CN101269868B - Method for preparing poly-silicic acid iron sulfate - Google Patents
Method for preparing poly-silicic acid iron sulfate Download PDFInfo
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- CN101269868B CN101269868B CN2008100696421A CN200810069642A CN101269868B CN 101269868 B CN101269868 B CN 101269868B CN 2008100696421 A CN2008100696421 A CN 2008100696421A CN 200810069642 A CN200810069642 A CN 200810069642A CN 101269868 B CN101269868 B CN 101269868B
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Abstract
The invention discloses a preparation method of polymeric ferric silicate sulfate, which includes the steps of the preparation of ferric sulfate solution, the preparation of polysilicic acid, and the preparation technology of polymeric ferric silicate sulfate. Iron ore is used as the raw material to prepare a new generation of good quality water purifying agent polymeric ferric silicate sulfate which is a composite inorganic polymeric flocculant that has the characteristics of malysites and silicates and has the advantages of strong coagulability, large alum floc, and quick sedimentation, so the composite inorganic polymeric flocculant is in particular suitable for the treatment of gas field water, and has better water purification property and wide application range. The flocculant of the invention is added in the gas field water in the east of Sichuan, the better flocculating effect is achieved. The preparation method of the invention not only provides a feasible path for the comprehensive utilization of the iron ore, but also provides a technological route with low raw material for the flocculant production, thereby the purpose of treating the waste by the waste is achieved, and better economic benefit, social benefit, and environmental benefit are obtained.
Description
Technical field
The invention belongs to the flocculation agent preparing technical field, be specifically related to the preparation method of polysilicate sulfuric acid ferric flocculant.
Background technology
China is since later 1960s is used flocculation agent in water treatment since, inorganic flocculating agent is just with advantages such as its low toxicity, cheapness, preparation method are simple relatively occuping market dominant position all the time, and initial main what use is first-generation inorganic salts such as Tai-Ace S 150, aluminum chloride, iron(ic) chloride.S-generation inorganic flocculating agents such as PAC, PFC, PFS are successively developed and introduced to the eighties.
The advantage of inorganic flocculating agent is that it is more excellent than traditional inorganic salt flocculation agent flocculating effect, and cheaper than organic polymer coargulator price.But aspect form, the polymerization degree and corresponding cohesion-flocculating effect, inorganic flocculating agent still is in the position between conventional metals salt flocculation agent and the organic polymer coargulator.Its molecular weight and globule size and flocculation bridge formation ability are still far short of what is expected than organic polymer coargulator, but also have the instability problem of further hydrolysis reaction.These main weakness have been impelled the research and development of various composite inorganic flocculation agents.
The nineties, have more distinctive third generation inorganic flocculating agent-multi-kernel high-molecular inorganic flocculant: PAFC, PAFS, PASi etc. constantly are developed out, production cost increases or the product storage stability shortens but be limited to, and its commercial prod is also few.At present, in various water treatments the consumption maximum, use the widest remaining to utilize the PAC and the PFS of various raw materials and various explained hereafter.
In the actual application, the use meeting of aluminum salt flocculant brings secondary pollution to environment, active aluminum especially, and toxicity is bigger, and this has limited the use of polymeric aluminum to a certain extent.Being used for Drinking Water, process water, various trade effluent, town sewage and desliming water purification at present, to handle more be bodied ferric sulfate.But, polymerization iron product poor stability, polymerization promptly transferred precipitation in several hours to a week, and flocculating effect is lower, is not suitable for the processing to gas-field water.
Summary of the invention
At the prior art above shortcomings, the purpose of this invention is to provide a kind of is main raw material with iron ore, the industrial vitriol oil, service water glass, prepare cheaply, good stability, flocculating effect are good, and are applicable to the novel method of the polysilicate sulfuric acid ferric flocculant that gas-field water is handled.
The object of the present invention is achieved like this: a kind of preparation method of poly-silicic acid iron sulfate comprises following steps:
(1) preparation of ferrum sulfuricum oxydatum solutum:
1) powdered iron ore that iron ore is ground to form is calcined 2-3h under 750-900 ℃ of condition, cool off standby;
2) getting mass percent concentration is that the industrial sulphuric acid of 36%-40% is in the container that has whipping appts; Taking by weighing iron ore powder joins in the described sulphuric acid soln and mixes; Wherein iron ore and vitriolic mass ratio satisfy 1: 6 requirement:
3) again with the 2nd) step blended iron ore and sulphuric acid soln is under 100 ℃ constant temperature, reaction 2-3h obtains the acidic solution of sulfur acid iron, then through overcooling, filter the ferrum sulfuricum oxydatum solutum that obtains;
(2) preparation of poly-silicate solution: at room temperature, the sulphuric acid soln of getting mass percent concentration and be 20-40% is standby; Take by weighing modulus less than 3 service water glass, preparation SiO
2Content is the Na of 2-3%
2SiO
3Solution for standby; Measure described Na
2SiO
3Solution slowly joins in the above-mentioned ready sulphuric acid soln, and the vigorous stirring while adding stops when making pH value reach 2-4 adding, leave standstill 10min after, can obtain poly-silicate solution;
(3) preparation of poly-silicic acid iron sulfate: the ferrum sulfuricum oxydatum solutum that step (1) is obtained joins in the poly-silicate solution that step (2) obtains, and carries out polyreaction, stirs, and slaking obtains poly-silicic acid iron sulfate; Wherein, in the sulfur acid ferrous solution of adding in the amount of substance of iron and the poly-silicic acid ratio of the amount of substance of silicon be 2: 1.
