CN105152291B - Poly aluminium iron silicate acrylamide copolymer composite flocculation agent and preparation method thereof - Google Patents
Poly aluminium iron silicate acrylamide copolymer composite flocculation agent and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of poly aluminium iron silicate acrylamide copolymer composite flocculation agent and preparation method thereof, is characterized in 20 parts of Na2SiO3Add in 250 parts of deionized waters, pH value 2~5, react at room temperature 2~3 hours, activated silicic acid is made；AlCl is made with containing aluminium waste, waste hydrochloric acid containing iron and technical hydrochloric acid3And FeCl2Mixed crystal；1.2~25.0 parts of mixed crystals are added in 25 parts of activated silicic acids, reaction stands curing, poly aluminium iron silicate PAFSI is made；By 20 parts of acrylamide, 75~450 parts of deionized water, 5~20 parts of ion monomer, in 0.3~6 part of addition reaction bulb of polymeric monomer, stirring, pH value 5~9 leads to N2, 0.008~0.4 part of potassium peroxydisulfate is added in 40~70 DEG C, is reacted 12~36 hours, copolymer p AME is made；100 part of 5 g/L PAME solution is added in reaction bulb, 12~350 parts of 100 g/L PAFSI solution, pH value 1~4 are added under fast stirring, reacted 2~3 hours at 30~40 DEG C, react 2~4 hours, cure 24 hours then at 50~75 DEG C, PAFSI PAME composite flocculation agents are made.
Description
First, technical field
The present invention relates to a kind of poly aluminium iron silicate-acrylamide copolymer composite flocculation agent and preparation method thereof, this wadding
Solidifying agent available for oil-gas field fracturing return discharge opeing, Produced Water In Oil-gas Fields, Ngi, printing and dyeing, papermaking, weaving, steel, brewage, petrochemical industry, metallurgy and
The water process of the various wastewaters such as food, belongs to environmental project, inorganic chemistry, high polymer material and field of oilfield chemistry.
2nd, technical background
The shortage of water resources of China, especially in the Northwest, and the water pollution that all trades and professions are caused due to economic development
Than more serious, therefore, protection and waste water treatment for water resource are the key subjects of China environmental protection.In wastewater treatment
During, it is divided into one-level, two grades and tertiary treatment by degree for the treatment of, wherein coagulation belongs to physical treatment process, mainly removed
Undissolved suspended solid pollutant in waste water is removed, two stage treatment is mainly the organic pollution for removing and being dissolved in waste water, three-level
Processing is that on the basis of one-level, two stage treatment, processing phosphorus and nitrogen etc. can result in the soluble inorganic matter of waste water eutrophication
And the organic matter of difficult degradation etc..Coagulation is indispensable, typically using technique is simple, equipment investment is few, operation side
Just coagulant sedimentation, the key of this method is flocculant (also referred to as coagulant), and the coagulation performance and consumption of flocculant are straight
Connect the effect and expense for determining one-level water process.
The flocculant used at present is mainly inorganic polymer flocculant, organic polymer coargulator and composite flocculation agent.
