CN109650419B - Method and system for comprehensively utilizing aluminum industry sludge - Google Patents
Method and system for comprehensively utilizing aluminum industry sludge Download PDFInfo
- Publication number
- CN109650419B CN109650419B CN201710936690.5A CN201710936690A CN109650419B CN 109650419 B CN109650419 B CN 109650419B CN 201710936690 A CN201710936690 A CN 201710936690A CN 109650419 B CN109650419 B CN 109650419B
- Authority
- CN
- China
- Prior art keywords
- aluminum
- liquid separation
- solid
- sludge
- filtrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 142
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000010802 sludge Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 95
- 238000000926 separation method Methods 0.000 claims abstract description 68
- 239000000706 filtrate Substances 0.000 claims abstract description 51
- 239000000047 product Substances 0.000 claims abstract description 46
- 238000011084 recovery Methods 0.000 claims abstract description 36
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- 239000011575 calcium Substances 0.000 claims description 44
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 39
- 229910052791 calcium Inorganic materials 0.000 claims description 39
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 238000004090 dissolution Methods 0.000 claims description 18
- 230000029087 digestion Effects 0.000 claims description 17
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005277 cation exchange chromatography Methods 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 238000004064 recycling Methods 0.000 description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005360 mashing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method and a system for comprehensively utilizing sludge in aluminum industry. The method of the invention comprises the following steps: 1) Dissolving out the aluminum sludge by adopting a soluble alkali solution with the concentration of 2-3mol/L to obtain a solution; 2) Carrying out solid-liquid separation on the dissolved solution to obtain a first filtrate; 3) Adding soluble carbonate into the first filtrate for reaction, and carrying out solid-liquid separation on a reaction product to obtain calcium carbonate and a second filtrate; 4) Oxidizing the second filtrate, and treating an oxidation product by adopting cation exchange resin to obtain a treatment solution; 5) Adding a strong acid solution into the treatment solution until the pH value is 8.0-8.2, and then carrying out solid-liquid separation, washing and drying to obtain an Al (OH) 3 product. When the method and the system of the invention are used for comprehensively utilizing the sludge in the aluminum industry, the recovery rate of aluminum is high, the purity of the recovered product is high, and the method and the system have remarkable economic, environmental and social benefits.
Description
Technical Field
The invention relates to an aluminum sludge treatment method, in particular to a method and a system for comprehensively utilizing aluminum sludge.
Background
The aluminum sludge is an industrial emission produced in the processing process of aluminum profiles, and has very complex components and properties, wherein the main components comprise Al (OH) 3、Al2O3, and the other components comprise calcium, iron, potassium, sodium and the like. At present, most of aluminum profile factories in China directly adopt quicklime for neutralization treatment and then landfill, the method can cause a large amount of aluminum resource waste with economic value, and the high landfill cost not only aggravates the environmental protection pressure of enterprises, but also brings environmental burden, and additionally increases the treatment cost, so that the ecological environment protection and the sustainable utilization of resources cannot be considered.
The aluminum-rich composition characteristic of the aluminum industry sludge shows that the sludge has higher recycling potential, for example, the sludge can be reasonably developed and utilized, so that the recycling of aluminum can be realized, the environmental pollution is reduced, and the environmental protection burden of aluminum enterprises is greatly reduced. However, the existing aluminum industry sludge recycling treatment method is mostly not fine enough, so that the aluminum recovery rate is low, and the obtained aluminum-containing product generally contains impurities such as calcium, iron and the like, so that the utilization value of the aluminum-containing product is greatly reduced. Therefore, a method and a system for comprehensively utilizing sludge in aluminum industry, which have high aluminum recovery rate and high purity of recovered products, are particularly desired.
Disclosure of Invention
The invention provides a method and a system for comprehensively utilizing aluminum sludge, which have the advantages of high aluminum recovery rate, high purity of recovered products and remarkable economic, environmental and social benefits when being utilized for comprehensively utilizing the aluminum sludge.
The invention provides a method for comprehensively utilizing sludge in aluminum industry, which comprises the following steps:
1) Dissolving out the aluminum sludge by adopting a soluble alkali solution with the concentration of 2-3mol/L to obtain a solution;
2) Carrying out solid-liquid separation on the dissolved solution to obtain a first filtrate;
3) Adding soluble carbonate into the first filtrate for reaction, and carrying out solid-liquid separation on a reaction product to obtain calcium carbonate and a second filtrate;
4) Oxidizing the second filtrate, and treating an oxidation product by adopting cation exchange resin to obtain a treatment solution;
5) Adding a strong acid solution into the treatment solution until the pH value is 8.0-8.2, and then carrying out solid-liquid separation, washing and drying to obtain an Al (OH) 3 product.
