CN106698484B - The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge - Google Patents

The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge Download PDF

Info

Publication number
CN106698484B
CN106698484B CN201611218278.1A CN201611218278A CN106698484B CN 106698484 B CN106698484 B CN 106698484B CN 201611218278 A CN201611218278 A CN 201611218278A CN 106698484 B CN106698484 B CN 106698484B
Authority
CN
China
Prior art keywords
magnesium
aluminium
liquid
added
extraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611218278.1A
Other languages
Chinese (zh)
Other versions
CN106698484A (en
Inventor
许开华
张云河
盛广宏
郭苗苗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jingmen GEM New Material Co Ltd
Original Assignee
Jingmen GEM New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jingmen GEM New Material Co Ltd filed Critical Jingmen GEM New Material Co Ltd
Priority to CN201611218278.1A priority Critical patent/CN106698484B/en
Publication of CN106698484A publication Critical patent/CN106698484A/en
Application granted granted Critical
Publication of CN106698484B publication Critical patent/CN106698484B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00Compounds of magnesium
    • C01F5/02Magnesia
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00Compounds of magnesium
    • C01F5/14Magnesium hydroxide
    • C01F5/22Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/0693Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00Fireproofing materials
    • C09K21/02Inorganic materials
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/20Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/22Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/32Thermal properties
    • C01P2006/37Stability against thermal decomposition
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

The invention belongs to resource circulation utilization field, is related to one kind recovery extraction magnesium from heavy metal sewage sludge, refines, aluminium salt is reclaimed from copper water-supply pipe, then mixed precipitation, ageing, the method for preparing the high-purity composite flame-retardant agent of magnesium hydroxide, aluminium hydroxide.The present invention effectively realizes the synthetical recovery of valuable metal magnesium in heavy metal sewage sludge, while ensures the high-recovery of noble metal cobalt nickel.The rate of recovery of aluminium can reach more than 85% in copper water-supply pipe.The primary recovery of magnesium reaches more than 84.8%;Product purity is greatly improved to >=99.3%, and heat decomposition temperature reaches 365 DEG C.Have well-regulated pattern, it is easily scattered when being added as fire retardant.