Inorganic polymer flocculant is mainly aluminium polychloride (PAC), bodied ferric sulfate (PFS), poly-silicic acid iron sulfate (PFSS) and gathered
Aluminium iron silicate (PAFSI) etc., wherein that with the most use is PAC, compared with organic polymer coargulator, inorganic polymer flocculant
Molecular weight is low, adsorption bridging ability is weak, sludge quantity is more.Conventional organic polymer coargulator is poly dimethyl allyl chlorine
Change ammonium, cationic, anionic, non-ionic and amphoteric acrylic resin, and modified natural polymer flocculant
The modified starch and modified cellulose of such as cationic, are compared with inorganic polymer flocculant, and its flocculating setting time is short, are used
Measure much less, influenceed small by pH value of sewage water, the sludge quantity of generation is few, and flco is closely knit, but because its price height be used alone by
Limitation.Due to the inorganic and respective deficiency of organic polymer coargulator, both are compounded or compound in actual applications, played
Their synergy, improves flocculation treatment effect, reduces cost of water treatment.Compounding is physical method, be it is the most frequently used, also
It is that inorganic and organic polymer coargulator is successively added in waste water；Compound is chemical method, is exactly in certain temperature and pH
Under value, inorganic and organic polymer coargulator forms a kind of new composite flocculant by chemical reaction in the solution, with answering
Distribution type flocculant is compared, and the consumption of composite flocculant is lower.Although various flocculants have its advantage, current practice
The consumption of flocculant commodity is higher so that the expense of water process is higher, and the Aluminium residual after processing in clear water is higher, its main work(
Can be still removing suspended solid, it is very weak to the removal ability of inorganic matter and hardly degraded organic substance soluble in waste water, in addition,
Organic polymer coargulator is weaker to the flocculation ability of high slat-containing wastewater.Therefore, development coagulation performance is good, and consumption is low, without secondary
Pollution, multifunctional novel flocculant has important actual application value to effectively administering waste water, reduction water process expense.Liu
Gui Ping etc., chemical industry progress, 2010,29 (10):1990-1993, with the industry that bauxite, magnesia powder and mass fraction are 20%
Hydrochloric acid is that raw material is prepared for polyaluminium magnalium flocculant, when consumption of the flocculant in treatment of dyeing wastewater is 0.95g/L
When, turbidity and COD clearances are respectively 97.3% and 56.31%.Xu Linke etc., Agriculture of Anhui science, 2011,39 (27):
16747-16749, aluminium polychloride (PAC) and polyacrylamide (PAM) compound use, the pre- place for percolate
Reason, when PAC dosages are 20g/L, the COD clearances of percolate are 24.1%；In addition, adding 0.05g/L PAM
When, the increase of COD clearances is 47.4%, is as a result shown, PAC and PAM consumption are higher, and COD clearances are relatively low.He Yu
Phoenix etc., New Chemical Materials, 2014,42 (1):104-106, using aluminium chloride and farina as raw material, is prepared for polymerizeing chlorine
Change aluminium and be combined CMS (PAC-CMPS) flocculant, when consumption of the flocculant in potato starch wastewater processing is
During 0.8g/L, COD clearances are 87.8%, are as a result shown, the consumption of CMS is high in composite flocculation agent, and this causes its valency
Lattice are significantly larger than the price of aluminium polychloride commodity.The consumption of flocculant is higher in above three document, and this causes waste water to control
The expense of reason is higher, and especially aluminium polychloride containing organic macromolecule is combined the expense highest of CMS flocculant, because
Its consumption is high, and unit price is also far above inorganic polymer flocculant, in addition, not providing after water process in clear water
Aluminium residual content.
3rd, the content of the invention
The purpose of the present invention be for current flocculant commodity consumption it is higher, there is secondary pollution, water treatment efficiency is needed
The problems such as raising, can be used for oil-gas mining waste water, industrial wastewater and city domestic sewage coagulating treatment, safety collar there is provided one kind
The poly aluminium iron silicate of guarantor-acrylamide copolymer composite flocculation agent and preparation method thereof, is characterized in aluminium slag containing aluminium waste, aluminium
At least one of ash and waste hydrochloric acid containing iron are prepared for poly aluminium iron silicate PAFSI；Using acrylamide AM as main hydrophilic monomer,
With polymeric monomer allyl alkylphenol ethoxylate CH2=CH-CH2(OCH2CH2)n- O-C6H4- CmH2m+1, n=8~60, m
=1~9 and allyl alkyl APEO CH2=CH-CH2(OCH2CH2)n- O-CmH2m+1, n=8~60, m=2~9
At least one of as function comonomer, with ion monomer acrylic acid, methacrylic acid, 2- acrylamido -2- first
Base propane sulfonic acid, dimethyl diallyl ammonium chloride, EMA base trimethyl ammonium chloride, ethyl acrylate base trimethyl
At least one of ammonium chloride and 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides as another comonomer,
It is prepared for acrylamide copolymer PAME；Then PAFSI and PAME in after chemical reaction in aqueous at 50~75 DEG C,
It is prepared for composite flocculation agent PAFSI-PAME.
The inventors have found that composite flocculation agent PAME-PAFSI prepare in PAFSI and PAME mass ratio, recombination reaction
Temperature, pH value and reaction time, mole of aluminium and the mol ratio of iron component, aluminium and the total component of iron and silicon components in prepared by PAFSI
Total monomer concentration, ion monomer concentration, polymeric monomer concentration, copolymerization temperature and copolymerization in being prepared than, pH value, and PAME
The water treatment efficiency of composite flocculation agent can be significantly affected by closing pH value in reaction, and being introduced for of polymeric monomer increases polymer molecular chain
Rigidity and complexed metal cation, to improve the water treatment efficiency of composite flocculation agent, ion monomer is introduced for enhancing
The dissolubility of polymer and the suction-operated to suspended particulate in sewage.
