CN109867382B - Resource recovery method of metal ions in pickling waste liquid, product prepared by resource recovery method and application of product - Google Patents
Resource recovery method of metal ions in pickling waste liquid, product prepared by resource recovery method and application of product Download PDFInfo
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Abstract
The invention relates to a resource recovery method of metal ions in pickling waste liquid, a product prepared by the method and application of the product; the method comprises the following steps: (1) after the pickling waste liquid is settled and deslagged, adding soluble industrial salt and a precipitator, and adjusting the pH value of the waste liquid until metal ions in the waste liquid are completely precipitated to obtain pickling waste residues; (2) carrying out ball milling and extrusion processes on the acid pickling waste residue obtained in the step (1) to prepare an acid gas adsorbent; the acid gas adsorbent obtained by the invention is used for H2S、SO2All have better adsorption effect. The adsorbent product is prepared by taking the pickling waste liquid as a raw material, so that the resource recycling of metal ions in the pickling waste liquid is realized; the waste is prepared by waste, and the method has obvious environmental benefit.
Description
Technical Field
The invention relates to the field of resource utilization of pickling waste liquid, in particular to a resource recovery method of metal ions in pickling waste liquid, a product prepared by the resource recovery method and application of the product.
Background
The pickling waste liquid of the galvanizing factory is generated in the pickling process of galvanized steel pipes produced by the galvanizing factory, is wastewater containing iron and zinc, and generates ten million tons of wastewater every year; through the process of precipitation, separation and recycling of the wastewater in the galvanizing plant, 3000-5000 tons of pickling waste residues are generated in one medium-sized galvanizing plant each year on average. As a world with large production and consumption of galvanized pipes, acid pickling waste residues are produced in China in millions and even tens of millions of tons each year, and are accumulated in large areas, so that not only is a large amount of land occupied, but also soil and water resources are possibly polluted. How to realize the resource utilization of the metal ions in the wastewater of the galvanizing factory and the waste residues generated by the precipitation thereof is a difficult environmental protection and economic problem faced by the current galvanizing factory industry.
CN108238642A discloses a method for harmless recycling treatment of surface pickling waste liquid, which comprises the following steps: adding iron powder into the metal surface pickling waste liquid serving as a raw material, uniformly stirring to obtain a pretreatment solution, dropwise adding ammonia water, adjusting the pH value of the solution to 5-6, and filtering to obtain a semi-finished product solution; adding NaOH solution, and uniformly mixing to obtain an intermediate solution; filtering, washing, and spray drying to obtain solid semi-finished product; and (4) oxygen-enriched sintering at 400-900 ℃, and cooling to room temperature to obtain a finished product. The scheme produces a large amount of solid precipitate during operation, and the scheme does not give a method for treating the precipitate.
CN102603098A discloses a method for circularly treating stainless steel pickling waste liquid. The invention aims at various acid radical ions and metal ions (SO) in the stainless steel pickling waste liquid4 2-、F-、Cr3+、Ni2+、Fe2+、Fe3+) Firstly, alkali liquor is adopted to adjust the pH value of the pickling waste liquor to 7-10, and metal ions Cr3+、Ni2+、Fe2+And Fe3+Precipitating and drying to form a metallurgical raw material; then adding lime to the filtrate F-、CO3 2-And SO4 2-With CaF2、CaCO3And CaSO4Form precipitation; finally adding Na into the filtrate2CO3Obtaining CaCO3Precipitating with NaOH and Na as filtrate2CO3The mixed solution is directly returned to be used for precipitating metal ions in the stainless steel pickling waste liquid. According to the scheme, metal ions in the solution are separated from the solution in a precipitation mode, but a treatment mode of precipitates is not given, and resource utilization cannot be realized.
CN103643244A discloses a method for treating pickling waste liquid by microwave spray roasting, belonging to the technical field of microwave energy application and metallurgical environmental protection. Firstly heating the pickling waste liquid, then adding waste steel, iron filings or iron particles, cooling the pickling waste liquid after a section of pretreatment, adding strong ammonia water, simultaneously introducing air to react, and continuously addingAdding a flocculating agent for polymerization, and finally performing solid-liquid separation treatment to obtain solid waste and pretreated pickling waste liquid; atomizing the pretreated pickling waste liquid prepared in the step into small liquid drops by a spray gun, introducing the small liquid drops into a microwave oven by taking air as a carrier for roasting to obtain Fe2O3And the powder is mixed with gas generated in the process and is subjected to subsequent treatment to obtain a regenerated hydrochloric acid solution. The scheme generates a large amount of solid waste, does not provide a disposal mode of the solid waste, and is not beneficial to environment-friendly production.
CN105132932A discloses a recovery processing method of galvanized part backwashing waste acid liquor, which comprises the following steps: putting the galvanized part and the hanger which need to be rewashed into a special rewashing pool to be rewashed by hydrochloric acid to obtain the Zn-containing zinc2+、Fe2+The zinc-plated part backwashing waste acid solution with hydrochloric acid is separately recovered; putting the recovered back-washing waste acid liquid into a reaction container, respectively and sequentially adding hydrogen peroxide and ammonia water, adjusting the pH value of the waste acid liquid to be between 4 and 5, and oxidizing Fe2+Is Fe3+Generation of Fe (OH)3Precipitating, and filtering to remove; detecting the zinc-ammonia ratio of the filtrate, adding a proper amount of NH4Cl、ZnCl2And water to prepare the plating assistant agent with a certain ratio of zinc to ammonia. This scheme produces large amounts of Fe (OH)3Precipitation and no reasonable way of handling this precipitation is given.
