CN106395915B - A kind of synthetic method of poly-ferric sulfate chloride - Google Patents
A kind of synthetic method of poly-ferric sulfate chloride Download PDFInfo
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- CN106395915B CN106395915B CN201610777300.XA CN201610777300A CN106395915B CN 106395915 B CN106395915 B CN 106395915B CN 201610777300 A CN201610777300 A CN 201610777300A CN 106395915 B CN106395915 B CN 106395915B
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Abstract
The invention discloses a kind of synthetic method of poly-ferric sulfate chloride, first adjusts the Fe in iron content Waste Sulfuric Acid2+Content >=4.5wt%, H2SO4Content >=6.0wt%；Adjust the Fe in waste hydrochloric acid containing iron2+Content >=11wt%, HCl content >=6.0wt%；It is 1 according still further to mass ratio：0.25~1：1.39~1.49 add iron content Waste Sulfuric Acid, waste hydrochloric acid containing iron and ferrous sulfate heptahydrate, squeeze into cyclic oxidation reactor；Sodium chlorate solution and sodium nitrite solution are successively added, is passed through oxygen；When all iron content is 10.0~11.5wt%, Fe2+≤ 0.1wt%, react and terminate when basicity is 4~16%.Present invention reduces pollution of the spent acid to environment, and product stability is good, and flocculating effect is good, and production cost is low, and the production cycle substantially shortens, and saves energy consumption, reduce further production cost.
Description
Technical field
The present invention relates to a kind of synthetic method of poly-ferric sulfate chloride.
Background technology
China's titanium dioxide yield and the yield of steel are at the forefront in the world at present, but technique relatively falls behind, and titanium dioxide uses more
Production By Sulfuric Acid Process, a large amount of iron content Waste Sulfuric Acids are produced in process of production；Derusted, produced using hydrochloric acid in steel electroplating industry
A large amount of waste hydrochloric acid containing irons.Current solution party's fado produces a large amount of waste residues, and cost is very high to be neutralized with alkali.Part
Enterprise is the cost-effective row of stealing, and causes environmental pollution.
It is at present most important medicament in the sewage treatment area in China, iron system water treatment agent.Bodied ferric sulfate, trichlorine
Change the single Water purification medicaments such as iron to be commonly employed in fields such as various paper pulp wastewaters, dyeing waste water, municipal wastewaters.At present
This two kinds of products are mainly produced using iron ore acid extracting and ferrous oxidation method, and production cost is higher, easily produce pollution, system
About production-scale expansion.
Chinese patent CN02128373.7《The production new technique of polymerization ferric chloride purifying agent》Disclosed method is：With
Ferrous sulfate, chlorine are raw material, are aoxidized with gas-liquid belt pressing type inner loop mode blended absorbent.The method is using hypertoxic danger
Product chlorine is as oxidant, and reaction is whard to control, and the requirement to equipment is high, if misoperation causes chlorine, leakage easily causes
Poisoning.
Chinese patent CN201510202784.0《A kind of method that pickle liquor prepares poly-ferric sulfate chloride》It is disclosed
Method is：It is raw material with iron and steel pickling waste liquid, ferrous sulfate or iron powder and concentrated hydrochloric acid, the concentrated sulfuric acid, adds Pickering agent phosphorus
Hydrochlorate, 60-100 DEG C being then heated to, you add sodium nitrate, KI is reacted as catalyst, oxygen as oxidant,
The equipment being related to has recirculation reactor, gas branch device, tower reactor etc., total reaction time 13-31 hours.This method operates
It is cumbersome, it is necessary to additional energy heats, introduce too many foreign ion, equipment is complicated, hardly possesses in actual production operable
Property.
Chinese patent CN200910068445.2《A kind of technique for preparing poly-ferric sulfate chloride with hydrogen peroxide oxidation》It is public
The method opened is：Using ferrous sulfate and hydrochloric acid as raw material, aoxidized with hydrogen peroxide, basicity is adjusted with sodium hydroxide, and
Cured 10 days in ageing tank.This method takes oversize, high expensive.
