CN1552636A - Complexometric synergist, preparing method and use thereof - Google Patents
Complexometric synergist, preparing method and use thereof Download PDFInfo
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- CN1552636A CN1552636A CNA03136991XA CN03136991A CN1552636A CN 1552636 A CN1552636 A CN 1552636A CN A03136991X A CNA03136991X A CN A03136991XA CN 03136991 A CN03136991 A CN 03136991A CN 1552636 A CN1552636 A CN 1552636A
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- complexing
- agent
- silicate
- synergistic agent
- synergistic
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Abstract
A complexing synergist used as flocculant or for increasing the polymerization degree and bridging power of flocculant in the sewage treatment is prepared from complexing agent, silicate, H2O and Na2O. It can be used for treating sewage or preparing flocculant.
Description
Technical field
The present invention relates to a kind of complexing synergistic agent and preparation method thereof and application.
Background technology
China is since later 1960s begins to use flocculation agent in (dirt) water treatment, inorganic flocculating agent is with advantages such as its low toxicity, cheapness, preparation method are simple relatively occuping market dominant position all the time, the initial main first-generation inorganic salts such as Tai-Ace S 150, aluminum chloride, iron(ic) chloride that use.The eighties, successively develop and introduced polymerize aluminum chloride (aluminium chlorohydroxide) (PAC), poly-ferric chloride (PFC), polyaluminium sulfate (PAS), bodied ferric sulfate (PFS), polymer phosphate aluminium s-generation inorganic flocculating agent-inorganic polymer flocculants such as (PAP) (inorganicpolymer flocculants, IPF).
The advantage of IPF is that it is more excellent than traditional inorganic salt flocculation agent usefulness, and cheaper than organic polymer coargulator (OPF) price.But aspect form, the polymerization degree and corresponding cohesion-flocculating effect, IPF still is in the position between conventional metals salt coagulant and the OPF.Its molecular weight and globule size and flocculation bridge formation ability are still far short of what is expected than OPF, but also have the instability problem to further hydrolysis reaction, and these main weakness are impelled the various compound IPF of research and development.
The nineties, (multi-coreinorganic polymer flocculants, MC-IPF): aluminium iron polychloride (PAFC), PAFS (PAFS), polymer phosphate ferro-aluminum (PAFP), polymer aluminium silicate (PASi), polymeric silicicacid iron (PFSi), polymeric aluminium ferrum silicate (PAFSi) etc. constantly are developed out to have more the third generation inorganic flocculating agent-multi-kernel high-molecular inorganic flocculant of characteristic.Production cost increases or the product storage-stable phase shortens but be limited to, and the commercial prod of MC-IPF is also few.At present, in various water treatments the consumption maximum, use the widest remaining to utilize the PAC of various raw materials and various explained hereafter.
In the actual application, when institute's treating water change of water quality is big, dislike still that the PAC polymerization degree is big inadequately, flocculation bridge formation ability is weak, water outlet is muddy, is difficult to guarantee treatment effect.In addition, from the chemical terms of solution, PAC is the kinetics intermediate product of aluminium salt hydrolysis polymerization precipitin reaction process, is unsettled on the thermodynamics, general liquid PAC keeping life maximum half a year.The stability of solid PAC product is good slightly, but needs the liquid product drying when producing, and energy consumption is big, the cost height.Therefore the stable and synergistic of PAC is one of important method of production High Performance IP F, has to be extensive use of to be worth.
The purpose of synergy PAC mainly contained two: one, improved its over-all properties price ratio, and the 2nd, the stable staging life of raising product.In the process of preparation PAC, introduce one or more different negatively charged ion, utilize it to increase poly-effect, can obtain to contain the bigger synergy PAC product of molecular weight of different anions, as Chinese patent application CN1197038A, CN1088892A, CN1046563A.And to Manufactured PAC product, also can utilize organic high molecular polymer (as Soxylat A 25-7 PEO, polyacrylamide PAM etc.) synergy, both improved its stability, strengthened its flocculation ability again, as Chinese patent application CN1266822A, CN1266821A, CN1051157A, CN1044637A.Also can realize to general inorganic polymer flocculant synergic purposes such as PAC, as Chinese patent application CN1343632A, CN1240197A by adopting technologies such as special livering or surperficial carrier.Various synergy modified techniques all relate to the polymerization degree problem of hydroxyl complexing inorganic polymer in the effectively raising system how.
