CN109867382A - Resource recycle method, product and application thereof as made from it of metal ion in a kind of pickle liquor - Google Patents
Resource recycle method, product and application thereof as made from it of metal ion in a kind of pickle liquor Download PDFInfo
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- CN109867382A CN109867382A CN201811317168.XA CN201811317168A CN109867382A CN 109867382 A CN109867382 A CN 109867382A CN 201811317168 A CN201811317168 A CN 201811317168A CN 109867382 A CN109867382 A CN 109867382A
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- waste slag
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The present invention relates to resource recycle method, products and application thereof as made from it of metal ion in a kind of pickle liquor；It the described method comprises the following steps: (1) by after pickle liquor sedimentation slagging-off, adding soluble Nacl and precipitating reagent is added, adjust waste liquid pH value and precipitated completely to metal ions in waste liquor, obtain acid cleaning waste slag；(2) acid gas adsorption agent is prepared through ball milling and extrusion process in the acid cleaning waste slag for obtaining step (1)；The acid gas adsorption agent that the present invention obtains is to H2S、SO2There is preferable adsorption effect.The present invention prepares adsorbent product by raw material of pickle liquor, realizes and utilizes to the resource utilization of metal ion in pickle liquor；Waste recycling has apparent environmental benefit.
Description
Technical field
The present invention relates to a kind of moneys of metal ion in the resource utilization field of pickle liquor more particularly to pickle liquor
Source recovery method, product and application thereof as made from it.
Background technique
Zinc-plated factory's pickle liquor is generated by the acid cleaning process of zinc-plated factory production coating steel pipe, is that a kind of iron content is useless containing zinc
Water, it is annual to generate ten-million-ton scale waste water；Though average one medium-sized zinc-plated factory is every by zinc-plated factory's wastewater sedimentation separating and recovering technique
Year generates 3000-5000 tons of acid cleaning waste slags.China is as galvanized pipe production and consumption big country, the world, the acid cleaning waste slag generated every year
Up to millions of or even ten million ton of acid cleaning waste slag, large area accumulation, does not only take up a large amount of soils, and may to soil,
Water resource generates pollution.How to realize that the resource utilization for the waste residue that zinc-plated factory's waste water metal ions and its precipitating generate is current
The intractable environmental protection and economy problem that zinc-plated enterprise, factory faces.
CN108238642A discloses a kind of method of harmless resource utilization processing surface acid-washing waste liquid, including following step
It is rapid: to use metal surface pickle liquor for raw material, iron powder is added, stirs evenly, obtain preprocessing solution, ammonium hydroxide is added dropwise, adjust molten
Liquid pH to 5-6, filtering, obtains semi-finished product solution；NaOH solution is added, mixes, obtains intermediate solution；It is filtered, washed, is spray-dried
Solid blank is made；In 400~900 DEG C of oxygen-enriched sinterings, it is cooled to room temperature, obtains finished product.This scheme operating process generates a large amount of
Solid precipitating, and scheme does not provide the processing method of precipitating.
CN102603098A discloses a kind of circulation process method of stainless steel acid-washing waste liquid.The present invention is for stainless steel acid
Wash a variety of acid ions and metal ion (SO in waste liquid4 2-、F-、Cr3+、Ni2+、Fe2+、Fe3+), pickling is adjusted using lye first
The pH value of waste liquid reaches 7-10 for metal ion Cr3+、Ni2+、Fe2+And Fe3+Precipitating, drying form metallurgical raw material；Then by lime
Filtrate is added by F-、CO3 2-And SO4 2-With CaF2、CaCO3And CaSO4Form precipitating；Na is finally added into filtrate2CO3, obtain
CaCO3Precipitating, filtrate are NaOH and Na2CO3Mixed solution directly returns and is used for stainless steel acid-washing waste liquid precipitate metal ion.This
Scheme separates the metal ion in solution in a manner of precipitating with solution, but does not provide the processing mode of sediment, Wu Fashi
Existing resource utilization.
CN103643244A discloses a kind of method of microwave atomizing calcination process pickle liquor, belong to Pulse width and
Metallurgical environmental protection technical field.Pickle liquor is heated first, steel scrap, iron filings or abrasive grit is then added, it will be pretreated through one section
Concentrated ammonia liquor is added after pickle liquor is cooling, while after being passed through air reaction, continuously adding flocculant poly, finally carrying out solid-liquid point
From processing, solid waste and pretreated pickle liquor are obtained；The pretreated pickling that above-mentioned steps are prepared
Waste liquid is atomized into droplet by spray gun, is delivered droplets on using air as carrier and is introduced into microwave kiln roasting, obtains Fe2O3Powder,
What is generated in the process is mixed with gas after subsequent processing, obtains regeneration hydrochloric acid solution.This scheme produces a large amount of solid
Body waste, and the disposal options of solid waste are not provided, it is unfavorable for environmentally friendly production.
