acetate as binder, while having the function of reaming, passes through The releasable carbon dioxide gas of high-temperature calcination may advantageously facilitate the formation of hole, and discharge the space occupied originally, increase hole Hold.
Using galactomannans and winestone acid blend as expanding agent, the galactomannans has resistance to the present invention The good feature of acid, salt tolerant, stability after high-temp combustion, is conducive to expanded hole in addition, the kinetic diameter of its molecule is larger Diameter;The tartaric acid may advantageously facilitate the formation of hole through the releasable carbon dioxide gas of high-temperature calcination, and have certain Caking property, can promote powder compacting, improve the intensity of alumina spherulite, improve pore structure.
Since the pore size in aluminium oxide spheric granules is irregular, there are capillarities when dry, will lead to water Divide evaporation very uneven, so that macropore is easy to cause granule strength to drop prior to small orifice drying, using rapid draing under higher temperature Low and generate crack, the present invention uses temperature programming drying means, temperature is gradually increased in longer time, and in drying It is stirred continuously material in the process, avoids the occurrence of above situation.
Compared with prior art, the beneficial effects of the present invention are:
(1) prior art mostly uses commercial alumina or aluminium hydroxide to prepare activated alumina for main material, and of the invention The regeneration of solid waste is realized as raw material using aluminum i ndustry surface treatment solid waste, and avoids aluminium solid Waste pollution environment has great environment protection significance.
(2) activated alumina preparation method of the present invention, simple process, at low cost, product purity is high, to environment not Generate pollution, the activated alumina being prepared not only catalytic activity and selectivity with higher also have and biggish compare table The aperture of area and Kong Rong and reasonable layout, while there is good mechanical strength and heat resistance.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, but the present invention is not by following embodiment It records and limits.
Embodiment 1
The method that the embodiment of the present invention 1 prepares activated alumina using aluminum i ndustry surface treatment solid waste, including with Lower step:
(1) aluminum i ndustry is surface-treated solid waste 5 times wash with distilled water, removing remains in aluminium solid waste In sodium ion and other soluble impurities;
(2) dilute hydrochloric acid solution, adjusting pH value to 3, static 1min is added toward the aluminium solid waste that step (1) obtains; Add triethanolamine solution, adjusting pH value to 11, static 1min;
(3) the aluminium solid waste handled through step (2) is placed in 60 DEG C of baking ovens and is dried, then crushed, add The laurel alcohol ether phosphate for entering aluminium solid waste weight 2% stirs evenly, using colloid mill by aluminium solid waste Grain is ground to 25 μm, obtains material A;
(4) material A for obtaining step (3) is mixed with cellulose acetate, expanding agent, wherein the dosage of cellulose acetate It is the 6% of aluminium solid waste weight, expanding agent is made of galactomannans and tartaric acid with the mass ratio of 2:1, is used Amount is the 20% of aluminium solid waste weight, is subsequently placed in disk bowling machine and prepares spheric granules, the diameter of particle is 6mm;
(5) spheric granules for obtaining step (4), is placed in hydrothermal treatment device and handles 5h, and temperature is 100 DEG C, then Washing 1 time is carried out to spheric granules using isopropanol, obtains material B;
(6) material B is placed in baking oven and carries out temperature programming drying, specifically: dry initial temperature is 60 DEG C, heating speed Degree is 60 DEG C/h, drying time 4h, is subsequently placed in 700 DEG C of Muffle furnaces and carries out calcining 4h, cooled to room temperature is to get activity Aluminium oxide.
Embodiment 2
The embodiment of the present invention 2 prepares the method and embodiment of activated alumina using aluminum i ndustry surface treatment solid waste 1 is similar, and difference is, the surfactant being added in step (3) is fatty acyl amide nonionic surface active agent, as coconut palm Oleic acid diethyl amide.
Embodiment 3
The embodiment of the present invention 3 prepares the method and embodiment of activated alumina using aluminum i ndustry surface treatment solid waste 1 is similar, and difference is, the surfactant being added in step (3) is the mixing of phosphoric acid ester and fatty acid surfactant Object is made of laurel alcohol ether phosphate and lauric acid amide of ethanol with the mass ratio of 1:1.