The content of the invention
The technical problem to be solved in the present invention be overcome in the prior art iron content waste water processing cost it is high, effect is undesirable
A kind of defect, there is provided preparation method of poly-ferric sulfate chloride.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of synthetic method of poly-ferric sulfate chloride, comprises the following steps：
1) iron content Waste Sulfuric Acid, is added in the first stirring pool, by adding ferrous sulfate heptahydrate and sulfuric acid, is made in solution
Fe2+Content >=4.5wt%, H2SO4Content >=6.0wt%, obtain compound iron content Waste Sulfuric Acid；
2) waste hydrochloric acid containing iron, is added in the second stirring pool, by adding ferrous sulfate heptahydrate and hydrochloric acid, is made in solution
Fe2+Content >=11wt%, HCl content >=6.0wt%, obtain compound waste hydrochloric acid containing iron；
3) it is, 1 according to mass ratio in the 3rd stirring pool：0.25~1：1.39~1.49 addition compounding iron content Waste Sulfuric Acids,
Waste hydrochloric acid containing iron and ferrous sulfate heptahydrate are compounded, squeezes into cyclic oxidation reactor, circulating pump is opened and starts the cycle over；
4) sodium chlorate, is configured to the sodium chlorate solution that mass fraction is 40~50wt%；
5) sodium chlorate solution, is added into cyclic oxidation reactor, as reaction is carried out, material in reactor heating 10~
15 DEG C, the time that always adds of sodium chlorate solution is 5min, total dosage and the iron content in cyclic oxidation reactor of sodium chlorate solution
The mass ratio of waste hydrochloric acid, compounding iron content Waste Sulfuric Acid and ferrous sulfate heptahydrate gross mass is 0.0075~0.0094：1；
6) natrium nitrosum, is configured to the sodium nitrite solution that mass fraction is 20~25wt%；
7) sodium nitrite solution, is slowly added into cyclic oxidation reactor, while is passed through oxygen, makes reacting kettle inner pressure
For 0.15~0.30MPa, it is 1.5~3.0h that sodium nitrite solution, which always adds the time,；Total dosage of sodium nitrite solution is with following
The mass ratio of waste hydrochloric acid containing iron in epoxidation reaction kettle, compounding iron content Waste Sulfuric Acid and ferrous sulfate heptahydrate gross mass for 0.0144~
0.0288:1；
8), when reaction temperature reaches 75 ± 5 DEG C, and without bright in temperature of charge and cyclic oxidation reacting kettle inner pressure 10 minutes
During aobvious change, reaction terminates, and after the assay was approved, poly-ferric sulfate chloride finished product is made.
Further, Fe in waste hydrochloric acid containing iron2+1.5~4.5wt% of content, 13.0~24.0wt% of sulfuric acid content；Iron content
Fe in waste hydrochloric acid2+6.0~11.0wt% of content, content of hydrochloric acid 1.5~6.0%.
Further, the mass ratio of the dosage of oxygen and sodium nitrite solution is 0.6~0.75 in the step 7)：1.
Further, it is 10.0~11.5wt%, Fe to chemically examine all iron content in qualified finger product2+≤ 0.1wt%, basicity
For 4~16%.
Further, active ingredient >=85.0wt% of the ferrous sulfate heptahydrate, sulfuric acid active ingredient be 90.0~
98.0wt%, 30.0~32.5wt% of hydrochloric acid active ingredient；Active ingredient >=99wt% of sodium chlorate, natrium nitrosum and oxygen.
Further, described cyclic oxidation reactor includes the composition such as reactor main body, recycling ejector and circulating pump
Equipment set.
The beneficial effect that is reached of the present invention is：
First, the present invention prepares poly-ferric sulfate chloride using waste hydrochloric acid containing iron and waste hydrochloric acid containing iron, reduces spent acid to ring
The pollution in border, turns waste into wealth, and products obtained therefrom has economic value, fully utilizes resource.
2nd, the present invention improves the initial velocity of oxidation reaction, makes whole system temperature first using sodium chlorate as oxidant
Degree rises, and saves the energy consumption additionally to heat up, has facilitation to subsequent catalyst oxidation；Then the use of oxygen is oxidant,
The harm using chlorine or hydrogen peroxide is avoided, while saves cost；Course of reaction is without additionally add other catalyst and steady
Determine agent, do not introduce other impurities ion, ensure that the quality of product.