The present invention has following beneficial effect:
1, utilize iron ore for raw material prepares high-quality water purification agent poly-silicic acid iron sulfate of new generation, be the composite type inorganic polymer flocculation agent, have the characteristic of molysite class and silicates flocculation agent concurrently, it is strong to have coagulability, alumen ustum is big, and the advantage that sedimentation is fast is particularly suited for the processing of gas-field water; Have good water purification performance and range of application widely.
2, the iron ore raw material is cheap and easy to get and harmless, low, the good product quality of production cost; And the preparation method is simple, and operation is simple.
3, the present invention not only provides a feasible way to the comprehensive utilization of iron ore, and the operational path of a raw material cheapness is provided for flocculation agent production simultaneously, has reached the purpose of the treatment of wastes with processes of wastes against one another, has obtained good economic benefit, social benefit and environmental benefit.
Embodiment
The invention will be further described below by embodiment.
The present invention is a main raw material with iron ore, the industrial vitriol oil (36%-40%), water glass (service water glass), with water as reaction solvent, low, the good product quality of production cost; And the preparation method is simple, and operation is simple.
Embodiment 1
Step 1: the preparation of ferrum sulfuricum oxydatum solutum
Take by weighing after the 200g iron ore grinds to form-200 purpose powdered iron ore, put into muffle furnace at 800 ℃ of calcining 2h down, the cooling back is standby.Measure the 100ml mass percent concentration and be 40% sulphuric acid soln in the four-hole boiling flask that has whipping appts of 500ml, take by weighing aforementioned standby powdered iron ore 8.17g, join in the described sulphuric acid soln, react 2h down at 100 ℃, can obtain the solution of sulfur acid iron behind the cold filtration, wherein Fe2 (SO4) 3 concentration are 0.84mol/L.
Step 2: the preparation of polymeric silicicacid
At room temperature, getting mass percent concentration is 20% H
2SO
4Solution 100ml places beaker standby.Take by weighing service water glass specimen (modulus is 2.7), preparation SiO
2Content is 2% Na
2SiO
3Solution for standby.Measure 2% Na
2SiO
3Solution slowly joins above-mentioned ready 100ml mass percent concentration and is in 20% the sulphuric acid soln, and the vigorous stirring while adding makes pH value reach at 3 o'clock and stops to add, and behind the activation 10min, can obtain poly-silicate solution.
Step 3: the preparation of poly-silicic acid iron sulfate
Measure the poly-silicic acid 200ml that obtains by step 2 and place beaker to mix by the ferrum sulfuricum oxydatum solutum 151ml that step 1 obtains, make that the iron silicon mol ratio is 2: 1, behind the stirring 1h, leave standstill 24h again, can obtain flocculation agent---poly-silicic acid iron sulfate, recording its transmittance is 98%.
Embodiment 2
Step 1: the preparation of ferrum sulfuricum oxydatum solutum is identical with the step 1 of embodiment 1;
Step 2: the preparation of polymeric silicicacid
At room temperature, getting mass percent concentration is 20% H
2SO
4Solution 100ml places beaker standby.Take by weighing service water glass specimen (modulus is 2.7), preparation SiO
2Content is 2% Na
2SiO
3Solution for standby.Measure 2% Na
2SiO
3Solution slowly joins above-mentioned ready 100ml mass percent concentration and is in 20% the sulphuric acid soln, and the vigorous stirring while adding makes pH value reach at 3 o'clock and stops to add, and behind the activation 20min, can obtain poly-silicate solution.
Step 3: the preparation of poly-silicic acid iron sulfate
Measure the poly-silicic acid 200ml that obtains by step 2 and place beaker to mix by the ferrum sulfuricum oxydatum solutum 151ml that step 1 obtains, make that the iron silicon mol ratio is 2: 1, behind the stirring 1h, leave standstill 24h again, can obtain flocculation agent---poly-silicic acid iron sulfate, recording its transmittance is 99%.