Up-to-date studies show that, increases poly-hydroxyl complexing inorganic polymer with active (polymerization) silicic acid and is the most effective, most economical and industrial value is arranged most.But,, be difficult to realize its commercialization because the introducing of silicic acid component causes the stability of inorganic polymer flocculant to reduce greatly.
The present inventor has prepared a kind of complexing agent, and this complexing agent is made by mineral acid, aluminum contained compound, iron containing compounds, the mixed reaction of magnesium-containing compound, and its institute's metal ion conversion for the mass percent of oxide compound is: Al
2O
3, 5~25%; Fe
2O
3, 1~15%; MgO, 1~15%.This complexing agent can increase the molecular weight (increasing poly-) of common inorganic polymer flocculant by complexing action, thereby strengthens its flocculation ability; Also may be used solely to as the flocculation agent in the sewage disposal, but its polymerization degree and flocculation bridge formation ability still remain to be improved.
Summary of the invention
The purpose of this invention is to provide a kind of complexing synergistic agent,, increase the molecular weight of common inorganic polymer flocculant, reach it is increased poly-synergic purpose by stronger complexing action.
A kind of complexing synergistic agent, it is made up of complexing agent and silicate, and wherein complexing agent accounts for 20~80% of mass percent; The silicate conversion is SiO
2After account for 1~5% of mass percent; Surplus is H
2O and Na
2O.
The preferred mass per-cent of the contained material of described complexing synergistic agent is:
Complexing agent 40~60%;
SiO
2??????2~3%;
Surplus is H
2O and Na
2O.
The metal ion conversion of described complexing agent institute for the mass percent of oxide compound is: Al
2O
3, 5~25%; Fe
2O
3, 1~15%; MgO, 1~15%; All the other are H
2O and negatively charged ion.
Second purpose of the present invention provides a kind of method for preparing above-mentioned complexing synergistic agent.
A kind of method for preparing the complexing synergistic agent is complexing agent to be joined generate target product in the aqueous silicate solution.
The temperature of described reaction is advisable with 40~60 ℃.
Preferably modulus is greater than 3.0 water glass (water glass) for described silicate, and the concentration of its aqueous solution is preferably 5~20%, most preferably is 10~15%; Aqueous silicate solution need not to activate in advance with mineral acid.
Described complexing agent should slowly add in the sodium silicate aqueous solution of continuous stirring.
The preparation method of described complexing agent comprises following two kinds.
First method may further comprise the steps:
1) under 80~150 ℃, mineral acid, aluminum contained compound, iron containing compounds, magnesium-containing compound are mixed reaction;
2) obtaining the metal ion conversion of product institute through slaking for the mass percent of oxide compound is: Al
2O
3, 5~25%; Fe
2O
3, 1~15%; MgO, 1~15%; Surplus is H
2O and negatively charged ion.
Described aluminum contained compound is an aluminium hydroxide, a kind of or arbitrary combination in sodium aluminate, bauxite and the aluminum chloride.
Described iron containing compounds is an iron(ic) chloride, and magnesium-containing compound is a magnesium chloride.
Described mineral acid is the hydrochloric acid and the sulfuric acid miscellany of hydrochloric acid or 1: 1, and its preferred concentration is 5%~31%, most preferably is 10%~18%.
The described reaction times is 1.5~4h, and the curing time is 12~24h.
Second method may further comprise the steps:
1) at normal temperatures, mineral acid, iron containing compounds, magnesium-containing compound, metallic aluminium are mixed reaction;
2) obtaining the metal ion conversion of product institute through slaking for the mass percent of oxide compound is: Al
2O
3, 5~25%; Fe
2O
3, 1~15%; MgO, 1~15%; Surplus is H
2O and negatively charged ion.