CN105132932A discloses a kind of galvanized part and returns the recovery and treatment method for washing acid pickle, include the following steps: by
Need to return the galvanized part washed and suspender be placed in it is dedicated return wash pool and returned with hydrochloric acid wash, obtain containing Zn2+、Fe2+With the galvanized part of hydrochloric acid
It returns and washes acid pickle, individually recycle；Returning for recycling is washed acid pickle and is placed in reaction vessel, successively adds hydrogen peroxide, ammonium hydroxide respectively, adjusts
Acid pickle pH value is saved between 4-5, Oxidation of Fe2+For Fe3+, generate Fe (OH)3Precipitating, is removed by filtration；Detect the zinc ammonia of filtrate
Than adding appropriate NH4Cl、ZnCl2And water, zinc ammonia is made than certain fluxing agent.This scheme generates a large amount of Fe (OH)3Precipitating,
And do not provide the reasonable disposal options precipitated to this.
CN101172727A discloses a kind of purification treatment process of waste liquor of hydrochloric acid, comprising the following steps: (1) chlorohydric acid pickling is useless
Liquid enters after First Heat Exchanger is heated to 80-90 DEG C in free acid removal reactor tank, adds oxygen in free acid removal reactor tank
Change iron powder, the brown iron oxide of 40-50g is added in every liter of hydrochloric acid pickling waste liquor, obtains the spent acid of removal free hydrochloric acid；(2) it precipitates,
It is cooling, obtain cooling acid pickle；(3) neutralizer ammonium hydroxide is added, is formed Fe (OH)3Floccule body；It is bigger that flocculation aid formation is added again
Wadding body；(4) flocculation aid is added after precipitating again and forms bigger wadding body, precipitating；(5) the purified acid solution of step (4) enters net
In acid solution collecting tank after change, then it is pumped into acid storage tank by pipeline, the promotion of purified acid solution.This scheme forms largely
Flocculation sedimentation, and do not provide the processing method of above-mentioned precipitating.
Although above-mentioned document provides the method for processing pickle liquor, but all do not provide the regeneration precipitated obtained by pickle liquor
Utilize method；Therefore a kind of processing method of new pickle liquor and resource utilization through its gained solid phase waste are developed still
It is of great significance.
Summary of the invention
In view of problems of the prior art, the present invention provides a kind of recyclings of metal ion in pickle liquor to return
Receiving method, product and application thereof as made from it.The present invention is by obtaining acid to zinc-plated factory's waste liquid pretreatment modification and precipitating
Waste residue is successfully prepared zinc-plated factory's acid cleaning waste slag adsorbent, can be used for H in industrial smoke by extrusion technology2S、SO2Deng
The fertile absorber of acid toxic gas, the recycling for realizing zinc-plated factory's pickle liquor metal ion recycle, waste recycling,
With apparent environmental benefit.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of resource recycle method of metal ion in pickle liquor, the method
The following steps are included:
(1) it by after pickle liquor sedimentation slagging-off, adds soluble Nacl and precipitating reagent simultaneously is added, adjust waste liquid pH value to useless
Metal ion precipitates completely in liquid, obtains acid cleaning waste slag；
(2) acid gas adsorption agent is prepared through ball milling and extrusion process in the acid cleaning waste slag for obtaining step (1).
The present invention provides a kind of resource utilization approach of pickling waste waters waste residue, and one kind is prepared using acid cleaning waste slag
Acid gas adsorption cleanser product, the high added value for realizing zinc-plated factory's pickle liquor metal ion or acid sludge recycle and
In the secondary recycling of acid gas adsorption field of purification, a waste recycling novel technique is formed.
Preferably, step (1) described pickle liquor includes the pickle liquor of zinc-plated factory.
In the present invention, zinc-plated factory's acid cleaning waste slag is iron content or solid waste containing zinc, or aluminium metallurgy factory red mud, zinc-plated factory
Acid sludge, copper works' tailing etc..
Preferably, the soluble Nacl be containing zinc, magnesium, iron soluble sulphate or nitrate in any one
Or at least two combination, further preferably zinc nitrate and/or ferrous sulfate.
Preferably, the additive amount of the soluble Nacl is the 1%-10% of pickle liquor quality after slagging-off, such as
1%, 3%, 5%, 7%, 9% or 10%.
Preferably, step (1) precipitating reagent is any one in calcium oxide, caustic lime, carbide slag or industrial ammonia
Kind or at least two combination.
Preferably, the adjustable range of the pH value is 10-12, such as 10,10.3,10.6,10.9,11.2,11.5,11.8
Or 12.
Preferably, the time of the precipitating be 12h-48h, such as 12h, 16h, 20h, for 24 hours, 28h, 32h, 36h, 40h,
44h or 48h.
Preferably, step (2) described ball milling is that the acid cleaning waste slag for obtaining step (1) and absorbability enhancer carry out ball milling,
Obtain moulded pottery not yet put in a kiln to bake butt powder material A.
Preferably, the absorbability enhancer include in calcium oxide, zinc oxide, iron oxide or sodium carbonate any one or extremely
Few two kinds of combination.
It is further preferred that the absorbability enhancer is any two kinds in calcium oxide, zinc oxide, iron oxide or sodium carbonate
Combination；Such as the absorbability enhancer is the mixture of calcium oxide and zinc oxide, the mass ratio of calcium oxide and zinc oxide is 10:
1-1:1, such as 10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1 or 1:1；It or is the mixed of calcium oxide and iron oxide
The mass ratio of conjunction object, calcium oxide and iron oxide is 10:1-1:1, such as 10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:
1 or 1:1；Or the mixture for calcium oxide and sodium carbonate, the mass ratio of calcium oxide and sodium carbonate are 10:1-1:1, such as 10:
1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1 or 1:1；Or the mixture for iron oxide and sodium carbonate, iron oxide with
The mass ratio of sodium carbonate is 10:1-1:1, such as 10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1 or 1:1；Or it is
The mass ratio of the mixture of zinc oxide and iron oxide, zinc oxide and iron oxide be 10:1-1:1, such as 10:1,9:1,8:1,7:1,
6:1,5:1,4:1,3:1,2:1 or 1:1.