In the invention, the aluminum industry sludge is industrial emission generated in the processing process of the aluminum profile, and is not strictly limited; specifically, the water content of the aluminum sludge may be 60-70wt%, the aluminum content may be 5wt% or more, and the calcium content may be 5wt% or more.
In the invention, the digestion in the step 1) is used for separating calcium, aluminum and other components in the aluminum industry sludge from the aluminum industry sludge, thereby facilitating the subsequent separation and recovery; the dissolution may be carried out in a conventional manner, for example, dissolution may be carried out with stirring, thereby facilitating the release of the components such as calcium, aluminum, etc.
Further, the aluminum industry sludge in the step 1) can be crushed aluminum industry sludge; before leaching, the aluminum sludge is crushed, so that the components such as calcium, aluminum and the like can be completely separated from the aluminum sludge. Specifically, the aluminum sludge can be smashed into fluffy shape; for example, solid sludge with larger block hardness in the aluminum industry sludge can be crushed by a crusher.
The specific type of the soluble alkali solution is not critical, and for example, naOH solution and the like can be used. In particular, the present inventors have found through a great deal of research that: the concentration of the soluble alkali solution has a remarkable influence on the recovery of aluminum, and when the concentration of the soluble alkali solution is too high, the adsorption performance of the cation exchange resin on Fe 3+ can be influenced, so that the purity of the aluminum hydroxide product is reduced; if the concentration of the soluble alkali solution is too low, the calcium, aluminum and other components cannot be completely dissolved out, and the recovery rate thereof is lowered. The concentration of the proper soluble alkali solution should be set to 2-3mol/L, which can not only completely dissolve out the components such as calcium, aluminum and the like and ensure the recovery rate of the components such as calcium, aluminum and the like, but also can not reduce the purity of the aluminum hydroxide product.
The invention does not limit the dosage of the soluble alkali solution during dissolution, and only needs to submerge the sludge in the aluminum industry; specifically, 15-25L of soluble alkali solution can be added into 10kg of aluminum sludge for leaching. In addition, the stirring speed during dissolution can be 150-200r/min, and further 180-200r/min; the temperature of dissolution may be room temperature; the dissolution time can be 20-30min, and further 25-30min.
It is understood that after the aluminum sludge is dissolved by adopting 2-3mol/L NaOH solution, aluminum in the aluminum sludge exists in the dissolution liquid in the form of sodium metaaluminate (NaAlO 2).
In the present invention, the solid-liquid separation in step 2) is used for separating and removing solids, suspended solids, etc. in the dissolution liquid; the solid-liquid separation may be carried out in a conventional manner, such as filtration, centrifugation, etc. Specifically, press filtration can be adopted for solid-liquid separation; it will be appreciated that an alkali resistant filter medium should be used for pressure filtration to avoid damage to the filter medium by the alkaline dissolution liquid.
In particular, the present inventors have found through a great deal of research that: the pore diameter of the filter medium has obvious influence on the recovery of aluminum, and when the pore diameter of the filter medium is too small, the dissolved liquid is not easy to filter, so that the actual operation of solid-liquid separation is influenced; when the pore diameter of the filter medium is too large, part of suspended matters can enter the filtrate, so that the subsequent treatment is adversely affected, and the purity of the product is reduced; the pore size of a suitable filter medium should be set to 600-700 mesh, which is advantageous in ensuring product purity without affecting the actual operation of solid-liquid separation.
Further, the solid-liquid separation can be performed by a filter press, in particular by a polypropylene plate-and-frame filter press; the filter residue formed after solid-liquid separation contains calcium and a small amount of aluminum, and can be used in the ceramic process industry for recycling.
In the present invention, step 3) is used for recovering calcium; specifically, when soluble carbonate is added into the first filtrate, calcium in the first filtrate reacts with the added carbonate to generate calcium carbonate, and the calcium carbonate product can be recovered after solid-liquid separation. The soluble carbonate is not particularly limited, and may be sodium carbonate or the like, for example, and the concentration of the soluble carbonate may be 8 to 12mol/L. In addition, the temperature of the reaction may be room temperature and the time of the reaction may be 15 to 30 minutes.
In the present invention, step 4) is used to remove iron from the second filtrate; specifically, the oxidation is used for oxidizing Fe 2+ in the second filtrate into Fe 3+, and the cation exchange resin treatment can adsorb Fe 3+ in the oxidation product so as to achieve the aim of removing iron in the second filtrate.