Described metallic aluminium is various aluminium scraps, aluminium bits or aluminium foil, and iron containing compounds is an iron(ic) chloride, and magnesium-containing compound is a magnesium chloride.
Described mineral acid is the hydrochloric acid and the sulfuric acid miscellany of hydrochloric acid or 1: 1, and its preferred concentration is 5%~31%, most preferably is 10%~18%.
The described reaction times is 1.5~4h, and the curing time is 12~24h.
This complexing synergistic agent itself provided by the invention is because of having higher molecular weight, and adsorptive power and flocculation bridge formation ability are all very strong, also can use as the flocculation agent in the sewage disposal separately.
Advantage of the present invention and positively effect are: complexing synergistic agent of the present invention, can increase the flocculating property of flocculation agent, and improve the polymerization degree and the flocculation bridge formation ability of inorganic polymer flocculant, and itself also can be used as the flocculation agent in the sewage disposal.The preparation were established of complexing synergistic agent of the present invention to equipment require low, stable processing technique is simple and direct, and cost is low, does not have any pollutant emission, have good environment protecting, can be widely used in oilfield drilling waste liquid, oil extraction-generated waste water, refinery oily(waste)water and sanitary sewage disposal.Simultaneously, complexing agent synergistic agent of the present invention can also be as the raw materials for production of flocculation agent.
Embodiment
The preparation of embodiment 1, complexing synergistic agent
Under 80 ℃, with 200g H
2O, 200g 15%HCl, 100g Al (OH)
3, 50g MgCl
2And 50gFeCl
3, under slowly stirring, adding respectively in the there-necked flask, successive reaction 4h slowly joins product by 60g Na then
2SiO
3With 540g H
2O mixes the 600g Na that stirs the 30min gained at 30~40 ℃
2SiO
3In the aqueous solution, behind the reaction 60min, promptly get the complexing synergistic agent.The mass percent of its contained material is:
Complexing agent 50%;
SiO
2(conversion) 2.5%;
Surplus is H
2O and Na
2O.
The preparation of embodiment 2, complexing synergistic agent
Under 120 ℃, with 25mL H
2O, 20mL 31%HCl, 5g Al (OH)
3, 2.5g MgCl
2And 2.5gFeCl
3, under slowly stirring, adding respectively in the there-necked flask, successive reaction 2h slowly joins product by 5gNa then
2SiO
3With 40g H
2O mixes the 45g Na that stirs the 10min gained at 40 ℃
2SiO
3In the aqueous solution, behind the reaction 60min, promptly get the complexing synergistic agent.The mass percent of its contained material is:
Complexing agent 55%;
SiO
2(conversion) 2.5%;
Surplus is H
2O and Na
2O.
The preparation of embodiment 3, complexing synergistic agent
Under 150 ℃, with 100mL H
2O, 50mL 31%HCl, 20g Al (OH)
3, 5g MgCl
2And 5gFeCl
3, under slowly stirring, adding respectively in the there-necked flask, successive reaction 1.5h slowly joins product by 40g Na then
2SiO
3With 180g H
2O mixes the 220g Na that stirs the 30min gained down at 60 ℃
2SiO
3The aqueous solution behind the reaction 30min, promptly gets the complexing synergistic agent.The mass percent of its contained material is:
Complexing agent 45%;
SiO
2(conversion) 4.9%;
Surplus is H
2O and Na
2O.
The preparation of embodiment 4, complexing synergistic agent
Under the normal temperature, with 100mL H
2O, 50mL 18%HCl, 12g MgCl
2With 12g FeCl
3, 5g aluminium scrap bits or aluminium foil add in the there-necked flask under slowly stirring, successive reaction 1.5hr slowly joins product by 25g Na then
2SiO
3With 150g H
2O mixes the 175g Na that stirs the 30min gained
2SiO
3In the aqueous solution, behind the reaction 60min, promptly get the complexing synergistic agent.The mass percent of its contained material is:
Complexing agent 51%;
SiO
2(conversion) 2.0%;
Surplus is H
2O and Na
2O.