CN101172727A discloses a hydrochloric acid waste liquid purification treatment process, which comprises the following steps: (1) heating the hydrochloric acid pickling waste liquid to 80-90 ℃ through a first heat exchanger, then feeding the hydrochloric acid pickling waste liquid into a free acid removal reaction tank, adding ferric oxide powder into the free acid removal reaction tank, and adding 40-50g of ferric oxide powder into each liter of hydrochloric acid pickling waste liquid to obtain waste acid from which free hydrochloric acid is removed; (2) precipitating and cooling to obtain cooled waste acid liquid; (3) adding ammonia water as neutralizing agent to form Fe (OH)3A flocculating constituent; adding coagulant aid to form bigger floc; (4) adding coagulant aid after precipitation to form larger floc and precipitate; (5) and (4) feeding the acid liquor purified in the step (4) into a purified acid liquor collecting tank, and then feeding the purified acid liquor into an acid storage tank by a pipeline and a purified acid liquor lifting pump. This scheme forms a large amount of flocculation precipitation, and the treatment method of the above precipitation is not given.
The above documents provide a method for treating a spent pickling solution, but do not provide a method for recycling a precipitate obtained from the spent pickling solution; therefore, the development of a new treatment method of the pickling waste liquid and the resource utilization of the solid phase waste obtained by the method still have important significance.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a resource recovery method of metal ions in pickling waste liquid, a product prepared by the resource recovery method and application of the product. The invention obtains acid waste residue by pretreating, modifying and precipitating the waste liquid of the galvanizing factory, successfully prepares the acid pickling waste residue adsorbent of the galvanizing factory by an extrusion molding technology, and can be used for H in industrial flue gas2S、SO2The effective adsorbent of acidic toxic gas realizes the resource recycling of metal ions in the pickling waste liquid of the galvanizing factory, uses waste to prepare waste, and has obvious environmental benefit.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a resource recovery method for metal ions in pickling waste liquid, which comprises the following steps:
(1) after the pickling waste liquid is settled and deslagged, adding soluble industrial salt and a precipitator, and adjusting the pH value of the waste liquid until metal ions in the waste liquid are completely precipitated to obtain pickling waste residues;
(2) and (2) carrying out ball milling and extrusion processes on the acid pickling waste residue obtained in the step (1) to prepare the acid gas adsorbent.
The invention provides a resource utilization way of pickling waste water and waste residue, and the pickling waste residue is utilized to prepare an acid gas adsorption purifying agent product, so that the high-added-value recycling of metal ions or acid sludge in the pickling waste liquid of a galvanizing factory and the secondary reutilization in the field of acid gas adsorption purification are realized, and a new process technology for preparing waste by using waste is formed.
Preferably, the waste pickle liquor of step (1) comprises a waste pickle liquor of a galvanizing plant.
In the invention, the pickling waste residue of the galvanizing factory is iron-containing or zinc-containing solid waste, and can also be red mud of an aluminum smelting factory, acid sludge of a galvanizing factory, tailings of a copper smelting factory and the like.
Preferably, the soluble industrial salt is any one or a combination of at least two of soluble sulfate or nitrate containing zinc, magnesium and iron, and further preferably zinc nitrate and/or ferrous sulfate.
Preferably, the addition amount of the soluble industrial salt is 1-10% of the mass of the acid washing waste liquid after deslagging, such as 1%, 3%, 5%, 7%, 9% or 10%.
Preferably, the precipitator in the step (1) is any one or a combination of at least two of calcium oxide, alkaline lime, carbide slag or industrial ammonia water.
Preferably, the pH is adjusted in the range of 10-12, such as 10, 10.3, 10.6, 10.9, 11.2, 11.5, 11.8 or 12.
Preferably, the time of precipitation is 12h to 48h, such as 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h or 48 h.
Preferably, the ball milling in the step (2) is to perform ball milling on the acid washing waste residue obtained in the step (1) and an adsorption enhancer to obtain a dry-based powder raw material A of the clay blank.
Preferably, the adsorption enhancer comprises any one of calcium oxide, zinc oxide, iron oxide or sodium carbonate or a combination of at least two of them.
Further preferably, the adsorption enhancer is a combination of any two of calcium oxide, zinc oxide, iron oxide, or sodium carbonate; for example, the adsorption enhancer is a mixture of calcium oxide and zinc oxide, and the mass ratio of the calcium oxide to the zinc oxide is 10: 1-1: 1, e.g. 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1; or a mixture of calcium oxide and ferric oxide, wherein the mass ratio of the calcium oxide to the ferric oxide is 10: 1-1: 1, e.g. 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1; or a mixture of calcium oxide and sodium carbonate, wherein the mass ratio of the calcium oxide to the sodium carbonate is 10: 1-1: 1, e.g. 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1; or a mixture of iron oxide and sodium carbonate, wherein the mass ratio of the iron oxide to the sodium carbonate is 10: 1-1: 1, e.g. 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1; or a mixture of zinc oxide and ferric oxide, wherein the mass ratio of the zinc oxide to the ferric oxide is 10: 1-1: 1, e.g. 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1.
preferably, the addition amount of the adsorption enhancer is 0-50% of the mass of the acid pickling waste residue, and is not 0, such as 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%; preferably 1% to 50%.
Preferably, the extrusion process of step (2) comprises the steps of:
(a) mixing a mud blank dry-based powder raw material A obtained by ball-milling the pickling waste residue obtained in the step (1) and an adsorption enhancer with a forming auxiliary agent to obtain a mixture B;
(b) kneading the mixture B with water and a lubricant, and filtering to obtain a raw mud blank C;
(c) and extruding, molding and drying the raw mud blank C to prepare the acid gas adsorbent.
