CN107570108A - 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 method 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, is combined for the metal ion in extract solution 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 method of industrial waste, and in particular to the industrial waste such as kerosene shale ash, white clay, spent acid integrates
Utilize the preparing technical field with sewage waste liquor processing material.
Background technology
Three kinds of industrial waste compositions and its harm
1.1 kerosene shale ash compositions and its harm
Oil shale reserves are huge, are generally considered the important alternative energy source of oil and natural gas.Because oil shale is high-ash
Feature, kerosene shale ash are the most important accessory substances during processing and utilization, stack lime-ash and not only occupy substantial amounts of soil, and
And serious environmental pollution can be caused.Oil shale waste slag main component has quartz, feldspar and calcite, wherein quartz, feldspar contain
Measure of a 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 composition, China's oil
Shale lime-ash realizes innoxious kerosene shale ash, recycling and functionalized application for China's oil page substantially based on silicon, aluminium, iron
Rock industry is developed rapidly with positive facilitation.
White clay composition and its harm
White clay is caused key industry waste in paper making process, and nearly 0.5 ton of white clay will be produced by often producing 1 ton of thick slurry, because
This white clay enormous amount.Its main component is with CaCO3、CaSO4、CaCl2Based on calcium salt, also a small amount of SiO2.From white clay
Main component is also not difficult to show that white clay is in strong basicity, and general pH value is 10 or so.In addition to inorganic constituents, wherein also containing certain
Caused organic matter in the paper-making process of quantity, substantial amounts of soil is not only occupied, and serious environmental pollution can be caused.
Spent acid composition and its harm
In the production of steel product, it is required for being processed at cleaning treatment and corrosion steel surface with substantial amounts of hydrochloric acid
Reason, to improve surface and property.Slowly raised along with the concentration of metal ions in pickle liquor, after reaching finite concentration, acid
The cleaning and corrosion efficiency for washing waste liquid are decreased obviously, and eventually become spent acid.
Content of hydrochloric acid is 30 ~ 60g/L in spent acid, and total iron content is 60 ~ 130g/L, its ferrous ions content is 50 ~
120g/L, additionally containing heavy metal ion such as extremely a small amount of ppm levels 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 with hydrone in aqueous, causes the actual boiling point of hydrogen chloride to be more than
The boiling point of water, it is difficult to distill out can direct reuse higher concentration hydrochloric acid solution,.
Immediate prior art
In the prior art:White clay and kerosene shale ash are the method (application number that raw material prepares uranium absorption agent and curing agent
CN201410022521.7), in actual application find that some are needed to be further improved be present, outstanding behaviours with
Lower 3 points:
2.1 consumption acids enormous amounts.Because aluminum ions content prepares having a great influence for hydrated calcium silicate for the later stage, can 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 kerosene shale ash early stage
Slag needs to perform etching extraction with the hydrochloric acid of substantial amounts of high concentration after being activated, and extract solution is substantial amounts of acid solution.
Using sodium chloride activation method, recovery sodium chloride cost is high, 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 substantial amounts of NaCl, to the greatest extent
Pipe can realize NaCl reuse from material balance angle, former technique, without extra addition NaCl, but in actual production process by
In needing solid NaCl enormous amounts, problems be present:By naturally sun-cured method, it is difficult to meet actual continuous raw
The requirement of production;Using distillation mode, equipment investment is huge, and energy resource consumption is serious.Therefore the method activated using NaCl is entered
Row activation, it is difficult to realize continuous production.
It is difficult to effectively reclaim after the houghite adsorbent absorption of preparation.
At present, magnetic adsorbent is the major way for solving adsorbent recovery problem, using kerosene shale ash and white clay as raw material
The houghite of preparation can not 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 is carried with the complexity of synthetic ingredient
Rise, the difficulty of generation lamella crystal structure also gradually steps up.Kerosene shale ash complicated component, it is corresponding to white clay synthesis hydrotalcite-like material brilliant
The diffracted intensity in face is substantially reduced, and this explanation is constructed because various metals ion take part in flaggy, causes having for formed crystal
Sequence arrangement architecture is affected.Under normal circumstances, the preparation difficulty of calcium aluminum hydrotalcite will be difficult to magnalium hydrotalcite, this mainly by
Ionic radius, calcium ion are more easily generated the decision of the factors such as calcium carbonate.During magnetic hydrotalcite is prepared, to add certain
The magnetic-particle of quantity, these magnetic particles can be inserted among flaggy, and the lamellar structure influence for hydrotalcite is very big.Therefore with
Kerosene shale ash and white clay are that the polynary houghite difficulty such as magnetic calcium ferro-aluminum of the raw material preparation with excellent properties are very big.