The inventor finds that compared with the method that the second filtrate is directly treated by adopting cation exchange resin, fe 2+ is oxidized into Fe 3+ and then is treated by adopting cation exchange resin, the method can better remove iron in the second filtrate, thereby being beneficial to improving the purity of aluminum-containing products.
The oxidant adopted by the invention is not strictly limited, and is preferably an environment-friendly oxidant, such as hydrogen peroxide, and the mass content of the hydrogen peroxide can be about 30%. The amount of the oxidizing agent and the time of oxidation are not strictly limited, so long as Fe 2+ can be completely oxidized to Fe 3+; specifically, 80-150mL of hydrogen peroxide can be added into each kg of aluminum sludge for oxidization, and the oxidization time can be controlled to be 2-5min.
In addition, the cation exchange resin used is not strictly limited as long as it can adsorb Fe 3+ to remove it from the second filtrate; specifically, a D001 cation exchange resin having a good adsorption removal effect on Fe 3+ can be used.
In the present invention, in step 5), a strong acid solution (i.e., a neutralization solution) is added to the treatment solution to generate Al (OH) 3, and a solid-liquid separation, washing and drying are performed to obtain an Al (OH) 3 product (i.e., an aluminum-containing product).
The specific kind of the strong acid solution is not strictly limited, and for example, the solution can be HCl solution and the like; in particular, the concentration of HCl solution should not be too high, which would otherwise cause dissolution of Al (OH) 3 to reduce its recovery, and is suitably 2 to 3mol/L.
In particular, the present inventors have found through a great deal of research that: the amount of strong acid solution added (i.e., the final pH of the system) has a significant effect on the recovery of aluminum, and a suitable pH should be set to a range of 8.0-8.2; the pH range can fully precipitate Al (OH) 3, and is favorable for improving the recovery rate of aluminum.
After the method is adopted to comprehensively utilize the sludge in the aluminum industry, the recovery rate of aluminum can reach more than 98 percent; the purity of the Al (OH) 3 product can reach more than 99 percent; the iron content in the Al (OH) 3 product is only about 1 per mill. In addition, the content of Al 3+ in the treated waste liquid is less than 20ppm, the content of Ca 2+ is less than 50ppm and the content of Fe 3+ is 5-10ppm, so that the waste liquid is convenient for direct discharge or further recycling.
The invention also provides a system for comprehensively utilizing the aluminum sludge, which comprises:
a digestion device;
The inlet end of the first solid-liquid separation device is connected with the outlet end of the digestion device;
the calcium recovery device comprises a reaction device and a second solid-liquid separation device which are sequentially arranged, wherein the inlet end of the reaction device is connected with the outlet end of the first solid-liquid separation device;
The iron removing device comprises an oxidation device and a cation exchange chromatography device which are sequentially arranged, and the inlet end of the oxidation device is connected with the outlet end of the second solid-liquid separation device;
The aluminum recovery device comprises a neutralization device, a third solid-liquid separation device, a washing device and a drying device which are sequentially arranged, wherein the inlet end of the neutralization device is connected with the outlet end of the cation exchange chromatography device.
Further, the system of the invention also comprises a crushing device, wherein the outlet end of the crushing device is connected with the inlet end of the digestion device; the crushing device is used for crushing the aluminum industry sludge, so that components such as calcium, aluminum and the like are completely separated from the aluminum industry sludge.
Further, the crushing device is a tamper or a crusher. The masher is used for mashing the aluminum sludge into fluffy shapes; among the aluminum sludge, there is solid sludge with large block hardness, and the solid sludge can be crushed by a crusher.
In the invention, the digestion device is used for digestion of the sludge in the aluminum industry so as to form digestion liquid containing calcium and aluminum; the specific structure thereof is not strictly limited and may be a conventional device in the art. In particular, the digestion device can be provided with a stirring component, so that digestion is carried out under stirring conditions, and release of calcium, aluminum and other components in the aluminum industry sludge is facilitated.
In the invention, a first solid-liquid separation device is used for carrying out solid-liquid separation on the dissolved solution so as to obtain a first filtrate containing calcium and aluminum; the solid-liquid separation apparatus is not particularly limited and may be a solid-liquid separation apparatus conventionally used in the art.
In an embodiment, the first solid-liquid separation device may be a filter press.
Further, the filter press is a polypropylene plate-and-frame filter press; the polypropylene plate-and-frame filter press can avoid the damage of alkaline dissolution liquid to the filter medium.