Embodiment 4
The embodiment of the present invention 4 prepares the method and embodiment of activated alumina using aluminum i ndustry surface treatment solid waste 1 is similar, and difference is, the expanding agent in step (4) is made of galactomannans and tartaric acid with the mass ratio of 1:1.
Embodiment 5
The embodiment of the present invention 5 prepares the method and embodiment of activated alumina using aluminum i ndustry surface treatment solid waste 1 is similar, and difference is, the expanding agent in step (4) is made of galactomannans and tartaric acid with the mass ratio of 3:1.
Embodiment 6
The method that the embodiment of the present invention 6 prepares activated alumina using aluminum i ndustry surface treatment solid waste, including with Lower step:
(1) aluminum i ndustry is surface-treated solid waste 2 times wash with distilled water, removing remains in aluminium solid waste In sodium ion and other soluble impurities;
(2) dilute hydrochloric acid solution, adjusting pH value to 4, static 2min is added toward the aluminium solid waste that step (1) obtains; Add triethanolamine solution, adjusting pH value to 10, static 2min;
(3) the aluminium solid waste handled through step (2) is placed in 80 DEG C of baking ovens and is dried, then crushed, add The laurel alcohol ether phosphate for entering aluminium solid waste weight 3% stirs evenly, using colloid mill by aluminium solid waste Grain is ground to 25 μm, obtains material A;
(4) material A for obtaining step (3) is mixed with cellulose acetate, expanding agent, wherein the dosage of cellulose acetate It is the 10% of aluminium solid waste weight, expanding agent is made of galactomannans and tartaric acid with the mass ratio of 2:1, is used Amount is the 30% of aluminium solid waste weight, is subsequently placed in disk bowling machine and prepares spheric granules, the diameter of particle is 6mm;
(5) spheric granules for obtaining step (4), is placed in hydrothermal treatment device and handles 6h, and temperature is 100 DEG C, then Washing 2 times is carried out to spheric granules using isopropanol, obtains material B;
(6) material B is placed in baking oven and carries out temperature programming drying, specifically: dry initial temperature is 60 DEG C, heating speed Degree is 60 DEG C/h, drying time 5h, is subsequently placed in 800 DEG C of Muffle furnaces and carries out calcining 6h, cooled to room temperature is to get activity Aluminium oxide.
Comparative example 1
Comparative example 1 of the present invention prepares the method and embodiment of activated alumina using aluminum i ndustry surface treatment solid waste 1 is similar, and difference is, is washed using isopropanol to spheric granules in step (5), is changed to using deionized water to spherical Grain is washed.
The main character of activated alumina made from 1-6 of the embodiment of the present invention and comparative example 1
Group Specific surface area (m2/g) Kong Rong (cm3/g) Average pore size (nm) Crushing strength (N.-1)
Embodiment 1 382 0.572 6.47 220
Embodiment 2 370 0.553 6.32 215
Embodiment 3 400 0.635 6.72 242
Embodiment 4 364 0.540 6.23 209
Embodiment 5 375 0.557 6.30 214
Embodiment 6 372 0.560 6.50 217
Comparative example 1 350 0.492 5.82 212
As seen from the above table, the activated alumina being prepared using activated alumina preparation method of the present invention is all had big The characteristics of Kong Rong, bigger serface: Kong Rong >=0.5cm3/ g, specific surface area >=200m2/g.By embodiment 1-3 it is found that surface is living Property agent be phosphoric acid ester and fatty acid surfactant mixture, i.e., both formed with the mass ratio of 1:1, active oxygen obtained Specific surface area, Kong Rong, average pore size, the crushing strength for changing aluminium are best;By embodiment 1,4,5 it is found that expanding agent is by galactomannan Glycan and tartaric acid are formed with the proportion of 2:1, and activated alumina performance obtained is preferable;By comparative example 1 it is found that using low molecule High-temperature calcination again after alcohols washs spheric granules is conducive to hole diameter enlargement, increases specific surface area and Kong Rong, improves crushing Intensity.