Undeniably, in the prior art using oil shale as raw material, will wherein trivalent aluminium ion and ferric ion without
Purification & isolation, houghite, simple production process are prepared, but the weak point of the product shows 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 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, Industry Waste is realized
The recycling of thing and innoxious application, its 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 study ferrous
The comprehensive utilization mode of ion.Research emphasis in terms of two above is that waste acid reuse cooperates with what white clay, kerosene shale ash utilized
Effect.
The content of the invention
Based on the problems of prior art, the present invention carries out the optimization of essence for existing generation technique.There is provided
A kind of spent acid, white clay and kerosene shale ash prepare magnetic uranium adsorbent and the method for curing agent, comprise the following steps:
Step 1:
White clay, which is passed through at 940 DEG C under air conditionses, calcines 0.5-6 hours, after being cooled to room temperature, the white clay A after being calcined;Press
The ratio of the amount of calcium atom and aluminium atom material is 2:1-3:1 ratio, mix white clay and kerosene shale ash;Mixture is in 1260-
1270 DEG C are passed through under air conditionses, calcine 3-6 hours, after being cooled to room temperature, obtain mixture B;
Step 1 illustrates:Under the conditions of 1260 DEG C of white clay 940 DEG C, air is passed through, organic matter can be all converted to titanium dioxide by calcining
Carbon.Crystalline phase converts under the conditions of 1260-1270 DEG C, and kerosene shale ash and calcium oxide interact, realize kerosene shale ash activation and from
Efflorescence.
Step 2:
It is the white clay A after addition calcining in 5V spent acid to volume under rapid mixing conditions, when calcium ion concentration is 0.4
During 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;First
It is secondary to add the spent acid that volume is 3V, continue distillation to 3V, add the spent acid that volume is 2V for the second time, continuing distillation to volume is
4V, obtain evaporated mother liquor Q3;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 consumption portion after the calcining put into
Divide spent acid, therefore the concentration of the acid solution Q1 hydrogen chloride obtained is relatively low.During later stage is added, calcium ion concentration is higher, chlorination
The concentration of hydrogen is got a promotion, and phase of the hydrogen chloride in aqueous with hydrone is destroyed containing the higher calcium ion of concentration in acid solution
Interaction, hydrogen chloride content is 1.5-2.2 times of hydrogen chloride content in spent acid in Q2.This step acts on 1 by the white clay A after calcining
Calcium chloride solution is converted into, is laid the foundation for further reaction;Spent acid is divided into low concentration acid and high concentrated acid by effect 2, to enter
One step gradient is extracted and etching lays the foundation.
Step 3:
It is 1-2 that the white clay A after calcining is added into evaporated mother liquor Q3 to solution ph, adds H2O2Reacted to ferrous iron from
Sub- concentration is less than 0.02mol/L, adds 1-2 mol/L sodium hydroxide, and regulation pH value is 4-5, stirs 1 hour, 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 3 illustrates:Evaporated mother liquor Q3 is mainly the mixed liquor of ferrous ion and calcium ion, and the two is difficult to separate;Pass through oxygen
Change mode, not only realize trivalent ion and calcium ion separation;And obtain the calcium source for preparing hydrated calcium silicate and prepare magnetic
Ferric iron needed for particle.
Step 4:
Acid solution Q1 is measured, it is cumulative volume 50%-60% to measure volume, and it is 6-8 to add mixture B thereto to pH value, is stirred
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 extract 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 extract solution GL1 and washing lotion are solution GL2;
Step 4 illustrates:In the solution that pH value is 8, based on calcium ion.In order to ensure that calcium extraction is abundant, extracting liquid pH value choosing
For 4.2, but this has and causes extremely a small amount of magnesium and part aluminium to enter in solution, but divalence magnesium ion content is extremely low, and
The structure influence constructed for hydrotalcite that divalence magnesium ion participates in hydrotalcite flaggy is very small.Aluminium ion as reaction raw materials,
Therefore solution GL2 is without further separating.
