CN106367597B - It is a kind of that the method that magnesium prepares flame retardant of magnesium hydroxide is reclaimed from heavy metal sewage sludge - Google Patents
It is a kind of that the method that magnesium prepares flame retardant of magnesium hydroxide is reclaimed from heavy metal sewage sludge Download PDFInfo
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- CN106367597B CN106367597B CN201610758307.7A CN201610758307A CN106367597B CN 106367597 B CN106367597 B CN 106367597B CN 201610758307 A CN201610758307 A CN 201610758307A CN 106367597 B CN106367597 B CN 106367597B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention proposes a kind of method that magnesium is reclaimed from heavy metal sewage sludge：By heavy metal sewage sludge according to pure water and sludge dry biomass than 8 ~ 15：1 adds pure water, heats while stirring, is heated to 80 ~ 85 DEG C and is incubated, and 0.4 ~ 0.6g/L of addition dilute sulfuric acid is 7.0 ~ 8.0 up to measuring pH at 80 ~ 85 DEG C during heating stirring, continues to stir, obtains grain slag mixture and be dehydrated through plate compression, obtain filtrate 1；By filter residue hot wash filtering means dehydration, filtrate 2 is obtained；Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.The present invention also proposes a kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge based on the above method：Pretreatment washing, add alkali lye magnesium sinking, surface is modified, ageing, hydro-thermal process, dehydration, washing, drying.The present invention improves the primary recovery of magnesium while noble metal retrieving cobalt nickel rate and Flame Retardant Magnesium Hydroxide crude product purity is ensured.
Description
Technical field
The invention belongs to resource circulation utilization and technical field of wet metallurgy, more specifically to one kind from heavy metal-polluted
The method of recovery extraction flame retardant of magnesium hydroxide in mud.
Background technology
Industrial production magnesium hydroxide mainly has following five kinds of methods：(1) with lime stone and bittern reaction production hydroxide
Magnesium；(2) with sodium hydroxide and bittern, enriched bittern cake reaction hydrogen manufacturing magnesia；(3) using burnt magnesite, dolomite and bittern,
Enriched bittern cake reaction production magnesium hydroxide；(4) using MgO hydration generation magnesium hydroxides, MgO here must be light-burned product to ensure
The activity of hydration；(5) with ammoniacal liquor and bittern, enriched bittern cake reaction hydrogen manufacturing magnesia.Later stage is changed using surface modifier to magnesium hydroxide
Property, the flame retardant of magnesium hydroxide product for meeting fire resistance is made using conventional methods such as crystal seed method, hydro-thermal methods.Industrial production
The raw material sources of magnesium hydroxide are extensive, but the easy etching apparatus of bittern is thus higher to equipment requirement, magnesite and dolomite
Calcination process high energy consumption, therefore conventional method prepares magnesium hydroxide and industrially produces magnesium hydroxide mainly following five kinds of methods：
(1) with lime stone and bittern reaction production magnesium hydroxide；(2) with sodium hydroxide and bittern, enriched bittern cake reaction hydrogen manufacturing magnesia；(3)
Utilize burnt magnesite, dolomite and bittern, enriched bittern cake reaction production magnesium hydroxide；(4) MgO hydration generation hydroxides are utilized
Magnesium, MgO here must be light-burned products to ensure the activity of hydration；(5) aoxidized with ammoniacal liquor and bittern, enriched bittern cake reaction hydrogen manufacturing
Magnesium.Later stage is modified using surface modifier to magnesium hydroxide, is made using conventional methods such as crystal seed method, hydro-thermal methods and is met anti-flammability
The flame retardant of magnesium hydroxide product of energy.The raw material sources of industrial production magnesium hydroxide are extensive, but the easy etching apparatus of bittern because
And, the calcination process high energy consumption of magnesite and dolomite higher to equipment requirement, therefore conventional method prepares magnesium hydroxide flame retardant
The shortcomings that equipment requirement height, high energy consumption be present in agent.