Preferably, the additional amount of the absorbability enhancer be acid cleaning waste slag quality 0-50%, be free of 0, such as 1%,
5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%；Preferably 1%-50%.
Preferably, step (2) extrusion process the following steps are included:
(a) the moulded pottery not yet put in a kiln to bake butt powder for obtain after ball milling by acid cleaning waste slag and absorbability enhancer that step (1) obtains is former
Expect A and shaping assistant mixing, obtains mixture B；
(b) mixture B and water, lubricant are mediated, and is filtered, obtain raw moulded pottery not yet put in a kiln to bake C；
(c) by raw moulded pottery not yet put in a kiln to bake C extrusion molding, drying, the acid gas adsorption agent is prepared.
Preferably, step (a) shaping assistant include in clay, glass or cotton any one or at least two group
It closes.
Preferably, the shaping assistant includes clay, glass and cotton；Wherein, the quality of the quality and acid cleaning waste slag of glass
Than≤5%, 0, such as 0.1%, 1%, 2%, 3%, 4% or 5% is free of, preferably 0.1%-5%；The quality of cotton is useless for pickling
The 1%-10% of slag amount, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the clay include in kaolin, montmorillonite or convex-concave stick any one or at least two combination.
Preferably, the clay is any two kinds of combination in kaolin, montmorillonite or convex-concave stick；Such as the clay
For the mixture of kaolin and montmorillonite；Kaolin and the mass ratio of montmorillonite are 2:1-1:1, for example, 2:1,1.8:1,1.5:1,
1.3:1 or 1:1；Alternatively, the clay is the mixture of kaolin and convex-concave stick；The mass ratio of kaolin and convex-concave stick is 10:
1-1:1, such as 10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1 or 1:1；Alternatively, the clay is montmorillonite and convex
The mass ratio of the mixture of recessed stick, montmorillonite and convex-concave stick is 5:1-1:1, such as 5:1,4:1,3:1,2:1 or 1:1.
Preferably, the cotton includes wood pulp cotton and/or paper pulp cotton.
Preferably, the additional amount of the shaping assistant be acid cleaning waste slag quality 0-15%, be free of 0, such as 0.5%,
1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%；Preferably
0.5%-15%.
Preferably, step (b) lubricant include in lactic acid, cellulose, oleic acid or stearic acid any one or extremely
Few two kinds of combination；Such as the lubricant is the mixture of lactic acid and cellulose；The mass ratio of lactic acid and cellulose is 20:1-
10:1, such as 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 lubrication
Agent is lactic acid and stearic mixture；Lactic acid and stearic mass ratio are 5:1-1:1, for example, 5:1,4:1,3:1,2:1 or
1:1；Or the lubricant is lactic acid, cellulose and stearic mixture, the quality percentage of lactic acid contains in the mixture
Measuring is 50%-75%, such as 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72% or 75%；It is excellent
It is selected as 62.5%；The mass percentage of cellulose be 3%-12.5%, such as 3%, 4%, 5%, 6%, 7%, 8%, 9%,
10%, 11%, 12% or 12.5%；Preferably 6.25%；Stearic mass percentage is 22%-37.5%, such as
22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%,
37% or 37.5%, preferably 31.25%.
Preferably, the additional amount of the lubricant be acid cleaning waste slag quality 0-5%, be free of 0, such as 0.1%, 1%,
2%, 3%, 4% or 5%；Preferably 0.1%-5%；Such as 0.1%, 1%, 2%, 3%, 4% or 5%.
Preferably, the additional amount of the water of the kneading be acid cleaning waste slag quality 10%-30%, such as 10%, 12%,
15%, 17%, 20%, 22%, 25%, 27% or 30%.
Preferably, the product of step (c) extrusion molding is cylindrical body, and preferably diameter is 2-15mm, length 0-
10cm, without 0 cylindrical body.
Preferably, the temperature of the drying be 50-120 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C,
110 DEG C or 120 DEG C.
It preferably, further include roasting after the drying.
Preferably, the temperature of the roasting be 120-300 DEG C, such as 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C,
170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃
Or 300 DEG C.
As currently preferred technical solution, the resource utilization of metal ion in a kind of pickle liquor of the present invention
Method specifically includes the following steps:
(1) by after pickle liquor sedimentation slagging-off, soluble Nacl is added；It is described solubility Nacl additive amount be except
The 1%-10% of pickle liquor quality after slag；Precipitating reagent is added, the pH to 10-12 of waste liquid is adjusted, is separated after settling 12h-48h
Obtain acid cleaning waste slag；
(2) absorbability enhancer is added into acid cleaning waste slag described in step (1), carries out ball milling；The absorbability enhancer
Additional amount is the 1%-50% of acid cleaning waste slag quality；
(3) shaping assistant is added into step (2) products therefrom, carries out mixing；The additional amount of the shaping assistant is acid
Wash the 0.5%-15% of slag quality；
(4) water and lubricant are added into step (3) products therefrom, is filtered after being mediated using extruder；The water
Additional amount be acid cleaning waste slag quality 10%-30%；The additional amount of the lubricant is the 0.1%- of acid cleaning waste slag quality
5%；
(5) it by step (4) products therefrom extrusion molding, is dried at 50-120 DEG C, roasts, be prepared at 120-300 DEG C
To the acid gas adsorption agent.
