CN107570108B - A kind of processing method of spent acid, kerosene shale ash and white clay - Google Patents
A kind of processing method of spent acid, kerosene shale ash and white clay Download PDFInfo
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Abstract
The processing method of a kind of spent acid, kerosene shale ash and white clay, the present invention relates to the processing methods of industrial waste, and in particular to industrial waste kerosene shale ash, white clay, spent acid comprehensively utilize and the preparing technical field of heavy metal containing sewage liquid waste processing material.It is used as additive raising waste acidity recovery effect by adding white clay, separate oil shale ash and white clay mixture is extracted by gradient extracting method using recovery acid, the metal ion in extracting solution is combined and prepares magnetic hydrotalcite and hydrated calcium silicate.The present invention prepares high-performance adsorbent by raw material of industrial waste, and it is recyclable to realize such sorbing material.
Description
Technical field
The present invention relates to the processing methods of industrial waste, and in particular to the industrial wastes such as kerosene shale ash, white clay, spent acid integrate
Utilize the preparing technical field with sewage waste liquor processing material.
Background technology
Three kinds of industrial waste ingredients and its harm
1.1 kerosene shale ash ingredients and its harm
Oil shale reserves are huge, are generally considered the important alternative energy source of oil and natural gas.Due to the high ash of oil shale
The characteristics of dividing, kerosene shale ash is the most important by-product during processing and utilization, stacks lime-ash and not only occupies a large amount of soil
Ground, and serious environmental pollution can be caused.Oil shale waste slag main component has quartz, feldspar and calcite, wherein quartz, length
Stone content is relatively high.Following table is the kerosene shale ash chemical composition in the main oil shale producing region in China, chemically from the point of view of ingredient, I
State's oil shale waste slag realizes innoxious kerosene shale ash, recycling and functionalized application for China substantially based on silicon, aluminium, iron
The rapid development of oil shale industry has positive facilitation.
White clay ingredient and its harm
White clay is the key industry waste generated in paper making process, and nearly 0.5 ton will be generated in vain by often producing 1 ton of thick slurry
Mud, therefore white clay enormous amount.Its main component is with CaCO3、CaSO4、CaCl2It waits based on calcium salts, also a small amount of SiO2.From
The main component of white clay is also not difficult to obtain white clay in strong basicity, and general pH value is 10 or so.Other than inorganic constituents, wherein also containing
There is the organic matter generated in a certain number of paper-making process, not only occupy a large amount of soil, but also serious environment can be caused
Pollution.
Spent acid ingredient and its harm
In the production of steel product, it is required for being processed cleaning treatment and corrosion to steel surface with a large amount of hydrochloric acid
Processing, to improve surface and property.It is slowly increased along with the concentration of metal ions in pickle liquor, after reaching a certain concentration,
The cleaning of pickle liquor is decreased obviously with corrosion efficiency, eventually becomes spent acid.
Content of hydrochloric acid is 30 ~ 60g/L in spent acid, and total iron content is 60 ~ 130g/L, ferrous ions content for 50 ~
120g/L, additionally containing heavy metal ion such as extremely a small amount of ppm grades of manganese, lead, cadmium, copper, cobalt, nickel, therefore spent acid is a kind of tool
There are highly acid and highly toxic waste liquid.These acid are difficult to further recycle, and the recycling for hydrochloric acid is especially low dense
The recovery difficult for spending hydrochloric acid is very high.Hydrogen chloride interacts in aqueous solution with hydrone, and the practical boiling point of hydrogen chloride is caused to be more than
The boiling point of water, it is difficult to distill out can direct reuse higher concentration hydrochloric acid solution,.
The immediate prior art
In the prior art：White clay and kerosene shale ash prepare the method (application number of uranium absorption agent and curing agent for raw material
CN201410022521.7), in actual application find there are problems that some are needed to be further improved, outstanding behaviours with
Lower 3 points：
2.1 consumption acids enormous amounts.Since aluminum ions content prepares being affected for hydrated calcium silicate, meeting for the later stage
Generate ca aluminosilicate；In order to ensure the performance of hydrated calcium silicate, it should realize that aluminium ion fully extracts as far as possible.Therefore oil page early period
Rock lime-ash needs the hydrochloric acid with a large amount of high concentration to perform etching extraction after being activated, extracting solution is a large amount of acid solution.
Using sodium chloride activation method, recycling sodium chloride is of high cost, and efficiency is low.
Former technique needs the NaCl for adding kerosene shale ash quality 40-100% to be activated, it is therefore desirable to a large amount of NaCl, to the greatest extent
Pipe can realize the reuse of NaCl from material balance angle, former technique, without additionally adding NaCl, but in actual production process by
In needing solid NaCl enormous amounts, have the following problems：By naturally sun-cured method, it is difficult to meet practical continuous raw
The requirement of production；Using distillation mode, equipment investment is huge, and energy consumption is serious.Therefore the method activated using NaCl into
Row activation, it is difficult to realize continuous production.