The purpose of the present invention is realized by following technical measures, wherein the raw material number is unless otherwise specified, it is weight
Number.
1. poly aluminium iron silicate PAFSI preparation
By 20 parts of Na2SiO3It is added to 250 parts of deionized waters in three mouthfuls of reaction bulbs, solution is made in stirring, is adjusted with hydrochloric acid
The pH value of solution is 2~5, is reacted 2~3 hours at 20~30 DEG C, and activated silicic acid is made；Weigh containing 30 parts of aluminium waste, add
Into three mouthfuls of reaction bulbs, it is 33% 85~300 parts of technical hydrochloric acid to add 80~250 parts of waste hydrochloric acid containing iron and HCl mass fractions,
Reaction is stirred at room temperature 1~2 hour, the main component of product is AlCl in solution3And FeCl2, it is separated by filtration, filtrate is dense
Contraction obtains AlCl3And FeCl2Mixed crystal；1.2~25.0 parts of AlCl are added in 25 parts of activated silicic acids3And FeCl2Mix-crystal
Body, stirring reaction 1~2 hour at 40~70 DEG C, control ph is 1~4, then adds 0.1~8.0 part of oxidant, stirring
Reaction 1~2 hour, reaction temperature is controlled at 30~65 DEG C, stands curing 24 hours, and poly aluminium iron silicate PAFSI is made；
Wherein containing aluminium waste be at least one of aluminium slag and aluminium ash, the aluminium constituent mass fraction containing aluminium waste be 15%~
40%；Oxidant is NaClO, NaClO3、KClO3、NaClO4、KClO4And H2O2At least one of；Waste hydrochloric acid containing iron is to use salt
The waste liquid occurred in acid derusting, the mass fraction that the mass fraction of iron component is 10%~15%, HCl is 3%~8%.
2. acrylamide copolymer PAME preparation
By 20 parts of acrylamide, 75~450 parts of deionized water is added in three mouthfuls of reaction bulbs, adds ion monomer 5~20
Part, 0.3~6 part of polymeric monomer is stirred 30 minutes, and regulation solution ph is 5~9, and N is led under agitation2After 40 minutes, in 40~70
0.008~0.4 part of initiator potassium persulfate is added at DEG C, is reacted 12~36 hours, acrylamide copolymer PAME is made；
Wherein ion monomer is acrylic acid, methacrylic acid, 2- acrylamide-2-methylpro panesulfonic acids, dimethyl two
Allyl ammonium chloride, EMA base trimethyl ammonium chloride, ethylacrylate-trimethylammonium chloride and 2- acryloyls
At least one of amido -2- trimethoxysilyl propyl methacrylate ammonium chlorides；Polymeric monomer is allyl alkylphenol ethoxylate CH2=
CH-CH2(OCH2CH2)n- O-C6H4- CmH2m+1, n=8~60, m=1~9 and allyl alkyl APEO CH2=
CH-CH2(OCH2CH2)n- O-CmH2m+1At least one of, n=8~60, m=1~9.
3. poly aluminium iron silicate-acrylamide copolymer composite flocculation agent PAFSI-PAME preparation
PAME is completely dissolved, the aqueous solution that mass concentration is 5g/L is prepared into, PAFSI is made into mass concentration is
The 100g/L aqueous solution, and it is 1~4 to adjust the pH value of solution with watery hydrochloric acid, prevents precipitation from producing, weighs 100 parts of PAME molten
Liquid, is added in three mouthfuls of reaction bulbs, and 12~350 parts of PAFSI solution are then added under fast stirring, and solution is controlled with watery hydrochloric acid
PH value is 1~4, is reacted 2~3 hours at 30~40 DEG C and under stirring, is then heated to 50~75 DEG C, after reacting 2~4 hours,
Reaction 24 hours are stood at 20~35 DEG C, PAFSI-PAME composite flocculation agent colloids are made.
