# Unexposed photo paper



## pikpok (Mar 6, 2014)

Hi .

Im have in my company lot of Unexposed photo paper . How to recovery silver from it ?
Next question is how to recover silver from bleach and fixer solution ? My machine manufacture 600 liters per month this solution im think there is many silver to recovery .
Im find on youtube a film but i don't know how to do ? process look easy can any explain it ?
http://www.youtube.com/watch?v=yGxiuINZtV8

I will be grateful for any help
best regards
Peter


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## nickvc (Mar 6, 2014)

Welcome to the forum.
While English isn't your first language most of the forum is in English so use the search function top right of your screen and under authors look for Goldsilverpro or Juan Manuel Arcos Frank and in the topic post silver film that should give you plenty to read by our top experts.


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## rickbb (Mar 6, 2014)

The best and easiest way to recover silver from un-exposed film/paper is to use the normal photographic fixer to strip it. 

Then use an electrolytic recovery unit on the used fixer. 

This will yield 97%+ pure silver flake right away with no chemical processes to go though.


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## pikpok (Mar 6, 2014)

from must be made anode and cathode to this method work? 
im have something to add to the solution? 
what voltage applications?
best regards
Peter


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## butcher (Mar 6, 2014)

pikpok,

May I suggest doing some study on the subject you wish to learn, this will give you the best answer for your questions, the silver section of the forum there is information on just about every thing dealing with silver, even discussions dealing with your current question, you will also find many documents there like the Kodak film industry documents and patents...

This way one question with one answer does not lead to a hundred new questions with no answers, by studying you learn many answers even before you have the questions to ask, which will also lead to more questions but, know you know how to get those answers easily. 

This is the best answer I can think of to help you with this current question.


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## pikpok (Mar 7, 2014)

hi butcher !

Im ask there cuz in my google can't find any info  In my country recovery silver is illegal u need to have mine company and all permission , In other situation u have many trouble .
so people do not speak about it openly on the web :roll: my English is too bad to study all forum and translate all post is inaccurate :|


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## nickvc (Mar 7, 2014)

Get a good English speaking friend to translate for you or pay a translator, if you have volumes of this material or a constant supply it might be worth your costs.


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## butcher (Mar 7, 2014)

pikpok,

The process or processes, and answers can be found here on the forum, as a member you have free assess to this information, the search button will help you find what your looking for, I understand translation of document can be difficult, but if I wished to learn something I will go to the trouble needed to find the answer, If I was not interested enough to work to get those answers I would just sell the silver bearing film.

Search the forum you will find your answer in forum discussions and documents like these:
Or sell your scrap and buy silver with the money.

http://goldrefiningforum.com/phpBB3/search.php?keywords=Photo+paper+silver+recovery&terms=all&author=&sv=0&sc=1&sf=all&sk=t&sd=d&sr=posts&st=0&ch=300&t=0&submit=Search

https://www.google.com/search?hl=en&as_q=film+silver+recovery+&num=1000&ft=i&as_sitesearch=goldrefiningforum.com&as_qdr=all&as_occt=any

https://www.google.com/search?hl=en&as_q=Kodak+silver+recovery+papers+&num=1000&ft=i&as_sitesearch=goldrefiningforum.com&as_qdr=all&as_occt=any


http://goldrefiningforum.com/phpBB3/viewtopic.php?f=34&t=7361&p=66841&hilit=photo+paper#p66841

http://www.kodak.com/eknec/documents/f9/0900688a800f80f9/J210ENG.pdf


Juan Manuel Arcos Frank posted these(see attachments), and much other information searching his posts on the subjects would be of help.

__________



I do not have experience in recovery of silver from film or photo paper, but if I wish to do it all the information I would need is here on the forum for free, I would just have to do a little work to study it.
As I understand it there are different ways silver is used in film photography and X-ray, so choosing a method of recovery may be based on the type of scrap you are dealing with.

You did not give details of what type of film or photo paper you are dealing with, that can have a lot to do with the best recovery process needed.

If you know the type of paper or film you are working with try searching for a process to recover silver from that type of scrap, GSP (Gold Silver Pro), and Juan Manuel Arcos Frank both have made many excellent posts on these subjects.
GSP has made thousands of very helpful posts to anyone wishing to learn silver recovery, searching his post will be very helpful to your learning silver recovery.
GSP also has a book for sell that may help.
http://goldrefiningforum.com/phpBB3/viewtopic.php?f=34&t=7361&p=66841&hilit=photo+paper#p66841


That is the best I can help you to get silver from your photo paper, without doing the study for you, I could do the study for you, if you wish to pay for my time of studying silver recovery from photo paper, but I think you would find it cheaper and easier, and you would learn more doing the work yourself for free.

If you do some homework to learn more about what you are trying to do, then you will have enough knowledge of what you will be doing and then you could get into a conversation about the process and gain more help from the forum members.

Giving more information of the type of paper or film you have may also get you better results in your search for information.


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## pikpok (Mar 7, 2014)

hi ! 
thank for all link ! :idea: 
im try to learn all , and in kodak opinion in be very rich people  chemical from my process got 6-7,5 g silver per L so im think its good idea to recovery this silver  in month im produces near 600 L ! chemical  the assumption that electrolysis has 90% efficiency im can got 3 kg silver per month :mrgreen: .
im go learn more because my life is not a long time may change  

ps . two electrolysis tank ist good idea? 1 with hight voltage and 2ndr with small voltage ?


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## solar_plasma (Mar 7, 2014)

and remember, every new process learned should be tested in a small setup!


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## solar_plasma (Mar 7, 2014)

pikpok said:


> hi butcher !
> 
> Im ask there cuz in my google can't find any info  In my country recovery silver is illegal u need to have mine company and all permission , In other situation u have many trouble .
> so people do not speak about it openly on the web :roll: my English is too bad to study all forum and translate all post is inaccurate :|



I hope you have all those permissions. Otherwise this whole thing will not be worth even 10kg silver per month. You could sell those liquids to a legal refinery.


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## pikpok (Mar 7, 2014)

im dont have any permissions to relif this silver . In legal refinery pay to small price :twisted: because is management of the my country .


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## butcher (Mar 8, 2014)

pikpok,

Take the time needed to study, getting that education is where you will get the silver.

You still did not say what kind of photo paper you have, you did state it was unexposed, which may mean the silver is in an oxidized state,or an emulsion of silver salts or compounds, there can be several ways to get silver from film, much of how and why would depend on the type of film and the state of the silver, study more so you can ask the right questions and get more help to fill your education, as you learn more you will be able to ask questions (with more knowledge yourself, of the right question to ask,)and maybe one of the members knowledgeable in what your doing can help you out more, once you have a better understanding of what you have and what you may need to do...


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## Juan Manuel Arcos Frank (Mar 8, 2014)

Pikpok:

Follow Butcher´s advices,they are perfect and useful and will guide you toward pure silver.

By the way,where do you live?.

Kindest regards.

Manuel


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## pikpok (Mar 8, 2014)

butcher said:


> pikpok,
> You still did not say what kind of photo paper you have,


Im have normal papper for color prints Fuji Crystal archive .



Juan Manuel Arcos Frank said:


> Pikpok:
> 
> Follow Butcher´s advices,they are perfect and useful and will guide you toward pure silver.
> 
> ...



Im live in poland .


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## niteliteone (Mar 8, 2014)

pikpok said:


> butcher said:
> 
> 
> > pikpok,
> ...


Buy an old camera that uses this type of film and tell everyone you talk to you are an amateur photographer. That way you will have a reason to have the materials to process this film.
That will help you stay out of trouble as most countries around the EU are coming down hard on home refiners and recyclers.


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## Juan Manuel Arcos Frank (Mar 9, 2014)

Pikpok:

You can soak that unexposed paper into your spent blix/fix solution and recover all silver it contains.Now,you have to recover all silver in your blix/fix spent solution by using metallic replacement process,zinc/acid process,sodium sulphide process or using an ESRU(Electrolytic Silver Recovery Unit which is very expensive).

Look,take a piece of unexposed paper and dip it into your spent bleach/fixer solution and tell us what happens.

Pozdrowienia.

Manuel


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## pikpok (Mar 10, 2014)

Juan Manuel Arcos Frank said:


> Pikpok:
> Look,take a piece of unexposed paper and dip it into your spent bleach/fixer solution and tell us what happens.
> 
> Manuel


If dip the peper intro waste bleach/fix all silver are removed  Ist great idea !!!thanks a lot .
today im will try make prototype electrolysis unit and i will try recovery this silver.
Im have one more questtion Anode and catode must be make from copper or graphite ?


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## pikpok (Mar 10, 2014)

hi .
im make someone test with my chemical . matal replacament working fine but so slowly  
Im dont know how make electorissys or im make this wrong  cathode = stailess steel 333 anode = coper , tig electrode , alminium dont work or im make it wrong 
photo = metal replacement ( roll ist make from copper )


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## necromancer (Mar 10, 2014)

pikpok,

better to pay to learn English, then pay translator, if it is illegal to refine in your country.

that way only you will know about refining silver, & stay out of trouble.


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## goldsilverpro (Mar 10, 2014)

If you don't have a rotating cathode electrolysis unit (very expensive), you won't have much luck plating out the silver. You'll have a black mess. I personally would use sodium sulfide to precipitate silver sulfide, as per Manuel's method, and then melt in a crucible furnace with lengths of rebar.


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## Juan Manuel Arcos Frank (Mar 11, 2014)

Pikpok:

Forget electrolysis...focus on sodium sulfide or metallic replacement processes.

Kindest regards.

Manuel


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## pikpok (Mar 13, 2014)

hi all !
because i'm stubborn as a mule im make new electrolysis unit and this work fine :evil: 
from minute to minute i'm got more black powder on my Anode .
Next question is what is next?
To black powder add borax and melt ?
or any other idea what i'm can do ?


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## jimdoc (Mar 13, 2014)

pikpok said:


> hi all !
> because i'm stubborn as a mule im make new electrolysis unit and this work fine :evil:
> from minute to minute i'm got more black powder on my Anode .
> Next question is what is next?
> ...




You can listen to Manuel.

Jim


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## Anonymous (Mar 13, 2014)

jimdoc said:


> You can listen to Manuel.
> 
> Jim



I think that's a good post that's actually helpful. :shock:


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## nickvc (Mar 13, 2014)

If GSP or Manuel post about silver recovery I'd advise to listen.......


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## butcher (Mar 13, 2014)

pikpok,

You should listen to GSP and Manuel.

Electrolytic recovery of silver from a thiosulfate solution will not recover all of the silver from solution, if the process is done right you can deplete solution of a good portion of silver from the solution with this method, but it has to be done within strict parameters, and you will not get all of the silver out. the reason for a rotating drum cathode (or pumping solution over the cathode is to keep the silver solution in the vicinity of the cathode, otherwise the silver will form a sulfide,and you will gas off Hydrogen sulfide gas (dangerous)as you decompose the thiosulfate electrolyte, keeping the electrolyte pH in a proper range is also important in the electrolytic recovery method, too high of a pH can also cause problems and if ammonium thiosulfate is involved can produce ammonia, as well as several other factors that need to be considered.

Cementing the silver out with a metal replacement reaction, or precipitating the silver out as a sulfide with sodium sulfide, or potassium sulfide will get all of the silver out of solution, and you will have a lot less trouble using these processes.

Listen to the professionals in this, take their advice.

The black powder you have now is possibly a silver sulfide, and I bet most of your silver is still in solution, my guess here of coarse.

If the black powder is silver sulfide you will need to convert it to silver in the melt (using iron) as GSP had referred to previously.

Edited to correct mistake in wording of chemical compound used, thanks Dave for catching that mistake.


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## rickbb (Mar 14, 2014)

Black powder in your cell tells us that you have too much current converting the silver metal into silver sulfide as Butcher has pointed out. Making your own cell is hard to do, the current density is very low and hard to manage, it's why commercial units are not cheap, and home made units are frustrating to get setup right. 

They also depend on a certain amount of silver to be dissolved in solution, if you have too little in solution even a very low current will "burn", (for lack of a better way to say it), the silver converting it to sulfides. Commercial units have circuitry to detect the dissolved metal content and shut off or ramp up the current based on how much silver is in solution.

The only reason I mentioned it was because you stated you had a large volume to process. A commercial film/paper processer with an inline commercial recovery unit would be an very efficient method for a continuous large volume of film/paper, but does require a significant purchase of equipment.

I spent many years in the printing business and my setup would yield around 20 pounds of almost pure silver flake every 3 months. All you have to do is feed it the material. If you have a steady supply to process and can justify the cost, I'd look at purchasing the right tools for this.

If this is a one shot thing then a metal or chemical replacement method such has been recommended would be better for you.


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## pikpok (Mar 15, 2014)

rickbb said:


> I spent many years in the printing business and my setup would yield around 20 pounds of almost pure silver flake every 3 months. All you have to do is feed it the material. If you have a steady supply to process and can justify the cost, I'd look at purchasing the right tools for this.


Can you tell me about the process by PM ?


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## kurtak (Mar 16, 2014)

Ok - here are some pics of some silver I smelted from silver sulfide yesterday - The Ag/sulfide was given to me by a guy that used to have a one hour photo shop & was recovered from his picture fixer solutions - this same guy gave me about 20 pounds of this same material back in 2011 when I was still learning about refining so back then I posted a question about it - here is a link to that discussion --- http://goldrefiningforum.com/phpBB3/viewtopic.php?f=49&t=12404#p122640 --- there is also a discussion about acetylide's in that thread that some of you may find interesting

pikpok - follow the instructions given you by GSP & Manuel - they are the pros in dealing with this kind of material

when smelting your Ag sulfide you want to use a flux of 50/50 borax/soda ash ( I add a "little" fluorspar to make the flux more fluid in the smelt which helps with circulation in the crucible - you don't need it though) you also need a cone mold to pour your smelt into - a cone mold helps your metals separate from the slag & helps prevent ball metal from hanging up in the slag (a little fluorspar in the flux also helps prevent ball metal hanging up in the slag because it makes your flux more fluid when you pour to the cone mold - but again not needed)

be sure to put a piece of rebar (or other iron) in your crucible when you do the smelt - it the chemical reaction between the flux & the iron that causes the conversion of the silver sulfide to silver

Kurt


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## rickbb (Mar 16, 2014)

No need to PM the process, it's quite simple.

Go to a supplier of equipment to the printing industry. Purchase a graphics arts film processer and silver recovery unit. Have them install it and show you it's operation. 

Yes it may be a few thousand dollars, but how much film/paper do you have? How much silver will you get? Will this investment pay for itself? 

All questions you should be asking first instead of how do I get the silver now. Research the cost benefit ratio of each method first. Compare that to how much material you have/can get and how long will the stream of material last, etc.

You may be able to find good used systems from people who refurbish them for sale. There are a lot of fully automated systems that came out of retail stores from a few years back that offered 1 hour photo developing. 

Since the world has switched to digital photography and printing there should be many units on the market.

Google, eBay and Amazon are good places to start looking.

Otherwise you should follow the advise for chemical or metal replacement to recovery the silver that has been given. 

Those guys have more knowledge on the subject than anyone I know of.


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## Juan Manuel Arcos Frank (Mar 19, 2014)

Pikpok:

I think you like to walk...but not on the road and it is OK...It remembers me when I was young and made a lot of mistakes.

Do you really think that making an electrolytic cell is just matter of connecting two wires in a battery?...No way..it is more complicated than that...Do you want to take a look?...Ok...I am posting for you a diagram of my ESRU.

Of course...there are non rotating processes but I have never tried them...Do you want to try it?,OK,here is a rare patent about it ,do it, but remember that you asked for it and you will do it at your own risk.

Keep us posted about your progress.

Good luck.

Kindest regards.

Manuel


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## fonnie (Mar 20, 2014)

I have a thought of my own,

creating a electrolysis cell is not that difficult, even with fixed electrodes.

for the cathode, take some stainless steel sheet metal (304 or 316 should do)
for the anode, take some Arc Air electrodes (from a friendly welding company, used for weld removal). Those are carbon with a thin copper foil.

Strip the copper foil for almost the entire length (leaving some for better contact)

take a plastic container (storage box) and and suspend the electrode at a small distance from each other (1 inch)

now you need to pump the fixer around, so a small pump (fixer is corrosive, so select a good one) will do, as long as you keep the fixer flowing by the electrodes, keeping fresh fixer around the electrodes

you will need a power-source, preferably with adjustable current and voltage.

I work with badges of about 30 - 50 liter, pumping around, and adjusting current as the silvercontents goes down.

Don't expect to recover all the silver, it only works until a certain level. and you still have fixer as a waste.

if you keep current setting low (depending on the cathode surface) it will give you a shiny silver deposit, and no black sludge. It's a game of finding the best setting.

Current is the parameter, voltage will follow, so powersource on adjustable current, start low.

if your are going to process some 1000liters, it might take some time.

Never calculated the real cost of the project, most of the items were salvaged, but there is of course the electricity to consider.

I will try to take some photo's of my setup and try to post them

best regards

Fonnie


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## pikpok (Mar 24, 2014)

hi all  
fonnie u project are awesome 
have 2 anode ? 
im know fixer is corrosive  the best idea is using pump for aquarists there are only plastic and magnesium :mrgreen: 
today try will make unit like you then im post my progess here .

best regards
Peter


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## canukgold7 (Jun 5, 2016)

rickbb said:


> The best and easiest way to recover silver from un-exposed film/paper is to use the normal photographic fixer to strip it.
> 
> Then use an electrolytic recovery unit on the used fixer.
> 
> This will yield 97%+ pure silver flake right away with no chemical processes to go though.


Hi, please send me info about the recovery unit which you use.


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