CN1100700A

CN1100700A - Method for prodn. of polymeric ferrous sulphate solution

Info

Publication number: CN1100700A
Application number: CN 94107731
Authority: CN
Inventors: 曹瑞军; 梅冬
Original assignee: Xian Jiaotong University
Current assignee: Xian Jiaotong University
Priority date: 1994-07-13
Filing date: 1994-07-13
Publication date: 1995-03-29

Abstract

A preparation method for polymeric ferrous sulfate solution includes the steps of adding concentrated hydrochloric acid in a cauldron, adding iron sludge in batch and stirring, aften reacting for ten minutes, adding 30-65% hot sulfuric acid, after boiling, prefering that the adding rate ought to maintain boiling until the sludge dissolves entirely, then press filtrating, adding NaOH in the filtrate, after reacting for 10 min. adding oxidant, thus iron can be utilized once more after converting into oxide, meanwhile the solvent can be recovered, chemical pollution can be reduced.

Description

Method for prodn. of polymeric ferrous sulphate solution

Involved in the present invention is is the method for basic raw material production polymeric ferrous sulphate solution with iron mud.

In the prior art, producing the technology that bodied ferric sulfate adopted has: (1) is the synthesis technique (routine CN 87104053) of main raw material with the sulfuric acid pickling waste liquid; (2) be the technology of raw material and sulfuric acid reaction with magnetite powder or pyrite cinder (routine CN 871049,847) or flue dust (routine USPat.No 2.252.332) or with iron ore (routine US.pat.No.4,814,158); (3) be basic raw material (for example CN 1052,295 and special public clear 51-175260) synthetic technology with the ferrous sulfate crystal.But in existing technology, also do not produce polymeric ferrous sulphate solution as its basic raw material with contaminative solid waste-iron mud of giving off in the redox chemical process.Because the difference of system, even or identical system, also because different reaction conditionss, the proterties of resulting ferric oxide mud also has very big difference, the adsorbent that is contained and the amount of entrapment solvent are also different.These iron mud can harden and form lump, infringement soil, and emit wherein adsorbed material and solvent, wherein ubiquitous unreacted iron (content is quite big sometimes) is dropped, chemical pollution and financial loss have been caused, ironmaking is the bar outlet though take away again, and the loss of solvent even portioned product and the pollution that is caused thereof still are insurmountable with way far away freight charges.

The objective of the invention is to propose a kind of is the method that basic raw material is produced polymeric ferrous sulphate solution with iron mud, can make iron utilize once after being transformed into oxidation state so more, reclaim some solvent simultaneously, minimizing is because of discharging caused chemical pollution, and make a silk purse out of a sow's ear, thereby bring good economic benefit and social benefit.

Technology of the present invention realizes by the following method: add the catalyzer concentrated hydrochloric acid in still, stir down, add iron mud in batches, react after about ten minutes, the hot sulfuric acid of the 30-65% that newly prepares is added, after waiting to seethe with excitement, the speed that adds is advisable to keep boiling, to reclaim solvent, after adding, insulation reaction to iron mud dissolves fully, press filtration, in the filtrate of gained, add NaOH, after stirring reaction 5-10 minute, add the oxygenant oxidation more promptly.

For the boiling point of carrying secretly in the iron mud at the solvent below 100 ℃, can be by condenser be installed on still, the reaction heat distillation recovery of emitting when utilizing the iron mud that newly gives off to generate salt with sulfuric acid.Higher for those boiling points, and relatively more expensive often solvent and some chemical substance wherein, can select for use boiling point below 100 ℃, more cheap, toxicity is little, segregative solvent (for example ethanol) is washing earlier, separate, reclaim, and the lower solvent of these boiling points utilizes the reaction heat distillation of emitting when generating molysite to reclaim again.The amount of iron mud impurities is reduced, can reclaim the chemical solvents of those contaminate environment again, sometimes even can also reclaim some products, also utilize reaction heat.For isolate the iron mud that is discharged behind the product with vapour method, the content of its impurity and solvent sometimes can be very low, can directly use or wash and remove water-soluble impurity, and needn't consider the problem of solvent recuperation.

In order to quicken the reaction of iron mud and vitriolic effectively, it is catalyzer that the present invention has selected concentrated hydrochloric acid for use, makes speed of response obviously accelerate.The ratio of its consumption in total acid equivalent is big more, reacts fast more.