4. poly aluminium iron silicate-acrylamide copolymer composite flocculation agent PAFSI-PAME coagulation performance
(1) PAFSI-PAME dosages are as shown in table 1 to the removal effect of turbidity of sewage.As a result show, it is and conventional at present
Commodity PB1 gene is compared, PAFSI-PAME have it is much better go turbidity effect, in the case where reaching identical water quality requirement,
Consumption is much lower；Compared with commodity cation acrylamide copolymer CPAM conventional at present, PAME, which has, preferably removes turbidity
Effect, and consumption is lower.
(2) PAFSI-PAME dosages are as shown in table 2 to the removal effect of dirty Organic substance in water.COD COD
(Chemical Oxygen Demand) is chemically to measure in water sample to need the amount of oxidized reducing substances, is represented
The oxygen equivalent for the material (generally organic matter) that can be aoxidized in waste water by strong oxidizer.As a result show, with commodity conventional at present
PB1 gene and PAFSI are compared with PAME compounding, and PAFSI-PAME has the dirty Organic substance in water of much better removal
Effect；Compared with commodity cation acrylamide copolymer CPAM conventional at present, PAME has preferably to remove and had in sewage
The effect of machine thing, and consumption is lower.
(3) it is 2416.5NTU with 300mg/L PAFSI-PAME purification turbidity, COD presses for 13692.4mg/L certain oil field
It is 17.3 μ g/L to split the Residual Aluminum Content returned after discharge opeing in clear water, far below the standards for drinking water quality (GB5749- of China
2006) mass ratio that, i.e., Residual Aluminum Content is not more than PAME and PAFSI in 200 μ g/L, PAFSI-PAME in drinking water is 1:
60, but it is 229 to handle this oil field compression fracture to return the Residual Aluminum Content after discharge opeing in clear water with 300mg/L PAC and 8mg/L CPAM
μg/L.As a result show, PAME-PAFSI does not result in secondary pollution.
Poly aluminium iron silicate-acrylamide copolymer composite flocculation agent PAFSI-PAME of the present invention has the following advantages：
The waste residue that aluminium slag and aluminium ash are produced when being aluminium melting, the present invention is useless with least one of aluminium slag, aluminium ash and iron content
Hydrochloric acid is as the raw material for preparing poly aluminium iron silicate PAFSI, and this had both solved the dirt to environment containing aluminium waste and waste hydrochloric acid containing iron
Dye problem, saves the expense for disposing these waste materials again, in addition, with it is current commonly use at least one of aluminium chloride, aluminum sulfate and
At least one of iron chloride, ferrous sulfate are compared as the preparation method for preparing PAFSI raw materials, greatly reduce PAFSI's
Production cost；The present invention is using waste hydrochloric acid containing iron as the raw material for preparing PAFSI, and this had both solved iron component in PAFSI
Source problem, provides the hydrochloric acid prepared from containing aluminium waste needed for aluminium chloride again.PAFSI-PAME is PAFSI and PAME by changing
Learn what reaction was prepared, it had both had the good charge neutrality suction-operateds of PAFSI, had organic polymer PAME frame again
Bridge, net catch the volume effect of sweeping, compared with PAFSI and PAME compounding, and consumptions of the PAFSI-PAME in sewage disposal is much lower, but
Coagulability is stronger, and the effect of organics removal becomes apparent from.With the inorganic polymer flocculant and natural height of current document report
Molecule and its polymer-modified composite flocculation agent such as chitosan, starch, the compound acquisition of cationic modified starch are compared, this hair
High molecular molecular weight in the PAFSI-PAME molecular structures of bright preparation is bigger, but also contains long-chain branch, therefore, PAFSI-
Coagulations of the PAME in sewage, bridge formation ability are stronger, and consumption is lower, and settling velocity is fast, and flco is more closely knit, and sludge is more disposable,
Standards for drinking water quality 200 μ g/L of the aluminium content well below China after processing in clear water, does not result in secondary pollution；
The molecular structure of polyacrylamide polymer without polymeric monomer is line style, due to anion in sewage or cation to point
The electrostatic screen effect of subchain, strand of this kind of polymer in high salinity sewage is curling, therefore, current document report
The inorganic polymer flocculant in road is with the compound composite flocculation agent obtained of the polyacrylamide polymer without polymeric monomer in height
Flocculation ability in salinity sewage is weaker, and consumption is high, and PAME contains a small amount of long-chain branch, and this causes PAME-PAFSI in height
The conformation of its macromolecular chain still stretches in salinity sewage, still has strong suction in the high sewage of metal cation content
Attached frame bridge ability, consumption is extremely low, and the APEO in long-chain branch can be with such as K of the metal cation in sewage+、Na+、Ca2 +、Mg2+、Al3+Generation complexing, so as to preferably remove these metal cations.