It is difficult to realize effectively recycle after the houghite adsorbent absorption of preparation.
At present, magnetic adsorbent is the major way for solving the problems, such as adsorbent recycling, using kerosene shale ash and white clay as raw material
The houghite of preparation cannot be obtained by the method for simple doped magnetic medium can be with the houghite of magnetic recovery.
Preparing magnetic houghite with kerosene shale ash and white clay has technical difficulty
The absorption property of hydrotalcite is related to its lamella crystal close structure, but with the complexity of synthetic ingredient
It is promoted, the difficulty of generation lamella crystal structure is also gradually increased.Kerosene shale ash complicated component, it is corresponding to white clay synthesis hydrotalcite-like material
The diffracted intensity of crystal face is substantially reduced, this explanation is constructed since various metals ion takes part in plate layer, leads to formed crystal
Ordered arrangement structure is affected.Under normal conditions, the preparation difficulty of calcium aluminum hydrotalcite will be difficult to magnalium hydrotalcite, this is mainly
It is more easily generated what the factors such as calcium carbonate determined by ionic radius, calcium ion.During magnetic hydrotalcite is prepared, one is added
The magnetic-particle of fixed number amount, these magnetic particles can be inserted among plate layer, the lamellar structure of hydrotalcite is influenced very big.Therefore
It is difficult that the polynary houghites such as the magnetic calcium ferro-aluminum with excellent properties are prepared using kerosene shale ash and white clay as raw material.
Undeniably, in the prior art using oil shale as raw material, will wherein trivalent aluminium ion and ferric ion without
Purification ＆ isolation prepares houghite, simple production process, but the shortcoming of the product is shown during magnetic material is prepared
Reveal and.Improve the crystal structure of product, realize that the separation of iron aluminium is necessary；And iron is also the raw material for preparing magnetic particle.
Practical problem present in harm and the prior art based on three of the above industrial waste, the present invention intends to solve following
Technical problem：
1. preparing recyclable uranium absorption agent and curing agent as primary raw material using kerosene shale ash, white clay, spent acid, work is realized
The recycling of industry waste and innoxious application, emphasis are the recoverables for realizing adsorbent, realize functionalized application.
2. carrying out the optimization of essence for existing generation technique, the generation of haline water is reduced, ensures continuous-stable life
Production.
3. the application of spent acid：The recycling mode of one side research and probe low-concentration waste acid；On the other hand it studies ferrous
The comprehensive utilization mode of ion.Research emphasis in terms of two above is that waste acid reuse is cooperateed with what white clay, kerosene shale ash utilized
Effect.
Invention content
Based on the problems of prior art, the present invention carries out existing generation technique the optimization of essence.It provides
A kind of spent acid, white clay and kerosene shale ash prepare magnetic uranium adsorbent and the method for curing agent, include the following steps：
Step 1：
White clay is calcined 0.5-6 hours under being passed through air conditions at 940 DEG C, after being cooled to room temperature, the white clay after being calcined
A；It is 2 by the ratio of the amount of calcium atom and aluminium atom substance:1-3:1 ratio mixes white clay and kerosene shale ash；Mixture exists
1260-1270 DEG C is passed through under air conditions, calcines 3-6 hours, after being cooled to room temperature, obtains mixture B；
Step 1 illustrates：Under the conditions of 940 DEG C 1260 DEG C of white clay, air is passed through, organic matter can be all converted to two by calcining
Carbonoxide.Crystalline phase converts under the conditions of 1260-1270 DEG C, and kerosene shale ash interacts with calcium oxide, realizes the activation of kerosene shale ash
With from dusting.
Step 2：
Under rapid mixing conditions, to volume in 5V spent acid, the white clay A after calcining to be added in, when calcium ion concentration is
During 0.4 mol/L, stop launching the white clay A after calcining, it is V to distill to volume, after retort gas is condensed, obtains acid solution Q1；
The spent acid that volume is 3V is added for the first time, is continued distillation to 3V, is added the spent acid that volume is 2V for the second time, continue distillation to volume
For 4V, evaporated mother liquor Q3 is obtained；The condensed rear acid solution that obtains of retort gas during adding twice is labeled as Q2；
Step 2 illustrates：Calcium ion concentration is 0.4 mol/L in solution before distillation, and the white clay A after the calcining put into disappears
Part spent acid is consumed, therefore the concentration of acid solution Q1 hydrogen chloride obtained is relatively low.During later stage is added, calcium ion concentration is higher,
The concentration of hydrogen chloride gets a promotion, in acid solution containing the higher calcium ion of concentration destroy hydrogen chloride in aqueous solution with hydrone
Interaction, 1.5-2.2 times for hydrogen chloride content in spent acid of hydrogen chloride content in Q2.This step effect 1 will be after calcining
White clay A is converted into calcium chloride solution, lays the foundation for further reaction；Spent acid is divided into low concentration acid and high concentrated acid by effect 2,
It lays the foundation for the extraction of further gradient and etching.
