CN1590283A

CN1590283A - Preparation of metal aminosulfonate

Info

Publication number: CN1590283A
Application number: CN 03159266
Authority: CN
Inventors: 尚士清
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-08-28
Filing date: 2003-08-28
Publication date: 2005-03-09
Also published as: WO2005026047A1

Abstract

An aminosulfonate of metal chosen from Ni, Co, Sn, Pb and Cu for electroplating is prepared through metathesis between sulfate and barium aminosulfate, such as NiSO4-Ba(NH2SO3)2-Ni(NH2SO3)2+BaSO4.

Description

Preparation of metal sulfamates

Metal sulfamates, including salts of several metals such as nickel, cobalt, tin, lead, copper, etc., are the main plating salts, and are widely used in the plating or electroforming industry because of their many advantages, such as high solubility (e.g., nickel sulfamate, which has a solubility in water 3.5 times higher than nickel sulfate), low internal stress in the plated product (e.g., 1/4, which has an internal stress of only nickel sulfate, when plated or electroformed with nickel sulfamate), extremely high plating or electroforming speed (e.g., 4 times faster plating or electroforming speed than nickel sulfate), no environmental pollution, etc. However, some of the methods for producing these salts are quite complicated, and some of the raw materials are quite expensive, so that the product quality is either poor or the cost is too high, and these methods are:

1. the nickel carbonate method (soviet union patent 452543) is prepared by using sulfamic acid to mediate nickel carbonate, and a large amount of impurities are brought in due to the fact that a plurality of chemical raw materials are required to be added when the nickel carbonate is produced, and the quality of products is influenced.

2. The catalytic oxidation method (U.S. Pat. No. 3321273, 3620669 and Chinese patent 85105950, the latter is my invention) uses air, oxygen and hydrogen peroxide in sulfamic acid solution to directly prepare nickel sulfamate by catalytic oxidation of powdery nickel. However, the powdered nickel is expensive, so the product cost is high.

The invention overcomes the defects of the two methods, and adopts the reaction of nickel sulfate and barium sulfamate to prepare nickel sulfamate, wherein the reaction comprises the following steps:

(1)

the barium sulfate has very low solubility, so that the method is a fast irreversible reaction, the obtained by-product is also a common chemical raw material, and the solution left after the precipitation is separated is the required product.

According to the same method, cobalt sulfate is used as a raw material to prepare cobalt sulfamate:

(3)

the stannous sulfamate can be prepared by taking stannous sulfate as a raw material:

(4)

copper sulfate is used as a raw material to prepare the copper sulfamate:

(5) and so on.

The method has the advantagesthat: simple production process, no environmental pollution, cheap raw materials, lower production cost than any method, and the same product quality as the oxidation method.

Example 1 weighing nickel sulfate 15.4 g, dissolving in 200 ml water, adding barium sulfamate 32.9 g, reacting rapidly under stirring, separating out precipitated barium sulfate after reaction is finished, leaving solution which is nickel sulfamate, evaporating and drying to obtain Ni (NH) 32.2 g₂SO₃)₂·4H₂O

Example 2, 19.4 g of sulfamic acid was weighed out and dissolved in 200 ml of water, then 19.7 g of barium carbonate was slowly added, and the reaction was rapidly carried out under stirring according to the following formula:

(2) to be treated with CO₂After all is discharged, add15.4 g of nickel sulfate (preferably in solution) barium sulfate precipitate immediately, and the precipitate is separated from the solution as in example 1, and 32.2 g of Ni (NH) are obtained after evaporation and drying₂SO₃)₂·4H₂And O. Both reactions are carried out at ambient temperature.

Example 3 weighing cobalt sulfate 15.5 g, dissolving in 200 ml water, adding barium sulfamate 32.9 g, reacting rapidly, separating out precipitated barium sulfate after the reaction is finished, leaving the solution as cobalt sulfamate, evaporating and drying to obtain Co (NH) 32.2 g₂SO₃)₂·4H₂O (note that Ni and Co have no difference in atomic weight)

Of course, the same amount of sulfamic acid, barium carbonate and cobalt sulfate as in example 2 were weighed and reacted in the same manner to obtain the same results.

Example 4 weighing SnSO₄21.5 g, dissolved in 200 ml of water, then 32.9 g of barium sulfamate is added, the reaction is carried out rapidly, after the reaction is finished, precipitated barium sulfate is separated, the remaining solution is stannous sulfamate, and 30 g of Sn (NH) can be obtained after evaporation and drying₂SO₃)₂

Similarly, 19.4 g sulfamic acid and 19.7 g barium carbonate were weighed and reacted in 200 ml water to form barium sulfamate solution, then 21.5 g stannous sulfate was added to react with the barium sulfamate solution, and finally barium sulfate precipitate was separated, wherein the solution is also Sn (NH)₂SO₃)₂

EXAMPLE 5 weighing of CuSO₄16 g of the copper sulfate is dissolved in 200 ml of water, 32.9 g of the amino acid barium is added, the reaction is carried out rapidly, after the reaction is finished, the precipitated barium sulfate is separated, the remaining solution is the copper sulfamate, and the Cu (NH) can be obtained after evaporation and drying₂SO₃)₂·2H₂O29.8 g. Alternatively, the reaction was carried out in the same manner as in example 2.

Reference to the literature

1、U.S.S.R Patent 452543 74.12.5

2、U.S Patent 3321273 67.5.13

3、U.S Patent 3620669 71.11.16

4. Chinese patent 85105950

Claims

The present invention relates to an indirect method for preparing aminosulfonate, i.e. firstly preparing barium aminosulfonate, then making it react with correspondent sulfate to separate out various aminosulfonates by utilizing the property of very small solubility of barium sulfate

1. When preparing nickel sulfamate, barium sulfamate is prepared firstly according to the reaction formula (2), the reaction is carried out in aqueous solution at normal temperature, the reaction is continuously stirred, and CO₂When the reaction is stopped, the reaction is terminated.
2. Adding the dissolved nickel sulfate into the barium sulfamate solution prepared in the step (1), fully stirring and mixing at normal temperature to generate green nickel sulfamate, and then clarifying and separating the solution to obtain the required product nickel sulfamate.

The above two reactions are characterized in that the reaction is carried out in aqueous solution, and the reaction is very quick at normal temperature under the condition of continuous stirring.
3. The barium sulfamate prepared in the step (1) can also be used for preparing amino acid cobalt, when the aqueous solution of the salt is added into the barium sulfamate as in the step (2), and the pink cobalt sulfamate can also be obtained through stirring reaction, wherein the reaction conditions are the same as in the step (2).
4. Similarly, like (2), the solution of stannous sulfate is added into the solution of barium sulfamate, and milky stannous sulfamate can be obtained through stirring reaction.
5. And (2) dissolving copper sulfate, directly adding the copper sulfate into the barium sulfamate prepared in the step (1), and stirring for reaction to obtain blue copper sulfamate.

The above reactions are characterized by the formation of various sulfamates and the by-product barium sulfate.