Preferably, the forming aid of step (a) comprises any one of clay, glass fiber or cotton or a combination of at least two of the above.
Preferably, the forming aid comprises clay, glass fiber and cotton; wherein the mass ratio of the glass fiber to the pickling waste residue is less than or equal to 5%, and does not contain 0, such as 0.1%, 1%, 2%, 3%, 4% or 5%, preferably 0.1% -5%; the mass of the cotton is 1-10% of the mass of the pickling waste residue, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the clay comprises any one of kaolin, montmorillonite or attapulgite or a combination of at least two of them.
Preferably, the clay is a combination of any two of kaolin, montmorillonite or attapulgite; for example, the clay is a mixture of kaolin and montmorillonite; the mass ratio of the kaolin to the montmorillonite is 2: 1-1: 1, e.g. 2: 1. 1.8: 1. 1.5: 1. 1.3: 1 or 1: 1; or the clay is a mixture of kaolin and a convex-concave rod; the mass ratio of the kaolin to the convex-concave rod is 10: 1-1: 1, e.g. 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1; or the clay is a mixture of montmorillonite and a convex-concave rod, and the mass ratio of the montmorillonite to the convex-concave rod is 5: 1-1: 1, e.g. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1.
preferably, the cotton comprises wood pulp cotton and/or pulp cotton.
Preferably, the addition amount of the forming aid is 0-15% of the mass of the acid pickling waste residue, and is not 0, such as 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%; preferably 0.5% to 15%.
Preferably, the lubricant of step (b) comprises any one or a combination of at least two of lactic acid, cellulose, oleic acid or stearic acid; for example, the lubricant is a mixture of lactic acid and cellulose; the mass ratio of lactic acid to cellulose is 20: 1-10: 1, e.g. 20: 1. 19: 1. 18: 1. 17: 1. 16: 1. 15: 1. 14: 1. 13: 1. 12: 1. 11: 1 or 10: 1; or the lubricant is a mixture of lactic acid and stearic acid; the mass ratio of lactic acid to stearic acid is 5: 1-1: 1, e.g. 5: 1. 4: 1. 3: 1. 2: 1 or 1: 1; or the lubricant is a mixture of lactic acid, cellulose and stearic acid, the mass percentage of lactic acid in the mixture is 50% -75%, such as 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72% or 75%; preferably 62.5%; the mass percentage content of the cellulose is 3-12.5%, such as 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12% or 12.5%; preferably 6.25%; the stearic acid is present in an amount of 22% to 37.5% by mass, for example 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37% or 37.5%, preferably 31.25%.
Preferably, the lubricant is added in an amount of 0-5% by mass of the pickling waste residue, and is not added in an amount of 0, such as 0.1%, 1%, 2%, 3%, 4% or 5%; preferably 0.1% -5%; for example 0.1%, 1%, 2%, 3%, 4% or 5%.
Preferably, the amount of the kneaded water added is 10% to 30% by mass of the acid washing slag, for example, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, or 30%.
Preferably, the extruded product of step (c) is a cylinder, preferably a cylinder with a diameter of 2-15mm and a length of 0-10cm, excluding 0.
Preferably, the temperature of the drying is 50-120 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃.
Preferably, the drying further comprises roasting.
Preferably, the temperature of the calcination is 120-.
As a preferable technical scheme, the resource recovery method of metal ions in the pickling waste liquid comprises the following steps:
(1) after the pickling waste liquid is settled and deslagged, soluble industrial salt is added; the addition amount of the soluble industrial salt is 1-10% of the mass of the acid washing waste liquid after deslagging; adding a precipitator, adjusting the pH value of the waste liquid to 10-12, settling for 12-48 h, and separating to obtain pickling waste residues;
(2) adding an adsorption enhancer into the pickling waste residue obtained in the step (1), and carrying out ball milling; the addition amount of the adsorption enhancer is 1-50% of the mass of the pickling waste residue;
(3) adding a forming aid into the product obtained in the step (2) to mix; the addition amount of the forming auxiliary agent is 0.5-15% of the mass of the pickling waste residue;
(4) adding water and a lubricant into the product obtained in the step (3), kneading, and filtering by using an extruder; the adding amount of the water accounts for 10-30% of the mass of the pickling waste residues; the adding amount of the lubricant is 0.1-5% of the mass of the pickling waste residue;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 50-120 ℃, and roasting at 120-300 ℃ to prepare the acid gas adsorbent.
In a second aspect, the invention further provides the acidic gas adsorbent prepared by the method for recycling metal ions from the pickling waste liquid in the first aspect.
Preferably, the adsorbent is cylindrical in shape.
Preferably, the adsorbent has a diameter of 2 to 15mm, for example 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15 mm.
Preferably, the adsorbent is 0 to 10cm in length, excluding 0, e.g. 1cm, 2cm, 3cm, 4cm, 5cm, 6cm, 7cm, 8cm, 9cm or 10 cm.
In a third aspect, the present invention also provides the use of an acid gas adsorbent as described in the second aspect, for adsorbing acid gases; the acid gas comprises H2S and/or SO2。
Preferably, the acid gas is derived from coking flue gas, biomass boiler flue gas, biomass fermentation waste gas, biogas waste gas, coal bed gas or pyrolysis gas.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention successfully prepares the H in the industrial flue gas by pretreating, modifying and precipitating the waste liquid of the galvanizing factory to obtain the acid waste residue and adopting the extrusion molding technology2S、SO2The effective adsorbent of acidic toxic gas realizes the treatment of toxic and harmful substances in the waste gas;
(2) the acid gas adsorbent prepared by the invention is used for H2The saturated sulfur capacity of S can reach more than 45%, and the sulfur-containing composite material has the characteristics of high sulfur capacity, obvious adsorption effect and performance advantage;
(3) the method provided by the invention adopts the pickling waste liquid as a raw material to prepare the adsorbent, realizes resource recycling of metal ions in the pickling waste liquid of a galvanizing factory, uses waste to prepare waste, and has obvious environmental benefits.