Description

The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge
Technical field
The invention belongs to resource circulation utilization field, reclaims extraction from heavy metal sewage sludge more specifically to one kind Magnesium, reclaims aluminium salt from copper water-supply pipe, is then mixed with high purity magnesium hydroxide, the method for aluminium hydroxide composite anti-flaming agent.
Background technology
The world today, inorganic combustion inhibitor are widely studied and answered because of high-performance such as its is nontoxic, suppression cigarette, resistance combustion temperature height With especially aluminium hydroxide and magnesium hydroxide.The shortcomings that aluminium hydroxide occupies the market of maximum at present, but its resistance combustion temperature is relatively low Increasingly show, and the raw material sources for industrially producing magnesium hydroxide are extensive, but the easy etching apparatus of bittern is thus to equipment requirement It is higher, the calcination process high energy consumption of magnesite and dolomite, therefore conventional method prepare flame retardant of magnesium hydroxide exist equipment will Ask high, the shortcomings that high energy consumption.Single use magnesium hydroxide the high polymer poor compatibility with being filled, is not easy as fire retardant Disperse in filler, it is necessary to which higher loading just has preferable effect.The machine of high polymer material is influenceed while loading is high Tool and mechanical property.Typically by two or more inorganic combustion inhibitor compounding uses in actual use, though improve to a certain extent The performance that fire retardant is used alone, but different flame retardant machinery is mixed scattered inequality, it is difficult to play fire-retardant Optimum synergistic effect between agent, it is difficult to the fire retardant of suitable heat decomposition temperature is selected according to high polymer material.Therefore compound resistance The research and development of agent are fired into trend of the times.
The magnesium that the lateritic nickel ore used in extraction cobalt nickel industry contains mass fraction 20% or so, extracting metals cobalt nickel, phase The substantial amounts of sludge of association, magnesium are enriched in sludge and not utilized rationally in corresponding waste water control.It is suitable due to lacking To the processing method of magnesium resource, serious environmental pressure is caused with the wasting of resources.And aluminium polychloride is widely used as wadding The waterworks of solidifying agent containing substantial amounts of bauxite resource in copper water-supply pipe caused by sewage treatment plant with failing to obtain rational resource Change and utilize.Still largely handled with landfill, ocean dumping, the mode of agricultural application, human activity, secondary pollution etc. be present The limitation of aspect.
To sum up, in the sewage disposal after being extracted at present to lateritic nickel ore, caused heavy metal sewage sludge is rich in substantial amounts of magnesium.It is dirty Mud is after leaching process, and substantial amounts of magnesium is difficult to separate in leachate.Cobalt nickel manganese when leachate is used as ternary battery raw material It is low etc. purity.Prepare magnesium-aluminum composite flame retardant at this stage simultaneously and magnesium resource wide material sources but equipment requirement height, high energy consumption be present The problem of.The drawbacks of bauxite resource underutilization in copper water-supply pipe be present.
The content of the invention
Technology to be solved by this invention be problem be to provide one kind from different sludge reclaim magnalium prepare it is high-purity compound The method of fire retardant.
The inventive method from cobalt nickel produce when heavy metal sewage sludge caused by sewage disposal in reclaim magnesium, not only reduce a huge sum of money Belong to influence of the magnesium to cobalt nickel manganese purity in leachate when sludge recycles, also reclaimed magnesium, produced the Mg-Al composite of high-purity Fire retardant.
Technical scheme is as follows:
1)Heavy metal sewage sludge pre-processes:Lateritic nickel ore is extracted in the sewage disposal after cobalt nickel, produce heavy metal sewage sludge;Will Heavy metal sewage sludge is according to pure water and sludge dry biomass than 8:1~15:1 adds pure water, stirring, is heated to 80 ~ 85 DEG C and protects Temperature, it is 7.0 ~ 8.0 to add strong acid up to measuring pH at 80 ~ 85 DEG C during heating stirring, continues 10 ~ 15min of stirring, obtains water Slag mixture, is dehydrated through plate compression, obtains filtrate and filter residue;By filter residue hot wash filtering means dehydration 1 ~ 3 time, cleaning solution is obtained; Filtrate merges Ji Wei magnesium liquid with cleaning solution;
