CN1168838C

CN1168838C - Technology and equipment for purifying and removing iron by cupric sulfate solution catalyzing air oxidation method

Info

Publication number: CN1168838C
Application number: CNB99111745XA
Authority: CN
Inventors: 何柱生
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-08-18
Filing date: 1999-08-18
Publication date: 2004-09-29
Anticipated expiration: 2019-08-18
Also published as: CN1285416A

Abstract

The present invention relates to ferrum purifying and removing technology for a copper sulphate solution in copper concentrate wet metallurgy and cupric sulfate production, and equipment thereof. In the method, ferrous irons in the copper sulphate solution are oxidized into ferric irons by an air catalyst with an oxidation method, and afterwards, the ferrum is deposited by regulating the pH to be about 3.0 so that the requirement of purifying and removing the ferrum in the copper sulphate solution is met.

Description

Copper-bath catalytic air oxidation method iron purification technology

The present invention relates to the iron purification Processes and apparatus of copper-bath catalytic air oxidation method in the production of copper ore concentrates hydrometallurgy and copper sulfate.

Background technology of the present invention: the existing technology of the iron purification of copper-bath is with Manganse Dioxide (MnO in copper ore concentrates hydrometallurgy and copper sulfate production ₂) or hydrogen peroxide (H ₂O ₂), as oxygenant, its clear consumption is big, the production cost height.

Purpose of design of the present invention: avoid the weak point in the background technology, design a kind of with the red copper-bath catalytic air oxidation method iron purification Processes and apparatus of atmospheric oxidation agent to the copper-bath iron purification.

Design of the present invention: the present invention adopts the catalytic air oxidation method, is that oxygenant comes the copper-bath iron purification with the air, and not only production cost is low for it, and helps the copper sulfate Recycling Mother Solution and use and improve the various quality producies that contain brass work.

Ultimate principle of the present invention is based on following chemical reaction:

①

②

③

④

⑤

According to above-mentioned reaction formula,, for example sell hydrochlorate, as KNO when in the acidic solution (PH＜7) that contains ferrous sulfate, adding a small amount of nitrogenous compound ₃, NaNO ₃, Mg (NO ₃) ₂, Ca (NO ₃) ₂, NH ₄NO ₃In nitrate, and small amounts reduction initiator (as benzoyl peroxide, hydrogen peroxide, persulphate, superoxide, percarbonate etc.) is arranged, and when existing, redox reaction will begin rapidly.At this moment if in solution, blast air again, air will make the oxynitride that is reduced be reoxidised into higher nitrogen oxides, and itself and water effect can generate nitric acid or nitrous acid again, can go oxidation of divalent is become ferric iron again, circulation is run in the air from solution up to oxynitride so repeatedly.Run airborne oxynitride and then adopt volume " inorganic chemicals industry handbook (first volume) (second edition with Tianjin chemical research institute, Chemical Industry Press, Beijing, 1995:1014-1094) go up related process and the equipment of producing Nitrates and can produce corresponding nitrate, but here because its absorption liquid can be re-used as oxygenant (only need add a small amount of initiator) use, so can and needn't produce the solid salt with absorption liquid in producing.So constantly copper-bath is blasted air and adds catalyst solution, the ferrous ion in solution when corresponding cupric product requirements is produced in the check character symphysis till, then with bases (as NaOH, nitrogen water, KOH, Ca (OH) ₂, lime etc.) to transfer the solution pH value be about 3.0 to solution, just can make ferric iron generate precipitation, the clarification back or filter after clear liquid be the corresponding qualified copper-bath that contains brass work of further production.Its technical scheme: copper-bath iron purification technology, 1., adopt the catalytic air oxidation method; 2., in copper-bath, blast air, its air that blasts is: a, adopt the supercharging of supercharging air equipment, as air compressor, roots blower, multi-level small-flow blower fan, gas blower, induced draft fan etc.; The suction temperature of b, supercharging air equipment is an envrionment temperature, or-40 ℃～100 ℃; C, supercharging air equipment are 1KPa～10MPa to the supercharging of air; D, the air capacity that copper-bath is blasted are every m ³Copper-bath is 0～1000m ³/ h; The degree of depth that e, forced air are blown into copper-bath is 0～10000mm (being the depth of penetration of gas blow pipe); F, forced air also can be blown into from the solution bottom fully, can adopt gas distributor also can adopt the plate of boring that air dispersion is opened.3., in copper-bath, add catalyst solution, the catalyst solution that is adopted is: a, solution are the aqueous solution, wherein contain nitrogenous compound and initiator; B, wherein nitrogenous compound can be Tianjin chemical research institute and compiles " inorganic chemicals industry handbook (first volume) (second edition, Chemical Industry Press, Beijing, 1995:1014～1094) listed all kinds of nitrogenous compounds in are as the salt of various metals such as the potassium of nitric acid and nitrous acid, sodium, ammonium, calcium, magnesium, molybdenum, bismuth, copper; C, its initiator are all kinds of superoxide, persulphate, percarbonate, as sodium peroxide, calcium peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, SPC-D, percarbonic acid first, benzoyl peroxide or the like; Containing catalyst concn in d, the solution is 0～1000g/L, and containing initiator concentration is 0～500g/L; E, catalyst solution temperature are 0～100 ℃; F, catalyst solution adding speed are to 1m ³Copper-bath is 0～10m ³/ h, the joining day is 0～24h.Its catalyst solution with blast air and carry out simultaneously, and catalyzer can rouse the air of for some time after adding again.