The magnesium that the lateritic nickel ore used in extraction cobalt nickel industry contains mass fraction 20% or so, produces 1t metallic cobalt nickel,
Association about 55t sludge, magnesium are enriched in sludge and not utilized rationally.The valuable metals such as cobalt nickel manganese magnesium are rich in sludge,
At this stage to acidleach, the noble metals such as cobalt nickel manganese are recycled（The material liquid prepared as ternary battery material）, acidleach process
In caused a large amount of magnesium resources be enriched in system and circulate, magnesium is not opened a way suitably（Product or outer row is made）Therefore handle
It is difficult.Due to lacking suitably to the processing method of magnesium resource, serious environmental pressure is caused with the wasting of resources.
To sum up, at present to the heavy metal sewage sludge after extraction in processing procedure, substantial amounts of magnesium in leachate be present and be difficult to point
From low as purity such as ternary battery raw material cobalt nickel manganese, a large amount of magnesium resources can not be rationally using causing magnesium resource unrestrained in leachate
The problem of taking.The shortcomings that equipment requirement height, high energy consumption be present in fire retardant.
The content of the invention
In order to solve the above-mentioned technical problem, it is an object of the invention to propose a kind of side that magnesium is reclaimed from heavy metal sewage sludge
Method and a kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge, by this method to extracting cobalt nickel
Heavy metal sewage sludge after being extracted in industry（Hereinafter referred to as heavy metal sewage sludge）Handled, can not only be shortened from heavy metal sewage sludge
Middle recovery magnesium, improves the utilization rate of magnesium, while ensures the rate of recovery of the valuable noble metal subsequent treatment such as cobalt nickel in heavy metal sewage sludge
Higher purity, industry added value is improved, and it is simple for process, being capable of extensive industrialization.
The present invention proposes a kind of method that magnesium is reclaimed from heavy metal sewage sludge, comprises the following steps：
Pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 8：1~15：1 adds pure water, side
Side stirring is heated, 80 ~ 85 DEG C is heated to and is incubated, the dilute sulfuric acid that 0.4g/L ~ 0.6g/L is added during heating stirring is straight
It is 7.0 ~ 8.0 to pH is measured at 80 ~ 85 DEG C, continues 10 ~ 15min of stirring, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate
1 and filter residue 1；Filter residue 1 is used into hot wash filtering means dehydration 1 ~ 3 time, obtains filtrate 2；Filtrate 1 is 2-in-1 with filtrate and gained filtrate is
Magnesium liquid.
Preferably, by heavy metal sewage sludge according to pure water and sludge dry biomass than 15：1 adds pure water, in heating
Stirring, is heated to 85 DEG C and is incubated, and the dilute sulfuric acid that 0.6g/L is added during heating stirring is up to measuring pH at 85 DEG C
8.0, continue to stir 15min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；Filter residue 1 is used into hot wash
Filtering means dehydration 3 times, obtains filtrate 2；Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.