Test example one, activated alumina produced by the present invention are compared with the catalytic performance of commercial product
With commercially available activated alumina, (Shandong Bo Yang new material Science and Technology Co., Ltd. is provided, specific surface area respectively 326m2/ g, Kong Rong 0.431cm3/ g, average pore size 5.32nm) and the activity that is prepared of 1-5 of the embodiment of the present invention and comparative example 1 Aluminium oxide investigates catalyst to the conversion ratio and selectivity for preparing isobutene using biological isobutanol evaporation as catalyst. As a result it see the table below.
Testing index Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Commercial product
Conversion ratio (%) 95.32 93.68 98.84 92.73 94.70 87.12 82.74
Selectivity (%) 94.60 93.35 97.72 91.21 93.38 82.53 76.47
As seen from the above table, had using the activated alumina that activated alumina preparation method of the present invention is prepared excellent Catalytic activity and selectivity can make isobutanol conversion ratio with higher in reaction, and improve the selectivity of product isobutene, Good catalytic activity is shown, it is especially best with activated alumina catalytic performance made from embodiment 3, it is significantly better than commercially available Activated alumina.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change It also should be regarded as protection scope of the present invention into retouching.

Claims (8)

1. the method for preparing activated alumina using aluminum i ndustry surface treatment solid waste, which is characterized in that including following step It is rapid:
(1) aluminum i ndustry is surface-treated solid waste 2~6 times wash with distilled water, removing remains in aluminium solid waste In sodium ion and other soluble impurities;The aluminium solid waste is rich in oxide, hydroxide and the hydration of aluminium Object;
(2) the aluminium solid waste addition dilute hydrochloric acid solution obtained toward step (1), adjusting pH value to 2~4, static 1~ 2min;Add triethanolamine solution, adjusting pH value to 10~12, static 1~2min;
(3) the aluminium solid waste handled through step (2) is placed in 60~80 DEG C of baking ovens and is dried, then crushed, add The surfactant for entering aluminium solid waste weight 1~3% stirs evenly, using colloid mill by aluminium solid waste composition granule 5~50 μm are ground to, material A is obtained;
(4) material A for obtaining step (3) is mixed with cellulose acetate, expanding agent, is placed in disk bowling machine and is prepared spherical Grain, the diameter of particle are 2~8mm;
(5) spheric granules for obtaining step (4) is placed in 4~6h of processing in hydrothermal treatment device, and temperature is 90~100 DEG C, so Spheric granules is carried out washing 1~2 time using low molecule alcohol afterwards, obtains material B;
(6) material B is placed in baking oven to carry out temperature programming dry, be subsequently placed in 450~800 DEG C of Muffle furnaces carry out calcining 2~ 6h, cooled to room temperature is to get activated alumina;
The surfactant of the step (3) is at least one in phosphate ester surfactant and fatty acid surfactant Kind.
2. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It is characterized in that, the expanding agent of the step (4) is by galactomannans and tartaric acid with (1~3): 1 mass ratio forms.
3. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It is characterized in that, the dosage of step (4) cellulose acetate is the 4~10% of aluminium solid waste weight.
4. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It is characterized in that, the dosage of step (4) expanding agent is the 10~30% of aluminium solid waste weight.
5. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It is characterized in that, the low molecule alcohol of the step (5) is one of isopropanol, ethyl alcohol, n-butanol.
6. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It is characterized in that, the phosphate ester surfactant is single Tryfac 5573, laurel alcohol ether phosphate, palm stearin alcohol phosphoric acid One of ester, polyoxyethylene monoalkyl phosphoric acid esters and polyoxyethylene bisalkyl phosphate.
7. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It is characterized in that, the fatty acid surfactant is fatty acyl amide or fatty acid ester nonionic surface active agent.
8. the method according to claim 1 for preparing activated alumina using aluminum i ndustry surface treatment solid waste, It being characterized in that, the temperature programming of the step (6) is dry specifically: dry initial temperature is 60 DEG C, and heating rate is 60 DEG C/h, Drying time is 3~5h.
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