2)Magnesium liquid deliming:Magnesium liquid strong acid for adjusting pH to 2 ~ 3, the extraction of di (isooctyl) phosphate extractant is added, carries out 2 ~ 4 grades Counter-current extraction, extraction temperature are 20 ~ 30 DEG C, obtain raffinate 1;
3)Magnesium liquid removes silicon:Raffinate 1 is adjusted into pH value to 5.0 ~ 6.0 with highly basic, raffinate 2 is obtained, adds into raffinate 2 Aluminium polychloride and polyacrylamide, according to addition 5 ~ 15mg aluminium polychlorides and 0.1 ~ 0.5mg polypropylene in every liter of raffinate 2 The ratio of acid amides adds, and stirs 50 ~ 80min, filters to obtain filtrate and filter residue with vavuum pump, this filtrate is refined magnesium liquid;
4)Copper water-supply pipe pre-processes:To be the copper water-supply pipe of flocculant in 450 ~ 500 DEG C of calcination process using aluminium polychloride The turbid that 150 ~ 200g/L is made in pure water is added afterwards, stirring, is heated to 90 ~ 95 DEG C and is incubated, added during heating stirring Strong acid is 2.0 ~ 2.5 up to measuring pH at 90 ~ 95 DEG C, continues 10 ~ 15min of stirring, obtains grain slag mixture and be dehydrated through plate compression, Obtain filtrate and filter residue;By filter residue hot wash filtering means dehydration 1 ~ 3 time, cleaning solution is obtained;Filtrate merges gained with cleaning solution Aluminium liquid;
5)Add alkali lye magnesium sinking aluminium:Take step 3)Middle gained refines magnesium liquid, measures magnesium ion concentration in magnesium liquid, while take step 4)The aluminium liquid of gained, measure aluminium ion concentration;According to Mg and Al mol ratio 5:1~1:1 takes magnesium liquid to prepare mixed liquor with aluminium liquid; Strong base solution is added dropwise into mixed liquor, until mixed liquor pH value is 11.5~12.0, stirring, reacts 30-40min at 30 ~ 50 DEG C Magnalium is precipitated, obtains milky turbid;
6)Surface is modified:Calculation procedure 5)The magnesium hydroxide of middle sedimentation and the quality of aluminium hydroxide, to step 5)Gained breast Stearic acid is added in white turbid, added stearic acid quality accounts for the 2 ~ 6% of the quality sum of magnesium hydroxide and aluminium hydroxide, 60 Under the conditions of ~ 80 DEG C, to 70 ~ 100min of product modification;
7)Ageing:By step 6)Products therefrom is aged 2 ~ 6h at 65 ~ 80 DEG C;
8)Hydro-thermal process:By step 7)Products therefrom is dehydrated, until the quality sum of magnesium hydroxide and aluminium hydroxide accounts for always The 30 ~ 40% of quality, it is placed in autoclave and adjusts temperature to 150 ~ 180 DEG C, 3 ~ 8h of hydro-thermal process, obtain head product;
9)By step 8)Gained head product is dehydrated, and is replaced washing with industrial alcohol using hot water, is dried at 100-105 DEG C High-purity composite flame-retardant agent is made after grinding.
In such scheme, step 1)In, heavy metal sewage sludge adds pure water, in heating stirring, add 0.5mol/L ~ 1.0mol/L dilute sulfuric acid is until measure pH at 80 ~ 85 DEG C as 7.0 ~ 8.0.
Step 2)In, the pH to 2 ~ 3 of magnesium liquid is adjusted with 1 ~ 5mol/L hydrochloric acid, adds the extraction of di (isooctyl) phosphate extractant, Volume ratio=1/1 ~ 1/2 of organic phase and aqueous phase during extraction.
Step 3)In, raffinate 1 is adjusted into pH value to 5.0 ~ 6.0 with 2 ~ 5mol/L sodium hydrate aqueous solution.
Step 4)In, the turbid after copper water-supply pipe roasting plus water adds 0.5mol/L ~ 1.0mol/L in heating stirring Dilute sulfuric acid until measuring pH at 90 ~ 95 DEG C as 2.0 ~ 2.5.
Step 5)In, into mixed liquor be added dropwise 4 ~ 5mol/L NaOH aqueous solution, until mixed liquor pH value be 11.5~ 12.0。
Step 7)In, ageing process mixing speed is 100 ~ 150r/min.
The beneficial effects of the present invention are:
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%;The synthetical recovery of valuable metal magnesium in heavy metal sewage sludge is effectively realized, Avoid the deficiency that magnesium existing for existing recovery process is circulated in system, do not opened a way properly.Meanwhile in filtrate Ni content Do not detected less than 0.6mg/L, Co, Mn, Zn, Cu content is less than 0.2mg/L, so as to ensure that noble metal cobalt in the filter residue of recovery The high-recovery of nickel.Copper water-supply pipe(Using aluminium polychloride as flocculant)After pretreatment, the rate of recovery of aluminium can be with sludge Reach more than 85%, realize the recycling of bauxite resource in sludge.
2)The high purity magnesium hydroxide being prepared and aluminium hydroxide composite anti-flaming agent crude product:The once recovery of magnesium in product Rate(Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge)Reach more than 84.8%, reach as high as 85.7%;Product(Magnesium hydroxide+hydrogen Aluminum oxide)Purity is greatly improved to >=99.3%, specific surface area(BET)>=55.7m2/g, SEM result show magnesium hydroxide particle For hexagonal flake, heat decomposition temperature reaches 365 DEG C.Have well-regulated pattern, it is easily scattered when being added as fire retardant.
Embodiment
Embodiment 1