4th, embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that the present embodiment is served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the researcher in the field can be with
Some nonessential modifications and adaptations are made to the present invention according to the content of the invention described above.
Embodiment 1
By 10 grams of Na2SiO3It is added to 125 grams of deionized waters in three mouthfuls of reaction bulbs, solution is made in stirring, is adjusted with hydrochloric acid
The pH value of solution is 3, is reacted 2 hours at 25 DEG C, and activated silicic acid is made；Weigh the aluminium slag 30 that aluminium constituent mass fraction is 30%
Gram, it is added in three mouthfuls of reaction bulbs, adds 105 grams of the waste hydrochloric acid containing iron that iron component, HCl mass fractions are respectively 15% and 4%
129 grams of the technical hydrochloric acid with HCl mass fractions are 33%, is stirred at room temperature reaction 2 hours, is separated by filtration, filtrate is concentrated
AlCl is made3And FeCl2Mixed crystal；2.7 grams of AlCl are added in 25 grams of activated silicic acids3And FeCl2Mixed crystal, at 45 DEG C
Lower stirring reaction 2 hours, control ph is 2, then adds 0.25 gram of KClO3, stirring reaction 1 hour, reaction temperature control exist
45 DEG C, curing 24 hours are stood, poly aluminium iron silicate PAFSI is made；By 20 grams of acrylamide, 90 grams of deionized water add three mouthfuls it is anti-
Answer in bottle, add 6 grams of the dimethyl diallyl ammonium chloride, (polymerization of APEO of pi-allyl OPEO
Spend for 10) 0.5 gram, stir 30 minutes, regulation solution ph is 6, and N is led under agitation2After 40 minutes, trigger in being added at 50 DEG C
0.01 gram of agent potassium peroxydisulfate, reacts 16 hours, and acrylamide copolymer PAME is made；PAME is completely dissolved, quality is prepared into
Concentration is the 5g/L aqueous solution, PAFSI is made into the aqueous solution that mass concentration is 100g/L, and adjust solution with watery hydrochloric acid
PH value is 1.5, prevents precipitation from producing, and weighs 50 grams of PAME solution, adds in three mouthfuls of reaction bulbs, then adds under fast stirring
10 grams of PAFSI solution, control the pH value of solution to be 2 with watery hydrochloric acid, are reacted 3 hours at 30 DEG C and under stirring, are then heated to 60
DEG C, after reacting 3 hours, reaction 24 hours are stood at 30 DEG C, PAFSI-PAME composite flocculation agent colloids are made.
Embodiment 2
By 10 grams of Na2SiO3It is added to 125 grams of deionized waters in three mouthfuls of reaction bulbs, solution is made in stirring, is adjusted with hydrochloric acid
The pH value of solution is 2.5, is reacted 2 hours at 25 DEG C, and activated silicic acid is made；Weigh the aluminium ash that aluminium constituent mass fraction is 25%
30 grams, it is added in three mouthfuls of reaction bulbs, adds 90 grams of the waste hydrochloric acid containing iron that iron component, HCl mass fractions are respectively 10% and 5%
118 grams of the technical hydrochloric acid with HCl mass fractions are 33%, is stirred at room temperature reaction 2 hours, is separated by filtration, filtrate is concentrated
AlCl is made3And FeCl2Mixed crystal；7.8 grams of AlCl are added in 25 grams of activated silicic acids3And FeCl2Mixed crystal, at 50 DEG C
Lower stirring reaction 1.5 hours, control ph is 3, then adds 0.5 gram of NaClO3, stirring reaction 1 hour, reaction temperature control
At 50 DEG C, curing 24 hours are stood, poly aluminium iron silicate PAFSI is made；By 20 grams of acrylamide, 180 grams of deionized water adds three
In mouth reaction bulb, 9 grams of 2- acrylamido -2- trimethoxysilyl propyl methacrylates ammonium chloride, pi-allyl octyl phenol polyoxy second are added
1.2 grams of alkene ether (degree of polymerization of APEO is 20), is stirred 30 minutes, regulation solution ph is 5, and N is led under agitation240 points
Zhong Hou, in adding 0.025 gram of initiator potassium persulfate at 45 DEG C, reacts 24 hours, acrylamide copolymer PAME is made；Will
PAME is completely dissolved, and is prepared into the aqueous solution that mass concentration is 5g/L, and it is the water-soluble of 100g/L that PAFSI is made into mass concentration
Liquid, and it is 2 to adjust the pH value of solution with watery hydrochloric acid, prevents precipitation from producing, and weighs 50 grams of PAME solution, adds three mouthfuls of reaction bulbs
In, 42 grams of PAFSI solution are then added under fast stirring, control the pH value of solution to be 3 with watery hydrochloric acid, at 40 DEG C and under stirring
Reaction 1.5 hours, is then heated to 70 DEG C, after reacting 2 hours, and reaction 24 hours are stood at 30 DEG C, and PAFSI-PAME is made
Composite flocculation agent colloid.
