Antimisting agents

Details Antimisting agents Antimisting agents

2003-07-14

2004-12-21

Andrews, Melvyn (Department: 1742)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C205S094000, C205S585000

Reexamination Certificate

active

06833479

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to the control of mist formation during processes for the electrowinning, electroplating, and electroforming of metals from electrolyte solutions.
BACKGROUND OF THE INVENTION
In the production of metals by electrolysis of aqueous solutions, the electrowinning of the metals is usually carried out in tank cells. Developments in the electrowinning of metals from aqueous solutions have been directed toward improved demisting agents, improved anodes, improved additives, higher current densities, the use of ion-exchange membranes, better electrolyte quality control, and computer modeling of the processes.
Electroplating is the process of applying a metallic coating to an article by passing an electric current through an electrolyte in contact with an article. The ASTM adds some quality restriction by defining electroplating as electrodeposition of an adherent metallic coating on an electrode such that a surface having properties or dimensions different from those of the basic metal is formed.
Progress in electroplating is linked to improvements in materials of construction, power supplies and other plating equipment, purer industrial chemicals and anodes, improved additives such as demisting agents for the plating baths, and improved analytical test and control methods. The quality of electroplating is dependent on the basic metal surface. Cleaner, less porous castings and better casing alloys, and improved steel and steel finishes have helped significantly.
Electroforming involves the electrodeposition upon a mandrel or mold in which the separated electrodeposit is the manufactured article.
A problem common to all of the above electrolysis procedures is the presence of mist generated above the electrolyte solutions. In order to reduce the quantity of mist, antimisting (also referred to as demisting and mist-suppressing) agents are commonly added to the electrolyte solutions. However, the currently available antimisting agents are not completely satisfactory, due to limited demisting ability, high loss rate, interference with the electrolysis procedure, and/or ecological incompatibilities.
SUMMARY OF THE INVENTION
This invention relates to antimisting agents for the control of mist generated above electrolyte solutions during the electrowinning, electroplating, and electroforming of metals present in the electrolyte solutions.
The antimisting agents of the invention are alkoxylated compounds having the following structure:
R((AO)
n
H)
m
H
p
  (I)
wherein each AO group is independently an alkyleneoxy group selected from ethyleneoxy, 1,2-propyleneoxy, 1,2-butyleneoxy, and styryleneoxy groups; n is an integer of from 2 to 100; m is an integer of from 1 to the total number of —OH plus —NH hydrogens in the R group prior to alkoxylation; the sum of m plus p equals the number of —OH plus —NH hydrogens in the R group prior to alkoxylation; and the R group is a group selected from the following:
N(CH
2
CH
2
O)
3
  (II);
R
1
N(CH
2
CH
2
O)
2
where R
1
is a C
1
-C
24
alkyl, aryl, or aralkyl group  (III);
R
1
N
+
(CH
2
CH
2
O)
3
Y
−
where R
1
has the above meaning and  (IV)
Y
−
is an anion, preferably an inorganic anion such as a halogen anion, a hydrogen sulfate anion, one-half of a sulfate anion, or one-third of a phosphate ion;
NCH
2
CH
2
N  (V);
NCH
2
CH
2
NCH
2
CH
2
N  (VI);
CH
3
C(CH
2
O)
3
  (VII);
CH
3
CH
2
C(CH
2
O)
3
  (VIII);
C(CH
2
O)
4
  (IX); and
where y is an integer of from 0 to 3, z is an integer of from 0 to 3, provided that the sum of y plus z is 2 or 3.
The invention also relates to a method for controlling misting in electrolyte solutions of metal ions by adding thereto a mist suppressing quantity of at least one of the above demisting agents.
DETAILED DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term “about”.
In the alkoxylated compounds of formula I, the total number of alkyleneoxy groups present therein is preferably from 2 to 50, and more preferably from 2 to 30. Compounds that contain ethylenenoxy groups plus propylenenoxy, butyleneoxy, and/or styryleneoxy groups are highly preferred, especially those that contain from 2 to 25 ethyleneoxy groups and from 2 to 15 propyleneoxy, butyleneoxy, and/or styryleneoxy groups. The styryleneoxy groups can be unsubstituted, or can contain substituents on the phenyl group such as one or more C
1
-C
6
alkyl groups, C
1
-C
6
alkoxy groups and other groups that will not interfere with electrolysis. Also, compounds that are fully alkoxylated are preferred, i.e. compounds of formula I in which p=0.
Also, compounds wherein the R group is the formula II group, i.e. alkoxylated triethanolamine compounds are preferred for use herein especially those which contain from 6 to 15 ethyleneoxy groups, and from 6 to 15 propyleneoxy groups. Such compounds include, but are not limited to, the following; in which POP stands for polyoxypropylene and POE stands for polyoxyethylene, and the numbers following each POP and POE designation mean the number of each groups present in the compound; wherein the POE groups are positioned between the triethanolamine and the POP groups.
POP(6) POE(9)triethanolamine
POP(9) POE(9)triethanolamine
POP(12) POE(9)triethanolamine
POP(15) POE(9)triethanolamine
POP(6) POE(15)triethanolamine
POP(9) POE(15)triethanolamine
POP(12) POE(15)triethanolamine
POP(15) POE(15)triethanolamine
POP(3) POE(6)triethanolamine
POP(6) POE(6)triethanolamine
POP(9) POE (6)triethanolamine
POP(12) POE (6)triethanolamine
In the compounds of formula I in which the R group has the formula III, i.e. alkoxylated N-alkyl-diethanolamines, compounds in which the R
1
group contains from 1 to 18 carbon atoms are preferred. Also, compounds containing from 2 to 20 ethyleneoxy groups and from 2 to 15 propyleneoxy, butyleneoxy, and/or styryleneoxy groups are preferred.
In compounds of formula I in which the R group has the formula IV, i.e. alkoxylated N-alkyl-triethanolamonium salts, compounds in which the R
1
group contains from 1 to 20 carbon atoms are preferred. Also, compounds containing from 2 to 40, preferably from 3 to 25, ethyleneoxy groups, and from 2 to 20, preferably from 2 to 16, propyleneoxy, butyleneoxy and/or styryleneoxy groups are also preferred.
In the compounds of formula I in which the R group has the formula V, i.e. alkoxylated ethylenediamines, compounds containing from 2 to 40, preferably from 4 to 20, ethyleneoxy groups, and from 2 to 20, preferably 4 to 16 propyleneoxy, butyleneoxy, and/or styryleneoxy groups are preferred.
In the compounds of formula I in which the R group has the formula VI, i.e. alkoxylated diethylenetriamines, compounds containing from 2 to 60, preferably from 4 to 30, ethyleneoxy groups, and from 3 to 40, preferably 3 to 20 propyleneoxy, butyleneoxy, and/or styryleneoxy groups are preferred.
In the compounds of formula I in which the R group has the formula VII or VIII, i.e. alkoxylated trimethylol-ethane or -propane, compounds containing from 3 to 60, preferably from 4 to 40, ethyleneoxy groups, and from 3 to 40, preferably 4 to 30 propyleneoxy, butyleneoxy, and/or styryleneoxy groups are preferred.
In the compounds of formula I in which the R group has the formula IX, i.e. alkoxylated pentaerythritols, compounds containing from 4 to 60, preferably from 4 to 40, ethyleneoxy groups, and from 2 to 40, preferably 4 to 20 propyleneoxy, butyleneoxy, and/or styryleneoxy groups are preferred.
In the compounds of formula I in which the R group has the formula X, e.g. alkoxylated phenylenediamine, compounds containing from 4 to 60, preferably from 4 to 40, ethyleneoxy groups, and from 4 to 40, preferably 4 to 30 propyleneoxy, butyleneoxy, and/or styryleneoxy groups are preferred.
In all of the above compounds of formula I, in addition to the ethyleneoxy groups, pro

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