3rd, whole reaction only needs 2~4 hours, oxidation reaction process smooth sequential, without heating temperature-fall period suddenly, safety
Reliably, confined reaction, no pernicious gas come out, equipment and simple process, feasible, and equipment investment is low, simple to operate, is adapted to industry
Change large-scale production.The poly-ferric sulfate chloride of gained is compared with conventional polymeric ferric sulfate, and stability is good, and flocculating effect is more preferable,
Production cost is lower, and the production cycle substantially shortens, and saves energy consumption, reduce further production cost.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment
A kind of synthetic method of poly-ferric sulfate chloride, comprises the following steps：
1) 5.25t iron content Waste Sulfuric Acids, are added in the first stirring pool, Fe in waste hydrochloric acid containing iron2+Content is 4.0wt%, sulphur
Acid content is 20wt%, then adds 0.35t ferrous sulfate heptahydrates and 0.4t sulfuric acid, obtains compounding iron content Waste Sulfuric Acid；
2) waste hydrochloric acid containing iron, is added in the second stirring pool, Fe in waste hydrochloric acid containing iron2+Content is 8wt%, and content of hydrochloric acid is
3%., 0.35t ferrous sulfate heptahydrates and 0.4t sulfuric acid are then added, obtains compounding waste hydrochloric acid containing iron；
3), compounding iron content Waste Sulfuric Acid, compounding waste hydrochloric acid containing iron are squeezed into the 3rd stirring pool, add ferrous sulfate heptahydrate
8.94t, after stirring, cyclic oxidation reactor is squeezed into, open circulating pump and start the cycle over；
4) sodium chlorate, is configured to the sodium chlorate solution that mass fraction is 40~50wt%；
5) sodium chlorate solution, is added into cyclic oxidation reactor, while is heated up 10~15 DEG C, total throwing of sodium chlorate solution
It is 5min between added-time, total dosage of sodium chlorate solution is 188kg；
6) natrium nitrosum, is configured to the sodium nitrite solution that mass fraction is 20~25wt%；
7) sodium nitrite solution, is slowly added into cyclic oxidation reactor, while is passed through oxygen, makes reacting kettle inner pressure
For 0.15~0.30MPa, it is 1.5~3.0h that sodium nitrite solution, which always adds the time,；Total dosage of sodium nitrite solution is
335kg；It is passed through oxygen and amounts to 251kg.
8), when reaction temperature reaches 75 ± 5 DEG C, and without bright in temperature of charge and cyclic oxidation reacting kettle inner pressure 10 minutes
During aobvious change, reaction terminates, analysis ingredient.
9), analysis ingredient, all iron content is 10.0~11.5wt%, Fe in product2+≤ 0.1wt%, basicity be 4~
16%.
By the poly-ferric sulfate chloride product of embodiment and standard polymerization ferric sulfate, the purifying water effect pair of standard ferric trichloride
Than specific as follows：
The poly-ferric sulfate chloride product, standard polymerization ferric sulfate, each 0.6mL of standard ferric trichloride of the present embodiment are taken, is thrown
Enter in 1L pulp mills pulp-making waste-water secondary clarifier effluent, carry out coagulation stirring test, it is as a result as shown in the table：
As can be seen from the above table, poly-ferric sulfate chloride product of the invention is gone in COD, colourity, suspension
Except bodied ferric sulfate and ferric trichloride more common in rate have obvious advantage.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (6)
1. a kind of synthetic method of poly-ferric sulfate chloride, it is characterised in that comprise the following steps：
1) iron content Waste Sulfuric Acid, is added in the first stirring pool, by adding ferrous sulfate heptahydrate and sulfuric acid, makes the Fe in solution2+
Content >=4.5wt%, H2SO4Content >=6.0wt%, obtain compound iron content Waste Sulfuric Acid；
2) waste hydrochloric acid containing iron, is added in the second stirring pool, by adding ferrous sulfate heptahydrate and hydrochloric acid, makes the Fe in solution2+
Content >=11wt%, HCl content >=6.0wt%, obtain compound waste hydrochloric acid containing iron；
3) it is, 1 according to mass ratio in the 3rd stirring pool：0.25~1：1.39~1.49 add compounding iron content Waste Sulfuric Acid, compounding
Waste hydrochloric acid containing iron and ferrous sulfate heptahydrate, cyclic oxidation reactor is squeezed into, open circulating pump and start the cycle over；
4) sodium chlorate, is configured to the sodium chlorate solution that mass fraction is 40~50wt%；
5) sodium chlorate solution, is added into cyclic oxidation reactor, as reaction is carried out, material in reactor heating 10~15
DEG C, the time that always adds of sodium chlorate solution is 5min, and total dosage and the iron content in cyclic oxidation reactor of sodium chlorate solution are given up
The mass ratio of hydrochloric acid, compounding iron content Waste Sulfuric Acid and ferrous sulfate heptahydrate gross mass is 0.0075~0.0094：1；
6) natrium nitrosum, is configured to the sodium nitrite solution that mass fraction is 20~25wt%；
7) sodium nitrite solution, is slowly added into cyclic oxidation reactor, while is passed through oxygen, makes the reacting kettle inner pressure be
0.15~0.30MPa, it is 1.5~3.0h that sodium nitrite solution, which always adds the time,；Total dosage of sodium nitrite solution and circulation
The mass ratio of waste hydrochloric acid containing iron in oxidizing reactor, compounding iron content Waste Sulfuric Acid and ferrous sulfate heptahydrate gross mass for 0.0144~
0.0288:1；
8), when reaction temperature reaches 75 ± 5 DEG C, and become in temperature of charge and cyclic oxidation reacting kettle inner pressure 10 minutes without obvious
During change, reaction terminates, and after the assay was approved, poly-ferric sulfate chloride finished product is made.