Second aspect, the present invention also provides the recyclings of metal ion ion in pickle liquor as described in relation to the first aspect
The acid gas adsorption agent that recovery method is prepared.
Preferably, the shape of the adsorbent is cylindrical body.
Preferably, the diameter of the adsorbent be 2-15mm, such as 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm,
10mm, 11mm, 12mm, 13mm, 14mm or 15mm.
Preferably, the length of the adsorbent be 0-10cm, be free of 0, such as 1cm, 2cm, 3cm, 4cm, 5cm, 6cm,
7cm, 8cm, 9cm or 10cm.
The third aspect, the present invention also provides the purposes of the acid gas adsorption agent as described in second aspect, by the suction
Attached dose is used for absorbing acid gases；The sour gas includes H2S and/or SO2。
Preferably, it is useless to be originated from coking flue gas, biomass boiler flue gas, biomass ferment exhaust gas, biogas for the sour gas
Gas, coal bed gas or pyrolysis gas.
Compared with prior art, the present invention at least has the advantages that
(1) present invention is by obtaining acid waste residue, passing through extrusion molding skill to zinc-plated factory's waste liquid pretreatment modification and precipitating
Art is successfully prepared and can be used for H in industrial smoke2S、SO2Deng the fertile absorber of acid toxic gas, realize in exhaust gas
The processing of poisonous and harmful substance；
(2) the acid gas adsorption agent prepared by the present invention, for H2The saturation Sulfur capacity of S can reach 45% or more, have
The high feature of Sulfur capacity, adsorption effect is significant, has performance advantage；
(3) the method for the invention uses pickle liquor to prepare adsorbent for raw material, realizes zinc-plated factory's pickle liquor gold
The recycling for belonging to ion recycles, and waste recycling has apparent environmental benefit.
Detailed description of the invention
Fig. 1 is the process flow chart of metal ion resource recycle method in pickle liquor of the present invention.
Fig. 2 is the acid gas adsorption agent product that the embodiment of the present invention 1 is prepared.
Fig. 3 is the H for the acid gas adsorption agent that the embodiment of the present invention 1 is prepared2The Sulfur capacity test result of S.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Fig. 1 is the process flow chart of metal ion resource recycle method in pickle liquor of the present invention；The method
Specifically includes the following steps:
(1) by after pickle liquor sedimentation slagging-off, soluble Nacl is added, the pH of waste liquid is adjusted, separation of solid and liquid obtains acid
Wash waste residue；
(2) acid cleaning waste slag described in step (1) and absorbability enhancer are mixed；
(3) step (2) products therefrom is mixed with shaping assistant；
(4) by step (3) product and water, mix lubricant；
(5) step (4) product formed, dried, so that acid gas adsorption agent be made.
Following embodiment is all made of process flow shown in FIG. 1.
Embodiment 1
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, addition ferrous sulfate to its quality is pickle liquor matter after slagging-off
The 5% of amount, then adding caustic lime is 10% that precipitating reagent to its quality is pickle liquor quality after removing the gred, adjusts pickle liquor
PH to 12, metal ion precipitates completely, sedimentation for 24 hours, obtain acid cleaning waste slag；
(2) 10% calcium oxide that quality is acid cleaning waste slag quality is added into the acid cleaning waste slag of step (1) and carries out ball milling；
(3) glass that quality is 5% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Cotton with 2%, carries out mixing in batch mixer；
(4) be added into the product of step (3) quality be 25% water of acid cleaning waste slag quality, 3% stearic acid in pinching
It mediates in conjunction machine, and is filtered through extruder；
(5) by the product extrusion molding of step (4), acid gas adsorption agent is obtained in 120 DEG C of drying 12h.
Fig. 2 shows the acid gas adsorption agent that embodiment 1 is prepared, and are in cylindrical shape, through measuring, diameter is big
About in 3mm or so, length is in 2cm or so.