It is that this is primarily to avoided iron ion in mixture B from entering more than 4.1 to want strict control ph in this step
Enter in solution.Extraction and cleaning are required for the stirring of certain time, and its 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 extract solution intermediate ion, is the preparation of hydrotalcite
Lay the foundation.
Step 5:
Take acid solution Q1 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 quality
5-30 times of amount, ultrasonic wave added stir 1-3 hours, and being maintained at solution ph in whole whipping process by adding acid solution Q1 modes is
1.5-1.8, filtering, further repeats this step aforesaid operations 1-3 times, the filtrate of merging is labeled as filtrate TL1, and filter residue is labeled as
Second filter residue Z2;
Step 5 illustrates:This step purpose is the ferro-aluminum element in extraction mixture B.Solution ph is in whole whipping process
1.5-1.8 can realize that iron, aluminium more sufficiently extract.
Step 6:
Weigh acid solution Q2 to add in the second filter residue Z2, weigh acid solution Q2 mass as 3-10 times of silica quality in mixture B, surpass
Sound auxiliary stirring 1-3 hours, filtering, further repeat this step aforesaid operations 2 times, extract filtrate mark in this step for the first time
Filtrate TL2;Second of the filtrate and third time filtrate merged is labeled as filtrate TL3, and the filter residue finally obtained is labeled as the 3rd filter
Slag Z3;Filtrate TL3 is added in remaining acid solution Q1;
Step 6 illustrates:By a series of sour kerosene shale ash extracted and the mixture of white clay, substantial residual indissoluble thing and due to bag
The reason such as wrap up in and be difficult to the material extracted, on the one hand the metal ion in this moieties is the raw material for preparing hydrotalcite;The opposing party
If face metal ion residual quantity is excessive, the quality of further hydration calcium silicates can be impacted.This part metals ion concentration
Less, extraction difficulty is larger, it is necessary to high intensity hydrochloric acid and the repeatedly extraction completion 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- first 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 first
Material, it otherwise will change the proportioning of 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 aluminium element too high levels, it will generation ca aluminosilicate, influences properties of product.
Aluminium element content is very low in filtrate TL3, will not be impacted substantially for the proportioning of hydrotalcite raw material, and this part solution
Acid content is very high, directly as raw material use substantial amounts of alkali will be needed to be neutralized.The present invention adds filtrate TL3 remaining
Acid solution Q1 in the effect of this part acid as the extraction of next batch material, can be played, while continuous production, will also cause
This part aluminium ion, which turns into, prepares hydrotalcite raw material.
Step 7:
Merging filtrate TL1 and filtrate TL2, by adding 1-2 mol/L sodium hydroxide, regulation pH value is 4.2-4.5, stirring 1
Hour, filtering, take acid solution in Q2 to be made into the sour water that pH value is 3.7-4.0, be 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 7 illustrates:Regulation pH value can cause ferro element fully to precipitate for 4.2;The sour water cleaning filter that pH value is 3.7-4.0
Slag, it can further improve the rate of recovery of aluminium element.Solution GL1 is the higher calcium aluminium mixed solution of purity, directly as preparation
The raw material of 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
Example to F33 add spent acid, 45 DEG C of constant temperature, regulation pH value be 11, continue stirring 0.5 hour, Magnetic Isolation, be washed with deionized water to
Neutrality, alcohol are washed, and are dried, and obtain magnetic particle M;
Step 8 illustrates:Trivalent iron atom is obtained using the ferrous ion in spent acid, distillation oxidation and is separated from kerosene shale ash
The trivalent iron atom gone out prepares magnetic particle.Wherein spent acid is both divalence source of iron, again trivalent iron precipitate can be caused to be converted into
Ferric ion, while corresponding hydrochloric acid has been neutralized, reduce 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 material:1-20:1 ratio
Example adds magnetic particle M, and adjustment pH is 10-11, and 80 DEG C of waters bath with thermostatic control stir 4-8 hours, Magnetic Isolation, are washed to neutrality, alcohol
Wash, dry, obtain magnetic hydrotalcite;
Step 10:
According to the amount Na of material after 3rd filter residue Z3 dryings2O: SiO2=1-1.2 proportioning mixes with NaOH, and ground and mixed is uniform
Afterwards, 400 DEG C are calcined 3 hours, after cooling, according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds solution G1, temperature
40-80 DEG C is maintained at, adjustment pH value is 10-11, reacts 6-48h, is cooled down, filtering, and washing, alcohol are washed, dried, and acquire aquation silicon
Sour calcium.