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 0.5mol/L dilute sulfuric acid aqueous solution while stirring(Temperature is finally stable at 80 DEG C, pH=7.0 It is to 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 80-90 DEG C of the use hot wash filtering means dehydration 1 time 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 0.5mg/L in liquid, and Co, Mn, Zn are not detected, Cu's Content is 0.1mg/L, Na, Ca, although Cl-content is higher harmless to preparing product.
2. magnesium liquid deliming:
With 1mol/L salt acid for adjusting pH to 2, the extraction of di (isooctyl) phosphate extractant is added, compare O/A during extraction(Organic phase With the volume ratio of aqueous phase)=1/1,2 stage countercurrent extractions are carried out, extraction temperature is 20 DEG C, obtains raffinate 1.Wherein, di(2-ethylhexyl)phosphate is different The preparation method of monooctyl ester extractant is:Volume ratio 20% is diluted to sulfonated kerosene, and with 20%Wt NaOH aqueous solution saponification, extremely Saponification rate reaches 30%.Extraction phase is washed 2 times with the watery hydrochloric acid of pH=3.5, then carries out 1 grade of back extraction, back extraction with 0.5mol/L hydrochloric acid When compare O/A=2/1, back extraction temperature is 20 DEG C, and main purpose enables extractant to reuse.
3. magnesium liquid removes silicon:Raffinate 1 is adjusted into pH value to 5.0 with 2mol/L sodium hydrate aqueous solution, obtains raffinate 2,;Add aluminium polychloride and polyacrylamide into raffinate 2, according to addition 5 ~ 15mg aluminium polychlorides in every liter of raffinate 2 Added with the ratio of 0.1 ~ 0.5mg polyacrylamides;By temperature control at 50 °C, 50min is stirred, filtrate is filtered to obtain with vavuum pump With a small amount of filter residue, this filtrate is refined magnesium liquid;Filter residue 3-4 rear discharge of hot wash.
4. copper water-supply pipe pre-processes:By copper water-supply pipe(Using aluminium polychloride as flocculant)Add after 450 DEG C of calcination process Enter the turbid that 150g/L is made in pure water, heat while stirring, be heated to 90 DEG C and be incubated, added during heating stirring 0.5mol/L dilute sulfuric acid is 2.0 up to measuring pH at 90 DEG C, continues to stir 10min, obtains grain slag mixture and taken off through plate compression Water, obtain filtrate 1 and filter residue 1;Filter residue 1 is used into hot wash filtering means dehydration 1 time, obtains filtrate 2;Filtrate 1 is 2-in-1 with filtrate and gained is filtered Liquid is aluminium liquid(Liquor B).
5. add alkali lye magnesium sinking aluminium:The refined magnesium liquid 2000ml of gained in step 3 is taken, using Japanese Shimadzu atomic absorption spectrophotometry light Magnesium ion concentration in degree meter AA-7000 measurement magnesium liquids, adds magnalium amount of substance than 5:1 aluminum sulfate dissolving prepares mixed liquor, to The 5mol/L NaOH aqueous solution is slowly added dropwise in mixed liquor, for regulation pH value to 11.5, temperature 50 C fully reacts 30min magnesium sinkings Aluminium, obtain milky turbid;
6. surface is modified:According to magnesium aluminium ion concentration in magnesium liquid volume in step 5 and magnesium liquid, in calculation procedure 5 magnalium from Product quality during sub sedimentation completely, surface modifier stearic acid, institute's stiffened are added into step 5 products therefrom milky turbid Resin acid quality accounts for the 2% of calculated magnesium hydroxide and aluminium hydroxide quality, under the conditions of 60 DEG C, to mixture modification 70min.
7. ageing:Step 6 products therefrom is aged 2h at 65 DEG C, mixing speed is turned down in ageing process to 100r/ min。
8. hydro-thermal process:By step 7 products therefrom be dehydrated, until product in magnesium hydroxide accounted for aluminium hydroxide quality it is turbid The 30% of liquid quality, in the autoclave that gained turbid is added to inner liner polytetrafluoroethylene after concentration, volume is 1L, wherein autoclave Compactedness be 75%, be adjusted to temperature to 150 DEG C, hydro-thermal process 3h, obtain head product.
9. step 8 gained head product is dehydrated, replace washing with alcohol using hot water, made at 100 DEG C after drying grinding Obtain high purity magnesium hydroxide and aluminium hydroxide composite anti-flaming agent product.
The rate of recovery of magnesium in the present embodiment(Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge)Reachable 85.2%, product purity Up to 99.5%(Measured by the U.S.'s graceful ICP-OES Inductively coupled plasma optical emission spectrometers of profit), particle diameter distribution is at 0.9-4.7 μm Between, average grain diameter D50:2.01μm(Measured by the laser particle analyzer of Malvern 2000), specific surface area(BET)As a result it is 55.7m 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), heat decomposition temperature reaches 358 DEG C(Beijing for a long time scientific instrument factory thermogravimetric analyzer).It is right below Measuring apparatus does not repeat.
Embodiment 2