Fig. 3 is the Sulfur capacity test result of acid gas adsorption agent prepared by the embodiment of the present invention 1；This can be seen that by the figure
Adsorbent is to H2The saturation Sulfur capacity of S gas reaches 50% or more.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 2
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, addition zinc nitrate to its quality is pickle liquor quality after slagging-off
5%, then add carbide slag be precipitating reagent to its quality be slagging-off after pickle liquor quality 10%, adjust the pH of pickle liquor
To 11, metal ion precipitates completely, and sedimentation for 24 hours, obtains acid cleaning waste slag；
(2) 5% calcium oxide and 5% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Sodium carbonate carry out ball milling；
(3) glass that quality is 5% kaolin of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Cotton with 5%, carries out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 3% oleic acid in kneading
It mediates in machine, and is filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 2h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 4cm, diameter 6mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 3
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, 2% that quality is pickle liquor quality after removing the gred is added respectively
Zinc nitrate and 5% ferrous sulfate, then add carbide slag be precipitating reagent to its quality be slagging-off after pickle liquor quality 10%,
The pH to 12 of pickle liquor is adjusted, metal ion precipitates completely, and sedimentation for 24 hours, obtains acid cleaning waste slag；
(2) 5% zinc oxide and 10% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Sodium carbonate carry out ball milling；
(3) glass that quality is 5% kaolin of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Cotton with 1%, carries out mixing in batch mixer；
(4) oleic acid and 2% that quality is 25% water of acid cleaning waste slag quality, 1% is added into the product of step (3)
Stearic acid is mediated in kneader, and is filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 2h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 3cm, diameter 9mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 4
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, addition magnesium nitrate to its quality is pickle liquor quality after slagging-off
5%, then add industrial ammonia be precipitating reagent to its quality be slagging-off after pickle liquor quality 10%, adjust pickle liquor
PH to 10, metal ion precipitates completely, settles 48h, obtains acid cleaning waste slag；
(2) 10% sodium carbonate that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1) to carry out
Ball milling；
(3) 6% convex-concave stick, 5% glass that quality is acid cleaning waste slag quality are separately added into the product of step (2)
Cotton with 4%, carries out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 10% water, 5% lactic acid in kneading
It mediates in machine, and is filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 2h obtains sour gas suction at 50 DEG C of drying 12h, 300 DEG C
Attached dose, product length 10cm, diameter 15mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 5
(1) zinc-plated factory's pickle liquor is settled after removing the gred, the magnesium sulfate and ferric nitrate that addition mass ratio is 1:1 to its quality
Be slagging-off after pickle liquor quality 10%, then add calcium oxide be precipitating reagent to its quality be slagging-off after pickle liquor quality
10%, the pH to 12 of pickle liquor is adjusted, metal ion precipitates completely, settles 12h, obtains acid cleaning waste slag；
(2) it is separately added into 5% iron oxide that quality is acid cleaning waste slag quality into the acid cleaning waste slag of step (1) and carries out ball
Mill；
(3) quality is separately added into the product of step (2) to take off for 6% kaolin of acid cleaning waste slag quality, 3% illiteracy
Soil, 1% glass and 1% cotton, carry out mixing in batch mixer；
(4) be added into the product of step (3) quality be 30% water of acid cleaning waste slag quality, 1% cellulose in pinching
It mediates in conjunction machine, and is filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 2h obtains sour gas suction at 80 DEG C of drying 12h, 120 DEG C
Attached dose, product length 0.5cm, diameter 2mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 6
(1) zinc-plated factory's pickle liquor is settled after removing the gred, the zinc sulfate and ferric sulfate that addition mass ratio is 1:1 to its quality
Be slagging-off after pickle liquor quality 10%, then add carbide slag be precipitating reagent to its quality be slagging-off after pickle liquor quality
15%, the pH to 12 of pickle liquor is adjusted, metal ion precipitates completely, settles 48h, obtains acid cleaning waste slag；
(2) 20% calcium oxide and 2% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Zinc oxide carry out ball milling；
(3) quality is separately added into the product of step (2) to take off for 1% kaolin of acid cleaning waste slag quality, 1% illiteracy
Soil, 1% glass and 10% cotton, carry out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 10% water, 4% lactic acid, 0.2%
Cellulose mediated in kneader, and filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 2cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 7
The present embodiment by 6 step of embodiment (2) 20% calcium oxide and 2% zinc oxide replace with 25% oxidation
Calcium and 2% zinc oxide, other conditions are identical with embodiment 6, product length obtained be 2cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 8
(1) zinc-plated factory's pickle liquor is settled after removing the gred, the magnesium sulfate and ferric sulfate that addition mass ratio is 1:1 to its quality
It is 10% of pickle liquor quality after slagging-off, then adds carbide slag that mass ratio is 1:1 and caustic lime is precipitating reagent to its matter
Amount is 15% of pickle liquor quality after slagging-off, adjusts the pH to 12 of pickle liquor, and metal ion precipitates completely, settles 48h, obtains
To acid cleaning waste slag；
(2) be separately added into the acid cleaning waste slag of step (1) quality be acid cleaning waste slag quality 20% calcium oxide and
20% zinc oxide carries out ball milling；
(3) be separately added into the product of step (2) quality be acid cleaning waste slag quality 10% kaolin, 1% it is convex
Recessed stick, 1% glass and 2% cotton carry out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 4% lactic acid, 0.4%
Cellulose mediated in kneader, and filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 2cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 9
The present embodiment by 6 step of embodiment (2) 20% calcium oxide and 20% zinc oxide replace with 20% oxygen
Change the zinc oxide of calcium and 25%, other conditions are identical with embodiment 6, and product length obtained is 3cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 10