Step 3：
It is 1-2 that the white clay A after calcining is added into evaporated mother liquor Q3 to solution ph, adds in H2O2It is reacted to divalent
Iron concentration is less than 0.02mol/L, adds in the sodium hydroxide of 1-2 mol/L, and adjusting pH value is 4-5, is stirred 1 hour, mistake
Filter takes acid solution in Q2 to be made into the sour water that pH value is 4-5, cleans filter residue；Filtrate merges into solution G1 with washing lotion, and filter residue is labeled as filter
Slag F31；
Step 3 illustrates：Evaporated mother liquor Q3 is mainly the mixed liquor of ferrous ion and calcium ion, and the two is difficult to detach；It is logical
Peroxidating mode not only realizes trivalent ion and calcium ion separation；And obtain the calcium source for preparing hydrated calcium silicate and preparation
Ferric iron needed for magnetic particle.
Step 4：
Acid solution Q1 is measured, measurement volume is total volume 50%-60%, and it is 6-8 to add in mixture B thereto to pH value, is stirred
It mixes 0.5-3 hours, it is 4.2 to add acid solution Q1 to pH value, stirs 0.5-3 hours, is separated by filtration and obtains extracting solution GL1, take acid solution
Acid solution is made into the sour water that pH value is 4.1-4.5 in Q1, cleans filter residue, stirs 0.5-3 hours, the first filter residue Z1 is obtained after filtering,
It is solution GL2 to merge extracting solution GL1 and washing lotion；
Step 4 illustrates：In the solution for being 8 in pH value, based on calcium ion.In order to ensure that calcium extraction is abundant, extracting solution pH
Value is selected as 4.2, but this has extremely a small amount of magnesium and part aluminium is caused to enter in solution, but divalent magnesium ion content is extremely low,
And the structure influence constructed for hydrotalcite of divalent magnesium ion participation neatly slabstone layer is very small.Aluminium ion is former as reaction
Material, therefore solution GL2 is without further detaching.
Want in this step stringent control ph be more than 4.1, this primarily to avoid in mixture B iron ion into
Enter in solution.Extraction and cleaning are required for the stirring of certain time, and main purpose is to fully realize ion exchange, and allowing can
Ferric ion existing for energy enters mixture B with precipitation form, improves the purity of extracting solution intermediate ion, is the preparation of hydrotalcite
It lays the foundation.
Step 5：
Acid solution Q1 is taken to be made into the sour water that pH value is 1.5 to add in the first filter residue Z1, adds in quality as titanium dioxide in mixture B
Siliceous 5-30 times of amount, ultrasonic wave added stir 1-3 hours, and pH value of solution in entire whipping process is maintained at by adding acid solution Q1 modes
It is worth for 1.5-1.8, filtering further repeats this step aforesaid operations 1-3 time, and the filtrate of merging is labeled as filtrate TL1, filter residue mark
It is denoted as the second filter residue Z2；
Step 5 illustrates：This step purpose is the ferro-aluminum element in extraction mixture B.Solution ph in entire whipping process
It can realize that iron, aluminium more adequately extract for 1.5-1.8.
Step 6：
It weighs acid solution Q2 to add in the second filter residue Z2, weighs acid solution Q2 mass as silica quality 3-10 in mixture B
Times, ultrasonic wave added stirs 1-3 hours, and filtering further repeats this step aforesaid operations 2 times, extraction filter for the first time in this step
Liquid label filtrate TL2；Labeled as filtrate TL3, the filter residue finally obtained is labeled as second of the filtrate and third time filtrate merged
Third filter residue Z3；Filtrate TL3 is added in remaining acid solution Q1；
Step 6 illustrates：By it is a series of acid extraction kerosene shale ash and white clay mixture, substantial residual indissoluble object and by
The substance extracted is difficult in reasons such as packages, on the one hand the metal ion in this moieties is the raw material for preparing hydrotalcite；Separately
If on the one hand metal ion residual quantity is excessive, the quality of further hydration calcium silicates can be impacted.This part metals ion
Content is less, and extraction difficulty is larger, needs high intensity hydrochloric acid and repeatedly extraction is completed under the conditions of ultrasonic wave added.
More than 80% can be reached by the operation aluminium element recovery rate before step 6, recovery rate is 12- for the first time in step 6
15%, second of recovery rate about 1-2%, third time recovery rate is less than 1%.Extract must be as the original for preparing hydrotalcite for the first time
Material, the proportioning that otherwise will change hydrotalcite raw material.Although for the second time and third time recovery rate is very low, this is for later stage water
The preparation for changing calcium silicates is very important, because of aluminium element too high levels, it will generation ca aluminosilicate influences properties of product.
