CN1138009A

CN1138009A - Method for production of ferrous sulfate and ferrous ammonium sulfate

Info

Publication number: CN1138009A
Application number: CN 96118649
Authority: CN
Inventors: 曹瑞军; 梅冬
Original assignee: Xian Jiaotong University
Current assignee: Xian Jiaotong University
Priority date: 1996-03-28
Filing date: 1996-03-28
Publication date: 1996-12-18

Abstract

The process for producing ferrous sulfate and ferrous ammonium sulfate includes such steps as addition of iron slurry batchwise under catalytic action of concentrated sulfuric acid, addition of 50% hot sulfuric acid at a speed to keep boiling, recovering solvent by condenser, stirring for 30-60 min, disproportionative reaction and hot press filtering to obtain heptahydrated ferrous sulfate crystal, or further addition of sodium sulfate and ammonium sulfate in filtered liquid, heating to about 90 deg.C, and cooling to obtain hexahydrated ferrous ammonium sulfate crystal, and features high utilization rate of iron, and recovery of some solvent for less pollution.

Description

A kind of method of producing ferrous sulfate and ferrous ammonium sulphate

Involved in the present invention is is the production method of basic raw material production ferrous sulfate and ferrous ammonium sulphate with iron mud.

Mainly contain the method that following a few class is produced ferrous sulfate in the prior art: react with sulphur and (giving up) iron filings (1); Byproduct when (2) producing titanium dioxide, (3) reclaim(ed) sulfuric acid from the waste liquid behind the pickling iron and steel parts is ferrous, and (4) are with pyrite cinder or with iron ore powder and sulfuric acid reaction.Also have in the prior art resulting ferrous sulfate or its solution can further be produced ferrous ammonium sulphate.But, from prior art, also can not find the contaminative waste that gives off with in the chemical process of iron as reductive agent--iron mud is produced the method for ferrous sulfate and ferrous ammonium sulphate as its basic raw material.Iron mud is to use iron powder to do the industrial residue that reductive agent produces in a lot of organic oxidation reduction processes, because the difference of system, even or identical system also can be owing to the anti-part of different reactions, obtain the very big ferric oxide mud of proterties difference, the adsorbent that is contained, solvent of carrying secretly and amount are also different.These iron mud can harden and form lump, infringement soil, and the material of the absorption of emitting and the solvent carried secretly, unreacted iron wherein is dropped, and makes or chemical pollution and financial loss.Ironmaking is an outlet though take away again, and pollution that the loss of solvent causes and way far away freight charges still are insurmountable.

The objective of the invention is to propose a kind of is the production method that basic raw material is produced ferrous sulfate and ferrous ammonium sulphate with iron mud, can make iron utilize once in being transformed into the process of oxidation state so more, recyclable some solvent of while, minimizing is because of discharging caused chemical pollution and loss, thereby brings good economic benefit and social benefit.

Work of the present invention realizes by the following method: add the catalyzer concentrated hydrochloric acid in still, stir down, add the reaction of iron mud in batches, after the reaction about 10, about 50% the hot sulfuric acid that will newly prepare again stirs down and adds, during the boiling point of the solvent of being carried secretly near iron mud when temperature, the speed that adds is advisable to keep boiling, with the recovery solvent, after adding, after stirring reaction 30-50 minute, when treating that sampling filtering reaches required dissolution degree, add iron filings, stir and carry out anti-disproportionation reaction, temperature is controlled at 60-65 ℃, when bubble in the still obviously reduces, get the wherein ferric content of sample analysis, when meeting the requirements, press filtration while hot.The ferrous sulfate filtrate of gained heat is cooled to through placement and is bordering on room temperature, adds a small amount of broken grain kind accelerate crystallisation.Treat almost complete crystallisation, obtain green iron vitriol crystal after centrifugation, mother liquor can be recycled repeatedly, and after also can further concentrating, recrystallize is isolated iron vitriol, also can be made into the ferrous sulfate that other contains different number crystal water.

Produce ferrous ammonium sulphate, also can in the filtrate of above-mentioned technology, add Na ₂SO ₄(NH ₄) ₂SO ₄Calorify the solution of making higher concentration about 95 ℃, crystallisation by cooling, again through centrifugation, after the washing, obtain bright blue-greenish colour six aqueous ferrous sulfate ammonium crystal, mother liquor can be recycled, when treating that the mother liquor accumulation increases, but reconcentration, crystallization, isolate six aqueous ferrous sulfate ammoniums, the bath water amount is little, can merge with filtrate, in addition, also can be from iron mud, after making ferrous sulfate, by water than the vitriol oil than iron vitriol than ammonium sulfate be 1 than 0.0005-0.0001 than 1.1-1.3 than the weight ratio of 0.4-0.6 at 85-95 ℃ of solubilizing reaction, crystallisation by cooling obtains six aqueous ferrous sulfate ammonium crystal, and mother liquor can be recycled.