Embodiment 3
Step 1: the preparation of ferrum sulfuricum oxydatum solutum
Step 1 in the reference example 1;
Step 2: the preparation of polymeric silicicacid
At room temperature, getting mass percent concentration is 20% H
2SO
4Solution 100ml places beaker standby.Take by weighing service water glass specimen (modulus is 2.7), preparation SiO
2Content is 3% Na
2SiO
3Solution for standby.Measure 3% Na
2SiO
3Solution slowly joins above-mentioned ready 100ml mass percent concentration and is in 20% the sulphuric acid soln, and the vigorous stirring while adding makes pH value reach at 3 o'clock and stops to add, and behind the activation 10min, can obtain poly-silicate solution.
Step 3: the preparation of poly-silicic acid iron sulfate
Measure the poly-silicic acid 200ml that obtains by step 2 and place beaker to mix by the ferrum sulfuricum oxydatum solutum 227ml that step 1 obtains, make that the iron silicon mol ratio is 2: 1, behind the stirring 1h, leave standstill 24h again, can obtain flocculation agent---poly-silicic acid iron sulfate, recording its transmittance is 99%.
Embodiment 4
Step 1: the preparation of ferrum sulfuricum oxydatum solutum
The step 1 of reference example 1;
Step 2: the preparation of polymeric silicicacid
At room temperature, getting mass percent concentration is 40% H
2SO
4Solution 100ml places beaker standby.Take by weighing service water glass specimen (modulus is 2.7), preparation SiO
2Content is 2% Na
2SiO
3Solution for standby.Measure 2% Na
2SiO
3Solution slowly joins above-mentioned ready 100ml mass percent concentration and is in 20% the sulphuric acid soln, and the vigorous stirring while adding makes pH value reach at 2 o'clock and stops to add, and behind the activation 10min, can obtain poly-silicate solution.
Step 3: the preparation of poly-silicic acid iron sulfate
Measure the poly-silicic acid 200ml that obtains by step 2 and place beaker to mix by the ferrum sulfuricum oxydatum solutum 151ml that step 1 obtains, make that the iron silicon mol ratio is 2: 1, behind the stirring 1h, leave standstill 24h again, can obtain flocculation agent---poly-silicic acid iron sulfate, recording its transmittance is 93%.
Embodiment 5
Step 1: the preparation of ferrum sulfuricum oxydatum solutum
Identical with the step 1 among the embodiment 1;
Step 2: the preparation of polymeric silicicacid
At room temperature, getting mass percent concentration is 20% H
2SO
4Solution 100ml places beaker standby.Take by weighing service water glass (modulus is 2.7) sample, preparation SiO
2Content is 2% Na
2SiO
3Solution for standby.Measure 2% Na
2SiO
3Solution slowly joins above-mentioned ready 100ml mass percent concentration and is in 20% the sulphuric acid soln, and the vigorous stirring while adding makes pH value reach at 3 o'clock and stops to add, and behind the activation 10min, can obtain poly-silicate solution.
Step 3: the preparation of poly-silicic acid iron sulfate
Measure the poly-silicic acid 200ml that obtains by step 2 and place beaker to mix by the ferrum sulfuricum oxydatum solutum 151ml that step 1 obtains, make that the iron silicon mol ratio is 3: 1, behind the stirring 1h, leave standstill 24h again, can obtain flocculation agent---poly-silicic acid iron sulfate, recording its transmittance is 95%.
According to experiment as can be known: along with SiO
2The increase of content and soak time, the flocculating effect of flocculation agent improves.But work as SiO
2Content surpasses 2%, and when soak time surpassed 10min, flocculating effect improved not obvious.So best SiO
2Content is 2%, and best silicic acid soak time is 10min.
Along with the Fe/Si mole increases, the flocculating effect of flocculation agent improves.But when Fe/Si＞2, along with the increase of Fe/Si mol ratio, flocculating effect reduces on the contrary, so best Fe/Si mol ratio is 2.
Along with silicic acid activatory pH value increases, the flocculating effect of flocculation agent improves.But when the PH of silicic acid surpassed 3.0, the flocculating effect of flocculation agent reduced on the contrary.Best silicic acid activatory pH value is 3.0.
The using method of polysilicate sulfuric acid ferric flocculant of the present invention is as follows: regulating the gas-field water pH value with acid or alkali is 6～10, add flocculation agent of the present invention, on magnetic stirring apparatus, carry out coagulation experiment under the room temperature, stir 2min earlier fast, flocculation agent is fully disperseed, stir 8min more at a slow speed, after reacting completely, leave standstill 20min, get, carry out water quality analysis apart from the supernatant liquor at liquid level 30mm place.