Further, the pore diameter of the filter medium of the filter press is 600-700 meshes. The filter press with the aperture range is beneficial to improving the purity of products, and does not influence the actual operation of solid-liquid separation.
In the invention, the calcium recovery device is used for recovering the calcium in the first filtrate so as to obtain a calcium carbonate product; specifically, the reaction device is used for reacting the calcium in the first filtrate with the added soluble carbonate to generate calcium carbonate; the second solid-liquid separation device is used for carrying out solid-liquid separation on the reaction product so as to recycle the calcium carbonate product. The reaction device and the second solid-liquid separation device may be conventional devices in the art, and the second solid-liquid separation device may be, for example, a plate-and-frame filter press.
In the present invention, the iron removing means is for removing iron in the second filtrate; specifically, the oxidation device is used for oxidizing Fe 2+ in the second filtrate into Fe 3+, and the cation exchange chromatography device is used for adsorbing Fe 3+ so as to achieve the aim of removing iron in the second filtrate.
It will be appreciated that the cation exchange chromatography device is packed with a cation exchange resin; further, the cation exchange chromatography device is filled with D001 cation exchange resin, and has good adsorption removal effect on Fe 3+.
In the present invention, an aluminum recovery device is used for recovering aluminum from the treatment liquid to obtain an aluminum-containing product, wherein a neutralization device is used for neutralizing a strong acid solution (i.e., a neutralization liquid) with the treatment liquid to form Al (OH) 3 precipitate; the third solid-liquid separation device is used for carrying out solid-liquid separation on the neutralized mixed liquid so as to collect Al (OH) 3 precipitate; the washing device is used for washing the Al (OH) 3 precipitate; the drying device is used for drying the washed Al (OH) 3 precipitate, so that Al (OH) 3 product (namely aluminum-containing product) is obtained. Each of the above apparatuses may be a conventional apparatus in the art, wherein the third solid-liquid separation apparatus may be, for example, a plate-and-frame filter press, and the drying apparatus may be, for example, an oven.
The implementation of the invention has at least the following advantages:
1. The method and the system can solve the problems of difficult sludge recycling, difficult reduction, low purity of the recovered aluminum hydroxide, high impurity content, complex technical steps, large medicament dosage, more personnel configuration and the like in the aluminum industry in the prior art.
2. The method and the system can realize the recycling of resources, change waste into valuable, reduce the operation cost of enterprises, and ensure that the recovery rate of aluminum can reach more than 98 percent when comprehensively utilizing the sludge in the aluminum industry, and the purity of the obtained aluminum hydroxide product is more than 99 percent.
3. By adopting the method and the system of the invention to comprehensively utilize the aluminum sludge, the generated filter residues can be used for preparing bricks and cement so as to be used in the building material industry or the ceramic process industry, thereby further improving the utilization rate of the aluminum sludge; in addition, the concentration of metal ions in the solution discharged from the system is low, the content of Al 3+ is less than 20ppm, the content of Ca 2+ is less than 50ppm, the content of Fe 3+ is 5-10ppm, the discharge standard or reclaimed water recycling can be achieved through simple treatment, the environmental pollution is avoided, and the economic, environmental and social benefits are good.
Drawings
FIG. 1 is a process flow diagram of the integrated utilization of aluminum sludge in accordance with an embodiment of the present invention;
Fig. 2 is a schematic diagram of a system for comprehensive utilization of sludge in aluminum industry according to an embodiment of the present invention.
Reference numerals illustrate:
1: a digestion device; 2: a first solid-liquid separation device; 3: a reaction device; 4: a second solid-liquid separation device; 5: an oxidation device; 6: a cation exchange chromatography device; 7: a neutralization device; 8: a third solid-liquid separation device; 9: a washing device; 10: a drying device; 11: and a crushing device.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials and materials of each example and comparative example are as follows:
Aluminum industry sludge: sewage sediment from aluminum profile factories; the water content is 60-70wt%, the aluminum content is about 5.5wt%, the calcium content is about 5wt%, and the iron content is about 0.06 wt%;
Cation exchange resin: a D001 cation exchange resin was used.
Example 1
As shown in fig. 1, the method for comprehensively utilizing the aluminum industry sludge in the embodiment comprises the following steps:
1. Dissolution out
The aluminum sludge is smashed into fluffy shape, and if solid sludge with larger block hardness exists in the aluminum sludge, a crusher is adopted for crushing.
