CN1101896A - Process for producing compound poly-ferric aluminium sulfate - Google Patents
Process for producing compound poly-ferric aluminium sulfate Download PDFInfo
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- CN1101896A CN1101896A CN 94117429 CN94117429A CN1101896A CN 1101896 A CN1101896 A CN 1101896A CN 94117429 CN94117429 CN 94117429 CN 94117429 A CN94117429 A CN 94117429A CN 1101896 A CN1101896 A CN 1101896A
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- sulfate
- ferric
- aluminium
- compound poly
- ferrous
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Abstract
The process for producing compound poly-ferric aluminium sulfate features that under acid condition, in the presence of aluminium nutrate as catalyst, ferrous sulfate as raw material is oxidized, hydrolyzed and polymerized for one hr. to obtain product whose basicity is over 20%. Its advantages are shorter reaction period and basical elimination of environmental pollution.
Description
The present invention relates to be used for the production method of the flocculation agent of processing drinking water, waste water or sewage etc., relate to be used for the production method of the inorganic polymer flocculant-compound poly-ferric aluminium sulfate of processing drinking water, waste water or sewage etc. more precisely.
Bodied ferric sulfate is a kind of inorganic polymer flocculant that grew up in recent years, and bodied ferric sulfate and traditional flocculation agent such as iron trichloride, Tai-Ace S 150, chloro sulphuric acid iron phase ratio have advantages such as dosage is little, turbidity removal rate is high, good decolorizing effect.Preparation method of poly-ferric sulfate is varied, but all comprised ferrous sulfate in acidic solution through processes such as oxidation, hydrolysis and polymerizations.If divide by the difference of mode of oxidizing, preparation method of poly-ferric sulfate is divided into two big classes: (1) direct oxidation method, promptly adopt strong oxidizer H
2O
2, NaClO, KClO
3, MnO
2Ferrous ion is oxidized to iron ion Deng directly, obtains bodied ferric sulfate through hydrolysis and polymerization again; (2) catalytic oxidation promptly under the effect of catalyzer, utilizes air or oxygen that ferrous ion is oxidized to iron ion, obtains bodied ferric sulfate through hydrolysis and polymerization equally.Direct oxidation method is because the oxidant consumption amount is very big, and cost is too high, and the separation costs of the residue of in addition being introduced by oxygenant is bigger, does not separate and will influence the quality of product, so be difficult to suitability for industrialized production.
At present, produce bodied ferric sulfate both at home and abroad and generally adopt catalytic oxidation, mainly select NaNO for use
2, HNO
3As catalyzer, for example Japan's special permission discloses clear 51-17518 and discloses a kind of preparation method of poly-ferric sulfate, is with FeSO
4Be raw material, under certain temperature, pressure, with NaNO
2Be catalyzer, use atmospheric oxidation, get bodied ferric sulfate through hydrolysis, polyreaction.Publication number is CN 1040505A(1990) the Chinese patent application disclosed method be with NaNO
2Be catalyzer, FeSO
4With getting bodied ferric sulfate with sulfuric acid reaction after the atmospheric oxidation.Publication number is CN 1053322A(1991) the Chinese patent application disclosed method be with HNO
3Be catalyzer and oxygenant, FeSO
4At H
2SO
4Exist and after peroxidation, hydrolysis, polymerization, get bodied ferric sulfate down.Prior art adopts the method for above-mentioned Catalyst Production bodied ferric sulfate to have following shortcoming:
(1) reaction times oversize, need more than 17 hours, make that plant efficiency is low, cost is high;
(2) with NaNO
2Oxidizing reaction during for the Preparation of Catalyst bodied ferric sulfate is as follows:
As seen emit nitrogen oxide in the reaction process, polluted environment;
(3) with HNO
3Be the Catalyst Production bodied ferric sulfate, need a large amount of HNO
3, owing to use HNO
3Can produce nitrogen oxide, thereby increase the weight of pollution environment.
(4) all there is great dependency in these production methods to acidity, promptly Suan input amount must could guarantee not occur in the final product mixture ferric hydroxide precipitate very greatly, and the increase of the input amount of acid must reduce the basicity of product, thereby influences its flocculating effect.
The molecular formula of bodied ferric sulfate can be expressed as ［ Fe
2(OH)
n(SO)
3-n/2M, its corresponding basicity is n/6 * 100%, and the basicity of bodied ferric sulfate is high more, and promptly n is big more, and product polymerization degree m is also high more, and the alumen ustum of its formation is big more, and flocculating effect is good more, and the settling velocity of flco is fast more.The basicity of China's regulation bodied ferric sulfate first grade must reach more than 12%, and the basicity of Nippon Standard sample is defined as 8.33～16.7%, and basicity surpasses 16.67% polyaluminum sulfate iron product and is not reported so far.Therefore, the basicity of managing to improve bodied ferric sulfate just becomes an important channel of improving quality product.