Drawings
FIG. 1 is a process flow diagram of the resource recovery method of metal ions in the pickling waste liquid.
FIG. 2 shows the product acid gas adsorbent prepared in example 1 of the present invention.
FIG. 3 shows H of the acid gas adsorbent prepared in example 1 of the present invention2And S sulfur capacity test results.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
FIG. 1 is a process flow diagram of a resource recovery method for metal ions in pickling waste liquid according to the present invention; the method specifically comprises the following steps:
(1) after the pickling waste liquid is settled and deslagged, adding soluble industrial salt, adjusting the pH value of the waste liquid, and carrying out solid-liquid separation to obtain pickling waste residues;
(2) mixing the pickling waste residue obtained in the step (1) with an adsorption enhancer;
(3) mixing the product obtained in the step (2) with a forming aid;
(4) mixing the product of the step (3) with water and a lubricant;
(5) and (4) forming and drying the product obtained in the step (4) to obtain the acid gas adsorbent.
The following examples all employ the process scheme shown in figure 1.
Example 1
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, ferrous sulfate is added until the mass of the ferrous sulfate is 5% of that of the pickling waste liquid after deslagging, then alkaline lime is added as a precipitator until the mass of the alkaline lime is 10% of that of the pickling waste liquid after deslagging, the pH value of the pickling waste liquid is adjusted to 12, metal ions are completely precipitated, and settlement is carried out for 24 hours, so that pickling waste residues are obtained;
(2) adding calcium oxide with the mass being 10% of that of the acid pickling waste residue into the acid pickling waste residue obtained in the step (1) for ball milling;
(3) respectively adding montmorillonite accounting for 5% of the mass of the pickling waste residues, glass fiber accounting for 3% of the mass of the pickling waste residues and cotton accounting for 2% of the mass of the pickling waste residues into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water and 3% of stearic acid by mass of the acid-washing waste residue into the product obtained in the step (3), kneading in a kneader, and filtering by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), and drying at 120 ℃ for 12h to obtain the acid gas adsorbent.
Figure 2 shows an acid gas adsorbent prepared according to example 1 in the form of a cylinder having a diameter of about 3mm and a length of about 2 cm.
FIG. 3 shows the results of a sulfur capacity test of the acid gas adsorbent prepared in example 1 of the present invention; from this figure, it can be seen that the adsorbent pair H2The saturated sulfur capacity of S gas reaches more than 50%.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 2
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding zinc nitrate until the mass of the zinc nitrate is 5 percent of the mass of the pickling waste liquid after deslagging, then adding carbide slag as a precipitator until the mass of the carbide slag is 10 percent of the mass of the pickling waste liquid after deslagging, adjusting the pH value of the pickling waste liquid to 11, completely settling metal ions, and settling for 24 hours to obtain pickling waste residues;
(2) respectively adding calcium oxide and sodium carbonate which are 5 percent and 5 percent of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue for ball milling;
(3) respectively adding 5% of kaolin, 3% of glass fiber and 5% of cotton by mass of the acid-washing waste residue into the product obtained in the step (2), and mixing in a mixer;
(4) adding water accounting for 25% of the mass of the acid-washing waste residues and oleic acid accounting for 3% of the mass of the product obtained in the step (3) into a kneader, kneading, and filtering by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 2h to obtain the acid gas adsorbent, wherein the product is 4cm in length and 6mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 3
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, zinc nitrate and ferrous sulfate which account for 2% and 5% of the mass of the pickling waste liquid after deslagging are respectively added, then carbide slag is added as a precipitator until the mass of the carbide slag accounts for 10% of the mass of the pickling waste liquid after deslagging, the pH value of the pickling waste liquid is adjusted to 12, metal ions are completely precipitated, and the precipitation is carried out for 24 hours, so that pickling waste residue is obtained;
(2) respectively adding zinc oxide and sodium carbonate which account for 5% and 10% of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue to perform ball milling;
(3) respectively adding 5% of kaolin, 3% of glass fiber and 1% of cotton by mass of the acid-washing waste residue into the product obtained in the step (2), and mixing in a mixer;
(4) adding 25% of water, 1% of oleic acid and 2% of stearic acid by mass of the acid-washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 2h to obtain the acid gas adsorbent, wherein the product is 3cm in length and 9mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 4
(1) After settling and deslagging the pickling waste liquid of a galvanizing factory, adding magnesium nitrate until the mass of the magnesium nitrate is 5% of that of the pickling waste liquid after deslagging, then adding industrial ammonia water as a precipitator until the mass of the industrial ammonia water is 10% of that of the pickling waste liquid after deslagging, adjusting the pH value of the pickling waste liquid to 10, completely precipitating metal ions, and settling for 48 hours to obtain pickling waste residues;
(2) respectively adding sodium carbonate with the mass being 10% of that of the acid pickling waste residue into the acid pickling waste residue obtained in the step (1) for ball milling;
(3) respectively adding a convex-concave rod accounting for 6 percent of the mass of the pickling waste residues, a glass fiber accounting for 5 percent of the mass of the pickling waste residues and cotton accounting for 4 percent of the mass of the pickling waste residues into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 10% of water and 5% of lactic acid by mass of the acid-washing waste residue into the product obtained in the step (3), kneading in a kneader, and filtering by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 50 ℃ for 12h, and roasting at 300 ℃ for 2h to obtain the acid gas adsorbent, wherein the product has the length of 10cm and the diameter of 15 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 5
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1, adding magnesium sulfate and ferric nitrate until the mass of the magnesium sulfate and the ferric nitrate is 10% of the mass of the acid pickling waste liquid after deslagging, adding calcium oxide as a precipitator until the mass of the calcium oxide is 10% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 12 hours to obtain acid pickling waste residues;
(2) respectively adding iron oxide with the mass being 5% of that of the pickling waste residue into the pickling waste residue obtained in the step (1) for ball milling;
(3) respectively adding 6% of kaolin, 3% of montmorillonite, 1% of glass fiber and 1% of cotton by mass of the acid-washing waste residue into the product obtained in the step (2), and mixing in a mixer;