The present invention also proposes one kind from heavy metal sewage sludge based on a kind of above-mentioned method for reclaiming magnesium from heavy metal sewage sludge
The method that recovery magnesium prepares flame retardant of magnesium hydroxide, comprises the following steps：
Step 1, pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 8：1~15：1 addition is pure
Water, heat while stirring, be heated to 80 ~ 85 DEG C and be incubated, 0.4g/L ~ 0.6g/L dilute sulphur is added during heating stirring
Acid is 7.0 ~ 8.0 up to measuring pH at 80 ~ 85 DEG C, continues 10 ~ 15min of stirring, obtains grain slag mixture and be dehydrated through plate compression, obtained
Filtrate 1 and filter residue 1；Filter residue 1 is used into hot wash filtering means dehydration 1 ~ 3 time, obtains filtrate 2；Filtrate 1 and filtrate is 2-in-1 and gained filtrate
As magnesium liquid；
Step 2, alkali lye magnesium sinking is added：Gained magnesium liquid in the step 1 of certain volume is taken, magnesium ion concentration in magnesium liquid is measured, adds
The NaOH aqueous solution for entering 4 ~ 5mol/L adjusts pH value to 11.5 ~ 12.0, and in temperature, 50 ~ 70 DEG C are fully reacted 30-40min magnesium sinkings,
I.e. magnesium ion combines to form magnesium hydrate precipitate with hydroxide ion, obtains milky turbid；
Step 3, surface is modified：According to magnesium ion concentration in magnesium liquid volume in step 2 and magnesium liquid, in calculation procedure 2 magnesium from
Magnesium hydroxide quality during sub sedimentation completely, surface modifier stearic acid, institute are added into step 2 products therefrom milky turbid
Stiffened resin acid quality accounts for the 2 ~ 6% of calculated magnesium hydroxide quality, under the conditions of 60 ~ 80 DEG C, to magnesium hydroxide be modified 70 ~
100min；
Step 4, it is aged：Step 3 products therefrom is aged 2 ~ 6h at 65 ~ 80 DEG C, mixing speed is turned down in ageing process
To 100 ~ 150r/min；
Step 5, hydro-thermal process：Step 4 products therefrom is dehydrated, until magnesium hydroxide quality is accounted for obtained by step 4 in product
The 30 ~ 40% of product quality, temperature is adjusted in autoclave to 150 ~ 180 DEG C, 3 ~ 8h of hydro-thermal process, obtains slag specimen；
Step 6, step 5 gained slag specimen filtered into dehydration with vavuum pump, replace washing with alcohol using hot water, in 100-
Flame Retardant Magnesium Hydroxide crude product is made after being dried at 105 DEG C.
Preferably, in step 1, by heavy metal sewage sludge according to pure water and sludge dry biomass than 15：1 adds pure water,
Heat while stirring, be heated to 85 DEG C and be incubated, 0.6g/L dilute sulfuric acid is added during heating stirring until in 85 DEG C of surveys
It is 8.0 to obtain pH, continues to stir 15min, obtains grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；By the heat of filter residue 1
Water washing filtering means dehydration 3 times, obtains filtrate 2；Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.
Preferably, in step 2, magnesium ion concentration is by Japanese Shimadzu atomic absorption spectrophotometer AA- in the magnesium liquid
7000 measure.
Preferably, in step 5, plate compression or vavuum pump can be used to filter dehydration.
Beneficial effects of the present invention：
1）Heavy metal sewage sludge is by pre-processing water-washing process, wherein enter magnesium liquid after the wash-off of most magnesium, magnesium in magnesium liquid
The ratio for accounting for magnesium in heavy metal sewage sludge reaches more than 99%；Meanwhile Ni content is less than 0.6mg/L in filtrate, Co, Mn, Zn are not examined
Go out, Cu content is less than 0.2mg/L, so as to ensure that the high-recovery of noble metal cobalt nickel in the filter residue of recovery.
2）The flame retardant of magnesium hydroxide crude product being prepared：The primary recovery of magnesium in product（Product magnesium accounts for heavy metal
The ratio of magnesium in sludge）Reach more than 85.4%, reach as high as 86.2%；Product purity >=96.5%, specific surface area（BET）≤
15.2m2/g, the microcosmic internal strain η≤2.8x10 in 101 faces-3；SEM results show that magnesium hydroxide particle is hexagonal flake, have rule
Pattern, easily disperse when being easy to add as fire retardant.
3）The synthetical recovery of valuable metal magnesium in heavy metal sewage sludge is effectively realized, is avoided existing for existing recovery process
The deficiency that magnesium is circulated in system, do not opened a way properly（With the cobalt nickel manganese together conduct of leaching in leachate of the magnesium after acidleach
Material liquid, the recycling to cobalt nickel manganese interfere）；
4）Recycled in its entirety rational technology is easy, efficiency high, has considerable economic value.