For specific iron powder reducing chemical process, its each batch is discharged the net weight of the mud that taps a blast furnace, and institute's bonded oxygen amount is to be calculated by the transformation efficiency of former reduction process and the input amount of iron powder, no matter how complicated the mixture that is generation ferric oxide or Z 250 or other form and unreacted iron powder is, its amount that adds acid can followingly be calculated, ferric oxide mud regarded as by two portions form, oxygen is all with Fe ₂O ₃Form exist, other is considered as Fe entirely.Each mole Fe in theory ₂O ₃Can with 6 mole HCI, or the H of 3 moles ₂SO ₄Complete reaction, each mole Fe can with 2 mole HCI or 1 mole H ₂SO ₄Reaction.The adding total amount of actual acid is than all excessive 5-15% of theory, many more also can, but have little significance.Hydrochloric acid can account for 5-30% in total acid equivalent, its content is big more, and speed of response is got over piece, therefore but also the sodium sulfate of Xiao Haoing is many more, and there is the problem of time and benefit here in cost up, need be determined on a case-by-case basis, the required iron powder mole number of adding is Fe in the iron mud in theory ₂O ₃Mole number deduct the mole number of unreacted iron powder in the iron mud, actual input amount is after amount 5-15%, and is many more also feasible, but has little significance.Add Na ₂SO ₄Mole number be 1/2 of CI mole number, (NH ₄) ₂SO ₄Add-on and the FeSO of generation ₄, 7H ₂The mole number of O equates.

For the boiling point of carrying secretly in the iron mud at the solvent below 100 ℃, can be by condenser be installed, the reaction heat distillation of emitting when utilizing new iron mud of discharging to generate salt with acid is reclaimed, higher for the boiling point of carrying secretly in the iron mud, and relatively more expensive often solvent, can select for use boiling point below 100 ℃, cheap, little, the segregative solvent of toxicity (for example ethanol) is washed earlier, and the lower solvent of boiling point utilizes and generates the reaction heat of emitting when containing molysite and distilled recovery.Iron mud impurities amount was reduced, can reclaim the chemical solvents of those contaminate environment again, also recyclable sometimes portioned product has also utilized reaction heat.And to isolate the iron mud of being discharged after the reaction product with vapour method, the content of its impurity and solvent just can fall seldom, can directly use, also need not consider to reclaim the problem of solvent, even small amount of impurities is arranged, also will separate to generate contain the molysite crystal after, hold very much and separate.

In order to quicken the reaction of iron mud and vitriolic effectively, it is catalyzer that the present invention has selected dense HCI for use, makes speed of response obviously accelerate, and its consumption is big more, reacts fast more.

In a word, the realization of Technology of the present invention need not used autoclave, and the reaction times can shorten again greatly, and two kinds of products can shared same set of equipment, and facility investment is reduced, and production efficiency improves greatly, and reclaims some solvent, has very strong practicality.

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

Embodiment 1, iron vitriol synthetic:

Net weight is 230 kilograms has the following adding of brownish black iron mud stirring of a small amount of water entrainment to add in the reactor of 160 kilograms of concentrated hydrochloric acids (35-36%), add to stir to make and stick with paste 5 minutes right left sides of dress mixture reaction, 50% of adding preparation at that time hot sulfuric acid is 640 kilograms again, the speed that adds is advisable to keep boiling, added the back insulation reaction 5 minutes, the observation dissolving situation of taking a sample after meeting the requirements, adds 60 kilograms of iron powders, stirring reaction, adding water temperature adjustment degree is 60-65 ℃, and the amount that adds entry is 125 liters, when bubble in the still obviously reduces, get sample and analyze ferric content, after meeting the requirements, press filtration while hot, filtrate is placed crystallisation by cooling, when medial temperature is 25 ℃, after four days, centrifugation gets 693 kilograms of green vitriols, is Fe by iron mud ₃O ₄Counting first once through yield is 73%, and when room temperature was 25 ℃, mother liquid obtained about 71 liters, recycled next time.Or after treating that mother liquor runs up to a certain degree, add Na ₂SO ₄, condensing crystal is isolated the iron vitriol crystal.

Synthesizing of embodiment 2, six aqueous ferrous sulfate ammoniums

1120 kilograms the iron vitriol of producing among the embodiment 1 is added to contain in 1000 premium on currency that 0.5-1 rises the vitriol oil calorifies about 65 ℃, the constant temperature stirring and dissolving is after the dissolving, with 524 kilograms (NH4) ₂SO4 adds, and continues to stir, and treats (NH ₄) ₂SO ₄After the dissolving, stop heating fully, be cooled to 22-23 ℃, centrifuging obtains the (NH of pale bluish green ₄) ₂SO ₄.FeSO ₄.6H ₂About 1210 kilograms of O crystal, first once through yield is with FeSO ₄.7H ₂O counts 77%, but the about 1000 liters of recirculation of mother liquor are used.