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 1.0mol/L dilute sulfuric acid aqueous solution while stirring(Temperature is finally stable at 85 DEG C, pH=8.0 It is to 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 80-90 DEG C of the use hot wash filtering means dehydration 3 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 0.6mg/L in liquid, and Co, Mn, Zn are not detected, Cu's Content 0.2mg/L, Na, Ca, although Cl-content is higher to preparing product harmless.
2. magnesium liquid deliming:With 5mol/L salt acid for adjusting pH to 3, the extraction of di (isooctyl) phosphate extractant is added, extracts phase Compare O/A(The volume ratio of organic phase and aqueous phase)=1/2,4 stage countercurrent extractions are carried out, extraction temperature is 30 DEG C, obtains raffinate 1.Its In, the preparation method of di (isooctyl) phosphate extractant is:Volume ratio 30% is diluted to sulfonated kerosene, and with 30%Wt NaOH water Solution saponification, reach 40% to saponification rate.Extraction phase is washed 2 times with the watery hydrochloric acid of pH=4.5, then carries out 1 with 2.0mol/L hydrochloric acid Level back extraction, compare O/A=1/1 during back extraction, back extraction temperature is 30 DEG C, and main purpose enables extractant to reuse.
3. magnesium liquid removes silicon:Raffinate 1 is adjusted into pH value to 6.0 with 5mol/L sodium hydrate aqueous solution, obtains raffinate 2,;Into raffinate 2 plus aluminium polychloride and polyacrylamide, according to added in every liter of raffinate 2 15mg aluminium polychlorides and The ratio of 0.5mg polyacrylamides adds;By temperature control at 70 °C, 80min is stirred, filtrate and a small amount of is filtered to obtain with vavuum pump Filter residue, this filtrate are refined magnesium liquid;Filter residue 3-4 rear discharge of hot wash.
4. copper water-supply pipe pre-processes:By copper water-supply pipe(Using aluminium polychloride as flocculant)Add after 500 DEG C of calcination process Enter the turbid that 200g/L is made in pure water, heat while stirring, be heated to 95 DEG C and be incubated, added during heating stirring 1.0mol/L dilute sulfuric acid is 2.5 up to measuring pH at 95 DEG C, continues to stir 15min, obtains grain slag mixture and taken off through plate compression Water, 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 is filtered Liquid is aluminium liquid(Liquor B).
5. add alkali lye magnesium sinking aluminium:The exquisite magnesium liquid 2000ml of gained in step 3 is taken, using Japanese Shimadzu atomic absorption spectrophotometry Magnesium ion concentration in photometer AA-7000 measurement magnesium liquids, while measure aluminium ion concentration in aluminium liquid.Suitable body is added into magnesium liquid Long-pending aluminium liquid, make magnalium amount of substance than 3:1 prepares mixed liquor, and the 4mol/L NaOH aqueous solution is slowly added dropwise into mixed liquor, adjusts PH value is saved to 11.7, temperature 60 C, 35min magnesium sinking aluminium is fully reacted, obtains milky turbid.
6. surface is modified:According to magnesium ion concentration in magnesium liquid volume in step 5 and magnesium liquid, magnesium aluminium ion in calculation procedure 5 The quality of magnesium hydroxide and aluminium hydroxide when settling completely, surface modification is added into step 5 products therefrom milky turbid Agent stearic acid, added stearic acid quality accounts for the 4% of the quality of calculated magnesium hydroxide and aluminium hydroxide, under the conditions of 70 DEG C, To mixture modification 90min;
7. ageing:Step 6 products therefrom is aged 4h at 70 DEG C, mixing speed is turned down in ageing process to 150r/ Min, obtain milky turbid.
8. hydro-thermal process:Step 7 products therefrom is dehydrated, until the quality of magnesium hydroxide and aluminium hydroxide accounts in product The 40% of turbid quality, after concentration gained turbid be added to inner liner polytetrafluoroethylene, volume be 1L autoclave in, its mesohigh The compactedness of kettle is 75%, is adjusted to temperature to 180 DEG C, hydro-thermal process 5h, obtains head product.
9. step 8 gained head product is dehydrated, replace washing with alcohol using hot water, made at 105 DEG C after drying grinding Obtain high purity magnesium hydroxide and aluminium hydroxide composite anti-flaming agent product.
The rate of recovery of magnesium in the present embodiment(Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge)85.7% can be reached, product Purity can reach 99.4%, and particle diameter distribution is between 1.0-5.2 μm, 2.14 μm of average grain diameter, and BET results are 56.4m2/g, SEM results show that particle is hexagonal flake, and heat decomposition temperature reaches 361 DEG C.
Embodiment 3