Brief description of the drawings
Fig. 1 is the technique course diagram of the present invention.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
A kind of method that magnesium is reclaimed from heavy metal sewage sludge, comprises the following steps：
Pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 8：1 adds pure water, opens electric furnace liter
Temperature, adjust pH to 7.0 with 0.4g/L dilute sulfuric acid aqueous solution while stirring（Temperature is finally stable at 80 DEG C, and pH=7.0 are herein
At a temperature of measure）, continue to stir 10min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；Filter residue 1 is used
80-90 DEG C of hot wash filtering means dehydration 1 time, obtains filtrate 2.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.Magnesium in magnesium liquid
Accounting for the ratio of magnesium in heavy metal sewage sludge, to reach more than 99%, Ni content be 0.5mg/L, and Co, Mn, Zn are not detected, and Cu content is
0.1mg/L, Na, Ca, although Cl-content is higher harmless to preparing magnesium hydroxide.
Embodiment 2
A kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge based on embodiment 1, including with
Lower step：
1. pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 8：1 adds pure water, opens electricity
Stove heats up, and adjusts pH to 7.0 with 0.4g/L dilute sulfuric acid aqueous solution while stirring（Temperature is finally stable at 80 DEG C, and pH=7.0 are
Measure at this temperature）, continue to stir 10min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；Will filter
80-90 DEG C of the use hot wash filtering means dehydration 1 time of slag 1, obtains filtrate 2.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.Magnesium liquid
Middle magnesium accounts for the ratio of magnesium in heavy metal sewage sludge, and to reach more than 99%, Ni content be 0.5mg/L, and Co, Mn, Zn are not detected, and Cu's contains
Measure as 0.1mg/L, Na, Ca, although Cl-content is higher harmless to preparing magnesium hydroxide.
2. add alkali lye magnesium sinking：Gained magnesium liquid 2000ml in step 1 is taken, using Japanese Shimadzu atomic absorption spectrophotometer
Magnesium ion concentration in AA-7000 measurement magnesium liquids, the 5mol/L NaOH aqueous solution, regulation pH value to 11.5, temperature 50 is slowly added dropwise
DEG C, 30min magnesium sinkings are fully reacted, i.e. magnesium ion combines to form magnesium hydrate precipitate with hydroxide ion, obtains milky turbid.
3. surface is modified：According to magnesium ion concentration in magnesium liquid volume in step 2 and magnesium liquid, magnesium ion is complete in calculation procedure 2
Magnesium hydroxide quality during bulk deposition, surface modifier stearic acid, institute's stiffened are added into step 2 products therefrom milky turbid
Resin acid quality accounts for the 2% of calculated magnesium hydroxide quality, and under the conditions of 60 DEG C, 70min is modified to magnesium hydroxide.
4. ageing：Step 3 products therefrom is aged 2h at 65 DEG C, turned down in ageing process mixing speed to 100 ~
150r/min。
5. hydro-thermal process：Step 4 products therefrom is dehydrated, until magnesium hydroxide quality accounts for step 4 products therefrom in product
Quality 30%, in the autoclave that gained turbid is added to inner liner polytetrafluoroethylene after concentration, volume is 1L, wherein autoclave is filled out
Degree of filling is 75%, is adjusted to temperature to 150 DEG C, hydro-thermal process 3h, obtains slag specimen.
It is dehydrated 6. step 5 gained slag specimen is filtered with vavuum pump, replaces washing with alcohol using hot water, dried at 100 DEG C
Flame Retardant Magnesium Hydroxide crude product is made after dry.
Flame Retardant Magnesium Hydroxide needs to meet at 3 points（Normative reference HGT 4531-2013 magnesium hydroxide for fire retardant）：Production
Product purity >=93.0%, specific surface area（BET）≤ 20.0m2/g, the microcosmic internal strain η≤3.0x10 in 101 faces-3；In addition also need to produce
Product magnesium hydroxide particle has well-regulated pattern, easily disperses when being easy to add as fire retardant.