Claims

1, a kind of method of producing ferrous sulfate, it is characterized in that, in still, add the catalyzer concentrated hydrochloric acid, stir down and mix down, add iron mud reacts in batches, it is left back to react 10 minutes right sides, about 50% the hot sulfuric acid that will newly prepare again stirs down and adds, during the boiling point of the solvent of being carried secretly near iron mud when temperature, the speed of adding is advisable to keep to seethe with excitement, and the steam that will contain solvent passes through condenser, to reclaim solvent, after adding, after stirring reaction 30=60 minute, after reaching required solubleness, add iron filings, anti-disproportionation reaction is carried out in stirring, and temperature is controlled at 60-65 ℃, when reaching required level of response, press filtration while hot, gained filtrate obtains the iron vitriol crystal through crystallisation by cooling.

2, a kind of method of producing ferrous ammonium sulphate, it is characterized in that in still, adding the catalyzer concentrated hydrochloric acid, stir down, add iron mud reacts in batches, react after about 10 minutes, about 50% the hot sulfuric acid that will newly prepare again stirs down and adds, and during the boiling point of the solvent of being carried secretly near iron mud when temperature, the speed of adding is advisable to keep to seethe with excitement, the steam that will contain solvent passes through condenser, with the recovery solvent, after adding, after stirring reaction 30-60 minute, after reaching required solubleness, add iron filings, stir and carry out anti-disproportionation reaction, temperature is controlled at 60-65 ℃, when reaching required level of response, press filtration while hot adds sodium sulfate in gained filtrate and ammonium sulfate is heated to the solution of making higher concentration about 95 ℃, and crystallisation by cooling obtains six aqueous ferrous sulfate ammonium crystal

3, a kind of method of producing ferrous ammonium sulphate, it is characterized in that in still, adding the catalyzer concentrated hydrochloric acid, stir down, add iron mud reacts in batches, react after about 10 minutes, the hot sulfuric acid on the 50% right left side that will newly prepare again stirs down and adds, when solvent boiling point that temperature is carried secretly near iron mud, the speed that adds with keep can seethe with excitement be advisable with contain solvent steam pass through condenser, with the recovery solvent, after adding, after stirring reaction 30-60 minute, after reaching required solubleness, add iron filings, stir and carry out anti-disproportionation reaction, temperature is controlled at 60-65 ℃, when reaching to required level of response, press filtration while hot, gained filtrate obtains the iron vitriol crystal through crystallisation by cooling.Then by water than the vitriol oil than seven or six ferrous sulfate than ammonium sulfate be 1 than 0.0005-0.001 than 1.1-1.3 than the weight ratio of 0.4-0.6 at 85-95 ℃ of solubilizing reaction, crystallisation by cooling gets final product.

4, the method for production ferrous sulfate according to claim 1, it is characterized in that, for carrying the iron mud of boiling point secretly at solvent more than 100 ℃, use boiling point at the solvent wash below 100 ℃ earlier, and then utilize iron mud and acid to act on institute's liberated heat distillation, recovery boiling point at the solvent below 100 ℃.

5, according to the method for claim 2 or 3 described production ferrous ammonium sulphates, 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 ℃, reason utilizes iron mud and acid to act on institute's liberated heat distillation, reclaim boiling point at the solvent below 100 ℃ then.

6. the method for production ferrous sulfate according to claim 1, it is characterized in that, iron mud regarded as by ferric oxide and iron powder form, total acid content can react with 6 mole hydrochlorides by one mole of ferric oxide, or can react with three mol sulfuric acid, 1 mole of iron powder can add with the 105=115% of the total amount sum of two mole hydrochlorides or mol sulfuric acid reaction, wherein hydrochloric acid accounts for 5-30% in the equivalents of total acid, and the iron powder amount of being added adds by the 105-115% of the difference of ferric oxide in the iron mud and iron powder mole number

7, the method of production ferrous sulfate according to claim 2, it is characterized in that, iron mud regarded as by ferric oxide and iron powder form, total acid content can react with six mole hydrochlorides or three mol sulfuric acid by one mole of ferric oxide, one mole of iron powder can add with the 105-115% of the total amount sum of two mole hydrochlorides or mol sulfuric acid reaction, wherein, hydrochloric acid accounts for 5-30% in the equivalent of total acid, the iron powder amount of being added adds by the 105-115% of the difference of ferric oxide of being looked in the iron mud and iron powder mole number, the mole number that adds sodium sulfate is 1/2nd of a hydrochloric acid mole number, the add-on of ammonium sulfate and FeSO ₄7H ₂The mole number of O equates.

8, the method for production ferrous ammonium sulphate according to claim 3, it is characterized in that, iron mud regarded as by ferric oxide and iron powder form, total acid content by one mole of ferric oxide can with six mole hydrochlorides or the reaction of three mol sulfuric acid, one mole of iron powder can add with the 105-1115% of the total amount sum of two mole hydrochlorides or mol sulfuric acid reaction.Wherein hydrochloric acid accounts for 5-30% in the equivalents of total acid, the iron powder amount of being added divides the 105-115% of the difference of mole to add by ferric oxide of being looked in the iron mud and iron, the mole number that adds sodium sulfate is 1/2nd of a hydrochloric acid mole number, the add-on of ammonium sulfate and FeSO ₄7H ₂The mole number of O equates.