Taking 10kg of crushed aluminum sludge, and adding 20L of 2mol/L sodium hydroxide solution to submerge the aluminum sludge; then, the mixture was eluted at room temperature for 30 minutes with a stirring speed of 180r/min to obtain an eluted solution containing calcium and aluminum.
2. Solid-liquid separation
Filtering the dissolved solution by adopting a polypropylene plate-and-frame filter press, wherein the aperture of a filter medium of the polypropylene plate-and-frame filter press is 600 meshes, and respectively collecting filtrate (called first filtrate) and filter residues; wherein, the filtrate is used for subsequent calcium recovery, and the filter residue contains calcium and a small amount of aluminum and can be used for comprehensive utilization in the ceramic process industry.
3. Calcium recovery
Adding 1.5L of 10mol/L sodium carbonate solution into the first filtrate, and reacting for 30min at room temperature; subsequently, the reaction product is subjected to pressure filtration to obtain calcium carbonate and a second filtrate.
4. Iron removal
Adding 120mL of 30% hydrogen peroxide into the second filtrate, standing and oxidizing for 5min, wherein Fe 2+ in the second filtrate is oxidized into Fe 3+; then, ion exchange treatment is carried out by adopting cation exchange resin, fe 3+ in the oxidation product is adsorbed by the cation exchange resin so as to remove the Fe 3+ from the second filtrate, and the treated treatment liquid is collected.
5. Aluminum recovery
And adding 2mol/L HCl solution into the treatment liquid until the pH value of the system reaches about 8.0, then adopting a filter press to filter and press, collecting a filter cake, repeatedly washing and filtering, and drying in a baking oven at 106 ℃ to obtain 1.65kg of white aluminum-containing product.
The detection shows that the recovery rate of aluminum is 98%, and the content of aluminum hydroxide in the aluminum-containing product is 99.5wt%; in addition, all waste solutions were collected and pooled; through detection, the content of Al 3+ in the waste liquid is about 10ppm, the content of Ca 2+ is about 35ppm, the content of Fe 3+ is about 5ppm, and the waste liquid is a neutral solution with low metal ion concentration, so that the waste liquid is convenient for direct discharge or further recycling.
Example 2
The method for comprehensively utilizing the aluminum industry sludge comprises the following steps:
1. Dissolution out
The aluminum sludge is smashed into fluffy shape, and if solid sludge with larger block hardness exists in the aluminum sludge, a crusher is adopted for crushing.
Taking 10kg of crushed aluminum sludge, and adding 20L of 3mol/L sodium hydroxide solution to submerge the aluminum sludge; then, the mixture was eluted at room temperature for 30 minutes with a stirring speed of 200r/min to obtain an eluted solution containing calcium and aluminum.
2. Solid-liquid separation
Filtering the dissolved solution by adopting a polypropylene plate-and-frame filter press, wherein the aperture of a filter medium of the polypropylene plate-and-frame filter press is 700 meshes, and respectively collecting filtrate (called first filtrate) and filter residues; wherein, the filtrate is used for subsequent calcium recovery, and the filter residue contains calcium and a small amount of aluminum and can be used for comprehensive utilization in the ceramic process industry.
3. Calcium recovery
Adding 1.5L of 10mol/L sodium carbonate solution into the first filtrate, and reacting for 30min at room temperature; subsequently, the reaction product is subjected to pressure filtration to obtain calcium carbonate and a second filtrate.
4. Iron removal
Adding 150mL of 30% hydrogen peroxide into the second filtrate, standing and oxidizing for 3min, wherein Fe 2+ in the second filtrate is oxidized into Fe 3+; then, ion exchange treatment is carried out by adopting cation exchange resin, fe 3+ in the oxidation product is adsorbed by the cation exchange resin so as to remove the Fe 3+ from the second filtrate, and the treated treatment liquid is collected.
5. Aluminum recovery
And adding 3mol/L HCl solution into the treatment liquid until the pH value of the system reaches about 8.2, then adopting a filter press to filter and press, collecting a filter cake, repeatedly washing and filtering, and drying in a baking oven at 106 ℃ to obtain a white aluminum-containing product.
The detection shows that the recovery rate of aluminum is 98.4 percent, and the content of aluminum hydroxide in the aluminum-containing product is 99.2 weight percent; in addition, all waste solutions were collected and pooled; through detection, the content of Al 3+ in the waste liquid is about 15ppm, the content of Ca 2+ is about 42ppm, the content of Fe 3+ is about 8ppm, and the waste liquid is a neutral solution, so that the metal ion concentration is low, and the direct discharge or the further recycling is convenient.