Beneficial effect
1. preparing recyclable uranium absorption agent and curing agent as primary raw material using kerosene shale ash, white clay, spent acid, Industry Waste is realized
The recycling of thing and innoxious application, are the recoverables for realizing adsorbent, realize functionalized application.
2. white clay substitutes 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 synergy:
Synergy 1:The calcining purifying of white clay and the step of activation one of kerosene shale ash are completed, and white clay is not only the calcium in synthesizing
Source, or the activator of kerosene shale ash.
Synergy 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, obtain hydrogen chloride in the acid solution of face
The higher acid solution of content, is easy to extract.
Synergy 3:Spent acid mother liquor after distillation adds hydrogen peroxide, on the one hand realizes that calcium iron separates, on the other hand realizes
Oxidation for ferrous ion, meets the preparation requirement of magnetic particle.
Synergy 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 extraction acid source, the source of iron of 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 the usage amount of acid is reduced.Same high strength acid extraction in the prior art,
The residue of a large amount of acid can be caused, 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 substantial progress.
Brief description of the drawings
Accompanying drawing 1 is process route flow chart of the invention.
Embodiment
Embodiment 1
Step 1:
White clay, which is passed through at 940 DEG C under air conditionses, calcines 0.5-6 hours, after being cooled to room temperature, the white clay A after being calcined;Press
The ratio of the amount of calcium atom and aluminium atom material is 2:1-3:1 ratio, white clay and kerosene shale ash are mixed, mixture is in 1260-
1270 DEG C are passed through under air conditionses, calcine 3-6 hours, after being cooled to room temperature, obtain mixture B;
Step 2:
It is in 5V spent acid to volume, the white clay A after addition calcining, into acid solution, calcium ion concentration is under rapid mixing conditions
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 during adding 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 H2O2Reacted to ferrous iron from
Sub- concentration is less than 0.02mol/L, adds 1-2 mol/L sodium hydroxide, and regulation pH value is 4-5, stirs 1 hour, 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, it is cumulative volume 50%-60% to measure volume, and it is 6-8 to add mixture B thereto to pH value, is stirred
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 extract 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 extract solution GL1 and washing lotion are solution GL2;
Step 5:
Take acid solution Q1 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 quality
5-30 times of amount, ultrasonic wave added stir 1-3 hours, and being maintained at solution ph in whole whipping process by adding acid solution Q1 modes is
1.5-1.8, filtering, further repeats this step aforesaid operations 1-3 times, the filtrate of merging is labeled as filtrate TL1, and filter residue is labeled as
Second filter residue Z2;
Step 6:
Weigh acid solution Q2 to add in the second filter residue Z2, weigh acid solution Q2 mass as 3-10 times of silica quality in mixture B, surpass
Sound auxiliary stirring 1-3 hours, filtering, further repeat this step aforesaid operations 2 times, extract filtrate mark in this step for the first time
Filtrate TL2;Second of the filtrate and third time filtrate merged is labeled as filtrate TL3, and the filter residue finally obtained is labeled as the 3rd filter
Slag Z3;Filtrate TL3 is added in remaining acid solution Q1;
Step 7:
Merging filtrate TL1 and filtrate TL2, by adding 1-2 mol/L sodium hydroxide, regulation pH value is 4.2-4.5, stirring 1
Hour, filtering, take acid solution in Q2 to be made into the sour water that pH value is 3.7-4.0, be 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 spent acid, 45 DEG C of constant temperature, regulation pH value be 11, continue stirring 0.5 hour, Magnetic Isolation, be washed with deionized water to
Neutrality, alcohol are washed, and are dried, and 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 material:1-20:1 ratio
Example adds magnetic particle M, and adjustment pH is 10-11, and 80 DEG C of waters bath with thermostatic control stir 4-8 hours, Magnetic Isolation, are washed to neutrality, alcohol
Wash, dry, obtain magnetic hydrotalcite;
Step 10:
According to the amount Na of material after 3rd filter residue Z3 dryings2O: SiO2=1-1.2 proportioning mixes with NaOH, and ground and mixed is uniform
Afterwards, 400 DEG C are calcined 3 hours, after cooling, according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds solution G1, temperature
40-80 DEG C is maintained at, adjustment pH value is 10-11, reacts 6-48h, is cooled down, filtering, and washing, alcohol are washed, dried, and acquire aquation silicon
Sour calcium.