A kind of 2. synthetic method of poly-ferric sulfate chloride as claimed in claim 1, it is characterised in that Fe in iron content Waste Sulfuric Acid2 +1.5~4.5wt% of content, 13.0~24.0wt% of sulfuric acid content；Fe in waste hydrochloric acid containing iron2+6.0~11.0wt% of content, salt
Acid content 1.5~6.0%.
A kind of 3. synthetic method of poly-ferric sulfate chloride as claimed in claim 1, it is characterised in that oxygen in the step 7)
The dosage of gas and the mass ratio of sodium nitrite solution are 0.6~0.75：1.
4. a kind of synthetic method of poly-ferric sulfate chloride as claimed in claim 1, it is characterised in that chemically examine qualified finger product
Middle all iron content is 10.0~11.5wt%, Fe2+≤ 0.1wt%, basicity are 4~16%.
5. a kind of synthetic method of poly-ferric sulfate chloride as claimed in claim 1, it is characterised in that the seven water sulfuric acid is sub-
Active ingredient >=85.0wt% of iron, sulfuric acid active ingredient are 90.0~98.0wt%, hydrochloric acid active ingredient 30.0~
32.5wt%；Active ingredient >=99wt% of sodium chlorate, natrium nitrosum and oxygen.
A kind of 6. synthetic method of poly-ferric sulfate chloride as claimed in claim 1, it is characterised in that described cyclic oxidation
Reactor includes reactor main body, recycling ejector and circulating pump.
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| CN107601577B (en) * | 2017-09-01 | 2023-08-11 | 河北正润环境科技有限公司 | Device and method for preparing polymeric ferric chloride by utilizing steel finishing pickling waste liquid |
| CN109081382A (en) * | 2018-10-25 | 2018-12-25 | 马鞍山健鼎化工有限公司 | A kind of processing technology of bodied ferric sulfate |
| CN111233047A (en) * | 2020-03-31 | 2020-06-05 | 龙佰四川钛业有限公司 | Preparation of polymeric ferric sulfate by comprehensive utilization of titanium white waste byproducts |
| CN111672276A (en) * | 2020-06-01 | 2020-09-18 | 深圳市长隆科技有限公司 | Resource utilization process of waste gas in production process of polymeric ferric sulfate |
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| CN101519228A (en) * | 2009-04-13 | 2009-09-02 | 赵立民 | Process for preparing poly-ferric sulfate chloride by oxidation of oxyful |
| CN101786707A (en) * | 2010-02-23 | 2010-07-28 | 湖南科技大学 | Method for preparing water purifying agent poly-ferric sulfate chloride by utilizing iron-containing wastewater in potassium fluotitanate production |
| CN104817149A (en) * | 2015-04-24 | 2015-08-05 | 鲁西化工集团股份有限公司 | Method and system for preparing ferric sulfate polychloride from acid pickling waste solution |
| CN104986805A (en) * | 2015-06-23 | 2015-10-21 | 河北冀泽生物科技有限公司 | Production method for polyferric chloride sulfate |
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|---|---|---|---|---|
| CN101519228A (en) * | 2009-04-13 | 2009-09-02 | 赵立民 | Process for preparing poly-ferric sulfate chloride by oxidation of oxyful |
| CN101786707A (en) * | 2010-02-23 | 2010-07-28 | 湖南科技大学 | Method for preparing water purifying agent poly-ferric sulfate chloride by utilizing iron-containing wastewater in potassium fluotitanate production |
| CN104817149A (en) * | 2015-04-24 | 2015-08-05 | 鲁西化工集团股份有限公司 | Method and system for preparing ferric sulfate polychloride from acid pickling waste solution |
| CN104986805A (en) * | 2015-06-23 | 2015-10-21 | 河北冀泽生物科技有限公司 | Production method for polyferric chloride sulfate |
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