(4) adding water accounting for 30% of the mass of the acid-washing waste residues and cellulose accounting for 1% of the mass of the acid-washing waste residues into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 120 ℃ for 2h to obtain the acid gas adsorbent, wherein the product has the length of 0.5cm and the diameter of 2 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 6
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1, adding the zinc sulfate and the ferric sulfate to the mass of 10% of the mass of the acid pickling waste liquid after deslagging, adding the carbide slag as a precipitator to the mass of 15% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residue;
(2) respectively adding calcium oxide and zinc oxide which account for 20% and 2% of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue to perform ball milling;
(3) respectively adding 1% of kaolin, 1% of montmorillonite, 1% of glass fiber and 10% of cotton by mass of the acid-washing waste residue into the product obtained in the step (2), and mixing in a mixer;
(4) adding 10% of water, 4% of lactic acid and 0.2% of cellulose by mass of the acid-washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 2cm in length and 3mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 7
This example was conducted under exactly the same conditions as in example 6 except that 20% of calcium oxide and 2% of zinc oxide in step (2) of example 6 were replaced with 25% of calcium oxide and 2% of zinc oxide, and a product having a length of 2cm and a diameter of 3mm was obtained.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 8
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1, adding magnesium sulfate and ferric sulfate to the mass of 10% of the mass of the acid pickling waste liquid after deslagging, and adding the mixture in a mass ratio of 1: 1, taking the carbide slag and the alkaline lime as precipitants until the mass of the carbide slag and the alkaline lime is 15% of that of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residues;
(2) respectively adding calcium oxide and zinc oxide which account for 20% of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue for ball milling;
(3) respectively adding 10% of kaolin, 1% of convex-concave rod, 1% of glass fiber and 2% of cotton by mass of the acid-washing waste residue into the product obtained in the step (2), and mixing in a mixer;
(4) adding 25% of water, 4% of lactic acid and 0.4% of cellulose by mass of the acid-washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 2cm in length and 3mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 9
This example was conducted under exactly the same conditions as in example 6 except that 20% of calcium oxide and 20% of zinc oxide in step (2) of example 6 were replaced with 20% of calcium oxide and 25% of zinc oxide, and a product having a length of 3cm and a diameter of 3mm was obtained.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 10
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1: 1, adding zinc sulfate, magnesium sulfate and ferric sulfate to the mass of 10% of the mass of the acid pickling waste liquid after deslagging, and adding the materials in a mass ratio of 1: 1, taking the carbide slag and the calcium oxide as precipitants until the mass of the carbide slag and the calcium oxide is 10% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste slag;
(2) respectively adding calcium oxide accounting for 25% of the mass of the acid-washing waste residue and iron oxide accounting for 2.5% of the mass of the acid-washing waste residue in the step (1) into the acid-washing waste residue to perform ball milling;
(3) respectively adding 5% of kaolin, 5% of convex-concave rods, 2% of glass fiber and 2% of cotton by mass of the acid-washing waste residues into the product obtained in the step (2), and mixing in a mixer;
(4) adding 25% of water, 4.5% of lactic acid and 0.9% of stearic acid by mass of the acid washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 2cm in length and 3mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 11
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1: 1, adding zinc sulfate, magnesium nitrate and ferric sulfate to the mass of 10% of the mass of the acid pickling waste liquid after deslagging, and adding the zinc sulfate, the magnesium nitrate and the ferric sulfate in a mass ratio of 1: 1, taking calcium oxide and industrial ammonia water as a precipitator until the mass of the calcium oxide and the industrial ammonia water is 10% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residues;
(2) respectively adding calcium oxide and iron oxide which account for 10 percent of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue for ball milling;
(3) respectively adding montmorillonite accounting for 5% of the mass of the acid-washing waste residue, a convex-concave rod accounting for 1%, glass fiber accounting for 1% and cotton accounting for 1% of the mass of the acid-washing waste residue into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 1% of lactic acid and 1% of stearic acid by mass of the acid-washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 6cm in length and 5mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 12
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1: 1, adding zinc nitrate, magnesium nitrate and ferrous sulfate to the mass of 10% of the mass of the acid pickling waste liquid after deslagging, and adding the mixture in a mass ratio of 1: 1, taking the alkaline lime and the industrial ammonia water as precipitants until the mass of the alkaline lime and the industrial ammonia water is 10% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residues;
(2) respectively adding calcium oxide and 1% sodium carbonate with the mass being 10% of that of the acid pickling waste residue into the acid pickling waste residue in the step (1) for ball milling;
(3) respectively adding montmorillonite accounting for 3% of the mass of the acid pickling waste residues, a convex-concave rod accounting for 3%, glass fiber accounting for 1% and cotton accounting for 1% of the mass of the acid pickling waste residues into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 2% of lactic acid, 0.5% of cellulose and 1.5% of stearic acid by mass of the acid washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product has the length of 10cm and the diameter of 6 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 13
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1: 1, adding zinc nitrate, magnesium nitrate and ferrous sulfate to the mass of 10% of the mass of the acid pickling waste liquid after deslagging, and adding the mixture in a mass ratio of 1: 1: 1, taking the carbide slag, the alkaline lime and the industrial ammonia water as a precipitator until the mass of the precipitator is 10% of that of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residues;
(2) respectively adding calcium oxide and sodium carbonate which account for 10 percent of the mass of the acid-washing waste residue in the step (1) into the acid-washing waste residue for ball milling;