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, zinc sulfate, magnesium sulfate and the sulfuric acid that mass ratio is 1:1:1 are added
Iron to its quality is 10% of pickle liquor quality after slagging-off, then adding carbide slag that mass ratio is 1:1 and calcium oxide is precipitating
Agent to its quality is 10% of pickle liquor quality after removing the gred, adjusts the pH to 12 of pickle liquor, and metal ion precipitates completely, is sunk
48h is dropped, acid cleaning waste slag is obtained；
(2) be separately added into the acid cleaning waste slag of step (1) quality be acid cleaning waste slag quality 25% calcium oxide and
2.5% iron oxide carries out ball milling；
(3) convex-concave that quality is 5% kaolin of acid cleaning waste slag quality, 5% is separately added into the product of step (2)
Stick, 2% glass and 2% cotton carry out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 4.5% lactic acid,
0.9% stearic acid is mediated in kneader, and is filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 2cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 11
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, zinc sulfate, magnesium nitrate and the sulfuric acid that mass ratio is 1:1:1 are added
Iron to its quality is 10% of pickle liquor quality after slagging-off, then it is heavy for adding calcium oxide that mass ratio is 1:1 and industrial ammonia
Shallow lake agent to its quality is 10% of pickle liquor quality after removing the gred, adjusts the pH to 12 of pickle liquor, and metal ion precipitates completely,
48h is settled, acid cleaning waste slag is obtained；
(2) be separately added into the acid cleaning waste slag of step (1) quality be acid cleaning waste slag quality 10% calcium oxide and
10% iron oxide carries out ball milling；
(3) convex-concave that quality is 5% montmorillonite of acid cleaning waste slag quality, 1% is separately added into the product of step (2)
Stick, 1% glass and 1% cotton carry out mixing in batch mixer；
(4) be added into the product of step (3) quality be 25% water of acid cleaning waste slag quality, 1% lactic acid, 1%
Stearic acid is mediated in kneader, and is filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 6cm, diameter 5mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 12
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, zinc nitrate, magnesium nitrate and the sulfuric acid that mass ratio is 1:1:1 are added
Ferrous iron to its quality is 10% of pickle liquor quality after removing the gred, then adds caustic lime and industrial ammonia that mass ratio is 1:1
For precipitating reagent to its quality be slagging-off after pickle liquor quality 10%, adjust the pH to 12 of pickle liquor, metal ion is complete
Precipitating settles 48h, obtains acid cleaning waste slag；
(2) 10% calcium oxide and 1% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Sodium carbonate carry out ball milling；
(3) convex-concave that quality is 3% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Stick, 1% glass and 1% cotton carry out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 2% lactic acid, 0.5%
Cellulose and 1.5% stearic acid mediated in kneader, and filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 10cm, diameter 6mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 13
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, zinc nitrate, magnesium nitrate and the sulfuric acid that mass ratio is 1:1:1 are added
Ferrous iron to its quality is 10% of pickle liquor quality after slagging-off, then add mass ratio be the carbide slag of 1:1:1, caustic lime and
Industrial ammonia is 10% that precipitating reagent to its quality is pickle liquor quality after removing the gred, adjusts the pH to 12 of pickle liquor, metal
Ion precipitates completely, settles 48h, obtains acid cleaning waste slag；
(2) be separately added into the acid cleaning waste slag of step (1) quality be acid cleaning waste slag quality 10% calcium oxide and
10% sodium carbonate carries out ball milling；
(3) convex-concave that quality is 3% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Stick, 3% kaolin, 1% glass and 1% cotton, mixing is carried out in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 3% lactic acid, 0.25%
Cellulose and 0.75% stearic acid mediated in kneader, and filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 9cm, diameter 10mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 14
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, zinc sulfate, magnesium nitrate and the sulfuric acid that mass ratio is 1:1:1 are added
Ferrous iron to its quality is 5% of pickle liquor quality after removing the gred, then adds calcium oxide, carbide slag, alkali that mass ratio is 1:1:1:1
Property lime and industrial ammonia be that precipitating reagent to its quality is pickle liquor quality after slagging-off 10%, adjust the pH of pickle liquor to
12, metal ion precipitates completely, settles 48h, obtains acid cleaning waste slag；
(2) 10% iron oxide and 1% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Sodium carbonate carry out ball milling；
(3) glass that quality is 10% montmorillonite of acid cleaning waste slag quality, 1% is separately added into the product of step (2)
The fine cotton with 1%, carries out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 3% lactic acid, 0.3%
Cellulose and 1.5% stearic acid mediated in kneader, and filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains adsorbent, product at 80 DEG C of drying 12h, 180 DEG C
Length is 7cm, diameter 11mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 15
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, addition ferrous sulfate to its quality is pickle liquor matter after slagging-off
The 2% of amount, then adding caustic lime is 10% that precipitating reagent to its quality is pickle liquor quality after removing the gred, adjusts pickle liquor
PH to 12, metal ion precipitates completely, sedimentation for 24 hours, obtain acid cleaning waste slag；
(2) 5% iron oxide and 5% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Sodium carbonate carry out ball milling；
(3) glass that quality is 10% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
The fine cotton with 2%, carries out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 2% lactic acid, 1.5%
Oleic acid and 1.5% stearic acid mediated in kneader, and filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 8cm, diameter 5mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 16
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, addition ferrous sulfate to its quality is pickle liquor matter after slagging-off
The 5% of amount, then adding carbide slag is 10% that precipitating reagent to its quality is pickle liquor quality after removing the gred, adjusts pickle liquor
PH to 12, metal ion precipitates completely, and sedimentation for 24 hours, obtains acid cleaning waste slag；