Aluminium element content is very low in filtrate TL3, and the proportioning of hydrotalcite raw material will not be impacted substantially, and this part solution
Acid content is very high, a large amount of alkali will be needed to be neutralized directly as raw material use.The present invention adds in filtrate TL3 remaining
Acid solution Q1 in can play the effect of this part acid, while continuous production as the extraction of next batch material, also will so that
This part aluminium ion, which becomes, prepares hydrotalcite raw material.
Step 7：
Merging filtrate TL1 and filtrate TL2, by adding in the sodium hydroxide of 1-2 mol/L, adjusting pH value is 4.2-4.5, is stirred
It mixes 1 hour, filters, acid solution in Q2 is taken to be made into the sour water that pH value is 3.7-4.0, is cleaned by ultrasonic filter residue；It is filtered caused by this step
Washing lotion caused by liquid, this step and solution GL2 merge into solution GL3, and filter residue is labeled as filter residue F32；
Step 7 illustrates：Adjusting pH value can cause ferro element fully to precipitate for 4.2；The sour water that pH value is 3.7-4.0 cleans
Filter residue can further improve the rate of recovery of aluminium element.Solution GL1 is the higher calcium aluminium mixed solution of purity, directly as system
The raw material of standby hydrotalcite.
Step 8：
Filter residue F31 and filter residue F32 are mixed into F33, are 2 according to the ratio between amount of trivalent iron atom and ferrous iron atom species:1
Ratio to F33 add in spent acid, 45 DEG C of constant temperature, adjust pH value be 11, continue stirring 0.5 hour, Magnetic Isolation uses deionized water
Neutrality is washed till, alcohol is washed, dry, obtains magnetic particle M；
Step 8 illustrates：Using in spent acid ferrous ion, distillation oxidation obtain trivalent iron atom and from kerosene shale ash
The trivalent iron atom isolated prepares magnetic particle.Wherein spent acid is both divalent source of iron and ferric iron sediment is turned
Ferric ion is turned to, while has neutralized corresponding hydrochloric acid, reduces the dosage of later stage alkali.
Step 9：
Solution GL3 pH=4-6 are adjusted, 40 DEG C of constant temperature are 5 according to the ratio between amount of calcium atom and iron atom substance:1-20:1
Ratio add in magnetic particle M, adjustment pH is 10-11,80 DEG C of waters bath with thermostatic control stirring 4-8 hours, Magnetic Isolation, in being washed to
Property, alcohol is washed, dry, obtains magnetic hydrotalcite；
Step 10：
According to the amount Na of substance after third filter residue Z3 dryings2O: SiO2The proportioning of=1-1.2 is mixed with NaOH, ground and mixed
After uniformly, 400 DEG C roast 3 hours, after cooling, according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds in solution G1,
Temperature is maintained at 40-80 DEG C, and adjustment pH value is 10-11, reacts 6-48h, is cooled down, and filtering, washing, alcohol are washed, dried, and acquire water
Change calcium silicates.
Advantageous effect
1. preparing recyclable uranium absorption agent and curing agent as primary raw material using kerosene shale ash, white clay, spent acid, work is realized
The recycling of industry waste and innoxious application are the recoverables for realizing adsorbent, realize functionalized application.
2. white clay replaces sodium chloride, reduces the generation of haline water, ensure continuous and stable production as activator.
3. waste processing is not the combination of simple three kinds of wastes, three kinds of waste processing have synergistic effect：
Synergistic effect 1：The calcining purifying of white clay and one step of activation of kerosene shale ash are completed, and white clay is not only in synthesizing
The activator of calcium source or kerosene shale ash.
Synergistic effect 2：White clay is waste acidity recovery agent, and white clay is dissolved in spent acid, on the one hand obtains calcium chloride solution；The opposing party
Hydrogen chloride is destroyed containing the higher calcium ion of concentration to interact with hydrone in aqueous solution, obtain hydrogen chloride in the acid solution of face
The higher acid solution of content, is easy to extract.
Synergistic effect 3：Spent acid mother liquor after distillation adds in hydrogen peroxide, on the one hand realizes the separation of calcium iron, on the other hand realizes
Oxidation for ferrous ion, meets the preparation requirement of magnetic particle.
Synergistic effect 4：Kerosene shale ash is calcium source, source of iron, silicon source；White clay is the activator of kerosene shale ash, acid recovery agent, calcium
Source；Spent acid is the source of iron for extracting acid source, magnetic particle.
4 present studies employ the mode of step by step arithmetic, pass through the grading extraction mode under different pH condition, a side
Face can improve the purity of extraction ion；On the other hand reduce the usage amount of acid.Same high strength acid extraction in the prior art,
It can lead to the residue of a large amount of acid, the later stage needs a large amount of alkali to be neutralized.Therefore have compared with existing kerosene shale ash extractive technique
The characteristics of prominent and substantive progress.
Description of the drawings
Process route flow chart of the attached drawing 1 for the present invention.