(3) respectively adding montmorillonite accounting for 3% of the mass of the acid-washing waste residue, a convex-concave rod accounting for 3%, kaolin accounting for 3%, glass fiber accounting for 1% and cotton accounting for 1% of the mass of the acid-washing waste residue into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 3% of lactic acid, 0.25% of cellulose and 0.75% of stearic acid by mass of the acid washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 9cm in length and 10mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 14
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1: 1, adding zinc sulfate, magnesium nitrate and ferrous sulfate to the mass of which is 5 percent of the mass of the acid pickling waste liquid after deslagging, and adding the zinc sulfate, the magnesium nitrate and the ferrous sulfate in a mass ratio of 1: 1: 1: 1, taking calcium oxide, carbide slag, alkaline lime and industrial ammonia water as a precipitator until the mass of the precipitator is 10% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residue;
(2) respectively adding iron oxide and 1% sodium carbonate with the mass being 10% of that of the acid pickling waste residue into the acid pickling waste residue in the step (1) for ball milling;
(3) respectively adding montmorillonite, glass fiber and cotton which account for 10 percent, 1 percent and 1 percent of the mass of the acid-washing waste residue into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 3% of lactic acid, 0.3% of cellulose and 1.5% of stearic acid by mass of the acid washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the adsorbent, wherein the length of the product is 7cm, and the diameter of the product is 11 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 15
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, ferrous sulfate is added until the mass of the ferrous sulfate is 2% of that of the pickling waste liquid after deslagging, then alkaline lime is added as a precipitator until the mass of the alkaline lime is 10% of that of the pickling waste liquid after deslagging, the pH value of the pickling waste liquid is adjusted to 12, metal ions are completely precipitated, and settlement is carried out for 24 hours, so that pickling waste residues are obtained;
(2) respectively adding iron oxide and sodium carbonate which account for 5 percent of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue for ball milling;
(3) respectively adding montmorillonite accounting for 10% of the mass of the acid-washing waste residue, glass fiber accounting for 3% of the mass of the acid-washing waste residue and cotton accounting for 2% of the mass of the acid-washing waste residue into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 2% of lactic acid, 1.5% of oleic acid and 1.5% of stearic acid by mass of the acid washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 8cm in length and 5mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 16
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, ferrous sulfate is added until the mass of the ferrous sulfate is 5% of that of the pickling waste liquid after deslagging, then carbide slag is added as a precipitator until the mass of the carbide slag is 10% of that of the pickling waste liquid after deslagging, the pH value of the pickling waste liquid is adjusted to 12, metal ions are completely precipitated, and the precipitation is carried out for 24 hours, so that pickling waste residue is obtained;
(2) respectively adding zinc oxide and iron oxide with the mass being 10% of that of the acid pickling waste residue in the step (1) into the acid pickling waste residue to perform ball milling;
(3) respectively adding montmorillonite accounting for 5% of the mass of the pickling waste residues, glass fiber accounting for 3% of the mass of the pickling waste residues and cotton accounting for 2% of the mass of the pickling waste residues into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 2% of stearic acid, 1.5% of oleic acid and 1.5% of cellulose by mass of the acid washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 6cm in length and 4mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 17
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, ferrous sulfate is added until the mass of the ferrous sulfate is 5% of that of the pickling waste liquid after deslagging, then alkaline lime is added as a precipitator until the mass of the alkaline lime is 10% of that of the pickling waste liquid after deslagging, the pH value of the pickling waste liquid is adjusted to 12, metal ions are completely precipitated, and settlement is carried out for 24 hours, so that pickling waste residues are obtained;
(2) respectively adding zinc oxide and iron oxide which account for 15% of the mass of the acid pickling waste residue in the step (1) into the acid pickling waste residue to perform ball milling;
(3) respectively adding montmorillonite accounting for 5% of the mass of the pickling waste residues, glass fiber accounting for 3% of the mass of the pickling waste residues and cotton accounting for 2% of the mass of the pickling waste residues into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 1% of lactic acid, 1% of stearic acid, 1% of oleic acid and 1% of cellulose by mass of the acid-washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 5cm in length and 3mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 18
(1) After the pickling waste liquid of a galvanizing factory is settled and deslagged, adding the waste liquid in a mass ratio of 1: 1: 1, adding calcium carbide slag as a precipitator until the mass of the calcium carbide slag is 10% of the mass of the acid pickling waste liquid after deslagging, adjusting the pH value of the acid pickling waste liquid to 12, completely precipitating metal ions, and settling for 48 hours to obtain acid pickling waste residues;
(2) respectively adding zinc oxide with the mass being 5 percent of that of the acid pickling waste residue, iron oxide with the mass being 5 percent of that of the acid pickling waste residue and sodium carbonate with the mass being 5 percent of that of the acid pickling waste residue into the acid pickling waste residue obtained in the step (1) for ball milling;
(3) respectively adding montmorillonite accounting for 5% of the mass of the pickling waste residues, glass fiber accounting for 3% of the mass of the pickling waste residues and cotton accounting for 2% of the mass of the pickling waste residues into the product obtained in the step (2), and mixing the materials in a mixer;
(4) adding 25% of water, 1% of lactic acid, 1% of stearic acid, 1% of oleic acid and 1% of cellulose by mass of the acid-washing waste residue into the product obtained in the step (3), kneading the mixture in a kneader, and filtering the kneaded mixture by an extruder;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 80 ℃ for 12h, and roasting at 180 ℃ for 3h to obtain the acid gas adsorbent, wherein the product is 3cm in length and 1mm in diameter.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 19
This example replaces the zinc oxide in step (2) of example 18 with calcium oxide; otherwise, exactly the same conditions as in example 18 were used, the product having a length of 6cm and a diameter of 2 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 20
This example replaces the iron oxide in step (2) of example 18 with calcium oxide; otherwise, exactly the same conditions as in example 18 were used, the product having a length of 7cm and a diameter of 3 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2Is full ofAnd the results of the sulfur capacity test are shown in table 1.