Embodiment 5, complexing synergistic agent are to the flocculating effect of oil extraction-generated waste water
With the complexing agent of the foregoing description 1, breathe out oil field Wen Jisang-rice and step on the oil well produced sewage of joint station and carried out the flocculation evaluation test telling.Existing oil well produced sewage in the sewage of this joint station has oil well borehole operation sewage and joint station sanitary sewage again, and is more difficult than the oil extraction-generated waste water of general one-component.The general water quality of this station combined sewage is that the pH value is about 6.0, oleaginousness 1000~1500mg/L, suspended substance 200~500mg/L.Table 1 is with the treatment effect of complexing synergistic agent of the present invention and the used several general goods flocculation agents of this joint station relatively, and the sewage of getting after the flocculation treatment need not filter direct measurement, with the sedimentation operating mode of simulation in slurry tank.As can be seen, all minimum with suspended solids (machine is assorted) and oleaginousness in the sewage after the complexing synergistic agent processing of the present invention when the adding consistency of each flocculation agent is 200mg/L, show that it has better flocculating effect.
Table 1 complexing synergistic agent of the present invention and commodity flocculation agent compare the treatment effect of oil extraction-generated waste water
Flocculation agent and manufacturer thereof | Handle the assorted content of machine/(mgL in the sewage of back -1) | Handle oleaginousness/(mgL in the sewage of back -1) |
The oily(waste)water former state that does not add flocculation agent | ????317 | ????1275 |
200ppm complexing synergistic agent of the present invention | ????18 | ????30 |
The SEG-3 of 200ppm Binzhou Chemical Plant, Shandong Prov. | ????26 | ????43 |
The WG-1 of 200ppm Shaanxi petrochemical industry designing institute | ????28 | ????47 |
200ppm tells and breathes out auxiliary reagent factory HC-01 of oil | ????23 | ????39 |
The oil extraction-generated waste water after embodiment 6, usefulness complexing synergistic agent are handled and the compatibleness of local water
Table 2 is the water sample after with complexing synergistic agent of the present invention oil extraction-generated waste water being handled and the evaluation of local water consistency.Oil extraction-generated waste water during reinjection into reservoir, as incompatible with local water, then can cause serious scale problems after treatment.Make simulated sewage sample (D) with the sewage after handling through " tell and breathe out warm rice bran oil field oil extraction-generated waste water+40ppmNaOH+200ppm complexing synergistic agent of the present invention ", mix with this oil field stratum water (E) of different ratios respectively again, at 75 ℃ of airtight heating 72hr.Take out back EDTA titration measuring Ca
2+, Mg
2+And Ba
2+The variation of total content.
The oil extraction-generated waste water (D) after table 2 is handled with complexing synergistic agent of the present invention and the compatibleness of local water (E)
Sequence number | Volume ratio (D: E) | Before bathing heat | After bathing heat | Ca 2++Mg 2++Ba 2+Velocity of variation/% | ||
Ca 2++Mg 2++Ba 2+??/(mg·L -1) | ??pH | ?Ca 2++Mg 2++Ba 2+??/(mg·L -1) | ?pH | |||
????1 | ??4∶1 | ????1087 | ??8.0 | ????1013 | ?6.4 | ????-6.8 |
????2 | ??3∶2 | ????1691 | ??7.5 | ????1667 | ?6.4 | ????-1.4 |
????3 | ??2∶3 | ????2224 | ??7.5 | ????2030 | ?6.4 | ????-8.7 |
????4 | ??1∶4 | ????2539 | ??7.5 | ????2310 | ?6.4 | ????-9.0 |
????5 | ??0∶5 | ????3087 | ??7.0 | ????2922 | ?6.2 | ????-5.4 |
As can be seen from Table 2: various mixed samples are clarified no fouling, Ca behind 75 ℃ of airtight heating 72hr
2+, Mg
2+And Ba
2+The basic no change of total content shows that the compatibleness of oil extraction-generated waste water after handling with complexing synergistic agent of the present invention and local water is better, can not result in blockage to formation pore after the re-injection.