The rate of recovery of magnesium in the present embodiment（Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge）Reachable 85.4%, product purity
Up to 97.3%（Measured by the U.S.'s graceful ICP-OES Inductively coupled plasma optical emission spectrometers of profit）, particle diameter distribution is at 0.8-10.8 μm
Between, average grain diameter D50：7.12μm（Measured by the laser particle analyzer of Malvern 2000）, specific surface area（BET）As a result it is 15.2m
²/g（NOVA full-automatic N2 adsorptions in the U.S. measure than Surface Tester）, Electronic Speculum（SEM）As a result it is hexagonal flake to show particle（By
FEI surface sweeping Electronic Speculum in the U.S. measures）, the microcosmic internal strain η in 101 faces：2.8x10-3（Full-automatic X-ray diffractometer D/max-IIIA is surveyed
）, measuring apparatus is not repeated below.
Embodiment 3
A kind of method that magnesium is reclaimed from heavy metal sewage sludge, comprises the following steps：
Pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 15：1 adds pure water, drives electric furnace
Heating, adjust pH to 8.0 with 0.6g/L dilute sulfuric acid aqueous solution while stirring（Temperature is finally stable at 85 DEG C, pH=8.0 be
Measured at a temperature of this）, continue to stir 15min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；By filter residue 1
With 80-90 DEG C of hot wash filtering means dehydration 3 times, filtrate 2 is obtained.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.In magnesium liquid
Magnesium accounts for the ratio of magnesium in heavy metal sewage sludge, and to reach more than 99%, Ni content be 0.6mg/L, and Co, Mn, Zn are not detected, Cu content
0.2mg/L, Na, Ca, although Cl-content is higher harmless to preparing magnesium hydroxide.
Embodiment 4
A kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge based on embodiment 3, including with
Lower step：
1. pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 15：1 adds pure water, opens electricity
Stove heats up, and adjusts pH to 8.0 with 0.6g/L dilute sulfuric acid aqueous solution while stirring（Temperature is finally stable at 85 DEG C, and pH=8.0 are
Measure at this temperature）, continue to stir 15min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；Will filter
80-90 DEG C of the use hot wash filtering means dehydration 3 times of slag 1, obtains filtrate 2.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.Magnesium liquid
Middle magnesium accounts for the ratio of magnesium in heavy metal sewage sludge, and to reach more than 99%, Ni content be 0.6mg/L, and Co, Mn, Zn are not detected, and Cu's contains
0.2mg/L, Na, Ca are measured, although Cl-content is higher harmless to preparing magnesium hydroxide.
2. add alkali lye magnesium sinking：Gained magnesium liquid 2000ml in step 1 is taken, using Japanese Shimadzu atomic absorption spectrophotometer
Magnesium ion concentration in AA-7000 measurement magnesium liquids, the 4mol/L NaOH aqueous solution, regulation pH value to 11.7, temperature 60 is slowly added dropwise
DEG C, 35min magnesium sinkings are fully reacted, i.e. magnesium ion combines to form magnesium hydrate precipitate with hydroxide ion, obtains milky turbid.
3. surface is modified：According to magnesium ion concentration in magnesium liquid volume in step 2 and magnesium liquid, magnesium ion is complete in calculation procedure 2
Magnesium hydroxide quality during bulk deposition, surface modifier stearic acid, institute's stiffened are added into step 2 products therefrom milky turbid
Resin acid quality accounts for the 4% of calculated magnesium hydroxide quality, and under the conditions of 70 DEG C, 90min is modified to magnesium hydroxide；
4. ageing：Step 3 products therefrom is aged 4h at 70 DEG C, turned down in ageing process mixing speed to 100 ~
150r/min, obtain milky turbid.
5. hydro-thermal process：Step 4 products therefrom is dehydrated, until magnesium hydroxide quality accounts for step 4 products therefrom in product
The 40% of quality, in the autoclave that gained turbid is added to inner liner polytetrafluoroethylene after concentration, volume is 1L, wherein autoclave
Compactedness is 75%, is adjusted to temperature to 180 DEG C, hydro-thermal process 5h, obtains slag specimen.