Specific embodiment
Embodiment 1
Step 1：
White clay is calcined 0.5-6 hours under being passed through air conditions at 940 DEG C, after being cooled to room temperature, the white clay after being calcined
A；It is 2 by the ratio of the amount of calcium atom and aluminium atom substance:1-3:1 ratio, mixes white clay and kerosene shale ash, mixture exist
1260-1270 DEG C is passed through under air conditions, calcines 3-6 hours, after being cooled to room temperature, obtains mixture B；
Step 2：
Under rapid mixing conditions, to volume in 5V spent acid, the white clay A after calcining to be added in, until calcium ion is dense in acid solution
It spends for 0.4 mol/L, it is V to distill to volume, after retort gas is condensed, obtains acid solution Q1；It is 3V's to add volume for the first time
Spent acid continues distillation to 3V, adds the spent acid that volume is 2V for the second time, it is 4V to continue distillation to volume, obtains evaporated mother liquor Q3；
Merge the acid solution added condense in the process twice, labeled as acid solution Q2；
Step 3：
It is 1-2 that the white clay A after calcining is added into evaporated mother liquor Q3 to solution ph, adds in H2O2It is reacted to divalent
Iron concentration is less than 0.02mol/L, adds in the sodium hydroxide of 1-2 mol/L, and adjusting pH value is 4-5, is stirred 1 hour, mistake
Filter takes acid solution in Q2 to be made into the sour water that pH value is 4-5, cleans filter residue；Filtrate merges into solution G1 with washing lotion, and filter residue is labeled as filter
Slag F31；
Step 4：
Acid solution Q1 is measured, measurement volume is total volume 50%-60%, and it is 6-8 to add in mixture B thereto to pH value, is stirred
It mixes 0.5-3 hours, it is 4.2 to add acid solution Q1 to pH value, stirs 0.5-3 hours, is separated by filtration and obtains extracting solution GL1, take acid solution
Acid solution is made into the sour water that pH value is 4.1-4.5 in Q1, cleans filter residue, stirs 0.5-3 hours, the first filter residue Z1 is obtained after filtering,
It is solution GL2 to merge extracting solution GL1 and washing lotion；
Step 5：
Acid solution Q1 is taken to be made into the sour water that pH value is 1.5 to add in the first filter residue Z1, adds in quality as titanium dioxide in mixture B
Siliceous 5-30 times of amount, ultrasonic wave added stir 1-3 hours, and pH value of solution in entire whipping process is maintained at by adding acid solution Q1 modes
It is worth for 1.5-1.8, filtering further repeats this step aforesaid operations 1-3 time, and the filtrate of merging is labeled as filtrate TL1, filter residue mark
It is denoted as the second filter residue Z2；
Step 6：
It weighs acid solution Q2 to add in the second filter residue Z2, weighs acid solution Q2 mass as silica quality 3-10 in mixture B
Times, ultrasonic wave added stirs 1-3 hours, and filtering further repeats this step aforesaid operations 2 times, extraction filter for the first time in this step
Liquid label filtrate TL2；Labeled as filtrate TL3, the filter residue finally obtained is labeled as second of the filtrate and third time filtrate merged
Third filter residue Z3；Filtrate TL3 is added in remaining acid solution Q1；
Step 7：
Merging filtrate TL1 and filtrate TL2, by adding in the sodium hydroxide of 1-2 mol/L, adjusting pH value is 4.2-4.5, is stirred
It mixes 1 hour, filters, acid solution in Q2 is taken to be made into the sour water that pH value is 3.7-4.0, is cleaned by ultrasonic filter residue；It is filtered caused by this step
Washing lotion caused by liquid, this step and solution GL2 merge into solution GL3, and filter residue is labeled as filter residue F32；
Step 8：
Filter residue F31 and filter residue F32 are mixed into F33, are 2 according to the ratio between amount of trivalent iron atom and ferrous iron atom species:1
Ratio to F33 add in spent acid, 45 DEG C of constant temperature, adjust pH value be 11, continue stirring 0.5 hour, Magnetic Isolation uses deionized water
Neutrality is washed till, alcohol is washed, dry, obtains magnetic particle M；
Step 9：
Solution GL3 pH=4-6 are adjusted, 40 DEG C of constant temperature are 5 according to the ratio between amount of calcium atom and iron atom substance:1-20:1
Ratio add in magnetic particle M, adjustment pH is 10-11,80 DEG C of waters bath with thermostatic control stirring 4-8 hours, Magnetic Isolation, in being washed to
Property, alcohol is washed, dry, obtains magnetic hydrotalcite；
Step 10：
According to the amount Na of substance after third filter residue Z3 dryings2O: SiO2The proportioning of=1-1.2 is mixed with NaOH, ground and mixed
After uniformly, 400 DEG C roast 3 hours, after cooling, according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds in solution G1,
Temperature is maintained at 40-80 DEG C, and adjustment pH value is 10-11, reacts 6-48h, is cooled down, and filtering, washing, alcohol are washed, dried, and acquire water
Change calcium silicates.