Example 21
This example replaces the sodium carbonate in step (2) of example 18 with calcium oxide; otherwise, exactly the same conditions as in example 18 were applied, and the product had a length of 9cm and a diameter of 5 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Example 22
This example replaces 5% zinc oxide, 5% iron oxide and 5% sodium carbonate in step (2) of example 18 with 5% calcium carbonate, 5% zinc oxide, 5% iron oxide and 5% sodium carbonate; otherwise, exactly the same conditions as in example 18 were used, the product having a length of 5cm and a diameter of 4 mm.
The adsorbent prepared in this example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Comparative example 1
In comparison with example 1, in this comparative example, no ferrous sulfate was added in step (1), and the other conditions were exactly the same as in example 1.
The adsorbent prepared in this comparative example was subjected to H2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Comparative example 2
This comparative example employed only step (1) in example 1, and steps (2) to (5) were not performed.
Carrying out H on the pickling waste residue obtained in the comparative example2Saturated sulfur capacity test of S, SO2The results of the saturated sulfur capacity test of (2) are shown in Table 1.
Examples 1-22 and comparative examples 1-2 were subjected to H2Saturated sulfur capacity and SO of S2The standards adopted by the saturated sulfur capacity test are HG/T5318-2018 and GB/T7702.14-2008 respectively.
The adsorption performance test data of the acid gas adsorbents obtained in examples 1 to 22 and comparative examples 1 to 2 are shown in table 1:
TABLE 1
As can be seen from table 1, the adsorption capacity of the acid gas adsorbents prepared in examples 1 to 22 for acid gas is significantly better than that of comparative examples 1 to 2, which shows that the acid gas adsorbents prepared by the resource recovery method for metal ions in pickling waste liquid according to the present invention have a good adsorption effect for acid gas, and realize the waste treatment by waste, and have a practical application prospect.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (27)
1. A method for preparing an acid gas adsorbent by resource recovery of metal ions in pickling waste liquid is characterized by comprising the following steps:
(1) after the pickling waste liquid is settled and deslagged, adding soluble industrial salt and a precipitator, and adjusting the pH value of the waste liquid until metal ions in the waste liquid are completely precipitated to obtain pickling waste residues;
the pickling waste liquid comprises pickling waste liquid of a galvanizing factory; the addition amount of the soluble industrial salt is 1-10% of the mass of the acid washing waste liquid after deslagging; the precipitator is any one or the combination of at least two of calcium oxide, alkaline lime, carbide slag or industrial ammonia water, the pH value is adjusted within the range of 10-12, and the precipitation time is 12-48 h;
(2) carrying out ball milling and extrusion processes on the acid pickling waste residue obtained in the step (1) to prepare an acid gas adsorbent;
performing ball milling on the acid pickling waste residue obtained in the step (1) and an adsorption enhancer to obtain a mud blank dry-based powder raw material A; the adsorption enhancer comprises any one or the combination of at least two of calcium oxide, zinc oxide, iron oxide or sodium carbonate;
the soluble industrial salt is any one or combination of at least two of soluble sulfate or nitrate containing zinc, magnesium and iron.
2. The method for preparing the acid gas adsorbent through resource recovery according to claim 1, wherein the soluble industrial salt is zinc nitrate and/or ferrous sulfate.
3. The method for preparing the acid gas adsorbent by resource recovery according to claim 1, wherein the addition amount of the adsorption enhancer is 0-50% of the mass of the pickling waste residue, and is 0-free.
4. The method for preparing the acid gas adsorbent by resource recovery according to claim 1, wherein the addition amount of the adsorption enhancer is 1-50% of the mass of the pickling waste residue.
5. The method for preparing the acid gas adsorbent by resource recovery according to claim 1, wherein the extrusion process in the step (2) comprises the following steps:
(a) mixing a mud blank dry-based powder raw material A obtained by ball-milling the pickling waste residue obtained in the step (1) and an adsorption enhancer with a forming auxiliary agent to obtain a mixture B;
(b) kneading the mixture B with water and a lubricant, and filtering to obtain a raw mud blank C;
(c) and extruding, molding and drying the raw mud blank C to prepare the acid gas adsorbent.
6. The method for preparing the acid gas adsorbent through resource recycling according to claim 5, wherein the forming aid in the step (a) comprises any one or a combination of at least two of clay, glass fiber or cotton.
7. The method for preparing an acid gas adsorbent by resource recovery as claimed in claim 6, wherein the clay comprises one or a combination of at least two of kaolin, montmorillonite or attapulgite.