The object of the present invention is to provide a kind of preparation method of poly-ferric sulfate, shorten the reaction times, enhance productivity, reduce cost.
The present invention also aims to provide a kind of preparation method of poly-ferric sulfate, adopt new catalyzer, just can finish entire reaction,, reduce environmental pollution so that emit nitrogen oxide in the basically eliminate reaction process with few consumption.
The prior purpose of the present invention is to provide a kind of preparation method of poly-ferric sulfate, adopts new catalyzer, this production method is greatly reduced the dependency of acidity, thereby can significantly improve basicity, improves the flocculating effect of product greatly.
Production method of the present invention is to be raw material with the ferrous sulfate, and aluminum nitrate is a catalyzer, obtains the compound poly-ferric aluminium sulfate product through peroxidation, hydrolysis, polyreaction under acidic conditions.
The catalyzer that the present invention adopts is industrial aluminum nitrate, also can be to form the aluminum oxide of aluminum nitrate or the mixture of aluminium salt and nitric acid.
Because it is catalyzer that the present invention adopts aluminum nitrate, contain aluminium in the product that the reaction back is formed, form compound poly-ferric aluminium sulfate.Facts have proved that containing aluminium in the polyaluminum sulfate iron product has promoter action to handling waste water etc.
In fact, the contriver once selected for use nitrate such as peroxy-nitric acid sodium, zinc nitrate, manganous nitrate to make catalyzer, and the polyiron sulfate that makes there is no promoter action to handling waste water, and also contain sodium in the product, impurity such as zinc and manganese.It is catalyzer that the contriver also selects peroxy-nitric acid, iron nitrate for use, and the bodied ferric sulfate that makes is purified product, but does not also have particular performances.In the present invention, aluminum nitrate is not only a kind of catalyzer, and it still is a kind of buffer reagent, thereby has alleviated the dependency of reaction system to acidity significantly, makes acidity become so unimportant to the influence of reaction; It is again the promotor of a kind of hydrolysis and polyreaction simultaneously, makes oxidation, hydrolysis and polymerization process more balancedly carry out synchronously; Aluminum nitrate also is a kind of stable metallic salt oxygenant, is characterized in that consumption is few, thus must discharge a large amount of nitrogen oxides when having avoided employing produced in conventional processes bodied ferric sulfate, basically eliminate environmental pollution.
Specific embodiment of the present invention is that 28.0%～32.0% weight percent sulfuric acid is ferrous, 4.5%～7.0% weight percent sulfuric acid, 1.0%～10.0% weight nitric acid aluminium, 51.0%～66.5% weight adds in the reactor, being stirred to each component mixes, the oxygen valve of outwarding winding, oxygen flow is adjusted in 0.03～0.10 reactor volume/min scope, and begin to heat, control reaction temperature is in 110～150 ℃ of scopes, and by regulating purging valve system pressure is controlled between 1.0～4.0atm, react and promptly made a kind of homogeneous in about 1 hour, red-brown thickness compound poly-ferric aluminium sulfate.
The ferrous sulfate that the present invention adopts can be industrial ferrous sulfate or sulfur acid ferrous slag, waste residue, and the sulfuric acid that the present invention adopts can be industrial sulphuric acid or vitriolated spent acid.
The present invention compared with prior art has following advantage:
(1) because the present invention adopts aluminum nitrate to make catalyzer, makes the product of producing contain the aluminium composition, become compound poly-ferric aluminium sulfate, promoter action is arranged handling waste water etc.
(2) the present invention is owing to adopt the aluminum nitrate catalyzer of minute quantity just can finish entire reaction course, thereby can reduce even avoid the pollution to environment.
(3) production method of the present invention can alleviate the dependency of reaction system to acidity, reaches product more than 20% thereby can produce basicity.
(4) the present invention produces the method reaction times weak point of compound poly-ferric aluminium sulfate, about 1 hour, has improved production efficiency greatly, has reduced cost.
Below in conjunction with embodiment the present invention is made and to further specify.
Embodiment 1
629 kilograms of industrial ferrous sulfates, 90.2 kilograms of sulfuric acid, 37.4 kilograms of industrial nitric acid aluminium and 1243.4 kg of water are added 3m successively
3In the reactor, start stirrer, each component mixed rapidly, the oxygen valve of slowly outwarding winding then, with the Flow-rate adjustment of oxygen at 5.4m
3/ h, and begin heating, control reaction temperature and is controlled at system pressure between 1.0～3.5 by regulating purging valve in 115～125 ℃ of scopes, and the system pressure experience raises, reduces, raises, reduces, three circulations like this.Be reflected in 42 minutes and finish, obtain a kind of homogeneous, the thick compound poly-ferric aluminium sulfate product of red-brown, its basicity is 20.59%, and total iron content is 170.4g/L, can not detect ferrous ion.