Embodiment 2
The present embodiment and embodiment 1 are basically identical, the difference lies in：Calcium atom and aluminium atom object are pressed described in step 1
The ratio of the amount of matter is 2:1-3:1 ratio, mixes white clay and kerosene shale ash, mixture are passed through air conditions at 1260-1270 DEG C
Under, it calcines 3-6 hours, preferably：It is 2.2 by the ratio of the amount of calcium atom and aluminium atom substance:1 ratio mixes white clay and oil
Shale ashes, mixture are calcined 6 hours in the case where 1260-1270 DEG C is passed through air conditions.
Embodiment 2 illustrates：For calcium aluminum hydrotalcite, the ratio of the amount of calcium atom and aluminium atom substance is 2:1-3:1 is to prepare
The preferred condition of hydrotalcite, 2:1 is first choice, due to being likely to result in the fuctuation within a narrow range of corresponding ion ratio in extraction process, because
The ratio that this chooses 2.2 is relatively reasonable.Calcium aluminium ratio relatively low simultaneously, it is possible to reduce the quantity of high-temperature process white clay is needed,
Advantageously reduce the processing cost of kerosene shale ash.
Embodiment 3
The present embodiment and embodiment 1 are basically identical, the difference lies in：Adding into evaporated mother liquor Q3 described in step 3
The white clay A after calcining is added to solution ph to be 1-2, the white clay A preferably into evaporated mother liquor Q3 after addition calcining is to pH value of solution
Be worth is 1.8.
Embodiment 3 illustrates：Preferably solution ph is 1.8, you can to ensure that iron ion fully dissolves participation reaction, again
The processing capacity of white clay can be increased.The processing capacity for white clay is such as further enhanced, solution ph further increases, it will
Ferric hydroxide precipitate is generated, wraps up in miscellaneous ferrous iron, and then causes to be not thorough ferrous oxidation.
Embodiment 4
The present embodiment and embodiment 1 are basically identical, the difference lies in：Adjusting pH value described in step 3 is 4-5, is stirred
It mixes 1 hour, filters, acid solution in Q2 is taken to be made into the sour water that pH value is 4-5, cleans filter residue；It is 4.2 preferably to adjust pH value, stirring
1 hour, filtering took acid solution in Q2 to be made into the sour water that pH value is 4.2, cleans filter residue.
Embodiment 4 illustrates：Experiment detection finds that ferric ions precipitation is more complete, is when pH value is 4.0-4.2
Ensure to prepare hydrated calcium silicate quality in the later stage, therefore preferably 4.2.
Embodiment 5
The present embodiment and embodiment 1 are basically identical, the difference lies in：The mixture of addition thereto B described in step 4
In to pH value be 6-8；It is 8 to add in preferably and thereto in mixture B to pH value.
Embodiment 5 illustrates：Early period, different kinds of ions entered solution under acid solution effect, and ion occurs with the raising of pH value
It exchanges, until the higher iron and aluminum ions of pH value are more thorough from solution precipitation.It is 8 to select to pH value, may be such that metal ion fully precipitates,
It can realize that gradient is extracted again by adjusting pH value by precipitating.In addition pH value is 8, can improve the treating capacity of mixture B.
Embodiment 6
The present embodiment and embodiment 1 are basically identical, the difference lies in：Acid solution in Q2 is taken to be made into pH described in step 7
It is worth the sour water for 3.7-4.0；Acid solution in Q2 is preferably taken to be made into the sour water that pH value is 3.7.
Embodiment 6 illustrates：It is 3.7 that pH is preferably adjusted in the present embodiment, can aluminium hydroxide be dissolved, but for
The dissolving of ferric hydroxide precipitate is very small, preferably realizes the separation of iron aluminium.
Embodiment 7
The present embodiment and embodiment 1 are basically identical, the difference lies in：It is former according to calcium atom and iron described in step 9
The ratio between amount of sub- substance is 5:1-20:1 ratio adds in magnetic particle M；Preferably according to the amount of calcium atom and iron atom substance
The ratio between be 5:1 ratio adds in magnetic particle M.
Embodiment 7 illustrates：Magnetic hydrotalcite specific saturation magnetization 8.2emu/g obtained in the present embodiment, 25 DEG C,
PH=6, uranium absorption capacity are 124mg/g.Spent acid usage amount is larger in this invention, improves the usage amount of magnetic particle and can increase
The recuperability energy of strong material, while improve the utilizability of spent acid.
Embodiment 8
The present embodiment and embodiment 1 are basically identical, the difference lies in：Described in step 10 according to calcium silicon matter
The ratio between amount 0.8:1-1.5:1 ratio adds in solution G1；Preferably according to the ratio between amount of calcium silicon matter 1.5:1 ratio adds in molten
Liquid G1.
Embodiment 8 illustrates：Hydrated calcium silicate uranium absorption distribution ratio obtained in the present embodiment is more than 22000.