8. The method for preparing the acid gas adsorbent through resource recovery according to claim 6, wherein the cotton comprises wood pulp cotton and/or pulp cotton.
9. The method for preparing the acid gas adsorbent by resource recovery according to claim 5, wherein the addition amount of the forming aid is 0-15% of the mass of the pickling waste residue, and is 0-free.
10. The method for preparing the acid gas adsorbent by resource recovery according to claim 9, wherein the addition amount of the forming aid is 0.5-15% of the mass of the pickling waste residue.
11. The method for preparing the acid gas adsorbent through resource recycling according to claim 5, wherein the lubricant in the step (b) comprises any one or a combination of at least two of lactic acid, cellulose, oleic acid or stearic acid.
12. The method for preparing the acid gas adsorbent by resource recovery according to claim 5, wherein the amount of the lubricant added is 0-5% of the mass of the pickling waste residue and is 0-free.
13. The method for preparing the acid gas adsorbent through resource recovery according to claim 12, wherein the addition amount of the lubricant is 0.1-5% of the mass of the pickling waste residue.
14. The method for preparing the acid gas adsorbent through resource recovery according to claim 5, wherein the addition amount of the kneaded water is 10% -30% of the mass of the acid pickling waste residue.
15. The method for preparing an acid gas adsorbent by resource recovery as claimed in claim 5, wherein the extrusion-molded product of the step (c) is a cylindrical body.
16. The method for preparing an acid gas adsorbent by resource recovery as claimed in claim 15, wherein the extrusion-molded product of the step (c) is a cylinder having a diameter of 2 to 15mm and a length of 0 to 10cm, excluding 0.
17. The method for preparing the acid gas adsorbent through resource recovery according to claim 16, wherein the drying temperature is 50-120 ℃.
18. The method for preparing the acid gas adsorbent by resource recovery according to claim 5, wherein the drying further comprises roasting.
19. The method for preparing acid gas adsorbent by resource recovery as claimed in claim 18, wherein the temperature of the calcination is 120-300 ℃.
20. The method for preparing the acid gas adsorbent by resource recovery according to claim 1, wherein the method comprises the following steps:
(1) after the pickling waste liquid is settled and deslagged, soluble industrial salt is added; the addition amount of the soluble industrial salt is 1-10% of the mass of the acid washing waste liquid after deslagging; adding a precipitator, adjusting the pH value of the waste liquid to 10-12, settling for 12-48 h, and separating to obtain pickling waste residues;
(2) adding an adsorption enhancer into the pickling waste residue obtained in the step (1), and carrying out ball milling; the addition amount of the adsorption enhancer is 1-50% of the mass of the pickling waste residue;
(3) adding a forming aid into the product obtained in the step (2) to mix; the addition amount of the forming auxiliary agent is 0.5-15% of the mass of the pickling waste residue;
(4) adding water and a lubricant into the product obtained in the step (3), kneading, and filtering by using an extruder; the adding amount of the water accounts for 10-30% of the mass of the pickling waste residues; the adding amount of the lubricant is 0.1-5% of the mass of the pickling waste residue;
(5) and (4) extruding and molding the product obtained in the step (4), drying at 50-120 ℃, and roasting at 120-300 ℃ to prepare the acid gas adsorbent.
21. The method for preparing the acid gas adsorbent by recycling the metal ions in the pickling waste liquid as claimed in claim 1.
22. The acid gas sorbent of claim 21, wherein the acid gas sorbent is in the shape of a cylinder.
23. The acid gas sorbent of claim 21, wherein the acid gas sorbent has a diameter of from 2mm to 15 mm.
24. The acid gas sorbent of claim 21, wherein the acid gas sorbent has a length of 0-10cm, excluding 0.
25. The acid gas sorbent of claim 24, wherein the acid gas sorbent has a length of from 0.1 cm to 10 cm.
26. Use of the acid gas adsorbent of any one of claims 21-25, wherein the adsorbent is used for adsorbing H2S and/or SO2。
27. The use of claim 26, wherein the acid gas is derived from coker flue gas, biomass boiler flue gas, biomass fermentation off-gas, biogas off-gas, coal bed gas, or pyrolysis gas.
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| CN110577299B (en) * | 2019-10-18 | 2021-08-27 | 河北渤海远达环境检测技术服务有限公司 | Method for treating hot galvanizing pickling wastewater and preparing carbon-loaded iron-zinc binary metal composite material |
| CN112892467B (en) * | 2019-12-04 | 2022-05-31 | 武汉科林化工集团有限公司 | Method for preparing flue gas desulfurization powder adsorbent by using liquid-solid waste |
| CN115350694B (en) * | 2022-06-08 | 2024-03-19 | 上海大学 | Method for preparing formed acid gas adsorbent by utilizing iron-containing waste residues and formed acid gas adsorbent prepared by method |
| CN116832793A (en) * | 2023-06-20 | 2023-10-03 | 昆明理工大学 | Industrial wastewater adsorbent and preparation method thereof |
| CN116798760B (en) * | 2023-07-12 | 2024-03-12 | 重庆上甲电子股份有限公司 | Method and flux for preparing soft magnetic manganese zinc ferrite composite material by utilizing manganese anode slime and zinc slime |
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| JPS54154158A (en) * | 1978-05-26 | 1979-12-05 | Katsukawa Heitarou | Method of disposing waste water containing heavy metal |
| CN102974304A (en) * | 2012-11-28 | 2013-03-20 | 常州大学 | Method for synthesizing hydrotalcite by using industrial acid washing wastewater |
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