1. heavy metal sewage sludge pre-processes:By heavy metal sewage sludge according to pure water and sludge dry biomass than 10:1 addition is pure Water, electric furnace heating is opened, adjust pH to 7.5 with 0.7mol/L dilute sulfuric acid aqueous solution while stirring(Temperature is finally stable at 82 DEG C, PH=7.5 are to measure at this temperature), continue to stir 12min, obtain grain slag mixture and be dehydrated through plate compression, obtain filtrate 1 and filter Slag 1;By 80-90 DEG C of the use hot wash filtering means dehydration 2 times of filter residue 1, filtrate 2 is obtained.Filtrate 1 is 2-in-1 with filtrate and gained filtrate is Magnesium liquid.Magnesium accounts for the ratio of magnesium in heavy metal sewage sludge to reach more than 99%, Ni content is 0.3mg/L in magnesium liquid, and Co, Mn, Zn are not examined Go out, Cu content 0.1mg/L, Na, Ca, although Cl-content is higher harmless to preparing product.
2. magnesium liquid deliming:With 3mol/L salt acid for adjusting pH to 2.5, the extraction of di (isooctyl) phosphate extractant is added, during extraction Compared to O/A(The volume ratio of organic phase and aqueous phase)=1/1.5,3 stage countercurrent extractions are carried out, extraction temperature is 25 DEG C, obtains raffinate 1.Wherein, the preparation method of di (isooctyl) phosphate extractant is:Volume ratio 25% is diluted to sulfonated kerosene, and with 25%Wt's NaOH aqueous solution saponification, reaches 35% to saponification rate.Extraction phase is washed 2 times with the watery hydrochloric acid of pH=4.0, then with 1.0mol/L hydrochloric acid 1 grade of back extraction is carried out, compare O/A=1.5/1 during back extraction, back extraction temperature is 25 DEG C, and it is sharp that main purpose enables extractant to repeat With.
3. magnesium liquid removes silicon:Raffinate 1 is adjusted into pH value to 5.5 with 3mol/L sodium hydrate aqueous solution, obtains raffinate 2;Into raffinate 2 plus aluminium polychloride and polyacrylamide, according to added in every liter of raffinate 2 10mg aluminium polychlorides and The ratio of 0.2mg polyacrylamides adds;By temperature control at 60 °C, 60min is stirred, filtrate and a small amount of is filtered to obtain with vavuum pump Filter residue, this filtrate are refined magnesium liquid;Filter residue 3-4 rear discharge of hot wash.
4. copper water-supply pipe pre-processes:By copper water-supply pipe(Using aluminium polychloride as flocculant)Add after 480 DEG C of calcination process Enter the turbid that 180g/L is made in pure water, heat while stirring, be heated to 93 DEG C and be incubated, added during heating stirring 0.7mol/L dilute sulfuric acid is 2.3 up to measuring pH at 93 DEG C, continues to stir 13min, obtains grain slag mixture and taken off through plate compression Water, obtain filtrate 1 and filter residue 1;Filter residue 1 is used into hot wash filtering means dehydration 2 times, obtains filtrate 2;Filtrate 1 is 2-in-1 with filtrate and gained is filtered Liquid is aluminium liquid(Liquor B).
5. add alkali lye magnesium sinking aluminium:The refined magnesium liquid 2000ml of gained in step 3 is taken, using Japanese Shimadzu atomic absorption spectrophotometry Magnesium ion concentration in photometer AA-7000 measurement magnesium liquids, while aluminium ion concentration in aluminium liquid is measured, magnalium thing is added into magnesium liquid Mass ratio 1:1 aluminium liquid prepares mixed liquor, is slowly added dropwise the 4.5mol/L NaOH aqueous solution into mixed liquor, regulation pH value to 12.0, temperature 70 C, 40min magnesium sinking aluminium is fully reacted, obtains milky turbid.
6. surface is modified:According to magnesium ion concentration in magnesium liquid volume in step 5 and magnesium liquid, magnesium ion is complete in calculation procedure 5 The quality of magnesium hydroxide and aluminium hydroxide during bulk deposition, surface modifier is added into step 5 products therefrom milky turbid Stearic acid, added stearic acid quality accounts for the 6% of the quality of calculated magnesium hydroxide and aluminium hydroxide, right under the conditions of 80 DEG C Product modification 100min;
7. ageing:Step 6 products therefrom is aged 6h at 80 DEG C, mixing speed is turned down in ageing process to 130r/ Min, obtain milky turbid.
8. hydro-thermal process:Step 7 products therefrom is dehydrated, until the quality of magnesium hydroxide and aluminium hydroxide accounts in product The 35% of turbid quality, after concentration gained turbid be added to inner liner polytetrafluoroethylene, volume be 1L autoclave in, its mesohigh The compactedness of kettle is 75%, is adjusted to temperature to 170 DEG C, hydro-thermal process 8h, obtains head product.
9. step 8 gained head product is dehydrated, replace washing with alcohol using hot water, made at 102 DEG C after drying grinding Obtain high purity magnesium hydroxide and aluminium hydroxide composite anti-flaming agent product.
The rate of recovery of magnesium in the present embodiment(Product magnesium accounts for the ratio of magnesium in heavy metal sewage sludge)85.5% can be reached, product Purity can reach 99.7%, and particle diameter distribution is between 1.1-5.7 μm, 2.25 μm of average grain diameter, and BET results are 57.4m2/g, SEM results show that particle is hexagonal flake, and heat decomposition temperature reaches 361 DEG C.