Embodiment 9
The present embodiment and embodiment 2 are basically identical, the difference lies in：Being added into evaporated mother liquor Q3 described in rapid 3
White clay A after calcining to solution ph be 1-2, the white clay A preferably into evaporated mother liquor Q3 after addition calcining to solution ph
It is 1.8；
Adjusting pH value described in step 3 is 4-5, is stirred 1 hour, filtering, and acid solution in Q2 is taken to be made into pH value as 4-5's
Sour water cleans filter residue；It is 4.2 preferably to adjust pH value, is stirred 1 hour, filtering, and acid solution in Q2 is taken to be made into the acid that pH value is 4.2
Water cleans filter residue；
It is described in step 4 and to add in thereto in mixture B to pH value be 6-8；Add in preferably and thereto mixing
In object B to pH value be 8；
Acid solution in Q2 is taken to be made into the sour water that pH value is 3.7-4.0 described in step 7；Acid solution in Q2 is preferably taken to be made into pH
It is worth the sour water for 3.7；
Described in step 9 is 5 according to the ratio between amount of calcium atom and iron atom substance:1-20:1 ratio adds in magnetic particles
Sub- M；It is 5 preferably according to the ratio between amount of calcium atom and iron atom substance:1 ratio adds in magnetic particle M；
Described in step 10 according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds in solution G1；Preferably
The ratio between amount according to calcium silicon matter 1.5:1 ratio adds in solution G1.
Embodiment 10
The present embodiment and embodiment 2 are basically identical, the difference lies in：Described in step 4 and addition mixing thereto
In object B to pH value be 6-8；It is 8 to add in preferably and thereto in mixture B to pH value；
Acid solution in Q2 is taken to be made into the sour water that pH value is 3.7-4.0 described in step 7；Acid solution in Q2 is preferably taken to be made into pH
It is worth the sour water for 3.7；
Described in step 9 is 5 according to the ratio between amount of calcium atom and iron atom substance:1-20:1 ratio adds in magnetic particles
Sub- M；It is 5 preferably according to the ratio between amount of calcium atom and iron atom substance:1 ratio adds in magnetic particle M；
Described in step 10 according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds in solution G1；Preferably
The ratio between amount according to calcium silicon matter 1.5:1 ratio adds in solution G1.
Claims (10)
1. the processing method of a kind of spent acid, kerosene shale ash and white clay, includes the following steps：
Step 1：
White clay is calcined 0.5-6 hours under being passed through air conditions at 940 DEG C, after being cooled to room temperature, the white clay A after being calcined；It presses
The ratio of the amount of calcium atom and aluminium atom substance is 2:1-3:1 ratio mixes white clay and kerosene shale ash, and mixture is in 1260-
1270 DEG C are passed through under air conditions, calcine 3-6 hours, after being cooled to room temperature, obtain mixture B；
Step 2：
Under rapid mixing conditions, to volume in 5V spent acid, the white clay A after calcining to be added in, until calcium ion concentration is in acid solution
0.4 mol/L, it is V to distill to volume, after retort gas is condensed, obtains acid solution Q1；The spent acid that volume is 3V is added for the first time,
Continue distillation to 3V, add the spent acid that volume is 2V for the second time, it is 4V to continue distillation to volume, obtains evaporated mother liquor Q3；Merge
The acid solution condensed in the process is added twice, labeled as acid solution Q2；
Step 3：
It is 1-2 that the white clay A after calcining is added into evaporated mother liquor Q3 to solution ph, adds in H2O2Reacted to ferrous iron from
Sub- concentration is less than 0.02mol/L, adds in the sodium hydroxide of 1-2 mol/L, and adjusting pH value is 4-5, is stirred 1 hour, and filtering takes
Acid solution is made into the sour water that pH value is 4-5 in Q2, cleans filter residue；Filtrate merges into solution G1 with washing lotion, and filter residue is labeled as filter residue
F31；
Step 4：
Acid solution Q1 is measured, measurement volume is total volume 50%-60%, and it is 6-8 to add in mixture B thereto to pH value, is stirred
0.5-3 hours, it was 4.2 to add acid solution Q1 to pH value, stirs 0.5-3 hours, is separated by filtration and obtains extracting solution GL1, take acid solution Q1
Middle acid solution is made into the sour water that pH value is 4.1-4.5, cleans filter residue, stirs 0.5-3 hours, the first filter residue Z1 is obtained after filtering, closes
And extracting solution GL1 and washing lotion are solution GL2；
Step 5：
Acid solution Q1 is taken to be made into the sour water that pH value is 1.5 to add in the first filter residue Z1, it is siliceous in mixture B to add in quality
5-30 times of amount, ultrasonic wave added stirring 1-3 hours, being maintained at solution ph in entire whipping process by adding acid solution Q1 modes is
1.5-1.8, filtering, further repeats this step aforesaid operations 1-3 times, and labeled as filtrate TL1, filter residue is labeled as the filtrate of merging
Second filter residue Z2；
Step 6：