(2) 10% zinc oxide and 1% that quality is acid cleaning waste slag quality is separately added into the acid cleaning waste slag of step (1)
Iron oxide carry out ball milling；
(3) glass that quality is 5% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Cotton with 2%, carries out mixing in batch mixer；
(4) into the product of step (3) be added quality be acid cleaning waste slag quality 25% water, 2% stearic acid,
1.5% oleic acid and 1.5% cellulose are mediated in kneader, and are filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 6cm, diameter 4mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 17
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, addition ferrous sulfate to its quality is pickle liquor matter after slagging-off
The 5% of amount, then adding caustic lime is 10% that precipitating reagent to its quality is pickle liquor quality after removing the gred, adjusts pickle liquor
PH to 12, metal ion precipitates completely, sedimentation for 24 hours, obtain acid cleaning waste slag；
(2) be separately added into the acid cleaning waste slag of step (1) quality be acid cleaning waste slag quality 15% zinc oxide and
15% iron oxide carries out ball milling；
(3) glass that quality is 5% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Cotton with 2%, carries out mixing in batch mixer；
(4) the hard of 25% water, 1% lactic acid, 1% that quality is acid cleaning waste slag quality is added into the product of step (3)
Resin acid, 1% oleic acid and 1% cellulose are mediated in kneader, and are filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 5cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 18
(1) by after the sedimentation slagging-off of zinc-plated factory's pickle liquor, zinc sulfate, magnesium nitrate and the sulfuric acid that mass ratio is 1:1:1 are added
Ferrous iron to its quality be slagging-off after pickle liquor quality 10%, then add carbide slag be precipitating reagent to its quality be slagging-off after acid
The 10% of waste liquid quality is washed, the pH to 12 of pickle liquor is adjusted, metal ion precipitates completely, settles 48h, obtains acid cleaning waste slag；
(2) it is 5% zinc oxide of acid cleaning waste slag quality, 5% that quality is separately added into the acid cleaning waste slag of step (1)
Iron oxide and 5% sodium carbonate carry out ball milling；
(3) glass that quality is 5% montmorillonite of acid cleaning waste slag quality, 3% is separately added into the product of step (2)
Cotton with 2%, carries out mixing in batch mixer；
(4) the hard of 25% water, 1% lactic acid, 1% that quality is acid cleaning waste slag quality is added into the product of step (3)
Resin acid, 1% oleic acid and 1% cellulose are mediated in kneader, and are filtered through extruder；
(5) by the product extrusion molding of step (4), roasting 3h obtains sour gas suction at 80 DEG C of drying 12h, 180 DEG C
Attached dose, product length 3cm, diameter 1mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 19
Zinc oxide in 18 step of embodiment (2) is replaced with calcium oxide by the present embodiment；Other conditions and embodiment 18 are complete
It is exactly the same, product length 6cm, diameter 2mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 20
Iron oxide in 18 step of embodiment (2) is replaced with calcium oxide by the present embodiment；Other conditions and embodiment 18 are complete
It is exactly the same, product length 7cm, diameter 3mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 21
Sodium carbonate in 18 step of embodiment (2) is replaced with calcium oxide by the present embodiment；Other conditions and embodiment 18 are complete
It is exactly the same, product length 9cm, diameter 5mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Embodiment 22
The present embodiment replaces 5% zinc oxide, 5% iron oxide and 5% sodium carbonate in 18 step of embodiment (2)
For 5% calcium carbonate, 5% zinc oxide, 5% iron oxide and 5% sodium carbonate；Other conditions and the complete phase of embodiment 18
Together, product length 5cm, diameter 4mm.
H is carried out to adsorbent manufactured in the present embodiment2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
Comparative example 1
This comparative example is added without ferrous sulfate in step (1) compared with Example 1, and other conditions and embodiment 1 are complete
It is identical.
The adsorbent of this comparative example preparation carries out H2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test the results are shown in Table
1。
Comparative example 2
This comparative example is only with step (1) in embodiment 1, without step (2) to (5).
The acid cleaning waste slag that this comparative example obtains carries out H2The saturation Sulfur capacity of S is tested, SO2Saturation Sulfur capacity test result see
Table 1.
H is carried out to embodiment 1-22 and comparative example 1-22The saturation Sulfur capacity and SO of S2Saturation Sulfur capacity test accepted standard
Respectively HG/T 5318-2018 and GB/T7702.14-2008.
The absorption property test data of acid gas adsorption agent made from embodiment 1-22 and comparative example 1-2 is as shown in table 1:
Table 1
As can be seen from Table 1, acid gas adsorption agent made from embodiment 1-22 is bright for the adsorption capacity of sour gas
It is aobvious to be better than comparative example 1-2, illustrate sour gas made from the resource recycle method of metal ion in pickle liquor of the present invention
Body adsorbent has good adsorption effect for sour gas, realizes waste recycling, has actual application prospect.
The Applicant declares that the present invention is explained by the above embodiments detailed construction feature of the invention, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention must rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And increase, selection of concrete mode of accessory etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. the resource recycle method of metal ion in a kind of pickle liquor, which is characterized in that the described method comprises the following steps:
(1) it by after pickle liquor sedimentation slagging-off, adds soluble Nacl and precipitating reagent is added, adjust waste liquid pH value into waste liquid
Metal ion precipitates completely, obtains acid cleaning waste slag；
(2) acid gas adsorption agent is prepared through ball milling and extrusion process in the acid cleaning waste slag for obtaining step (1).
2. resource recycle method as described in claim 1, which is characterized in that step (1) described pickle liquor includes zinc-plated
The pickle liquor of factory；
Preferably, the soluble Nacl be containing zinc, magnesium, iron soluble sulphate or nitrate in any one or extremely
Few two kinds of combination, further preferably zinc nitrate and/or ferrous sulfate；
Preferably, the additive amount of the soluble Nacl is the 1%-10% of pickle liquor quality after slagging-off.