Embodiment 3
By 10 grams of Na2SiO3It is added to 125 grams of deionized waters in three mouthfuls of reaction bulbs, solution is made in stirring, is adjusted with hydrochloric acid
The pH value of solution is 4, is reacted 3 hours at 30 DEG C, and activated silicic acid is made；Weigh the aluminium slag 30 that aluminium constituent mass fraction is 40%
Gram, it is added in three mouthfuls of reaction bulbs, adds 165 grams of the waste hydrochloric acid containing iron that iron component, HCl mass fractions are respectively 15% and 4%
231 grams of the technical hydrochloric acid with HCl mass fractions are 33%, is stirred at room temperature reaction 1.5 hours, is separated by filtration, and filtrate is dense
Contraction obtains AlCl3And FeCl2Mixed crystal；12.0 grams of AlCl are added in 25 grams of activated silicic acids3And FeCl2Mixed crystal, 50
Stirring reaction 1.5 hours at DEG C, control ph is 3.5, then adds 2.6 grams of NaClO, stirring reaction 1 hour, reaction temperature control
System stands curing 24 hours at 55 DEG C, and poly aluminium iron silicate PAFSI is made；By 20 grams of acrylamide, 270 grams of additions of deionized water
In three mouthfuls of reaction bulbs, 15 grams of ethylacrylate-trimethylammonium chloride, pi-allyl nonyl APEO (polyoxyethylene are added
The degree of polymerization of ether is 30) 2.8 grams, is stirred 30 minutes, and regulation solution ph is 5.5, and N is led under agitation2After 40 minutes, in 55 DEG C
Lower 0.05 gram of initiator potassium persulfate of addition, reacts 24 hours, acrylamide copolymer PAME is made；PAME is completely dissolved,
The aqueous solution that mass concentration is 5g/L is prepared into, PAFSI is made into mass concentration is the 100g/L aqueous solution, and uses watery hydrochloric acid
The pH value for adjusting solution is 4, prevents precipitation from producing, and weighs 50 grams of PAME solution, adds in three mouthfuls of reaction bulbs, is then quickly stirring
75 grams of PAFSI solution of lower addition are mixed, control the pH value of solution to be 3.5 with watery hydrochloric acid, are reacted 2.5 hours at 35 DEG C and under stirring,
65 DEG C are then heated to, after reacting 2.5 hours, reaction 24 hours are stood at 30 DEG C, PAFSI-PAME composite flocculation agents are made
Colloid.