It weighs acid solution Q2 to add in the second filter residue Z2, weighs acid solution Q2 mass as 3-10 times of silica quality in mixture B, surpass
Sound auxiliary stirring 1-3 hours, filtering further repeats this step aforesaid operations 2 times, extracts filtrate label in this step for the first time
Filtrate TL2；Second of the filtrate and third time filtrate merged labeled as filtrate TL3, labeled as third filter by the filter residue finally obtained
Slag Z3；Filtrate TL3 is added in remaining acid solution Q1；
Step 7：
Merging filtrate TL1 and filtrate TL2, by adding in the sodium hydroxide of 1-2 mol/L, adjusting pH value is 4.2-4.5, stirs 1
Hour, filtering takes acid solution in Q2 to be made into the sour water that pH value is 3.7-4.0, is cleaned by ultrasonic filter residue；Filtrate caused by this step,
Washing lotion caused by this step and solution GL2 merge into solution GL3, and filter residue is labeled as filter residue F32；
Step 8：
Filter residue F31 and filter residue F32 are mixed into F33, are 2 according to the ratio between amount of trivalent iron atom and ferrous iron atom species:1 ratio
Example to F33 add in spent acid, 45 DEG C of constant temperature, adjust pH value be 11, continue stirring 0.5 hour, Magnetic Isolation, be washed with deionized water to
Neutrality, alcohol are washed, dry, obtain magnetic particle M；
Step 9：
Solution GL3 pH=4-6 are adjusted, 40 DEG C of constant temperature are 5 according to the ratio between amount of calcium atom and iron atom substance:1-20:1 ratio
Example adds in magnetic particle M, and adjustment pH is 10-11, and 80 DEG C of waters bath with thermostatic control are stirred 4-8 hours, and Magnetic Isolation is washed to neutrality, alcohol
It washes, it is dry, obtain magnetic hydrotalcite；
Step 10：
According to the amount Na of substance after third filter residue Z3 dryings2O: SiO2The proportioning of=1-1.2 is mixed with NaOH, and ground and mixed is uniform
Afterwards, it roasts 3 hours for 400 DEG C, after cooling, according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds in solution G1, temperature
40-80 DEG C is maintained at, adjustment pH value is 10-11, reacts 6-48h, is cooled down, and filtering, washing, alcohol are washed, dried, and acquire aquation silicon
Sour calcium；
The white clay is generated industrial waste in paper making process；
The spent acid is processed steel surface the acid after cleaning treatment and corrosion treatment for hydrochloric acid.
2. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：Step 1 is former by calcium
The ratio of the amount of son and aluminium atom substance is 2.2:1 ratio, mixes white clay and kerosene shale ash, and mixture is logical at 1260-1270 DEG C
Enter under air conditions, calcine 6 hours.
3. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：To steaming in step 3
Evaporate in mother liquor Q3 the white clay A after addition calcining to solution ph be 1.8.
4. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：It is adjusted in step 3
PH value is 4.2, is stirred 1 hour, filtering, and acid solution in Q2 is taken to be made into the sour water that pH value is 4.2, cleans filter residue.
5. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：In step 4 and to
It is 8 wherein to add in mixture B to pH value.
6. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：Q2 is taken in step 7
Middle acid solution is made into the sour water that pH value is 3.7.
7. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：In step 9 according to
The ratio between calcium atom and the amount of iron atom substance are 5:1 ratio adds in magnetic particle M.
8. a kind of processing method of spent acid, kerosene shale ash and white clay as described in claim 1, it is characterised in that：It is pressed in step 10
The ratio between amount according to calcium silicon matter 1.5:1 ratio adds in solution G1.
9. a kind of processing method of spent acid, kerosene shale ash and white clay as claimed in claim 2, it is characterised in that：To steaming in step 3
Evaporate in mother liquor Q3 the white clay A after addition calcining to solution ph be 1.8；
It is 4.2 that pH value is adjusted in step 3, is stirred 1 hour, filtering, and acid solution in Q2 is taken to be made into the sour water that pH value is 4.2, cleaning filter
Slag；
Add in step 4 and thereto mixture B to pH value be 8；
Acid solution in Q2 is taken to be made into the sour water that pH value is 3.7 in step 7；
According to the ratio between amount of calcium atom and iron atom substance it is 5 in step 9:1 ratio adds in magnetic particle M；
According to the ratio between amount of calcium silicon matter 1.5 in step 10:1 ratio adds in solution G1.
10. a kind of processing method of spent acid, kerosene shale ash and white clay as claimed in claim 2, it is characterised in that：In step 4 simultaneously
Thereto add in mixture B to pH value be 8；
Acid solution in Q2 is taken to be made into the sour water that pH value is 3.7 in step 7；
According to the ratio between amount of calcium atom and iron atom substance it is 5 described in step 9:1 ratio adds in magnetic particle M；
According to the ratio between amount of calcium silicon matter 1.5 in step 10:1 ratio adds in solution G1.
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