Embodiment 2
The present embodiment and embodiment 1 are basically identical, and difference is:Described in step 1 by calcium atom and aluminium atom material
The ratio of amount is 2:1-3:1 ratio, mixes white clay and kerosene shale ash, mixture are forged in the case where 1260-1270 DEG C is passed through air conditionses
3-6 hours are burnt, be preferably:It is 2.2 by the ratio of the amount of calcium atom and aluminium atom material:1 ratio, mix white clay and oil shale
Ash, mixture are calcined 6 hours in the case where 1260-1270 DEG C is passed through air conditionses.
Embodiment 2 illustrates:For calcium aluminum hydrotalcite, the ratio of the amount of calcium atom and aluminium atom material is 2:1-3:1 is to prepare
The preferable 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.Simultaneously relatively low calcium aluminum ratio, 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, and difference is:Being added into evaporated mother liquor Q3 described in step 3 is forged
White clay A after burning is 1-2 to solution ph, and the white clay A preferably into evaporated mother liquor Q3 after addition calcining to solution ph 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 disposal ability of white clay can be increased.The disposal ability for white clay is such as further enhanced, solution ph further raises, it will
Ferric hydroxide precipitate is produced, wraps up in miscellaneous ferrous iron, and then is caused not thorough for ferrous oxidation.
Embodiment 4
The present embodiment and embodiment 1 are basically identical, and difference is:Regulation pH value described in step 3 is 4-5, stirring 1
Hour, filtering, take acid solution in Q2 to be made into the sour water that pH value is 4-5, clean filter residue;It is 4.2 preferably to adjust pH value, and stirring 1 is small
When, filtering, take acid solution in Q2 to be made into the sour water that pH value is 4.2, clean filter residue.
Embodiment 4 illustrates:Experiment detection finds that when pH value is 4.0-4.2 ferric ions precipitation is more complete, is
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, and difference is:In the mixture of addition thereto B described in step 4 extremely
PH value is 6-8;It is 8 to add preferably and thereto in mixture B to pH value.
Embodiment 5 illustrates:Early stage, different kinds of ions entered solution under acid solution effect, and ion occurs with the rise of pH value
Exchange, separated out to the higher iron and aluminum ions of pH value from solution more thorough.Selection is 8 to pH value, may be such that metal ion fully precipitates,
It can realize that gradient is extracted by adjusting pH value again by precipitating.In addition pH value is 8, can improve mixture B treating capacity.
Embodiment 6
The present embodiment and embodiment 1 are basically identical, and difference is:Take in Q2 acid solution to be made into pH value to be described in step 7
3.7-4.0 sour water;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 preferably that regulation pH is 3.7 in the present embodiment, aluminium hydroxide can 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, and difference is:Described in step 9 according to calcium atom and iron atom thing
The ratio between amount of matter is 5:1-20:1 ratio adds magnetic particle M;Preferably according to the ratio between amount of calcium atom and iron atom material
For 5:1 ratio adds 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, and difference is:The amount according to calcium silicon matter described in step 10 it
Than 0.8:1-1.5:1 ratio adds solution G1;Preferably according to the ratio between amount of calcium silicon matter 1.5:1 ratio adds solution
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, and difference is:Calcining is added into evaporated mother liquor Q3 described in rapid 3
White clay A afterwards is 1-2 to solution ph, and the white clay A preferably into evaporated mother liquor Q3 after addition calcining to solution ph is
1.8;
Regulation pH value described in step 3 is 4-5, is stirred 1 hour, filtering, takes acid solution in Q2 to be made into the sour water that pH value is 4-5,
Clean filter residue;It is 4.2 preferably to adjust pH value, is stirred 1 hour, filtering, takes acid solution in Q2 to be made into the sour water that pH value is 4.2, clearly
Filter wash slag;
It is described in step 4 and to add thereto in mixture B to pH value be 6-8;Preferably and add thereto in mixture B
It is 8 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;Preferably take in Q2 acid solution to be made into pH value to be
3.7 sour water;
Described in step 9 is 5 according to the ratio between amount of calcium atom and iron atom material:1-20:1 ratio adds magnetic particle M;
It is 5 preferably according to the ratio between amount of calcium atom and iron atom material:1 ratio adds 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 solution G1;Preferably according to
The ratio between amount of calcium silicon matter 1.5:1 ratio adds solution G1.