Embodiment 2
Production method is with embodiment 1, and wherein the prescription of material is as follows:
Ferrous sulfate: 606.8 kilograms;
Sulfuric acid: 108.2 kilograms;
Aluminum nitrate: 113.4 kilograms;
Water: 1171.6 kilograms.
Reaction conditions is as follows:
The flow of oxygen: 9m
3/ h;
Temperature of reaction: 110～120 ℃;
System pressure: 1.4～3.5atm.
This is reflected in 28 minutes and finishes, and promptly makes a kind of homogeneous, the thick compound poly-ferric aluminium sulfate product of red-brown, and its basicity is 19.12%, and total iron content is that 175.2g/L can not detect ferrous ion.
Embodiment 3
Production method is with embodiment 1, and wherein the prescription of material is as follows:
Ferrous sulfate: 573.6 kilograms;
Sulfuric acid: 138.8 kilograms;
Aluminum nitrate: 194.4 kilograms;
Water: 1093.2 kilograms.
Reaction conditions is as follows:
The flow of oxygen: 14.4m
3/ h;
Temperature of reaction: 135～145 ℃;
System pressure: 1.0～4.0atm.
Reaction was carried out 22 minutes, promptly made a kind of homogeneous, the thick compound poly-ferric aluminium sulfate product of red-brown, and its basicity is 19.98%, and total iron content is 168.5g/L, can not detect ferrous ion.
Embodiment 4
Production method is with embodiment 1, and wherein the prescription of material is as follows:
Ferrous sulfate: 629.0 kilograms;
Sulfuric acid: 99.2 kilograms;
Aluminum nitrate: 22.6 kilograms;
Water: 1249.2 kilograms.
Reaction conditions is as follows:
The flow of oxygen: 18m
3/ h;
Temperature of reaction: 140～150 ℃;
System pressure: 1.4～3.5atm.
Reaction has been carried out 75 minutes, promptly makes a kind of homogeneous, the thick compound poly-ferric aluminium sulfate product of red-brown, and its basicity is 19.43%, and total iron content is 172.9g/L, can not detect ferrous ion.
Table 1 is with the compound poly-ferric aluminium sulfate flocculation agent of the inventive method production and with NaNO
2Or HNO
3Flocculating effect contrast for the polymeric ferric sulfate flocculant of Catalyst Production.
The person of getting village section Pearl River water detects, and its turbidity is 50ppm.
Measuring method: get the Glass Containers that 1 liter of river is put into 2 liters, stirred 3 minutes fast, add flocculation agent, stirred slowly 10 minutes with the speed of 60rpm again, left standstill then 20 minutes, get supernatant liquor and survey its turbidity with 180rpm speed.
Table 1
| Sequence number | Flocculation agent | Basicity (%) | Consumption (ppm) | Delivery turbidity (ppm) |
| 1 | The compound poly-ferric aluminium sulfate of embodiment 1 | 20.59 | 10 | 2.7 |
| 2 | The compound poly-ferric aluminium sulfate of embodiment 2 | 19.12 | 10 | 2.9 |
| 3 | The compound poly-ferric aluminium sulfate of embodiment 3 | 19.98 | 10 | 2.3 |
| 4 | The compound poly-ferric aluminium sulfate of embodiment 4 | 19.43 | 10 | 4.1 |
| 5 | With HNO 3Bodied ferric sulfate for Catalyst Production | 14.53 | 30 | 4.6 |
| 6 | With NaNO 2PFAS for Catalyst Production | 12.94 | 35 | 4.8 |
Table 1 data presentation obviously is better than existing flocculant poly ferric sulfate with the flocculating effect of the compound poly-ferric aluminium sulfate that the inventive method is produced.
Claims (2)
1, a kind of production method of compound poly-ferric aluminium sulfate is characterized in that with the ferrous sulfate being that raw material, aluminum nitrate are catalyzer, carries out oxidation, hydrolysis, polyreaction under acidic conditions.