Example 3
As shown in fig. 2, the system for comprehensive utilization of aluminum sludge according to the present invention comprises: a dissolution device 1; the inlet end of the first solid-liquid separation device 2 is connected with the outlet end of the digestion device 1; the calcium recovery device comprises a reaction device 3 and a second solid-liquid separation device 4 which are sequentially arranged, wherein the inlet end of the reaction device 3 is connected with the outlet end of the first solid-liquid separation device 2; the iron removing device comprises an oxidation device 5 and a cation exchange chromatography device 6 which are sequentially arranged, and the inlet end of the oxidation device 5 is connected with the outlet end of the second solid-liquid separation device 4; the aluminum recovery device comprises a neutralization device 7, a third solid-liquid separation device 8, a washing device 9 and a drying device 10 which are sequentially arranged, wherein the inlet end of the neutralization device 7 is connected with the outlet end of the cation exchange chromatography device 6.
Further, the system may further comprise a crushing device 11, wherein an outlet end of the crushing device 11 is connected with an inlet end of the dissolution device 1; the crushing device 11 is used for crushing the aluminum industry sludge, so that components such as calcium, aluminum and the like are completely separated from the aluminum industry sludge.
The crushing device 11 is not strictly limited, and can be a stamping machine or a crusher; wherein, the masher can be used for mashing aluminum sludge into fluffy shape, and solid sludge with larger block hardness in the aluminum sludge can be crushed by a crusher.
In the invention, a digestion device 1 is used for digestion of sludge in the aluminum industry to form digestion liquid containing calcium and aluminum; the specific structure thereof is not strictly limited and may be a conventional device in the art. In particular, the leaching device 1 can be provided with stirring components, thereby facilitating leaching under stirring conditions and being beneficial to release of calcium, aluminum, iron and other components in the aluminum industry sludge.
In the invention, the first solid-liquid separation device 2 is used for carrying out solid-liquid separation on the dissolved solution so as to obtain a first filtrate containing calcium and aluminum; the solid-liquid separation apparatus is not particularly limited and may be a solid-liquid separation apparatus conventionally used in the art.
In an embodiment, the first solid-liquid separation device 2 may be a filter press; specifically, the filter press may be a polypropylene plate-and-frame filter press; the polypropylene plate-and-frame filter press can avoid the damage of alkaline dissolution liquid to the filter medium.
Further, the pore size of the filter medium of the filter press is 600-700 meshes. The filter press with the aperture range is beneficial to improving the purity of products, and does not influence the actual operation of solid-liquid separation.
In the invention, the calcium recovery device is used for recovering the calcium in the first filtrate so as to obtain a calcium carbonate product; specifically, the reaction device 3 is used for reacting the calcium in the first filtrate with the added carbonate to generate calcium carbonate; the second solid-liquid separation device 4 is used for carrying out solid-liquid separation on the reaction product so as to recycle the calcium carbonate product. The reaction apparatus 3 and the second solid-liquid separation apparatus 4 may be conventional apparatuses in the art, and the second solid-liquid separation apparatus 4 may be, for example, a plate-and-frame filter press.
In the present invention, the iron removing means is for removing iron in the second filtrate; specifically, the oxidation device 5 is used for oxidizing Fe 2+ in the second filtrate into Fe 3+, and the cation exchange chromatography device 6 is used for adsorbing Fe 3+ so as to achieve the purpose of removing iron in the second filtrate. Wherein the cation exchange chromatography device 6 is filled with a D001 cation exchange resin.
In the present invention, the aluminum recovery means is used for recovering aluminum from the treatment liquid to obtain an aluminum-containing product, wherein the neutralization means 7 is used for neutralization of the strong acid solution (i.e., the neutralization liquid) with the treatment liquid to form Al (OH) 3 precipitate; the third solid-liquid separation device 8 is used for carrying out solid-liquid separation on the neutralized mixed liquid so as to collect Al (OH) 3 precipitate; the washing device 9 is used for washing the Al (OH) 3 precipitate; the drying apparatus 10 is used to dry the washed Al (OH) 3 precipitate to obtain Al (OH) 3 product (i.e., aluminum-containing product). Each of the above-mentioned apparatuses may be a conventional apparatus in the art, wherein the third solid-liquid separation apparatus 8 may be, for example, a plate-and-frame filter press or the like, and the drying apparatus 10 may be, for example, an oven or the like.
The system has simple structure and convenient operation, and when the system is used for treating the aluminum industry sludge, the recovery rate of aluminum can reach more than 98 percent, the purity of the obtained aluminum hydroxide product reaches 99 percent, and the system has obvious economic, environmental and social benefits.