Claims (9)
1, a kind of complexing synergistic agent, it is made up of complexing agent and silicate, and wherein complexing agent accounts for 20~80% of mass percent; The silicate conversion is SiO
2After account for 1~5% of mass percent; Surplus is H
2O and Na
2O.
2, complexing synergistic agent according to claim 1 is characterized in that: the mass percent of described each component of complexing synergistic agent is:
Complexing agent 40~60%;
SiO
2???????2~3%;
Surplus is H
2O and Na
2O.
3, a kind of method for preparing the complexing synergistic agent is complexing agent to be joined generate target product in the aqueous silicate solution.
4, method according to claim 3 is characterized in that: described silicate is modulus greater than 3.0 water glass (water glass),
5, method according to claim 4 is characterized in that: the concentration of described sodium silicate aqueous solution is 5~20%.
6, method according to claim 5 is characterized in that: the concentration of described sodium silicate aqueous solution is 10~15%.
7, method according to claim 3 is characterized in that: the temperature of described reaction is 40~60 ℃.
8, method according to claim 3 is characterized in that: described complexing agent is joined in the aqueous silicate solution process that generates target product is that complexing agent is slowly added in the sodium silicate aqueous solution of continuous stirring.
9, the application of the complexing synergistic agent in the claim 1 in sewage disposal and flocculation agent preparation.
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CN 03136991 CN1257108C (en) | 2003-05-26 | 2003-05-26 | Complexometric synergist, preparing method and use thereof |
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CN 03136991 CN1257108C (en) | 2003-05-26 | 2003-05-26 | Complexometric synergist, preparing method and use thereof |
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CN1552636A true CN1552636A (en) | 2004-12-08 |
CN1257108C CN1257108C (en) | 2006-05-24 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103663663A (en) * | 2013-12-18 | 2014-03-26 | 湘潭大明机电科技有限公司 | Efficient composite heavy metal chelating agent |
CN106622681A (en) * | 2016-12-16 | 2017-05-10 | 中蓝连海设计研究院 | Ore slurry flocculating agent and preparation method and application thereof |
CN107487822A (en) * | 2017-08-24 | 2017-12-19 | 江苏亚峰科技集团有限公司 | One kind processing flocculant for sewage and preparation method and application |
CN111620422A (en) * | 2020-06-17 | 2020-09-04 | 辽宁三谷农业科技有限公司 | Production method of silicon and aluminum-containing humate flocculation water purifying agent |
CN112552991A (en) * | 2020-11-24 | 2021-03-26 | 西安热工研究院有限公司 | Method for removing metal elements in gear oil |
-
2003
- 2003-05-26 CN CN 03136991 patent/CN1257108C/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103663663A (en) * | 2013-12-18 | 2014-03-26 | 湘潭大明机电科技有限公司 | Efficient composite heavy metal chelating agent |
CN103663663B (en) * | 2013-12-18 | 2016-09-21 | 江俞 | High efficiency composition heavy metal chelant |
CN106622681A (en) * | 2016-12-16 | 2017-05-10 | 中蓝连海设计研究院 | Ore slurry flocculating agent and preparation method and application thereof |
CN107487822A (en) * | 2017-08-24 | 2017-12-19 | 江苏亚峰科技集团有限公司 | One kind processing flocculant for sewage and preparation method and application |
CN111620422A (en) * | 2020-06-17 | 2020-09-04 | 辽宁三谷农业科技有限公司 | Production method of silicon and aluminum-containing humate flocculation water purifying agent |
CN111620422B (en) * | 2020-06-17 | 2021-07-06 | 辽宁三谷农业科技有限公司 | Production method of silicon and aluminum-containing humate flocculation water purifying agent |
CN112552991A (en) * | 2020-11-24 | 2021-03-26 | 西安热工研究院有限公司 | Method for removing metal elements in gear oil |
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