It is dehydrated 6. step 5 gained slag specimen is filtered with vavuum pump, replaces washing with alcohol using hot water, dried at 105 DEG C
Flame Retardant Magnesium Hydroxide crude product is made after dry.
The rate of recovery of magnesium in the present embodiment（Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge）86.2% can be reached, product
Purity can reach 97.5%, and particle diameter distribution is between 1.0-11.6 μm, 8.23 μm of average grain diameter, and BET results are 13.8m2/g,
SEM results show that particle is hexagonal flake, the microcosmic internal strain η in 101 faces：2.4x10-3。
Embodiment 5
A kind of method that magnesium is reclaimed from heavy metal sewage sludge, comprises the following steps：
Pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 10：1 adds pure water, drives electric furnace
Heating, adjust pH to 7.5 with 0.5g/L dilute sulfuric acid aqueous solution while stirring（Temperature is finally stable at 82 DEG C, pH=7.5 be
Measured at a temperature of this）, continue to stir 12min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；By filter residue 1
With 80-90 DEG C of hot wash filtering means dehydration 2 times, filtrate 2 is obtained.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.In magnesium liquid
Magnesium accounts for the ratio of magnesium in heavy metal sewage sludge, and to reach more than 99%, Ni content be 0.3mg/L, and Co, Mn, Zn are not detected, Cu content
0.1mg/L, Na, Ca, although Cl-content is higher harmless to preparing magnesium hydroxide.
Embodiment 6
A kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge based on embodiment 5, including with
Lower step：
1. pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 10：1 adds pure water, opens
Electric furnace heats up, and adjusts pH to 7.5 with 0.5g/L dilute sulfuric acid aqueous solution while stirring（Temperature is finally stable at 82 DEG C, pH=7.5
It is to measure at this temperature）, continue to stir 12min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter residue 1；Will
80-90 DEG C of the use hot wash filtering means dehydration 2 times of filter residue 1, obtains filtrate 2.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.Magnesium
Magnesium accounts for the ratio of magnesium in heavy metal sewage sludge to reach more than 99%, Ni content is 0.3mg/L in liquid, and Co, Mn, Zn are not detected, Cu's
Content 0.1mg/L, Na, Ca, although Cl-content is higher harmless to preparing magnesium hydroxide.
2. add alkali lye magnesium sinking：Gained magnesium liquid 2000ml in step 1 is taken, using Japanese Shimadzu atomic absorption spectrophotometer
Magnesium ion concentration in AA-7000 measurement magnesium liquids, the 4.5mol/L NaOH aqueous solution, regulation pH value to 12.0, temperature is slowly added dropwise
70 DEG C, 40min magnesium sinkings are fully reacted, i.e. magnesium ion combines to form magnesium hydrate precipitate with hydroxide ion, obtains milky white color cloud
Liquid.
3. surface is modified：According to magnesium ion concentration in magnesium liquid volume in step 2 and magnesium liquid, magnesium ion is complete in calculation procedure 2
Magnesium hydroxide quality during bulk deposition, surface modifier stearic acid, institute's stiffened are added into step 2 products therefrom milky turbid
Resin acid quality accounts for the 6% of calculated magnesium hydroxide quality, and under the conditions of 80 DEG C, 100min is modified to magnesium hydroxide；
4. ageing：Step 3 products therefrom is aged 6h at 80 DEG C, turned down in ageing process mixing speed to 100 ~
150r/min, obtain milky turbid.
5. hydro-thermal process：Step 4 products therefrom is dehydrated, until magnesium hydroxide quality accounts for step 4 products therefrom in product
The 35% of quality, in the autoclave that gained turbid is added to inner liner polytetrafluoroethylene after concentration, volume is 1L, wherein autoclave
Compactedness is 75%, is adjusted to temperature to 170 DEG C, hydro-thermal process 8h, obtains slag specimen.
It is dehydrated 6. step 5 gained slag specimen is filtered with vavuum pump, replaces washing with alcohol using hot water, dried at 102 DEG C
Flame Retardant Magnesium Hydroxide crude product is made after dry.