Comparative example 1
The procedure of example 1 was repeated except that the second filtrate was not oxidized in step 4, but the second filtrate was directly treated with a cation exchange resin.
The aluminum hydroxide content in the aluminum-containing product was found to be only 94.3 wt.%.
Comparative example 2
The solid-liquid separation (step 2), the calcium recovery (step 3), the iron removal (step 4) and the aluminum recovery (step 5) of example 1 were directly performed on the aluminum sludge without leaching the aluminum sludge (i.e., without performing step 1 of example 1); as a result, it was found that the aluminum-containing product could not be recovered.
Comparative example 3
The procedure of example 1 was repeated except that 5mol/L sodium hydroxide solution was added to the crushed aluminum sludge for elution in the elution of step 1.
The content of aluminum hydroxide in the aluminum-containing product was detected to be only 95.2wt%.
Comparative example 4
The procedure of example 1 was repeated except that in step 5), a 2mol/L HCl solution was added to the second mixed solution until the pH of the system reached about 7.5.
The recovery rate of aluminum was detected to be only 93.3%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (2)
1. The method for comprehensively utilizing the aluminum industry sludge is characterized by comprising the following steps of:
1) Dissolving out the aluminum sludge by adopting a soluble alkali solution with the concentration of 2-3mol/L to obtain a solution; the aluminum industry sludge is crushed aluminum industry sludge slag after crushing treatment; the dissolution is carried out under stirring, wherein the stirring speed is 150-200r/min, and the dissolution time is 20-30min;
2) Performing solid-liquid separation on the dissolved solution by adopting a polypropylene plate-and-frame filter press to obtain a first filtrate; the aperture of the filter medium of the polypropylene plate-and-frame filter press is 600-700 meshes;
3) Adding soluble carbonate into the first filtrate for reaction, and carrying out solid-liquid separation on a reaction product to obtain calcium carbonate and a second filtrate; the concentration of the soluble carbonate is 8-12mol/L;
4) Oxidizing the second filtrate, and treating an oxidation product by adopting cation exchange resin to obtain a treatment solution; the oxidation is carried out by adopting hydrogen peroxide, and the oxidation time is controlled to be 2-5min;
5) Adding a strong acid solution into the treatment solution until the pH value is 8.0-8.2, and then carrying out solid-liquid separation, washing and drying to obtain an Al (OH) 3 product; the concentration of the strong acid solution is 2-3mol/L;
The purity of the Al (OH) 3 product is more than 99 percent; the content of Al 3+ in the waste liquid obtained by the solid-liquid separation is less than 20ppm, the content of Ca 2 + is less than 50ppm, and the content of Fe 3+ is 5-10ppm.
2. A system for comprehensive utilization of aluminum sludge, characterized in that it is used for implementing the method for comprehensive utilization of aluminum sludge according to claim 1, said system for comprehensive utilization of aluminum sludge comprises:
a digestion device;
The inlet end of the first solid-liquid separation device is connected with the outlet end of the digestion device;
the calcium recovery device comprises a reaction device and a second solid-liquid separation device which are sequentially arranged, wherein the inlet end of the reaction device is connected with the outlet end of the first solid-liquid separation device;
The iron removing device comprises an oxidation device and a cation exchange chromatography device which are sequentially arranged, and the inlet end of the oxidation device is connected with the outlet end of the second solid-liquid separation device;
The aluminum recovery device comprises a neutralization device, a third solid-liquid separation device, a washing device and a drying device which are sequentially arranged, wherein the inlet end of the neutralization device is connected with the outlet end of the cation exchange chromatography device;
the device also comprises a crushing device, wherein the outlet end of the crushing device is connected with the inlet end of the digestion device;
the first solid-liquid separation device is a filter press;
The pore diameter of the filter medium of the filter press is 600-700 meshes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710936690.5A CN109650419B (en) | 2017-10-10 | 2017-10-10 | Method and system for comprehensively utilizing aluminum industry sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710936690.5A CN109650419B (en) | 2017-10-10 | 2017-10-10 | Method and system for comprehensively utilizing aluminum industry sludge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109650419A CN109650419A (en) | 2019-04-19 |