Adopt polysilicate sulfuric acid ferric flocculant of the present invention to be: to get the 500ml water sample to the detailed process of the processing of gas-field water, after regulating waste water PH and be 7.0 with dilute sulphuric acid, the amount that adds flocculation agent PFSS of the present invention is 200g, is to stir 2min under the 300r/min at rotating speed, and flocculation agent is fully disperseed, the adjusting rotating speed is 80r/min, stir 10min, leave standstill 20min after, get apart from the supernatant at liquid level 30mm place, carry out water quality analysis, the COD clearance can reach 75%.
Specify that the % that this paper relates to (percentage concentration) is weight percent concentration.
The invention discloses a kind of preparation method and application thereof of flocculation agent.Comprise choosing of raw material, steps such as the preparation of poly-silicic acid iron sulfate, the product of the present invention preparation is the composite type inorganic polymer flocculation agent, has the characteristic of molysite class and silicates flocculation agent concurrently, has good water purification performance and range of application widely.In the gas-field water of east, river, add flocculation agent of the present invention, reach good flocculating effect.
Claims (2)
1. the preparation method of a poly-silicic acid iron sulfate is characterized in that comprising following steps:
(1) preparation of ferrum sulfuricum oxydatum solutum:
1) powdered iron ore that iron ore is ground to form, calcination 2-3h under 750-900 ℃ of condition cools off standby;
2) getting mass percent concentration is that the sulphuric acid soln of 36%-40% is in the container that has whipping appts; Taking by weighing iron ore powder joins in the described sulphuric acid soln and mixes; Wherein iron ore and vitriolic mass ratio satisfy 1: 6 requirement;
3) again with the 2nd) step blended iron ore and sulphuric acid soln is under 100 ℃ constant temperature, reaction 2-3h obtains the acidic solution of sulfur acid iron, then through overcooling, filter the ferrum sulfuricum oxydatum solutum that obtains;
(2) preparation of poly-silicate solution: at room temperature, the sulphuric acid soln of getting mass percent concentration and be 20-40% is standby; Take by weighing modulus less than 3 fourth industry water glass, preparation SiO
2Content is the Na of 2-3%
2SiO
3Solution for standby; Measure described Na
2SiO
3Solution slowly joins in the above-mentioned ready sulphuric acid soln, and the vigorous stirring while adding stops when making pH value reach 2-4 adding, leave standstill 10min after, can obtain poly-silicate solution;
(3) preparation of poly-silicic acid iron sulfate: with the iron silicon mol ratio is 2: 1 conditions, the solution of the sulfur acid iron that step (1) is obtained joins in the poly-silicate solution that step (2) obtains, and carries out polyreaction, stirs 1h, leave standstill 24h again, can obtain the polysilicate sulfuric acid ferric flocculant.
2. according to the preparation method of the described polysilicate sulfuric acid ferric flocculant of claim 1, it is characterized in that: described sodium silicate solution is the solution of water glass preparation, SiO
2Weight percent amount is 2%, and sulfuric acid concentration is controlled at 20%, and pH value is controlled in 3, and the silicic acid soak time is 10min.
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| CN101823721A (en) * | 2010-03-19 | 2010-09-08 | 合肥学院 | Method for producing poly silicate aluminium ferric flocculating agent by utilizing coal gangue |
| CN101830549B (en) * | 2010-06-02 | 2011-10-19 | 武汉理工大学 | Directly-treating method for high-basicity and high-turbidity difficultly-treated flotation colloidal ore pulp of hematite with high phosphorus content |
| CN102616910A (en) * | 2012-03-31 | 2012-08-01 | 昆明理工大学 | Method for preparing inorganic high molecular flocculating agent ferric polysilicate from yellow phosphorus furnace slag |
| CN104211153A (en) * | 2014-09-22 | 2014-12-17 | 陕西华陆化工环保有限公司 | Preparation method of polyiron silicate sulfate flocculant |
| CN105293666A (en) * | 2015-12-12 | 2016-02-03 | 沧州泓海化工有限公司 | Composite flocculant |
| CN105502606A (en) * | 2016-01-17 | 2016-04-20 | 济南大学 | Aggregated inorganic iron flocculant prepared from abandoned warm paste |
| CN112358021A (en) * | 2020-12-31 | 2021-02-12 | 常州市五洲化工有限公司 | Preparation method of composite coagulant |
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| CN1389407A (en) * | 2001-06-03 | 2003-01-08 | 邵阳市佑华净水材料有限公司 | Solid ferric silicosulfate polymer and its production process |
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| CN1389407A (en) * | 2001-06-03 | 2003-01-08 | 邵阳市佑华净水材料有限公司 | Solid ferric silicosulfate polymer and its production process |
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