The rate of recovery of magnesium in the present embodiment（Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge）85.8% can be reached, product
Purity can reach 96.5%, and particle diameter distribution is between 1.2-11.9 μm, 7.82 μm of average grain diameter, and BET results are 14.6m2/g,
SEM results show that particle is hexagonal flake, the microcosmic internal strain η in 101 faces：2.7x10-3。
Claims (4)
1. a kind of reclaim the method that magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge, it is characterised in that including following step
Suddenly：
Step 1, pretreatment washing：By heavy metal sewage sludge according to pure water and sludge dry biomass than 8：1~15：1 adds pure water,
Heat while stirring, be heated to 80 ~ 85 DEG C and be incubated, 0.4g/L ~ 0.6g/L dilute sulfuric acid is added during heating stirring
Until it is 7.0 ~ 8.0 that pH is measured at 80 ~ 85 DEG C, continues 10 ~ 15min of stirring, obtain grain slag mixture and be dehydrated through plate compression, must be filtered
Liquid 1 and filter residue 1；Filter residue 1 is used into hot wash filtering means dehydration 1 ~ 3 time, obtains filtrate 2；Filtrate 1 is 2-in-1 with filtrate and gained filtrate is
For magnesium liquid；
Step 2, alkali lye magnesium sinking is added：Gained magnesium liquid is taken in the step 1 of certain volume, measures magnesium ion concentration in magnesium liquid, add 4 ~
The 5mol/L NaOH aqueous solution adjusts pH value to 11.5 ~ 12.0, and in temperature, 50 ~ 70 DEG C are fully reacted 30-40min magnesium sinkings, are obtained
Milky turbid；
Step 3, surface is modified：According to magnesium ion concentration in magnesium liquid volume in step 2 and magnesium liquid, magnesium ion is complete in calculation procedure 2
Magnesium hydroxide quality during bulk deposition, surface modifier stearic acid, institute's stiffened are added into step 2 products therefrom milky turbid
Resin acid quality accounts for the 2 ~ 6% of calculated magnesium hydroxide quality, under the conditions of 60 ~ 80 DEG C, to magnesium hydroxide be modified 70 ~
100min；
Step 4, it is aged：Step 3 products therefrom is aged 2 ~ 6h at 65 ~ 80 DEG C, mixing speed is turned down to 100 in ageing process
~150r/min；
Step 5, hydro-thermal process：Step 4 products therefrom is dehydrated, until magnesium hydroxide quality accounts for step 4 products therefrom in product
The 30 ~ 40% of quality, temperature is adjusted in autoclave to 150 ~ 180 DEG C, 3 ~ 8h of hydro-thermal process, obtains slag specimen；
Step 6, step 5 gained slag specimen filtered into dehydration with vavuum pump, replace washing with alcohol using hot water, at 100-105 DEG C
Flame Retardant Magnesium Hydroxide crude product is made after lower drying.
2. a kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge according to claim 1, its
It is characterised by：
In step 1, by heavy metal sewage sludge according to pure water and sludge dry biomass than 15：1 adds pure water, heats while stirring,
It is heated to 85 DEG C and is incubated, addition 0.6g/L dilute sulfuric acid is 8.0 up to measuring pH at 85 DEG C during heating stirring, is continued
15min is stirred, grain slag mixture is obtained and is dehydrated through plate compression, obtain filtrate 1 and filter residue 1；By the hot wash filtering means dehydration of filter residue 1
3 times, obtain filtrate 2；Filtrate 1 is 2-in-1 with filtrate and gained filtrate is magnesium liquid.
3. a kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge according to claim 1, its
It is characterised by：
In step 2, magnesium ion concentration is measured by Japanese Shimadzu atomic absorption spectrophotometer AA-7000 in the magnesium liquid.
4. a kind of method that recovery magnesium prepares flame retardant of magnesium hydroxide from heavy metal sewage sludge according to claim 1, its
It is characterised by：
In step 5, plate compression or vavuum pump can be used to filter dehydration.
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