| CN109650419B true CN109650419B (en) | 2024-07-02 |
Family
ID=66109513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710936690.5A Active CN109650419B (en) | 2017-10-10 | 2017-10-10 | Method and system for comprehensively utilizing aluminum industry sludge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109650419B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950961A (en) * | 2014-04-04 | 2014-07-30 | 中国科学院过程工程研究所 | Method for preparing aluminum hydroxide from industrial waste residue generated in aluminum alloy surface treatment |
| CN207347180U (en) * | 2017-10-10 | 2018-05-11 | 广东科达洁能股份有限公司 | A kind of system comprehensively utilized to Aluminum sludge |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259969B (en) * | 2008-03-27 | 2010-09-01 | 马鞍山钢铁股份有限公司 | Technique for preparing aluminum oxide |
| CN102092754B (en) * | 2010-12-23 | 2012-08-15 | 内蒙古昶泰资源循环再生利用科技开发有限责任公司 | Method for removing impurity iron in aluminum sulfate solution through ion exchange |
| CN103693665B (en) * | 2012-12-28 | 2015-11-18 | 中国神华能源股份有限公司 | A kind of coal ash for manufacturing is for the method for high purity aluminium oxide |
| CN104512917B (en) * | 2013-09-28 | 2016-04-27 | 沈阳铝镁设计研究院有限公司 | A kind of method utilizing ammoniacal liquor decomposed powder coal ash dissolution fluid to prepare aluminium hydroxide |
| CN104229859B (en) * | 2014-10-10 | 2016-06-01 | 河南工信环保科技有限公司 | A kind of iron contamination of removing in copper-bath the method for enriching Cu ion |
-
2017
- 2017-10-10 CN CN201710936690.5A patent/CN109650419B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950961A (en) * | 2014-04-04 | 2014-07-30 | 中国科学院过程工程研究所 | Method for preparing aluminum hydroxide from industrial waste residue generated in aluminum alloy surface treatment |
| CN207347180U (en) * | 2017-10-10 | 2018-05-11 | 广东科达洁能股份有限公司 | A kind of system comprehensively utilized to Aluminum sludge |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109650419A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106319218B (en) | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum-silicon waste | |
| CN103738986B (en) | A kind of dolomite calcination water-soluble separating calcium and magnesium produce the method for magnesium hydroxide and calcium carbonate | |
| CN109078962B (en) | Combined treatment method of arsenic-containing acidic wastewater, red mud and carbide slag | |
| CN112342389A (en) | Method for recovering valuable metal from waste chemical catalyst | |
| CN106906365A (en) | Rare earth oxide production wastewater treatment and rare earth recycling technique | |
| CN108584901B (en) | Method for recovering ceramic-grade iron phosphate from polymetallic hazardous wastes | |
| CN110846512A (en) | Method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing | |
| CN213887551U (en) | Continuous washing energy-saving treatment device for waste incineration fly ash or fly ash after hydrochloric acid washing | |
| CN109650419B (en) | Method and system for comprehensively utilizing aluminum industry sludge | |
| CN207347180U (en) | A kind of system comprehensively utilized to Aluminum sludge | |
| CN108373249B (en) | Resource utilization method and treatment system for high-chlorine iron-containing waste sludge | |
| CN108163880B (en) | Method for preparing gypsum powder by using zinc smelting waste acid | |
| CN107399888B (en) | Method for recovering aluminum in sludge of aluminum profile plant | |
| CN110713199A (en) | Treatment method of gallium extraction waste liquid obtained after extracting aluminum and gallium by fly ash acid method and water purifying agent | |
| CN109650683B (en) | Method and system for recycling calcium and aluminum from aluminum industry sludge | |
| CN112723688B (en) | Red mud dealkalization technology | |
| CN114602926A (en) | Device and process for resourceful treatment of waste incineration fly ash | |
| CN114195175A (en) | Method for extracting lithium and recovering nickel, cobalt and manganese metal from lithium iron phosphate powder mixed with ternary powder | |
| CN111304442A (en) | Method for removing F, Cl in secondary zinc oxide soot and preparing pure electrolyte | |
| CN110760697A (en) | Method for recovering cobalt sulfate from tungsten waste smelting slag | |
| CN218596477U (en) | System for utilize arsenic sulfide sediment preparation arsenic trioxide | |
| CN214167606U (en) | Utilize boiler tail gas to handle device of high alkali of polyformaldehyde industry high organic matter waste liquid | |
| CN218903034U (en) | Reutilization system for waste carbon dioxide and steel slag | |
| CN114959319B (en) | Method for treating solid matters obtained by mixed rare earth concentrate alkaline decomposition process | |
| CN114908259B (en) | Method for selectively extracting beryllium from beryllium-containing sludge based on hydrothermal ore phase regulation and control |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |