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recovery of gold from ores with chlorine in 1898

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Hi Realms

I did a little searching and found this site:

http://www.stabilised-chlorine-tablet.co.uk/

The formula for this compound, trichloro-s-triazinetrione (trichloroisocyanuric acid), is C3Cl3N3O3 and this article states that, when mixed with water, the chlorine becomes hypochlorous acid. It does have a tendency to lower ph as it also produces isocyanuric acid, which may or may not be a good thing, depending on what my experiments turn up.

The only disadvantage I can see is the slow release thing. It might be just as easy to buy dry calcium hypochlorite and mix it with water, again giving us the hypochlorous acid.
 
Interesting article about the hypochorous acid <--> hypochlorite shift (HOCl <--> OCl) that is mandated by the ph of the chlorine solution.

http://www.poolhelp.com/HOCI_OCI.aspx

As HOCl is the most active oxidiser of the two (80-120 x more so than OCl) it is desirable to maximise the HOCL, which happens at a ph of 5 (see chart on link). However, as ph 5 is acidic, it may be necessary to compromise for a lower percentage of HOCl, by raising the ph closer to 7, to avoid the release of chlorine gas and the dissolving of iron and its oxides at the lower ph's.
 
Chlorination. I - from the "Australian Town and Country Journal (NSW)" January 31, 1891

The chlorination process of extracting gold From its matrix, and from from concentrates, is freely alluded to in newspapers and amongst miners; and yet, as a rule, the principle is but vaguely understood, even by men who make mining their business. Our explanation will be principally for persons who understand but little, if anything, of chemistry. To the scientific man, the great affinity of chlorine for the precious metals has been known almost ever since the distinguished German chemist, Schule, first discovered chlorine, about the year 1774. Chlorine, then, is an element, that is a simple substance, out of which nothing can be produced but itself. It is a gas, and has many remarkable properties- bleaching almost all colored substances, and being very heavy as compared with common air, and being also very deleterious to breathe. It is largely consumed by man and the lower animals in food as common salt, which contains a little more than half of pure chlorine. It conies into uso in mining in consequence chiefly of its great affinity or liking for gold and silver. If it can get sufficiently near it will seize hold of them, appropriating a certain portion to itself, making what is called chloride of gold ot silver. It being so abundant in nature, salt being so common, it is made cheaply-a little dilute sulphuric acid put on salt liberates chlorine gas, and its attraction for silver can be witnessed by the curious any day in the Sydney Mint by watching the chlorine gas being put into the bottom of the molten gold in the pot, and as it bubbles up to top seeing it seize hold of the silver, carrying it to the top of the gold as a chloride of silver. In using chlorine to extract gold you simply crush the stone or matrix so fine that it can get at the gold and take hold of it as a chloride. The easiest way to do this is to'put the chlorine in a solution in water, and so powerful is its action on gold that it dissolves that metal, holding it in
solution as water holds sugar. There is no difficulty in making a solution of chlorine, as at ordinary temperatures water dissolves about twice its volume of chlorine. Thus then having liberated the gold from the stone by crushing, and having made chlorine gas, as can be done cheaply, say from common salt, and having passed the chlorine so made through water, and thus made a solution of chlorine, and bringing it and the crushed stone together, in a short time you have your chlorine solution, containing all the gold in solution that was in the crushed stone. Having then the auriferous chlorine solution decanted or run off from the sludge or crushed stone or pyrites, you put some thing into it which will deposit or throw down the gold. Either one of two things, both of them very cheap and easily obtained, will do this effectuality, viz., a solution of sulphate of iron, common green vitrol, or pieces of common wood charcoal. The first will throw all the gold down as a powder ; the other, wood charcoal, will take to itself the gold out of the solution as a brown film, and upon the charcoal being burned away the pure gold remains. This is the rationale or reason of what is called the chlorination process, and any person of ordinary capacity, upon reflecting upon the foregoing, will not fail to comprehend the method used through the aid of certain machinery, which we will presently describe. It may help to understand this subject if we remind the reader that each of the three chief processes of extracting gold from its matrix or stone or pyritous matter consists in bringing it into contact with some substance which has so great an affinity or liking for it that it is taken up or amalgamated, and then the amalgamating substance got rid of or the gold taken from it. Thus in the common stamper battery or grinding mill mercury is the amalgamat ing material, as all miners know, which takes up the gold. In smelting, matter containing gold is put by intense heat, often assisted by fluxes of various kinds, into a state of fusion, and then brought in contact with molten lead, which, like mercury, has an intense affinity for gold, and it is thus extracted-the lead in the one case and the mercury in the other being ultimately taken from the gold by evaporation, or as regards the lead by cupellation, which is in effect evaporation. As regards the third great process, viz., extracting by chlorine, we have explained upon what principle that is carried out, being, in fact, like the other two, merely making use of a substance which, by its great affinity, will seize hold of the gold and collect it, so to speak.
Of the three processes, the crushing and amalgamating with mercury, the smelting and amalgamating with lead, and the crushing and absorption by a solution of chlorine, each is suitable according to the way the gold is found in the stone or auriferous material. Rich pyrites or black sand, or concentrates, require smelting as a rule, because all the grinding, to whatever degree of fineness it may be carried, will not liberate all the gold from the iron and metals, so that mercury can act on it." Again, crushing by stampers or grinding in mills will be suitable where much of the gold is fairly coarse, and, as it is called, free in the stone. Arid chlorination comes in and is useful where gold is free in the stone, but is so very fine that in crushing in the ordinary way the mercury can't take hold of it but is carried away in the sludge or tailings. Chlorination also is useful in extracting the precious metal from concentrates, though in this case it may be found more suitable to sell them to the smelting works than to treat them by
chlorine at the mine.
Having thus described what may be termed the principles of chlorination, we now describe the appliances by which they are carried into effect. First, the stone is crushed dry, arid, as in the case of the iron-clad reef at Cargo where chlorination is carried on, by heavy steel rollers driven by steam power. Next the crushed stone is calcined in anordinary reverberatory calcining furnace to eliminate all the sulphur and arsenic which it is advisable to get rid of before treatment by chlorine. Then the calcined crushed stone is put into a large iron barrel about 8 ft long by about 3 ft in diameter* and lined with lead, because chlorine acts powerfully on iron as it does on gold and silver, but will not touch lead.

On page 25

A sufficient quantity of water is put in the barrel to make a thin sludge, then a quantity of chloride lime-that stuff much used as a disinfectant, and which is simply common lime saturated with chlorine gas-is put to the sludge, and upon that a small quantity of sulphuric acid. The barrel is then closed down air-tight, and made to
revolve very slowly. The acid acting on the lime evolves the chlorine, which is taken up by the water, and the chlorine solution takes up the gold in the stone. After some hours of the barrel revolving, the whole contents are turned out into
a cask or receptacle and allowed to settle. The clear liquor is then drawn off, and made to pass through a cask or vessel partly packed with common wood charcoal, which, as the auriferous chlorine solution passes through it, takes the gold
to itself; and upon tho charcoal being burned away, say in an iron pot, the pure gold remains. , This, then, is the chlorination process, which, we
think; our readers-even those quite unacquainted with chemistry-will clearly comprehend.
 
Found this on the Clorox site:

What’s in Clorox® Regular Bleach?

Ingredients that make up one percent or more of the contents of a product by weight are listed in descending order of concentration. Those that make up less than one percent — like fragrances, dyes and preservatives — are listed in alphabetical order.


Water

Sodium hypochlorite

Sodium chloride

Sodium carbonate

Sodium hydroxide

Sodium polyacrylate

--------------------------------------------------------------------------------------

From this list and the preamble to it, we can deduce that sodium hydroxide (NaOH) makes up less than 1% of the weight of a solution of bleach. The sodium carbonate is slightly basic and would contribute to the high ph of a bleach solution, as well.

If one unit of added hydrochloric acid (HCl) would neutralize one unit of NaOH according to the following formula:

NaOH + HCl = NaCl + H2O

and, using regular 34% muriatic acid for HCl it was a one to one tradeoff (it may be necessary to dilute the HCl to a much lower percentage while trying to establish the needed volume), in a litre of bleach it might require as little as 2 to 3 millilitres of HCL to adjust the ph to the desired 7-7.5.

I must say I am quite surprised that less than 1% NaOH in a bleach solution is sufficient to maintain the ph of the bleach over 12.
 
I'm patiently waiting for the ph meter I ordered on Ebay to arrive in the mail. I look forward to using it when it arrives.

Thinking over what you said, I looked again at one of the 1890's recipes for making a gold leaching chlorine solution. In this case, chlorine gas was introduced into a cylinder containing ground ore and water. Following, compressed air was introduced to a pressure of 60 psi, dissolving Cl2 gas in the water.

Once dissolved, the following happened:

Cl2 + H2O = HOCl + HCl

I had assumed the HCl produced would be of such low volume as to not alter the ph of the water (assumed to be 7) much below 5-6 but, I am not so sure anymore. Any ideas?

I know, from reading these older papers, that there was not much worry of the chlorine solutions dissolving iron (instead of gold) from iron oxides and, for this reason, I have to assume the ph of their chlorine solutions was not overly acidic. This, they claim, was one of the reasons for roasting ores; to convert iron and other base metals into oxides that would be impervious to their chlorine solution. Accordingly, it takes a very low ph (1-2?) to break the bond between the base metal and the oxygen.

This information is in contrast to an experiment I did with a sample of magnetite sand (Fe3O4). In a plastic container, I covered the magnetite with 1/2" of HCl. Within seconds, the HCl turned a dark amber colour; indicating I had made ferric chloride (FeCl3).
 
Traveller11,

I am not sure what you are working towards here,or where you are at, but figured I would add a thought and some equation’s I stole from Wikipedia.

Chlorine in water forms Hypochlorous acid and hydrochloric acid
Cl2 + H2O <--> HOCl +HCl
Notice the above reaction is reversible
HOCl + HCl <--> Cl2 +H2O

In acid Hypochlorous acid forms chlorine gas and water (remember the Chlorine gas reacts with metals to form metal chlorides or escapes the solution)
HCL + HOCl -->H2O +CL2 (gas)

Light or metal oxide’s (like copper oxide can break down the chlorine also
2Cl2 + H2O ---light--> 4HCl + H2O
(If copper oxide we would get copper chlorides)

Common Bleach sodium hypochlorite NaClO is a sodium salt of Hypochlorous acid HOCl
There are a couple ways bleach is made electrolysis of salt brine or chlorine gas dissolved in cold sodium hydroxide, both will contain salt NaCl and be caustic with NaOH (the caustic helps to keep chlorine gas in solution dissolved in the water) household bleach sodium hydroxide is mostly water around 92 to 97% H2O.

Cl2 +2 NaOH --> NaCl +H2O + NaClO

NaOH can help to keep the chlorine in the water as a basic solution, and as we know acid and a metal base will form a salt of that metal:
HCl + NaOH --> NaCl + H2O

Sodium hypochlorite and acid can form chlorine gas:
NaClO + HCl --> NaCl + H2O + CL2 (gas)

Now we also need to consider the sodium hypochlorite is actually a basic solution of salt and sodium hypochlorite and sodium hydroxide so adding acid not only generates chlorine gas which reacts with metals or escapes as gas from solution, the reaction of the base and acid also brings pH closer to neutral as well as forming more salts and water in solution.

As we stated bleach can me mostly water which can dilute an acidic solution as well as act to adjust it pH toward neutral forming salts of our acid as the chlorine gases off or reacts with metals in solution to form metal chlorides.

Also if bleach is heated or evaporated from solution it can form salts of sodium chloride NaCl and sodium chlorate's NaClO3.

Bleach and hydrogen peroxide give off oxygen and form chlorine gas and salt water
4NaClO + 2H2O2 --> 4NaOH + 2Cl2 +O2
(again we see where this would be adjusting pH of our acidic solutions)

So with this we can see how these solutions not only dilute our acid but also can work to neutralize it forming a lot of salt in solution as the chlorine or other gases react or escape from the leach solution,

Many bleach solutions also dilute the leach.
Alternatives are dry bleach powders or using gases to do the same job without the side reactions.

Iron hydroxide is very un-reactive; to acids the red rouge powder is almost impossible to dissolve into acid, you can dissolve gold from this red powder and not dissolve the iron or put it into solution (as an iron chloride) even with acids as strong as aqua regia, roasting techniques are very important steps, your goal is to remove sulfides and other unwanted compounds and convert the oxide or iron compounds to the most desirable state for your next leach, if we are leaching iron first we want the iron to go into solution, but in a chlorination of acid solution where your trying to leach gold were too much iron in solution would re-precipitate the leached gold and put iron into solution ,with gold depending on conditions, we would not want the iron is a state easily dissolved.
How you roast can help quite a bit of what state the iron is in, also most of the soluble iron can also be leached before going after the gold.

But concentrating the of the ore down to a very high percentage of gold to ore or base metals is also important, as you not only will have more trouble and cost and waste, trying to process a low gold to ore or base metal ratio your loses will be higher and the likelihood of success is reduce with the more ore or base metals involved.

As I said I am not sure where you are at on this or if this will even help any.
 
butcher said:
Traveller11,

I am not sure what you are working towards here,or where you are at, but figured I would add a thought and some equation’s I stole from Wikipedia.

Chlorine in water forms Hypochlorous acid and hydrochloric acid
Cl2 + H2O <--> HOCl +HCl
Notice the above reaction is reversible
HOCl + HCl <--> Cl2 +H2O

In acid Hypochlorous acid forms chlorine gas and water (remember the Chlorine gas reacts with metals to form metal chlorides or escapes the solution)
HCL + HOCl -->H2O +CL2 (gas)

Light or metal oxide’s (like copper oxide can break down the chlorine also
2Cl2 + H2O ---light--> 4HCl + H2O
(If copper oxide we would get copper chlorides)

Common Bleach sodium hypochlorite NaClO is a sodium salt of Hypochlorous acid HOCl
There are a couple ways bleach is made electrolysis of salt brine or chlorine gas dissolved in cold sodium hydroxide, both will contain salt NaCl and be caustic with NaOH (the caustic helps to keep chlorine gas in solution dissolved in the water) household bleach sodium hydroxide is mostly water around 92 to 97% H2O.

Cl2 +2 NaOH --> NaCl +H2O + NaClO

NaOH can help to keep the chlorine in the water as a basic solution, and as we know acid and a metal base will form a salt of that metal:
HCl + NaOH --> NaCl + H2O

Sodium hypochlorite and acid can form chlorine gas:
NaClO + HCl --> NaCl + H2O + CL2 (gas)

Now we also need to consider the sodium hypochlorite is actually a basic solution of salt and sodium hypochlorite and sodium hydroxide so adding acid not only generates chlorine gas which reacts with metals or escapes as gas from solution, the reaction of the base and acid also brings pH closer to neutral as well as forming more salts and water in solution.

As we stated bleach can me mostly water which can dilute an acidic solution as well as act to adjust it pH toward neutral forming salts of our acid as the chlorine gases off or reacts with metals in solution to form metal chlorides.

Also if bleach is heated or evaporated from solution it can form salts of sodium chloride NaCl and sodium chlorate's NaClO3.

Bleach and hydrogen peroxide give off oxygen and form chlorine gas and salt water
4NaClO + 2H2O2 --> 4NaOH + 2Cl2 +O2
(again we see where this would be adjusting pH of our acidic solutions)

So with this we can see how these solutions not only dilute our acid but also can work to neutralize it forming a lot of salt in solution as the chlorine or other gases react or escape from the leach solution,

Many bleach solutions also dilute the leach.
Alternatives are dry bleach powders or using gases to do the same job without the side reactions.

Iron hydroxide is very un-reactive; to acids the red rouge powder is almost impossible to dissolve into acid, you can dissolve gold from this red powder and not dissolve the iron or put it into solution (as an iron chloride) even with acids as strong as aqua regia, roasting techniques are very important steps, your goal is to remove sulfides and other unwanted compounds and convert the oxide or iron compounds to the most desirable state for your next leach, if we are leaching iron first we want the iron to go into solution, but in a chlorination of acid solution where your trying to leach gold were too much iron in solution would re-precipitate the leached gold and put iron into solution ,with gold depending on conditions, we would not want the iron is a state easily dissolved.
How you roast can help quite a bit of what state the iron is in, also most of the soluble iron can also be leached before going after the gold.

But concentrating the of the ore down to a very high percentage of gold to ore or base metals is also important, as you not only will have more trouble and cost and waste, trying to process a low gold to ore or base metal ratio your loses will be higher and the likelihood of success is reduce with the more ore or base metals involved.

As I said I am not sure where you are at on this or if this will even help any.

butcher

I think Traveller11 is wanting a way to generate the wet chlorine gas,so he can use it for ore leaching.I'm not 100% sure on that so please don't quote me on it.

If this is the reason then this needs to be looked at more carefully,it's a piece of the page that Traveller11 posted the link for up in his second post on this page.

The full equation may be represented like this:
Cl2 + H2O --> HOCl + HCl
HOCl --> OCl– + H+
HOCl is, of course, the “active ingredient”. The OCl– is a bank, or reservoir of less active chlorine.
A common pool industry myth is that when HOCl is used in a pool only OCl– remains. In reality, when HOCl is used, OCl– immediately converts back to HOCl to maintain the percentage division mandated by the pH.
Although the actual reactions in water may be complex, a few illustrations in simplified language may help to describe what happens.
For example, if a pool contained 3 ppm total chlorine at a pH of 7.5, there would be about 1.5 ppm HOCl and 1.5 OCl–. If 1 ppm chlorine demand is introduced into the water, the myth would have us believe that as the demand is met, the HOCl is lowered to 0.5 ppm with the OCl– remaining at 1.5 ppm. Assuming the pH to be unchanged, what actually happens is that the total chlorine is lowered to 2 ppm, the HOCl is lowered to 1 ppm, and the OCl– is lowered to 1 ppm. This happens even though it may have actually been only the faster and more potent HOCl that satisfied the chlorine demand. The subsequent shift of 0.5 OCl– to HOCl is virtually instantaneous.


The demand in his case would be ores,so basically it would keep generating chlorine wet gas until all the OCl- was shifted to HOCl.

This is why I use Bleach in my GEOMOD cell.I rejuvenate the chlorine by adding pool chlorine tablets and the anode turns the chlorine into gas,which eats the metals.So in theory this cell could do the same for ores.I plan to try ore in my cell real soon.If you haven't read the full article yet you should it might give you better insite on what he's wanting to do.I've read and reread it about 5-6 times now.Hope this adds something to the forum that is of use!



modtheworld44
 
Hello modtheworld44

I think we are working towards the same end but have slightly different interpretations of what is happening. Looking at some of these articles from the 1890's, I do not believe that producing chlorine gas in the presence of ore is what they were doing. Yes, the one process fed Cl2 gas into the cylinder with ore and water in it but, it was then immediately dissolved in the water and transformed into HOCl and HCl. I also believe this did not lower the ph of the water significantly and, if it was 7 to start with, would only be slightly lower than this with the Cl2 dissolved in it.

In other words, I believe these old timers ended up with a strong solution of hypochlorous acid/sodium hypochlorite in water with perhaps minute amounts of Cl2 gas being released. The evidence I give for this is that they did not bother trying to remove iron oxides such as magnetite and hematite from the ores prior to leaching. If this were attempted with the normal HCl/Clorox formula proscribing large amounts of HCl added to Clorox, the solution would be so acidic, it would break the bonds of the oxides and put iron into solution instead of gold.

It seems the oldtimers were dissolving gold with an almost neutral solution of HOCl/NaClO in water that, except for strength, differed very little from swimming pool water.
 
Traveller11 said:
Hello modtheworld44

I think we are working towards the same end but have slightly different interpretations of what is happening. Looking at some of these articles from the 1890's, I do not believe that producing chlorine gas in the presence of ore is what they were doing. Yes, the one process fed Cl2 gas into the cylinder with ore and water in it but, it was then immediately dissolved in the water and transformed into HOCl and HCl. I also believe this did not lower the ph of the water significantly and, if it was 7 to start with, would only be slightly lower than this with the Cl2 dissolved in it.

In other words, I believe these old timers ended up with a strong solution of hypochlorous acid/sodium hypochlorite in water with perhaps minute amounts of Cl2 gas being released. The evidence I give for this is that they did not bother trying to remove iron oxides such as magnetite and hematite from the ores prior to leaching. If this were attempted with the normal HCl/Clorox formula proscribing large amounts of HCl added to Clorox, the solution would be so acidic, it would break the bonds of the oxides and put iron into solution instead of gold.

It seems the oldtimers were dissolving gold with an almost neutral solution of HOCl/NaClO in water that, except for strength, differed very little from swimming pool water.

Traveller11

The point I'm trying to make is this,back in the old days bleach wasn't called bleach.What did they call it I'm not sure,but if I had to guess chlorine .They didn't use hcl with it because there was no need.

What do you smell the secant you open a bottle of bleach?
What is your guess as to why they pressurized the tank?
Why didn't they need hcl?

These are all the questions I have asked my self.



modtheworld44
 
From "The Chemistry of Gold Extraction" by John O. Marsden, C. Iain House

"An atmospheric leaching process using NaCl and NaOCl at ph 7 was developed by ISL Ventures in the late 1980's as an option for gold ores containing cyanide-soluble copper, because base metals are not leached under these conditions in this system. The use of isocyanuric acid (2,4,6 trihydroxy-s-triazine) was proposed to reduce the rate of consumption of the oxidant (ie. ClO- species, supplied by the NaOCl). Gold recoveries in excess of 80% were reported for several gold ores when NaOCl concentrations of 1 to 2 gm./litre were employed; however, high NaOCl consumptions (.5 to 1.0 kg./ton of ore) hamper the commercialization of the process."


This author refers to chlorine leaching in his book as a "chlorine/chloride" process with the chlorine being supplied, in its various shifting ph mandated forms, as hypochlorite, hypochlorous acid or chlorine gas. I was a bit puzzled as to the "chloride" part until I remembered that hydrochloric acid is also referred to as "hydrogen chloride" and is, indeed, a chloride. It appears that the inventors at ISL Ventures, in order to maintain a ph of 7, have traded the chloride HCl for the chloride NaCl.
 
Quote from modthe world:
Traveller11

The point I'm trying to make is this,back in the old days bleach wasn't called bleach.What did they call it I'm not sure,but if I had to guess chlorine .They didn't use hcl with it because there was no need.

What do you smell the secant you open a bottle of bleach?
What is your guess as to why they pressurized the tank?
Why didn't they need hcl?

These are all the questions I have asked my self.

-------------------------------------------------------------------------------------

There was a product, marketed in the late 1800's, called Dupont Mining Salts that was used by miners to leach gold from ores. Very little is known about it, as it has not been made in 100 years, but it is felt that it was powdered calcium hypochlorite and that it would make calcium hypochlorite bleach when dissolved in water. As calcium hypochlorite will make a solution with a pH 0f about 10.5 when dissolved in water, it is necessary to lower the pH to convert the hypochlorite ion into the oxidizer hypochlorous acid. However, no information is available to show this was done or what pH the solution would have to be lowered to in order to leach gold and only gold.

When I open a bottle of sodium hypochlorite bleach, I smell bleach and only bleach. With the pH of bleach at +12, chlorine gas cannot escape from solution.

The tank was pressurized to make chlorine gas dissolve in water. Once dissolved, a goodly portion of it becomes hypochlorous acid and hydrochloric acid.

I believe the reason they didn't add HCl was because they were not trying to lower the pH of the bleach solution anywhere near as much as the currently popular HCl/Clorox leach method does. While gold will go into solution at extremely low pH's, iron oxides will also release iron and put it into solution at very low pH's, as well. This is why the promoters of the modern HCl/Clorox method, with a 4:1 ratio of HCl to Clorox, insist that all forms of iron be removed from your ore prior to leaching. The method practiced by these oldtimers reputedly operated at pH's of from 3 to 8. They made no effort at all to remove iron from their ores prior to leaching. They did, however, roast their ores to convert iron sulphides and other forms of iron to oxides. As I quoted a few posts back, converting to iron oxides made the iron impervious to their chlorine leaching solutions. This fact alone proves to me their chlorine solutions were nowhere near as acidic as the modern HCl/Clorox method, as it requires an acidic solution of 1-2 pH to break the bonds of the oxides.

As most of us are dealing with iron oxides in our ores (black sand) there is no reason to roast our ores. Even the sulphides stand a good chance of not being touched by a chlorine solution with a pH of +3.

From "The Chemistry of Gold Extraction" by John O. Marsden and C. Iain House:

"Below pH 3, pyrite is attacked and dissolved in aqueous chloride solution using chlorine as the oxidant. However, between about pH 3 and 6, with hypochlorous species as the oxidant, the dissolution rate of pyrite is greatly reduced. One investigation has shown that the dissolution rate is reduced by a factor of four as the pH is increased from 2 to 4, and by a similar factor again when the pH is increased from 4 to 6. This presents an interesting process option for ores containing free gold with barren pyrite gangue, with the potential for selective gold dissolution above about pH 3."

While it will be necessary to lower the pH of a bleach solution (10.5-12), my research shows that, for a litre of solution, it may take only 1 or 2 (or less) millilitres of HCl to bring the pH of the bleach solution to the desired range of 5-7.5. It also appears now that it may help to add salt (NaCl) to the solution as a source of chloride. According to "The Chemistry of Gold Extraction", bringing the volume of NaCl in chlorine solution to over 3% will accelerate the dissolution process considerably.
 
Traveller11,
I have read about and tried it both ways.

Using HCl as the main ingredient of solution, and adding small amounts of NaClO, to generate chlorine and other compounds to dissolve gold.
And
Using NaClO and adding small amounts of HCl, to generate chlorine and other compounds to dissolve gold, which also works.

The latter I did notice in several researches where they were using this method to process Ore.

I just assumed it to be the same process only done backwards, with both methods just generating chlorine to oxidize and dissolve gold.

They both worked to dissolve gold, but I never thought of why they might choose the later process.

It sounds like maybe you have stumbled onto (or may have figured out) an explanation of why they would use this process, instead of the top method we normally discuss on the forum, your theory is making a lot of sense, dissolving gold with chlorine generation while keeping pH in a state to minimize attack of Iron and to help keep it from going into solution as much as possible.

Very interesting.
 
Thank you, butcher. It means a lot to me to hear encouraging words from you.

The words "stumbled onto" are probably the most correct. A while back, I was feeling somewhat frustrated at the prospect of having to remove all the iron oxides (black sand) from my concentrates, prior to leaching with HCl/Clorox, and, while looking for a good way to do this, just happened onto james122964's post about leaching with HCl/Clorox. He was quite adamant about "cutting way back" on the HCl and claimed that, with far less HCl in the solution, the black sands were barely touched in the leaching process while the gold went into solution easily.

When starting with sodium hypochlorite, I am really beginning to wonder if Cl2 is generated at all, if the pH of the bleach solution never falls below 5. I am starting to think it may become hypochlorous acid and that it is this HOCl doing the work.

As I related a couple of posts back, I studied an excerpt from "The Chemistry of Gold Extraction" by John O. Marsden. The part that interested me was a leaching process using NaCl and NaOCl at pH 7, with no mention of HCl being added. This process was developed in the 1980's by ISL Ventures for the express purpose of dealing with ores containing cyanide-soluble copper because "base metals are not leached under these conditions in this system". If this were true, can you imagine the implications here, not just for small miners such as myself dealing with oxide rich ores, but for refiners as well? As I stated in the previous post, Mr. Marsden refers to chlorination as a "chlorine/chloride" process, with the hypochlorite/hypochlorous contribution presumably being the "chlorine" component. I then assumed NaCl to be the "chloride" component and wondered how HCl fit into things, until I recalled that another name for HCl is hydrogen chloride and it is, indeed, a chloride.

I took the very bold step of emailing Mr. Marsden (can't say where I found his email address) to ask him if he would be amenable to answering a few questions in order to help set a small time miner on the right path. I hope he has the time to answer, as he is quite a prestigious man and is on many corporate boards and consults mining operations worldwide.
 
I do hope you can have a discussion with Mr. Marsden, I would also be very interested in what you learn.

I do not know enough chemistry to say whether Hypochlorous acid and that it is this HOCl doing the work or not, whether it would be a strong enough oxidizer to oxidize gold.

From the way I understand it we need a strong enough oxidizer to oxidize the gold, and free chlorides in solution for the oxidized gold to attach on to and form the gold chloride soluble in solution.

Hypochlorous acid HOCl being a weak acid, but also a strong oxidizer, strong enough to oxidize sulfides.

2FeS2 + 15HOCl + 7H2O --> 2Fe(OH)3 +2H(+) +SO4(-) + 15Cl(-)
Note insoluble iron hydroxide (which will not dissolve easily), and free hydrogen and chlorides!

I could not find direct evidence where any one directly says that gold will oxidize in HOCl, but they do use it as an oxidation agent with cyanide (suggesting it will be strong enough to oxidize the gold).

The fact that with chlorine in very acidic conditions where gold is oxidized by chlorine, and also noting that HOCl can also be in a solution with chlorine, at fairly low pH, with about pH one, and that it looks like a solution could be a mix of chlorine and hypochlorite, and at a slightly higher pH where gold will still dissolve, but chlorine content can be very low or possibly not in solution with HOCl, suggests to me that in fact HOCl may be a very effective oxidizing agent for gold, if this is fact then all we need is some anion in solution like chlorides for the oxidized gold to attach to, to be able to dissolve the gold into solution.

Of course most of this is somewhat speculation on my part, but it looks like the reaction of iron sulfide could actually somewhat helpful, the reaction, forming insoluble iron hydroxide and possibly helping to put gold into solution.

But then again I could also be like a old blind coon hound here, and just barking up the wrong tree,


http://www.freepatentsonline.com/4662938.pdf
electrolysis oxidation
http://cdn.intechopen.com/pdfs/27212/InTech-Electrooxidation_as_a_pretreatment_process_before_cyanidation.pdf
 
butcher and Traveller11

Here's some explanation on why they call bleach Bleach.

http://en.wikipedia.org/wiki/Bleach

When you open bleach you do smell chlorine.
Please read the above and below articles in their entirety,yes some of it is boring but it should shine some light on this thread.

This article is on chlorine and theres a table of it's oxidized states that yall should look at.Remember reading is fundamental. :mrgreen:

http://en.wikipedia.org/wiki/Chlorine

This is a great conversation we're in here and I enjoy shooting theories back and forth.If yall guys would make a small GEOMOD CELL yall would see what your wanting to see happen.Thanks for your time.


modtheworld44
 
From "Advances in Gold Ore Processing" by M.D. Adams:

"Pre-treatment of carbonaceous or sulfidic ores by roasting or pressure oxidation is normally required prior to chlorine or bromine leaching to render ores relatively inert, and consequently reduce reagent consumption. For example, the selective recovery of gold and silver was carried out recently by Puvvada and Murthy from a chalcopyrite concentrate. Gold and silver grades in the concentrate were 11 and 140 g/t, respectively. Laboratory-scale tests were conducted at room temperature on 20% solids slurry containing 25 g/L NaOCl and 0.35 M HCl. Increasing the NaCl concentration increased the rate as well as the extent of gold and silver extraction. Gold and silver recoveries of 42.7 and 45.0%, respectively, were obtained with 200 g/L NaCl. Dissolution of silver was found to be independent of NaOCl concentration. However, pressure oxidizing the copper concentrate and then leaching with NaOCl concentration of 25 g/L, 200 g/L NaCl and 0.35 M HCL for one hour resulted in gold and silver recoveries of 90.0 and 92.5%, respectively."
 
butcher said:
I do hope you can have a discussion with Mr. Marsden, I would also be very interested in what you learn.

I do not know enough chemistry to say whether Hypochlorous acid and that it is this HOCl doing the work or not, whether it would be a strong enough oxidizer to oxidize gold.

From the way I understand it we need a strong enough oxidizer to oxidize the gold, and free chlorides in solution for the oxidized gold to attach on to and form the gold chloride soluble in solution.

Hypochlorous acid HOCl being a weak acid, but also a strong oxidizer, strong enough to oxidize sulfides.

2FeS2 + 15HOCl + 7H2O --> 2Fe(OH)3 +2H(+) +SO4(-) + 15Cl(-)
Note insoluble iron hydroxide (which will not dissolve easily), and free hydrogen and chlorides!

I could not find direct evidence where any one directly says that gold will oxidize in HOCl, but they do use it as an oxidation agent with cyanide (suggesting it will be strong enough to oxidize the gold).

The fact that with chlorine in very acidic conditions where gold is oxidized by chlorine, and also noting that HOCl can also be in a solution with chlorine, at fairly low pH, with about pH one, and that it looks like a solution could be a mix of chlorine and hypochlorite, and at a slightly higher pH where gold will still dissolve, but chlorine content can be very low or possibly not in solution with HOCl, suggests to me that in fact HOCl may be a very effective oxidizing agent for gold, if this is fact then all we need is some anion in solution like chlorides for the oxidized gold to attach to, to be able to dissolve the gold into solution.

Of course most of this is somewhat speculation on my part, but it looks like the reaction of iron sulfide could actually somewhat helpful, the reaction, forming insoluble iron hydroxide and possibly helping to put gold into solution.

But then again I could also be like a old blind coon hound here, and just barking up the wrong tree,


http://www.freepatentsonline.com/4662938.pdf
electrolysis oxidation
http://cdn.intechopen.com/pdfs/27212/InTech-Electrooxidation_as_a_pretreatment_process_before_cyanidation.pdf


LOL Even an old hound gets the scent right every once in a while. :mrgreen:
 
Im new to this but Im trying to leach ore with chlorine and hci. My ore has been assayed at 2+ O/T. I have crushed it and ran it over a RP-4 table and have panned it also with no visible gold. Would like to know a possible mix using bleach or swimming pool chlorine. And if you can use sodium bisulfate to take the gold solution back to a powder. Can someone please help me by giving me a mix ratio as in 2 cups of this to 1 cup of this. I know that is really basic but that is what I need. Thank you
 
okieminer said:
Im new to this but Im trying to leach ore with chlorine and hci. My ore has been assayed at 2+ O/T. I have crushed it and ran it over a RP-4 table and have panned it also with no visible gold. Would like to know a possible mix using bleach or swimming pool chlorine. And if you can use sodium bisulfate to take the gold solution back to a powder. Can someone please help me by giving me a mix ratio as in 2 cups of this to 1 cup of this. I know that is really basic but that is what I need. Thank you

What I am about to give you has not been proven by me yet, although it is the best interpretation of methods from the 1890's I can make.

Pour liquid Clorox bleach (6%) into a container, or mix calcium hypochlorite powder (pool chlorine) and water to get a stronger hypochlorite solution. A 15% solution of calcium hypochlorite should be sufficient.

Wearing acid resistant gloves and clothing, respirator with cartridges to filter chlorine gas and safety glasses or face shield, begin adding tiny amounts of HCl to bleach. Be careful, as there will be some reaction as acid meets base. Between additions of HCl, test the pH of the solution with a pH meter. Slowly but surely bring the pH down to 7.5. At pH 7.5, about 50% of the hypochlorite will have become hypochlorous acid (HOCl). If you do not allow the solution to become acidic (- pH 7), chlorine gas production should be kept to a minimum and will not be detectable. However, under pH 5, great amounts of chlorine gas will be made.

Once the pH is at 7.5, stop adding HCl. At this point, add either sodium chloride or calcium chloride to about 20% of volume. Stir until dissolved. The actual amount of these chlorides is not critical as long as there is enough chloride present to put all of your gold into solution.

You must now have a plastic cylinder capable of holding your ground ore. Any copper or iron in your material that is not tied up as an oxide will spoil this process. This applies to any metal fittings on the cylinder, as well, as they will react with chlorine. The cylinder must be capable of being completely filled with chlorine solution, completely expelling any air inside the cylinder. Any large airspace inside the cylinder will allow the oxygen in the HOCl to be lost, making it into HCl and lowering the pH of the solution. An alternative is to pump air, through plastic fittings, into the cylinder until a pressure of 60 psi is obtained. This will also keep the HOCl from derading to HCl but requires a much sturdier cylinder capable of withstanding this elevated pressure. Remember, no metal in contactwith chlorine solution unless that metal is lead or titanium.

There must be a way of revolving this cylinder to keep all of the ore in contact with the chlorine solution during the period of leaching. Plastic bars lengthwise inside the cylinder will help to keep the ore mixed with the solution, something like the clay breaking bars inside a trommel keep things moving.

Once all this is done, revolve the cylinder for four hours, then open the cylinder and immediately (before the pH begins to drop) filter liquid to remove any ore solids. Wash ore with spray to recover any solution holding gold. Gold can then be precipitated from solution using sodium metabisulphite (not sodium bisulphate) or ferrous sulphate.


I am at the stage of building a small test unit from 4" ABS plumbing fittings and a 1/2" PVC ball valve. After that comes a platform with rollers on it where the cylinder can be driven by a belt from an electric motor. Although it looks simple, it gets quite complicated, and the real challenge will be scaling this up to a unit capable of processing 20 gallons at a time.

Please keep notes on anything you do and, if you discover anything worthy of note, I would appreciate your sharing this information.

Good luck!
 

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