The equipment that the present invention relates to is:

1, supercharging air equipment.Can be air compressor, roots blower, multimachine low discharge blower fan, gas blower, induced draft fan etc., boost (gauge pressure) is for more than the 1Kpa, to 1m ³Its gas flow of copper-bath is 0～1000m ³/ h, the gas suction temperature is envrionment temperature (as-10～100 ℃).

2, conduit with the air of supercharging with catheter guidance to the gas blow pipe that inserts in the copper-bath.

3, gas blow pipe shape such as Fig. 1.Ingress pipe partly is that the forced air that will be attracted by conduit guides to gas distributor, ingress pipe also can be straight tube or by the curved tube of the wall of container vertical component shape of splendid attire copper-bath, the gas distributor shape can be as " chemical equipment machinery " (press of Central Radio ﹠ TV University of Dong Daqin volume, Beijing, 1993:377～382) various forms of liquid distributor is identical in, also can handle (Fig. 1 for be the synoptic diagram of example) with the cross section interior shape by container of a pipe splendid attire copper-bath by the example of Fig. 1 with the bulge, the material of its pipe can be plastics or metal (stainless steel, 1Cr18Ni9Ti), the diameter of its pipe can be 0～100m/s design by the gas speed of blowing.The gas blow pipe interior diameter is φ 2～φ 1000.Also can adopt simultaneously air to be blown into (gas blow pipe can insert, and also comfortable container is blown into from container bottom) outward from the copper-bath bottom in container, with the plate in aluminium hole air distribution be opened again.

4, catalyzer storage tank.The catalyzer for preparing can be stored in the various containers, and in plastic tank, stainless steel cask, wooden barrel etc., available conduit siphon adds in the filling tube, and this moment, available certain clip on conduit waited dominant discharge as plastic clip, crocodile clip, iron clamp.Also can adorn a valve, to control the flow that it flows into filling tube in the storage tank bottom.

5, filling tube such as Fig. 2.Available its hole is the stainless steel tube of φ 2～φ 100, titanium pipe or plastics tubing, and one is fixed on the reaction vessel, and add catalyst solution from this end, and the other end need insert in the copper-bath, and its depth of penetration is 10～10000mm, and it inserts liquid layer and partly has aperture.

Operating procedure condition of the present invention is: will need the copper-bath (also can contain slag in copper-bath or other is insoluble to the solid particulate of dilute sulphuric acid) of iron purification to add and be equipped with in the reaction vessel of gas blow pipe and filling tube, start agitator (also can adopt and strengthen the air-blowing quantity pneumatic blending), start supercharging air equipment, and begin to blow, its air-blowing quantity is every 1m ³Copper-bath is 0～1000m ³/ h, the air blowing supercharging is at 1KPa～10MPa, the air blowing temperature is-40～100 ℃ (being that the air compressor machine intake air temperature is an envrionment temperature), begins to add catalyst solution then, catalyst solution consist of nitrogenous compound such as NaNO ₃Be 0～1000g/L, the concentration of initiator (as benzoyl peroxide etc.) is 0～500g/L, and the catalyst solution temperature is 0～100 ℃ (being ambient temperature), to 1m ³Copper-bath catalyst solution adding speed is 0～10m ³/ h, the joining day is that 0～24h copper-bath temperature is 0～100 ℃, and keeps copper-bath for acid, i.e. its PH＜7, tail gas is evacuated to the absorption tower with induced draft fan, with Na ₂CO ₃Solution absorption generates NaNO ₂And NaNO ₃Solution, blow air so always and add catalyzer, ferrous content in solution meets manufacturing technique requirent and is as the criterion after check, generally need ferrous ion concentration is reduced to the scope of 0～25g/L, and be about 3.0 with bases (as NaOH etc.) solution regulator solution pH value, make the ferric iron precipitation.Clear liquid after clarification or filtration, the clear liquid after the promptly liquid-solid separation are to meet produces the corresponding copper-bath that contains the brass work processing requirement.