Because iron mud is different from the basic raw material of prior art, its proterties is relevant with former chemical process, therefore determined the singularity of various proportioning raw materials methods in the technology of the present invention, for certain specific iron powder reducing chemical process, the transformation efficiency of input amount of each batch iron powder and former reduction process can be calculated the total content of ferro element in the total oxygen that exists with form of iron oxide in the iron mud and the iron mud and both summations by it, i.e. the net weight of iron mud (promptly remove entrapment solvent and adsorbent after " doing " weight).No matter how the composition of iron mud reality changes,, ferric oxide mud is regarded as by two portions formed, be i.e. Fe like this always the total acid content of required adding can followingly calculate ₂O ₃And Fe.Wherein, each mole Fe ₂O ₃Can with the sulfuric acid complete reaction of HCI or 3 moles of 6 moles, the Fe of each mole can with the HCl of two moles or the sulfuric acid reaction of a mole.Therefore, theoretical total acid content just can be calculated thus, but total amount is more or some also all can produce product less, and only raw material availability is high and low.The 100-105% that the actual total acid dosage of general selection is a theoretical amount is advisable; Hydrochloric acid shared amount in mixing acid is selected between the normal 3-30% of total acid to well, and its content is high more.Speed of response is fast more.Filtrate behind the dissolved iron mud need add alkali, and add-on is by each mole Fe ₂O ₃Add the normal alkali of 0.1-2, be preferably the normal sodium hydroxide of 0.3-1.5 or its aqueous solution.Also need at last to add identical normal oxygenant according to the mole number of Fe in the iron mud, actual add-on is the 105-120% of theoretical amount.Oxygenant can be H ₂O ₃, or sodium chlorate or clorox etc.During use, can be as required with this polymeric ferrous sulphate solution dilution.

Below non-limiting implementation example just in order to further specify the present invention, and not as limiting the scope of the invention, protection of the present invention is determined by claims.

Embodiment, bodied ferric sulfate synthetic:

The hydrochloric acid that in still, adds 200 liter 36%, adding under stirring and containing net weight is 270 kilograms of iron mud based on ferric oxide, after about about 10 minutes, add about 800 minutes jin of hot sulfuric acid of 50% of preparation just, the speed of adding is advisable to keep boiling, to reclaim solvent, after adding, insulated and stirred reaction about 30-60 minute, filtered while hot stirs down, in filtrate, add 1220 kilograms in 50% sodium hydroxide, after 5 minutes, stir down, slowly add 8 kilograms in 28% hydrogen peroxide, chemically examine with sample, after meeting the requirements, discharging, productive rate 97%.

Claims

1, a kind of production method of polymeric ferrous sulphate solution, it is characterized in that, in still, add the catalyzer concentrated hydrochloric acid, stir down, add iron mud in batches, react after about ten minutes, the hot sulfuric acid of the 30-65% that newly prepares is added, after little boiling, the speed that adds is advisable to keep boiling, the steam that will contain solvent is by condenser, with the recovery solvent, after adding, insulation reaction to iron mud dissolves fully, press filtration adds NaOH in the filtrate of gained, after stirring reaction 5-10 minute, add the oxygenant oxidation more promptly.

2, the production method of polymeric ferrous sulphate solution according to claim 1, it is characterized in that, for carrying the iron mud of boiling point secretly at solvent more than 100 ℃, wash at the solvent below 100 ℃ with boiling point earlier, to reclaim boiling point at the solvent more than 100 ℃, and then utilize iron mud and the liberated heat distillation of acid effect institute, reclaim boiling point at the solvent below 100 ℃.

3, according to the production method of claim 1,2 described polymeric ferrous sulphate solutions, its feature is being iron mud to be regarded as by ferric oxide and iron powder form, total acid content is chosen as the 100-105% of theoretical amount, acid can be hydrochloric acid, sulfuric acid or their mixture, the equivalent of generally getting hydrochloric acid in the mixing acid are the normal 5-30% of total acid; The amount that adds alkali is each mole Fe ₂O ₃Add the 0.1-2 equivalent, get the normal sodium hydroxide into 0.3-1.5, add the normal oxygenant of excessive 5-20% by the iron powder mole number, oxygenant can be H ₂O ₂, clorox, sodium chlorate etc.