2, according to the production method of claim 1, it is characterized in that 28.0%～32.0% weight percent sulfuric acid is ferrous, 4.5%～7.0% weight percent sulfuric acid, 1.0%～10.0% weight nitric acid aluminium, 51.0%～66.5% weight water add in the reactor, being stirred to each component mixes, the oxygen valve of outwarding winding, oxygen flow is adjusted in 0.03～0.10 reactor volume/min scope, and begin to heat, control reaction temperature and is controlled at system pressure between 1.0～4.0atm by regulating purging valve in 110～150 ℃ of scopes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117429A CN1037762C (en) | 1994-11-04 | 1994-11-04 | Process for producing compound poly-ferric aluminium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117429A CN1037762C (en) | 1994-11-04 | 1994-11-04 | Process for producing compound poly-ferric aluminium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101896A true CN1101896A (en) | 1995-04-26 |
| CN1037762C CN1037762C (en) | 1998-03-18 |
Family
ID=5038341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94117429A Expired - Fee Related CN1037762C (en) | 1994-11-04 | 1994-11-04 | Process for producing compound poly-ferric aluminium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037762C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999048814A1 (en) * | 1998-03-23 | 1999-09-30 | Imperial College Of Science, Technology & Medicine | Preparation and uses of mixed metal coagulants |
| CN100391861C (en) * | 2004-06-04 | 2008-06-04 | 刘启旺 | One step synthesis of polymerized aluminum-iron sulfurate from industrial waste slags |
| CN103991912A (en) * | 2014-06-17 | 2014-08-20 | 山东三丰集团股份有限公司 | Synthesis process of polymeric aluminum ferric sulfate |
| CN104710068A (en) * | 2015-03-16 | 2015-06-17 | 南京环保产业创新中心有限公司 | Treatment and recycling method for chloromethylated bead production wastewater |
| CN104973669A (en) * | 2015-06-10 | 2015-10-14 | 天津大港油田滨港集团博弘石油化工有限公司 | Preparation method of organically modified polymeric aluminum ferric sulfate flocculant |
| CN105906017A (en) * | 2016-06-23 | 2016-08-31 | 江门市江海区炜洁净水材料有限公司 | Preparing method for polymeric aluminum ferric sulfate water purifying agent |
| CN106517474A (en) * | 2016-10-12 | 2017-03-22 | 上海丰远环保科技有限公司 | Composite chemical nickel remover and application thereof |
| CN108675418A (en) * | 2018-05-17 | 2018-10-19 | 深圳市长隆科技有限公司 | A kind of polysilicate aluminium ferric flocculant and preparation method thereof |
| KR20230027635A (en) * | 2021-08-19 | 2023-02-28 | 최윤진 | Method of producing PloyAluminumFerricSulfate aqueous solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1659361A1 (en) * | 1989-02-20 | 1991-06-30 | Киевский Политехнический Институт Им.50-Летия Великой Октябрьской Социалистической Революции | Method of producing a coagulant |
| CN1051155A (en) * | 1989-10-27 | 1991-05-08 | 鞍山钢铁学院 | The process for making iron polymer that is used to purify waste water |
| CN1020445C (en) * | 1990-01-13 | 1993-05-05 | 廖为鑫 | Producing process for poly-ferric sulphate |
| CN1076914A (en) * | 1992-08-31 | 1993-10-06 | 山东建筑工程学院 | The production technique of bodied ferric sulfate and device |
-
1994
- 1994-11-04 CN CN94117429A patent/CN1037762C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999048814A1 (en) * | 1998-03-23 | 1999-09-30 | Imperial College Of Science, Technology & Medicine | Preparation and uses of mixed metal coagulants |
| CN100391861C (en) * | 2004-06-04 | 2008-06-04 | 刘启旺 | One step synthesis of polymerized aluminum-iron sulfurate from industrial waste slags |
| CN103991912A (en) * | 2014-06-17 | 2014-08-20 | 山东三丰集团股份有限公司 | Synthesis process of polymeric aluminum ferric sulfate |
| CN103991912B (en) * | 2014-06-17 | 2015-09-23 | 山东三丰集团股份有限公司 | A kind of synthesis technique of PFAS |
| CN104710068A (en) * | 2015-03-16 | 2015-06-17 | 南京环保产业创新中心有限公司 | Treatment and recycling method for chloromethylated bead production wastewater |
| CN104973669A (en) * | 2015-06-10 | 2015-10-14 | 天津大港油田滨港集团博弘石油化工有限公司 | Preparation method of organically modified polymeric aluminum ferric sulfate flocculant |
| CN105906017A (en) * | 2016-06-23 | 2016-08-31 | 江门市江海区炜洁净水材料有限公司 | Preparing method for polymeric aluminum ferric sulfate water purifying agent |
| CN106517474A (en) * | 2016-10-12 | 2017-03-22 | 上海丰远环保科技有限公司 | Composite chemical nickel remover and application thereof |
| CN108675418A (en) * | 2018-05-17 | 2018-10-19 | 深圳市长隆科技有限公司 | A kind of polysilicate aluminium ferric flocculant and preparation method thereof |
| KR20230027635A (en) * | 2021-08-19 | 2023-02-28 | 최윤진 | Method of producing PloyAluminumFerricSulfate aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037762C (en) | 1998-03-18 |
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