Embodiment 10
The present embodiment and embodiment 2 are basically identical, and difference is:It is described in step 4 and add thereto in mixture B
It is 6-8 to pH value;It is 8 to add 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;Preferably take in Q2 acid solution to be made into pH value to be
3.7 sour water;
Described in step 9 is 5 according to the ratio between amount of calcium atom and iron atom material:1-20:1 ratio adds magnetic particle M;
It is 5 preferably according to the ratio between amount of calcium atom and iron atom material:1 ratio adds 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 solution G1;Preferably according to
The ratio between amount of calcium silicon matter 1.5:1 ratio adds solution G1.
Claims (10)
1. the processing method of a kind of spent acid, kerosene shale ash and white clay, comprises the following steps:
Step 1:
White clay, which is passed through at 940 DEG C under air conditionses, calcines 0.5-6 hours, after being cooled to room temperature, the white clay A after being calcined;Press
The ratio of the amount of calcium atom and aluminium atom material is 2:1-3:1 ratio, white clay and kerosene shale ash are mixed, mixture is in 1260-
1270 DEG C are passed through under air conditionses, calcine 3-6 hours, after being cooled to room temperature, obtain mixture B;
Step 2:
It is in 5V spent acid to volume, the white clay A after addition calcining, into acid solution, calcium ion concentration is under rapid mixing conditions
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 during adding 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 H2O2Reacted to ferrous iron from
Sub- concentration is less than 0.02mol/L, adds 1-2 mol/L sodium hydroxide, and regulation pH value is 4-5, stirs 1 hour, 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, it is cumulative volume 50%-60% to measure volume, and it is 6-8 to add mixture B thereto to pH value, is stirred
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 extract 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 extract solution GL1 and washing lotion are solution GL2;
Step 5:
Take acid solution Q1 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 quality
5-30 times of amount, ultrasonic wave added stir 1-3 hours, and being maintained at solution ph in whole whipping process by adding acid solution Q1 modes is
1.5-1.8, filtering, further repeats this step aforesaid operations 1-3 times, the filtrate of merging is labeled as filtrate TL1, and filter residue is labeled as
Second filter residue Z2;
Step 6:
Weigh acid solution Q2 to add in the second filter residue Z2, weigh acid solution Q2 mass as 3-10 times of silica quality in mixture B, surpass
Sound auxiliary stirring 1-3 hours, filtering, further repeat this step aforesaid operations 2 times, extract filtrate mark in this step for the first time
Filtrate TL2;Second of the filtrate and third time filtrate merged is labeled as filtrate TL3, and the filter residue finally obtained is labeled as the 3rd filter
Slag Z3;Filtrate TL3 is added in remaining acid solution Q1;
Step 7:
Merging filtrate TL1 and filtrate TL2, by adding 1-2 mol/L sodium hydroxide, regulation pH value is 4.2-4.5, stirring 1
Hour, filtering, take acid solution in Q2 to be made into the sour water that pH value is 3.7-4.0, be 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 spent acid, 45 DEG C of constant temperature, regulation pH value be 11, continue stirring 0.5 hour, Magnetic Isolation, be washed with deionized water to
Neutrality, alcohol are washed, and are dried, and 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 material:1-20:1 ratio
Example adds magnetic particle M, and adjustment pH is 10-11, and 80 DEG C of waters bath with thermostatic control stir 4-8 hours, Magnetic Isolation, are washed to neutrality, alcohol
Wash, dry, obtain magnetic hydrotalcite;
Step 10:
According to the amount Na of material after 3rd filter residue Z3 dryings2O: SiO2=1-1.2 proportioning mixes with NaOH, and ground and mixed is uniform
Afterwards, 400 DEG C are calcined 3 hours, after cooling, according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds solution G1, temperature
40-80 DEG C is maintained at, adjustment pH value is 10-11, reacts 6-48h, is cooled down, filtering, and washing, alcohol are washed, dried, and acquire aquation silicon
Sour calcium.