Embodiment 4
By 10 grams of Na2SiO3It is added to 125 grams of deionized waters in three mouthfuls of reaction bulbs, solution is made in stirring, is adjusted with hydrochloric acid
The pH value of solution is 4.5, is reacted 2.5 hours at 30 DEG C, and activated silicic acid is made；Weigh the aluminium that aluminium constituent mass fraction is 20%
30 grams of ash, is added in three mouthfuls of reaction bulbs, adds the waste hydrochloric acid containing iron that iron component, HCl mass fractions are respectively 13% and 5%
216 grams are 33% 157 grams of technical hydrochloric acid with HCl mass fractions, and reaction 2 hours is stirred at room temperature, is separated by filtration, by filtrate
AlCl is made in concentration3And FeCl2Mixed crystal；18.0 grams of AlCl are added in 25 grams of activated silicic acids3And FeCl2Mixed crystal,
Stirring reaction 1 hour at 65 DEG C, control ph is 2, and it is 20% H then to add 0.7 gram of NaClO and 4.5 gram mass fractions2O2
Solution, stirring reaction 1 hour, reaction temperature is controlled at 60 DEG C, stands curing 24 hours, and poly aluminium iron silicate PAFSI is made；By third
20 grams of acrylamide, 360 grams of deionized water is added in three mouthfuls of reaction bulbs, adds 12 grams of methacrylic acid, pi-allyl octyl group polyoxy
5.3 grams of vinethene (degree of polymerization of APEO is 60), is stirred 30 minutes, regulation solution ph is 5, and N is led under agitation240
After minute, in adding 0.04 gram of initiator potassium persulfate at 60 DEG C, react 24 hours, acrylamide copolymer PAME is made；Will
PAME is completely dissolved, and is prepared into the aqueous solution that mass concentration is 5g/L, and it is the water-soluble of 100g/L that PAFSI is made into mass concentration
Liquid, and it is 2.5 to adjust the pH value of solution with watery hydrochloric acid, prevents precipitation from producing, and weighs 50 grams of PAME solution, adds three mouthfuls of reactions
Bottle in, then under fast stirring add 103 grams of PAFSI solution, with watery hydrochloric acid control solution pH value be 2,40 DEG C with stir
Lower reaction 2 hours is mixed, 70 DEG C are then heated to, after reacting 2 hours, reaction 24 hours are stood at 30 DEG C, PAFSI- is made
PAME composite flocculation agent colloids.
Embodiment 5
By 10 grams of Na2SiO3It is added to 125 grams of deionized waters in three mouthfuls of reaction bulbs, solution is made in stirring, is adjusted with hydrochloric acid
The pH value of solution is 2, is reacted 3 hours at 30 DEG C, and activated silicic acid is made；Weigh the aluminium slag 30 that aluminium constituent mass fraction is 35%
Gram, it is added in three mouthfuls of reaction bulbs, adds 182 grams of the waste hydrochloric acid containing iron that iron component, HCl mass fractions are respectively 12% and 5%
193 grams of the technical hydrochloric acid with HCl mass fractions are 33%, is stirred at room temperature reaction 2 hours, is separated by filtration, filtrate is concentrated
AlCl is made3And FeCl2Mixed crystal；23.5 grams of AlCl are added in 25 grams of activated silicic acids3And FeCl2Mixed crystal, at 60 DEG C
Lower stirring reaction 1.5 hours, control ph is 2, then adds 5.2 grams of NaClO3, stirring reaction 1.5 hours, reaction temperature control
System stands curing 24 hours at 65 DEG C, and poly aluminium iron silicate PAFSI is made；By 20 grams of acrylamide, 360 grams of additions of deionized water
In three mouthfuls of reaction bulbs, 4 grams of 2- acrylamide-2-methylpro panesulfonic acids, EMA base trimethyl ammonia chloride are added
13 grams of ammonium, 4.6 grams of pi-allyl octyl group APEO (degree of polymerization of APEO is 40), stirs 30 minutes, adjusts solution
PH value is 6, and N is led under agitation2After 40 minutes, in adding 0.06 gram of initiator potassium persulfate at 55 DEG C, react 24 hours, be made
Acrylamide copolymer PAME；PAME is completely dissolved, the aqueous solution that mass concentration is 5g/L is prepared into, PAFSI is made into matter
The aqueous solution that concentration is 100g/L is measured, and it is 3 to adjust the pH value of solution with watery hydrochloric acid, prevents precipitation from producing, weighs 50 grams
PAME solution, is added in three mouthfuls of reaction bulbs, and 156 grams of PAFSI solution are then added under fast stirring, and solution is controlled with watery hydrochloric acid
PH value be 2, reacted 3 hours at 30 DEG C and under stirring, be then heated to 75 DEG C, after reaction 3 hours, reaction is stood at 30 DEG C
24 hours, PAFSI-PAME composite flocculation agent colloids are made.