3. resource recycle method as claimed in claim 1 or 2, which is characterized in that step (1) precipitating reagent is oxidation
In calcium, caustic lime, carbide slag or industrial ammonia any one or at least two combination；
Preferably, the adjustable range of the pH value is 10-12；
Preferably, the time of the precipitating is 12h-48h.
4. resource recycle method as described in any one of claims 1-3, which is characterized in that step (2) described ball milling be by
The acid cleaning waste slag and absorbability enhancer that step (1) obtains carry out ball milling, obtain moulded pottery not yet put in a kiln to bake butt powder material A；
Preferably, the absorbability enhancer includes any one in calcium oxide, zinc oxide, iron oxide or sodium carbonate or at least two
The combination of kind；
Preferably, the additional amount of the absorbability enhancer is the 0-50% of acid cleaning waste slag quality, is free of 0；Preferably 1%-50%.
5. resource recycle method according to any one of claims 1-4, which is characterized in that step (2) described extrusion process
The following steps are included:
(a) by acid cleaning waste slag that step (1) obtains and absorbability enhancer carry out the moulded pottery not yet put in a kiln to bake butt powder material A obtained after ball milling with
Shaping assistant mixing obtains mixture B；
(b) mixture B and water, lubricant are mediated, and is filtered, obtain raw moulded pottery not yet put in a kiln to bake C；
(c) by raw moulded pottery not yet put in a kiln to bake C extrusion molding, drying, the acid gas adsorption agent is prepared.
6. resource recycle method as claimed in claim 5, which is characterized in that step (a) shaping assistant include clay,
In glass or cotton any one or at least two combination；
Preferably, the clay include in kaolin, montmorillonite or convex-concave stick any one or at least two combination；
Preferably, the cotton includes wood pulp cotton and/or paper pulp cotton；
Preferably, the additional amount of the shaping assistant is the 0-15% of acid cleaning waste slag quality, is free of 0；Preferably 0.5%-15%；
Preferably, step (b) lubricant includes any one in lactic acid, cellulose, oleic acid or stearic acid or at least two
The combination of kind；
Preferably, the additional amount of the lubricant is the 0-5% of acid cleaning waste slag quality, is free of 0；Preferably 0.1%-5%；
Preferably, the additional amount of the water of the kneading is the 10%-30% of acid cleaning waste slag quality.
7. such as resource recycle method described in claim 5 or 6, which is characterized in that the product of step (c) extrusion molding
For cylindrical body, preferably diameter is 2-15mm, length 0-10cm, without 0 cylindrical body；
Preferably, the temperature of the drying is 50-120 DEG C；
It preferably, further include roasting after the drying；
Preferably, the temperature of the roasting is 120-300 DEG C.
8. such as the described in any item resource recycle methods of claim 1-7, which is characterized in that the method includes following steps
It is rapid:
(1) by after pickle liquor sedimentation slagging-off, soluble Nacl is added；The additive amount of the solubility Nacl is after removing the gred
The 1%-10% of pickle liquor quality；Precipitating reagent is added, adjusts the pH to 10-12 of waste liquid, is settled isolated after 12h-48h
Acid cleaning waste slag；
(2) absorbability enhancer is added into acid cleaning waste slag obtained by step (1), carries out ball milling；The additional amount of the absorbability enhancer
For the 1%-50% of acid cleaning waste slag quality；
(3) shaping assistant is added into step (2) products therefrom, carries out mixing；The additional amount of the shaping assistant is useless for pickling
The 0.5%-15% of slag amount；
(4) water and lubricant are added into step (3) products therefrom, is filtered after being mediated using extruder；The water adds
Enter the 10%-30% that amount is acid cleaning waste slag quality；The additional amount of the lubricant is the 0.1%-5% of acid cleaning waste slag quality；
(5) it by step (4) products therefrom extrusion molding, dries at 50-120 DEG C, is roasted at 120-300 DEG C, institute is prepared
State acid gas adsorption agent.
9. the acid being prepared such as the resource recycle method of metal ion in the described in any item pickle liquors of claim 1-8
Property adsorbent；
Preferably, the shape of the adsorbent is cylindrical body；
Preferably, the diameter of the adsorbent is 2-15mm；
Preferably, the length of the adsorbent is 0-10cm, is free of 0；Preferably 0.1-10cm.
10. the purposes of acid gas adsorption agent as claimed in claim 9, which is characterized in that be used for the adsorbent to adsorb H2S
And/or SO2；
Preferably, the sour gas is originated from coking flue gas, biomass boiler flue gas, biomass ferment exhaust gas, biogas exhaust gas, coal
Layer gas or pyrolysis gas.
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| CN110577299A (en) * | 2019-10-18 | 2019-12-17 | 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 |
| 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 |
| CN112892467A (en) * | 2019-12-04 | 2021-06-04 | 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 |
| CN115350694A (en) * | 2022-06-08 | 2022-11-18 | 上海大学 | Method for preparing molded acid gas adsorbent by using iron-containing waste residues and molded acid gas adsorbent prepared by using method |
| 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 |
| CN116798760A (en) * | 2023-07-12 | 2023-09-22 | 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 |
| 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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