A kind of 2. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Described in step 1
It is 2 by the ratio of the amount of calcium atom and aluminium atom material:1-3:1 ratio, white clay and kerosene shale ash are mixed, mixture is in 1260-
1270 DEG C are passed through under air conditionses, calcine 3-6 hours, are 2.2 preferably by the ratio of the amount of calcium atom and aluminium atom material:1
Ratio, white clay and kerosene shale ash are mixed, mixture is calcined 6 hours in the case where 1260-1270 DEG C is passed through air conditionses.
A kind of 3. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Described in step 3
Into evaporated mother liquor Q3 addition calcining after white clay A to solution ph be 1-2, preferably into evaporated mother liquor Q3 addition calcine
White clay A afterwards to solution ph be 1.8.
A kind of 4. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Institute in step 3
The regulation pH value stated is 4-5, is stirred 1 hour, filtering, takes acid solution in Q2 to be made into the sour water that pH value is 4-5, cleans filter residue;It is preferred that
It is 4.2 for regulation pH value, stirs 1 hour, filtering, takes acid solution in Q2 to be made into the sour water that pH value is 4.2, clean filter residue.
A kind of 5. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Described in step 4
And to add thereto in mixture B to pH value be 6-8;It is 8 to add preferably and thereto in mixture B to pH value.
A kind of 6. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Described in step 7
Take acid solution in Q2 to be made into the sour water that pH value is 3.7-4.0;Acid solution in Q2 is preferably taken to be made into the sour water that pH value is 3.7.
A kind of 7. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Described in step 9
Be 5 according to the ratio between amount of calcium atom and iron atom material:1-20:1 ratio adds magnetic particle M;It is preferably former according to calcium
The ratio between amount of son and iron atom material is 5:1 ratio adds magnetic particle M.
A kind of 8. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 1, it is characterised in that:Institute in step 10
State according to the ratio between amount of calcium silicon matter 0.8:1-1.5:1 ratio adds solution G1;Preferably according to calcium silicon matter amount it
Than 1.5:1 ratio adds solution G1.
A kind of 9. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 2, it is characterised in that:Described in step 3
Into evaporated mother liquor Q3 addition calcining after white clay A to solution ph be 1-2, preferably into evaporated mother liquor Q3 addition calcine
White clay A afterwards to solution ph be 1.8;
Regulation pH value described in step 3 is 4-5, is stirred 1 hour, filtering, takes acid solution in Q2 to be made into the sour water that pH value is 4-5,
Clean filter residue;It is 4.2 preferably to adjust pH value, is stirred 1 hour, filtering, takes acid solution in Q2 to be made into the sour water that pH value is 4.2, clearly
Filter wash slag;
It is described in step 4 and to add thereto in mixture B to pH value be 6-8;Preferably and add thereto in mixture B
It is 8 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;Preferably take in Q2 acid solution to be made into pH value to be
3.7 sour water;
Described in step 9 is 5 according to the ratio between amount of calcium atom and iron atom material:1-20:1 ratio adds magnetic particle M;
It is 5 preferably according to the ratio between amount of calcium atom and iron atom material:1 ratio adds 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 solution G1;Preferably according to
The ratio between amount of calcium silicon matter 1.5:1 ratio adds solution G1.
A kind of 10. processing method of spent acid, kerosene shale ash and white clay as claimed in claim 2, it is characterised in that:Institute in step 4
It is stating and to add thereto in mixture B to pH value be 6-8;It is 8 to add 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;Preferably take in Q2 acid solution to be made into pH value to be
3.7 sour water;
Described in step 9 is 5 according to the ratio between amount of calcium atom and iron atom material:1-20:1 ratio adds magnetic particle M;
It is 5 preferably according to the ratio between amount of calcium atom and iron atom material:1 ratio adds 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 solution G1;Preferably according to
The ratio between amount of calcium silicon matter 1.5:1 ratio adds solution G1.
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