5th, subordinate list explanation
The turbidity of sewage of table 1 with PAFSI-PAME dosages change
Note：Sewage is that certain oil field compression fracture returns discharge opeing；PAME is cationic copolymer；A, b：Separately add 8mg/L CPAM；
c：Separately add 5mg/LPAME；d：PAFSI and PAME mass ratio is 60:1
The COD of sewage of table 2 with PAFS I-PAME dosages change
Note：Sewage is that certain oil field compression fracture returns discharge opeing；PAME is cationic copolymer；A, b：Separately add 8mg/L CPAM；
c：Separately add 5mg/LPAME；d：PAFSI and PAME mass ratio is 60:1.
Claims (1)
1. a kind of preparation method of poly aluminium iron silicate-acrylamide copolymer composite flocculation agent, including：
（1）Poly aluminium iron silicate PAFSI preparation
By 20 parts of Na2SiO3It is added to 250 parts of deionized waters in three mouthfuls of reaction bulbs, stirs, be with the pH value of hydrochloric acid conditioning solution
2~5, reacted 2~3 hours at 20~30 DEG C, activated silicic acid is made；Weigh containing 30 parts of aluminium waste, be added to three mouthfuls of reaction bulbs
In, it is 33% 85~300 parts of technical hydrochloric acid to add 80~250 parts of waste hydrochloric acid containing iron and HCl mass fractions, is stirred at room temperature
Reaction 1~2 hour, is separated by filtration, and filtrate is concentrated AlCl is made3And FeCl2Mixed crystal；Added in 25 parts of activated silicic acids
1.2~25.0 parts of AlCl3And FeCl2Mixed crystal, stirring reaction 1~2 hour at 40~70 DEG C, control ph is 1~4, so
0.1~8.0 part of oxidant is added afterwards, and stirring reaction 1~2 hour, temperature control stands curing 24 hours, system at 30~65 DEG C
Obtain poly aluminium iron silicate PAFSI；
It is at least one of aluminium slag and aluminium ash wherein containing aluminium waste, the aluminium constituent mass fraction containing aluminium waste is 15%~40%；
Oxidant is NaClO, NaClO3、KClO3、NaClO4、KClO4And H2O2At least one of；Waste hydrochloric acid containing iron is removed with hydrochloric acid
The waste liquid occurred in rust, the mass fraction that the mass fraction of iron component is 10%~15%, HCl is 3%~8%；
（2）Acrylamide copolymer PAME preparation
By 20 parts of acrylamide, 75~450 parts of deionized water is added in three mouthfuls of reaction bulbs, adds 5~20 parts of ion monomer, greatly
0.3~6 part of monomer, is stirred 30 minutes, and regulation solution ph is 5~9, and N is led under agitation2 After 40 minutes, at 40~70 DEG C
0.008~0.4 part of potassium peroxydisulfate is added, is reacted 12~36 hours, acrylamide copolymer PAME is made；
Wherein ion monomer is acrylic acid, methacrylic acid, 2- acrylamide-2-methylpro panesulfonic acids, the allyl of dimethyl two
Ammonium chloride, EMA base trimethyl ammonium chloride, ethylacrylate-trimethylammonium chloride and 2- acrylamides
At least one of base -2- trimethoxysilyl propyl methacrylate ammonium chlorides；Polymeric monomer is allyl alkylphenol ethoxylate CH2=
CH-CH2（OCH2 CH2）n- O-C6H4- CmH2m+1, n=8 ~ 60, m=1 ~ 9 and allyl alkyl APEO CH2=CH-
CH2（OCH2 CH2）n- O-CmH2m+1At least one of, n=8 ~ 60, m=1 ~ 9；
（3）Poly aluminium iron silicate-acrylamide copolymer composite flocculation agent PAFSI-PAME preparation
PAME is completely dissolved, be prepared into mass concentration be 5 g/L the aqueous solution, by PAFSI be made into mass concentration for 100 g/
The L aqueous solution, and it is 1~4 to adjust the pH value of solution with watery hydrochloric acid, prevents precipitation from producing, weighs 100 parts of PAME solution, plus
Enter in three mouthfuls of reaction bulbs, 12~350 parts of PAFSI solution are then added under fast stirring, the pH value of solution is controlled with watery hydrochloric acid
For 1~4, reacted 2~3 hours at 30~40 DEG C and under stirring, be heated to 50~75 DEG C, after reaction 2~4 hours, 20~
Reaction 24 hours are stood at 35 DEG C, PAFSI-PAME composite flocculation agent colloids are made.
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