Embodiment 1: by the iron purification of the copper-bath in the copper fine-powdery direct production copper sulfate process, the calcining of copper fine-powdery after catalytic boiling-bed by patented technology 99115724.9, leach with dilute sulphuric acid, leaching liquid-solid ratio is 1.8: 1, all in the leaching vat that bulging air (the gas blow pipe depth of penetration is 2m) and feeding equipment (the filling tube depth of penetration is 1m) are housed, liquor capacity is 3m for slag and copper-bath ³, 85 ℃, cupric 150g/L contains ferrous 30g/L, PH2.Start the agitator of leaching vat.Blast air, 40 ℃, gauge pressure 25Kpa, flow 10m ³/ h.And start device for absorbing tail gas, add nitrogenous compound then and (be NaNO here ₃(concentration 20%)) and drawn the aqueous catalyst solution of agent (being benzoyl peroxide (concentration is 0.1%) here), 35 ℃, flow is 60L/h.The catalyzer 2h that feeds in raw material continues to blast air 1h then.So after measured, the ferrous 2.5g/L that reduces in the copper-bath transfers solution PH 2.9 with NaOH solution (containing NaOH is 40g/L).This copper-bath can carry out liquid-solid separation condensing crystal, can obtain meeting the copper sulfate product of GB43793 premium grads.

Embodiment 2: by the copper-bath iron purification in the copper fine-powdery production electrolytic copper technology, the big calcining of copper fine-powdery after catalytic boiling-bed, with dilute sulphuric acid or electrolysis mother liquor leaching copper, leaching liquid-solid ratio is 2.2: 1, all in the reactor that bulging air (the gas blow pipe depth of penetration is 3m) and feeding equipment (the filling tube depth of penetration is 2m) are housed, liquor capacity is 10m for slag and copper-bath ³, solution temperature is 90 ℃, solution cupric 120g/L contains ferrous 28g/L, solution PH 1.8.Start the agitator of reactor, blast air, temperature is 38 ℃, and supercharging (gauge pressure) is 36Kpa, and flow is 28m ³/ h.And start the afterbody absorption unit, add catalyst solution then and (contain NH ₄NO ₃Be 18%, containing benzoyl peroxide is 0.2%), temperature is 30 ℃, and flow is 150L/h, and catalyzer is reinforced to be 2.3h.After adding, continues by catalyzer to blast air 1.5h, obtain copper-bath like this and contain the ferrous 1.0g/L that is, after transferring PH2.8 with NaOH, carry out liquid-solid separation and can obtain meeting the copper-bath of producing electrolytic copper, below undertaken by the processing step of production electrolytic copper in the hydrometallurgy.

Embodiment 3: the iron purification of general copper-bath, and the copper-bath cupric is 140g/L, contains the ferrous 30g/L that is, and solution temperature is 60 ℃, and liquor capacity is 4m ³, it is packed into is equipped with in the reactor of air blowing (gas blow pipe insert liquid layer be 1.8m) and feeding device (insertions liquid layer is 1m), begins blowing compressed air, and temperature is 20 ℃, and air-blowing quantity is 30m ³/ h, supercharging is 23KPa, and starts device for absorbing tail gas.Open feeding device then, add with the speed of 100L/h and contain NaNO ₂The solution of (concentration is 15%) and ammonium persulphate (concentration is 1%) stops to feed in raw material behind the reinforced 2.8h, continues air blowing 2.5h, can get that ferrous iron concentration is 0.25g/L in the solution, transfer PH3.1, this solution meets the production cupric sulfate crystals after the liquid-solid separation, electrolytic copper or produce various cupric product requirements.

Described percentage concentration is a concentration expressed in percentage by weight.

Claims

1, a kind of technology of copper-bath catalytic air oxidation method iron purification is characterized in that:

A, in copper-bath, blast air; Adopt the supercharging of supercharging air equipment, the suction temperature of supercharging air equipment is an envrionment temperature, and supercharging air equipment is to the pressure 23～36Kpa of air; The air capacity that copper-bath is blasted is every m ³Copper-bath is 2.8～7.5m ³/ h; Forced air is blown into the degree of depth＜=10m of copper-bath, or forced air is blown into from solution bottom fully, adopts gas distributor or with the plate of holing air dispersion is opened;

B, add catalyst solution in copper-bath: contain nitrogen compound and initiator in the catalyst solution, nitrogen compound is selected from 20% (weight) NaNO ₃Or 18% (weight) NH ₄NO ₃Or 15% (weight) NaNO ₂The initiator of corresponding above-mentioned nitrogen compound is respectively the ammonium persulphate of 0.1 (weight) benzoyl peroxide, 0.2% (weight) benzoyl peroxide or 1% (weight); 0 ℃～100 ℃ of the temperature of above-mentioned catalyst solution, catalyst solution adding speed is respectively every m ³Copper-bath is 20L/h, 15L/h, 25L/h, ferrous ion concentration＜25g/L to the solution, and adding NaOH solution regulator solution pH value is about 3, makes the ferric iron precipitation, solid-liquid separation.

2, copper-bath iron purification technology according to claim 1, it is characterized in that: catalyst solution and air blast simultaneously, and catalyzer rouses for some time air after adding again.

3, copper-bath iron purification technology according to claim 1 is characterized in that: supercharging air equipment is air compressor, roots blower, multi-level small-flow blower fan, gas blower, induced draft fan.