Claims (7)

1. a kind of reclaim the method that magnalium prepares composite flame-retardant agent from sludge, it is characterised in that comprises the following steps:
1)Heavy metal sewage sludge pre-processes:Lateritic nickel ore is extracted in the sewage disposal after cobalt nickel, produce heavy metal sewage sludge;Will a huge sum of money Belong to sludge according to pure water and sludge dry biomass than 8:1~15:1 adds pure water, stirring, is heated to 80 ~ 85 DEG C and is incubated, It is 7.0 ~ 8.0 that strong acid is added during heating stirring up to measuring pH at 80 ~ 85 DEG C, continues 10 ~ 15min of stirring, obtains grain slag and mix Compound, it is dehydrated through plate compression, obtains filtrate and filter residue;By filter residue hot wash filtering means dehydration 1 ~ 3 time, cleaning solution is obtained;Filtrate Merge with cleaning solution Ji Wei magnesium liquid;
2)Magnesium liquid deliming:Magnesium liquid strong acid for adjusting pH to 2 ~ 3, the extraction of di (isooctyl) phosphate extractant is added, carries out 2 ~ 4 stage countercurrents Extraction, extraction temperature are 20 ~ 30 DEG C, and the volume ratio of organic phase and aqueous phase is 1 during extraction:1~1:2, raffinate 1 is obtained, is extracted Mutually it is stripped with hydrochloric acid, extraction temperature is 20 ~ 30 DEG C, and the volume ratio of organic phase and aqueous phase is 1 during extraction:1~2:1;
3)Magnesium liquid removes silicon:Raffinate 1 is adjusted into pH value to 5.0 ~ 6.0 with highly basic, obtains raffinate 2, addition polymerization closes into raffinate 2 Aluminium chloride and polyacrylamide, according to addition 5 ~ 15mg aluminium polychlorides and 0.1 ~ 0.5mg polyacrylamides in every liter of raffinate 2 Ratio add, control 50 ~ 70 DEG C of temperature, stir 50 ~ 80min, filter to obtain filtrate and filter residue with vavuum pump, this filtrate is refined Magnesium liquid;
4)Copper water-supply pipe pre-processes:By using aluminium polychloride as the copper water-supply pipe of flocculant after 450 ~ 500 DEG C of calcination process plus Enter the turbid that 150 ~ 200g/L is made in pure water, stir, be heated to 90 ~ 95 DEG C and be incubated, strong acid is added during heating stirring Until it is 2.0 ~ 2.5 that pH is measured at 90 ~ 95 DEG C, continues 10 ~ 15min of stirring, obtain grain slag mixture and be dehydrated through plate compression, must be filtered Liquid and filter residue;By filter residue hot wash filtering means dehydration 1 ~ 3 time, cleaning solution is obtained;It is aluminium liquid that filtrate, which merges gained with cleaning solution,;
5)Add alkali lye magnesium sinking aluminium:Take step 3)Middle gained refines magnesium liquid, measures magnesium ion concentration in magnesium liquid, while take step 4)Institute The aluminium liquid obtained, measure aluminium ion concentration;According to Mg and Al mol ratio 5:1~1:1 takes magnesium liquid to prepare mixed liquor with aluminium liquid;It is added dropwise Strong base solution is into mixed liquor, until mixed liquor pH value is 11.5~12.0, stirring, 30-40min precipitations is reacted at 30 ~ 50 DEG C Magnalium, obtain milky turbid;
6)Surface is modified:Calculation procedure 5)The magnesium hydroxide of middle sedimentation and the quality of aluminium hydroxide, to step 5)Gained milky Stearic acid is added in turbid, added stearic acid quality accounts for the 2 ~ 6% of the quality sum of magnesium hydroxide and aluminium hydroxide, 60 ~ 80 Under the conditions of DEG C, to 70 ~ 100min of product modification;
7)Ageing:By step 6)Products therefrom is aged 2 ~ 6h at 65 ~ 80 DEG C;
8)Hydro-thermal process:By step 7)Products therefrom is dehydrated, until the quality sum of magnesium hydroxide and aluminium hydroxide accounts for gross mass 30 ~ 40%, be placed in autoclave adjust temperature to 150 ~ 180 DEG C, 3 ~ 8h of hydro-thermal process, obtain head product;
9)By step 8)Gained head product is dehydrated, and replaces washing with industrial alcohol using hot water, and grinding is dried at 100-105 DEG C High-purity composite flame-retardant agent is made afterwards.
2. according to the method for claim 1, it is characterised in that step 1)In, heavy metal sewage sludge adds pure water, heating stirring In, 0.5mol/L ~ 1.0mol/L dilute sulfuric acid is added until measuring pH at 80 ~ 85 DEG C as 7.0 ~ 8.0.
3. according to the method for claim 1, it is characterised in that step 4)In, the turbid after copper water-supply pipe roasting plus water exists In heating stirring, 0.5mol/L ~ 1.0mol/L dilute sulfuric acid is added until measuring pH at 90 ~ 95 DEG C as 2.0 ~ 2.5.
4. according to the method for claim 1, it is characterised in that step 2)In, with the pH of 1 ~ 5mol/L hydrochloric acid regulation magnesium liquid To 2 ~ 3, the extraction of di (isooctyl) phosphate extractant is added, volume ratio=1/1 ~ 1/2 of organic phase and aqueous phase during extraction.
5. according to the method for claim 1, it is characterised in that step 3)In, the hydroxide by raffinate 1 with 2 ~ 5mol/L Sodium water solution adjusts pH value to 5.0 ~ 6.0.
6. according to the method for claim 1, it is characterised in that step 5)In, 4 ~ 5mol/L NaOH are added dropwise into mixed liquor The aqueous solution, until mixed liquor pH value is 11.5~12.0.
7. according to the method for claim 1, it is characterised in that step 7)In, ageing process mixing speed is 100 ~ 150r/ min。
CN201611218278.1A 2016-12-26 2016-12-26 The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge Active CN106698484B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611218278.1A CN106698484B (en) 2016-12-26 2016-12-26 The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611218278.1A CN106698484B (en) 2016-12-26 2016-12-26 The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge

Publications (2)

Publication Number Publication Date
CN106698484A CN106698484A (en) 2017-05-24
CN106698484B true CN106698484B (en) 2017-11-10

Family

ID=58902272

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611218278.1A Active CN106698484B (en) 2016-12-26 2016-12-26 The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge

Country Status (1)

Country Link
CN (1) CN106698484B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1915828A (en) * 2006-09-11 2007-02-21 中国铝业股份有限公司 Method for preparing superfine aluminium hydroxide in flame retardant grade with high initial dehydration temperature
CN101186320A (en) * 2007-12-17 2008-05-28 中国铝业股份有限公司 Method for preparing aluminum hydroxide and magnesium hydroxide composite fire retardant
TW200951208A (en) * 2008-04-16 2009-12-16 Hi Van Corp Composite material for imparting flame retardancy
CN104445299A (en) * 2014-10-30 2015-03-25 瓮福(集团)有限责任公司 Method for preparing high-purity magnesium hydroxide
CN104593014A (en) * 2013-10-30 2015-05-06 青岛旺裕橡胶制品有限公司 Preparation method of aluminium-based composite flame retardant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1915828A (en) * 2006-09-11 2007-02-21 中国铝业股份有限公司 Method for preparing superfine aluminium hydroxide in flame retardant grade with high initial dehydration temperature
CN101186320A (en) * 2007-12-17 2008-05-28 中国铝业股份有限公司 Method for preparing aluminum hydroxide and magnesium hydroxide composite fire retardant
TW200951208A (en) * 2008-04-16 2009-12-16 Hi Van Corp Composite material for imparting flame retardancy
CN104593014A (en) * 2013-10-30 2015-05-06 青岛旺裕橡胶制品有限公司 Preparation method of aluminium-based composite flame retardant
CN104445299A (en) * 2014-10-30 2015-03-25 瓮福(集团)有限责任公司 Method for preparing high-purity magnesium hydroxide

Also Published As

Publication number Publication date
CN106698484A (en) 2017-05-24

Similar Documents

Publication Publication Date Title
CN106830030B (en) A kind of method using the safe and efficient production sandy alumina of aluminium ash
CN103011203B (en) Method for treatment of chlorinated waste molten salt generated in TiCl4 production process
CN107434315B (en) A kind of method of leaded zinc wirerope sludge and leaded waste hydrochloric acid integrated treatment
CN106745137A (en) A kind of method for producing ice crystal with cell cathode carbon block alkaline leaching liquid
CN107915242A (en) Asbestos tailings prepare method of magnesium oxide
Zhao et al. Precipitation of vanadium from Bayer liquor with lime
CN105238932B (en) The separation and recovery method of cobalt and manganese in cobalt manganese waste material
CN106745103A (en) The method that magnesite prepares magnesia or magnesia and fibrous magnesium hydroxide
CN110436595A (en) A kind of processing method of rare-earth industry waste water
CN106315630B (en) It is a kind of that the method for preparing high-purity Flame Retardant Magnesium Hydroxide is reclaimed from heavy metal sewage sludge
CN102126734A (en) Process for removing calcium from magnesite
CN104760980A (en) Preparation technology of highly-pure ultrafine alumina powder
CN106698484B (en) The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge
CN106587122A (en) Method for producing cryolites by using aluminum electrolytic cell cathode carbon block alkaline leaching solution
CN109942009A (en) A kind of preparation method of battery-level lithium carbonate
CN109437266A (en) It is a kind of to extract activity Al (OH) 3 Product Process using aluminium ash or rich-alumina residues
CN105860335B (en) A kind of preparation method of PVC heat stabilizer
CN103193238B (en) Method for producing superfine white carbon black, ferric hydroxide and aluminum oxide by using coal ash
CN106590689B (en) The method that magnalium prepares composite flame-retardant agent is recycled from different sludge
CN107298451A (en) A kind of double Application ways of low-grade magnesite magnesium carbon
CN106674590B (en) The method that magnalium prepares composite flame-retardant agent is recycled from sludge
CN112320826A (en) Method for jointly preparing high-purity magnesium oxide and refined ammonium sulfate by using low-grade magnesite
CN106590688B (en) The method that recycling magnalium prepares high-purity composite flame-retardant agent
CN104340994A (en) Comprehensive utilization method of circulating fluidized bed boiler fly ash
CN102502725A (en) Method for producing flame-retardant magnesium hydroxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant