CN100528740C - Method for producing amido nickel sulphonic acid - Google Patents
Method for producing amido nickel sulphonic acid Download PDFInfo
- Publication number
- CN100528740C CN100528740C CNB2007103038087A CN200710303808A CN100528740C CN 100528740 C CN100528740 C CN 100528740C CN B2007103038087 A CNB2007103038087 A CN B2007103038087A CN 200710303808 A CN200710303808 A CN 200710303808A CN 100528740 C CN100528740 C CN 100528740C
- Authority
- CN
- China
- Prior art keywords
- nickel
- sulfamic acid
- solution
- hydroxide
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a process for producing nickel sulfamic acid, which is characterized in that the preparation process comprises (1) nickel sulfate or nickel chloride is carried on nickel ammonia complex reaction with ammonia to obtain nickel ammonia complex solution, (2) nickel hydroxide is prepared by the reaction of the produced nickel ammonia complex solution and sodium hydrate, (3) the produced nickel hydroxide solution is washed and filtered, (4) nickel sulfamic acid solution is produced by the reaction of the filtered nickel hydroxide solution and sulfamic acid, and (5) nickel sulfamic acid is prepared by condensing and crystallizing nickel sulfamic acid solution. The process of the invention has the advantages that the cost is reduced by producing through combining with nickel sulfate, the product purity is high, the process condition is simple and the reaction endpoint is clear.
Description
Background technology
The present invention relates to a kind of method of producing nickel sulfamic acid.
Background technology
Nickel sulfamic acid, formal name used at school sulphonyl propylhomoserin nickel ckel sulfamic acid, molecular formula is Ni (NH
2SO
3)
24H
2O, molecular weight are 322.81.Be green crystal or light blue granular powder, solution is blackish green, and easily deliquescence is soluble in water.Being a kind of organic nickel salt, is the mixed crystallization of nickel, thionamic acid root and water, and its effective ingredient is a nickel sulfamic acid, and its quality is with nickel or Ni (NH
2SO
3)
24H
2The content of O is represented.The technology of producing has several at present: the one, and by hydrogen peroxide oxidation, the technical process of thionamic acid dissolving nickel powder method is called the dioxygen water law; The 2nd, being made the transition by nitric acid dissolve nickel sheet is nickelous carbonate or nickel hydroxide, with the technical process of thionamic acid reaction method, is called nitrate method; The 3rd, by the nickel salt solution after purifying directly with the alkali method that makes the transition.There is following shortcoming in above processing method: 1. adopting hydrogen peroxide oxidation, thionamic acid dissolving nickel powder method and nitric acid dissolve nickel sheet method all to need metal nickel powder or nickel sheet is raw material, and cost is higher; 2. also all need dissolving and transition, long 3. nickel salt solutions of flow process are that sodium sulfate in nickelous carbonate and the nickel hydroxide is difficult to washing with alkali method problem transition directly, and the main grade of product is low.
Summary of the invention
The objective of the invention is to the deficiency that exists at existing technology, provide that a kind of perfect crystalline, processing condition are simple, control easily, reaction end are clear and definite, the method for the production nickel sulfamic acid that the master is of high grade, cost is low of product.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method for preparing nickel sulfamic acid is characterized in that its preparation process comprises:
(1) single nickel salt or nickelous chloride and ammoniacal liquor are carried out the nickel ammino and close reaction, make the nickel ammino and close solution;
(2) the nickel ammino that makes is closed solution and sodium hydroxide prepared in reaction nickel hydroxide;
(3) with the hydroxide nickel solution that makes through washing, filter;
(4) reaction of nickel hydroxide after will filtering and thionamic acid generates nickel sulfamic acid solution;
(5) the nickel sulfamic acid solution condensing crystal is made nickel sulfamic acid.
A kind of method for preparing nickel sulfamic acid of the present invention, it is characterized in that described single nickel salt or nickelous chloride being added ammoniacal liquor when preparing the nickel ammino and closing solution, ammoniacal liquor slowly adds in single nickel salt or the nickelous chloride, and reaction makes the nickel ammino and closes solution, and terminal point pH is controlled to be 4.5-5.
A kind of method for preparing nickel sulfamic acid of the present invention, it is characterized in that described nickel ammino closes solution and sodium hydroxide prepared in reaction nickel hydroxide process, the nickel ammino closes the material of solution and sodium hydroxide than being nickel: the mol ratio of sodium hydroxide is 1: 2, reaction times 1h, and temperature is below 80 ℃.
A kind of method for preparing nickel sulfamic acid of the present invention, it is characterized in that the processing condition that nickel hydroxide after the described filtration and thionamic acid reaction generate nickel sulfamic acid are: with the thionamic acid solution of 2mol/L, the mol ratio of nickel hydroxide and thionamic acid is 1: 1, temperature is below 50 ℃, terminal point PH control 4.5.
A kind of method for preparing nickel sulfamic acid of the present invention, it is characterized in that described nickel sulfamic acid solution condensing crystal is to carry out evaporation concentration under 45-50 ℃ of temperature, be cooled to temperature below 20 ℃, crystallization obtains nickel sulfamic acid product and nickel sulfamic acid mother liquor, and mother liquor returns evaporation concentration and crystallisation by cooling.
The inventive method adopts is nickel sulfate solution in the nickel salt production process, belongs to intermediate material, do not need purified nickel powder or nickel sheet, so the cost of raw material reduces greatly; The nickel hydroxide crystalline particle that generates is bigger, can wash the sodium salt plasma of wherein carrying secretly completely, has guaranteed the quality of product, and the master of product is of high grade; Nickel hydroxide is pure, seldom enrichment of impurity in the nickel sulfamic acid mother liquor, so recycle mother liquor, raised the productive rate and the direct yield of product, reduced production cost.Not only processing condition are simple, control easily, and also reaction end is clear and definite; Can be in conjunction with the throughput that has the very fast formation nickel sulfamic acid of nickel salt and nickel hydroxide production technique now.
Method of the present invention is produced single nickel salt and nickel hydroxide technology in conjunction with extraction process, and produce easily according to the complexometry slowly-releasing and obtain bigger complete crystallization, and the principle of washing easily, a kind of processing method of producing nickel sulfamic acid is provided.Utilize this method to produce nickel sulfamic acid, not only processing condition are simple, control easily, and also reaction end is clear and definite, and the master of product is of high grade, does not need purified nickel powder or nickel sheet, has reduced cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
A kind of method for preparing nickel sulfamic acid is characterized in that its preparation process comprises:
(1) single nickel salt or nickelous chloride and ammoniacal liquor are carried out the nickel ammino and close reaction, make the nickel ammino and close solution;
(2) the nickel ammino that makes is closed solution and sodium hydroxide prepared in reaction nickel hydroxide;
(3) with the hydroxide nickel solution that makes through washing, filter;
(4) reaction of nickel hydroxide after will filtering and thionamic acid generates nickel sulfamic acid solution;
(5) the nickel sulfamic acid solution condensing crystal is made nickel sulfamic acid.
Single nickel salt or nickelous chloride add ammoniacal liquor when preparing the nickel ammino and closing solution, and ammoniacal liquor slowly adds in single nickel salt or the nickelous chloride, and reaction makes the nickel ammino and closes solution, and terminal point pH is controlled to be 4.5-5.Its reaction process is:
NiSO
4+NH
3·H
2O→[Ni(NH
3)x(H
2O)
2]
2++SO
4 2-
The nickel ammino closes solution and sodium hydroxide prepared in reaction nickel hydroxide process, and the nickel ammino closes the material of solution and sodium hydroxide than being nickel: the mol ratio of sodium hydroxide is 1: 2, and reaction times 1h is below temperature 8O ℃.
[Ni(NH
3)4(H
2O)
2]SO
4+2NaOH→Ni(OH)
2↓+Na
2SO
4+4NH
3+4H
2O
The processing condition that nickel hydroxide after the filtration and thionamic acid reaction generate nickel sulfamic acid are: with the thionamic acid solution of 2mol/L, the mol ratio of nickel hydroxide and thionamic acid is 1: 1, and temperature is below 50 ℃, terminal point pH control 4.5.
Ni(OH)
2+2H
2NSO
3H→Ni(H
2NSO
3)
3+2H
2O。
The nickel sulfamic acid solution condensing crystal is to carry out evaporation concentration under 45-50 ℃ of temperature, be cooled to below 20 ℃, and crystallization obtains nickel sulfamic acid product and nickel sulfamic acid mother liquor, and mother liquor returns evaporation concentration and crystallisation by cooling.
Embodiment 1
1. working concentration is single nickel salt or the nickel chloride solution of 80g/L, adds saturated ammoniacal liquor at the temperature condition below 50 ℃, and when the ammonia content of the complex solution that generates in the reaction solution stops logical ammonia during for 25-35g/L, 1. the nickel ammino that obtains blue look closes solution;
2. according to technical process Fig. 1,1. and sodium hydroxide solution get the nickel ammino and close solution, both ratios are nickel: the mol ratio of sodium hydroxide is 1: 2, under the temperature condition below 80 ℃, constantly mix, get the nickel hydroxide slurry 1., after filtration with washing after obtain filter cake 1. with filtrate 1., and with pure water pulp filter cake 1., obtain slurry 2.; Thionamic acid at the thionamic acid solution that is mixed with 2mol/L below 50 ℃; 1. filtrate return recovery ammonia, recycling;
With gained slurry in the technological process 2 2. with the thionamic acid solution of 2mol/L in the ratio of mol than 1: 1, in agitation condition and temperature below 50 ℃, slowly thionamic acid solution join slurry 2. in, all dissolve to slurry, terminal point pH is controlled at 4.5-5;
The nickel sulfamic acid solution that obtains at crystallisation by cooling below 20 ℃, obtains nickel sulfamic acid product and nickel sulfamic acid mother liquor 45-50 ℃ of following evaporation concentration, and mother liquor returns evaporation concentration and crystallisation by cooling;
Embodiment 2
Adopt the nickel sulfate solution (80g/L) after purifying, saturated ammoniacal liquor and industrial sodium hydroxide (120g/L), standby;
1. get above-mentioned nickel sulfate solution 1L (80g/L), add saturated ammoniacal liquor down at 50 ℃, when the ammonia content of the complex solution that generates in the reaction solution stops logical ammonia during for 25-35g/L, 1. the nickel ammino that obtains blue look closes solution, the time that add ammoniacal liquor this moment is 2 minutes, volume increases to 1.5 times, nickel ion concentration 52.6g/L.
2. get the nickel ammino and close solution 1.5L, average rate adds the about 0.9L of industrial sodium hydroxide (120g/L), solution gradually becomes green and suspends, constantly stir, when pH reaches 8-8.5, stop to add alkali, filter the hydroxide slurry material that obtains, filtrate is that individual curing reclaims nickel, filter cake washs with pure water, and the filter cake that obtains is afterwards used pure water pulp in 1: 1 again, obtains slurry 2..270 gram thionamic acids are joining below 50 ℃ in the 1.4L water, and compound concentration is the thionamic acid solution of 2mol/L, and is standby;
The concentration for preparing be the thionamic acid solution of 2mol/L join at the uniform velocity, slowly slurry 2. in, and constantly stir, all dissolve to the nickel hydroxide suspended substance, solution becomes must be clarified green, pH is 15 minutes to this process of 4.5-5.; The nickel sulfamic acid solution that obtains refilters, the undissolved nickel hydroxide of elimination, and filter residue dissolves next time again, and filtrate is purified nickel sulfamic acid solution, 45-50 ℃ of evaporation, at crystallisation by cooling below 20 ℃, obtains green nickel sulfamic acid product after the filtration; Mother liquor returns evaporation concentration.
Nickel sulfamic acid product 175 grams that obtain, main grade is 99%.The concentration of mother liquor nickel is 367ml for the 130.8g/L volume.
Embodiment 3
1. working concentration is single nickel salt or the nickel chloride solution of 80g/L, adds saturated ammoniacal liquor at 40 ℃ temperature condition, and when the ammonia content of the complex solution that generates in the reaction solution stops logical ammonia during for 30g/L, 1. the nickel ammino that obtains blue look closes solution;
2. according to technical process Fig. 1,1. and sodium hydroxide solution get the nickel ammino and close solution, both ratios are nickel: the mol ratio of sodium hydroxide is 1: 2, under the temperature condition below 80 ℃, constantly mix, get the nickel hydroxide slurry 1., after filtration with washing after obtain filter cake 1. with filtrate 1., and with pure water pulp filter cake 1., obtain slurry 2.; Thionamic acid at the thionamic acid solution that is mixed with 2mol/L below 45 ℃; 1. filtrate return recovery ammonia, recycling; Its reaction process is:
With gained slurry in the technological process 2 2. with the thionamic acid solution of 2mol/L in the ratio of mol than 1: 1, in agitation condition and temperature below 45 ℃, slowly thionamic acid solution join slurry 2. in, all dissolve to slurry, terminal point pH is controlled at 4.5-5; The nickel sulfamic acid solution that obtains at 20 ℃ of following crystallisation by cooling, obtains nickel sulfamic acid product and nickel sulfamic acid mother liquor 45-50 ℃ of following evaporation concentration, and mother liquor returns evaporation concentration and crystallisation by cooling;
Claims (5)
1. method for preparing nickel sulfamic acid is characterized in that its preparation process comprises:
(1) single nickel salt or nickelous chloride and ammoniacal liquor are carried out the nickel ammino and close reaction, make the nickel ammino and close solution;
(2) the nickel ammino that makes is closed solution and sodium hydroxide prepared in reaction nickel hydroxide;
(3) with the hydroxide nickel solution that makes through washing, filter;
(4) reaction of nickel hydroxide after will filtering and thionamic acid generates nickel sulfamic acid solution;
(5) the nickel sulfamic acid solution condensing crystal is made nickel sulfamic acid.
2. a kind of method for preparing nickel sulfamic acid according to claim 1, it is characterized in that described single nickel salt or nickelous chloride being added ammoniacal liquor when preparing the nickel ammino and closing solution, ammoniacal liquor slowly adds in single nickel salt or the nickelous chloride, react to single nickel salt or nickelous chloride and all dissolve, terminal point pH is controlled to be 4.5-5.
3. a kind of method for preparing nickel sulfamic acid according to claim 1, it is characterized in that described nickel ammino closes solution and sodium hydroxide prepared in reaction nickel hydroxide process, the nickel ammino closes the material of solution and sodium hydroxide than being nickel: the mol ratio of sodium hydroxide is 1: 2, reaction times 1h, temperature is below 80 ℃.
4. a kind of method for preparing nickel sulfamic acid according to claim 1, it is characterized in that nickel hydroxide and thionamic acid after the described filtration react the processing condition that generate nickel sulfamic acid: with the thionamic acid solution of 2mol/L, the mol ratio of nickel hydroxide and thionamic acid is 1: 1, temperature is below 50 ℃, terminal point pH control 4.5.
5. a kind of method for preparing nickel sulfamic acid according to claim 1, it is characterized in that described nickel sulfamic acid solution condensing crystal is to carry out evaporation concentration under 45-50 ℃ of temperature, be cooled to temperature crystallization below 20 ℃, obtain nickel sulfamic acid product and nickel sulfamic acid mother liquor, mother liquor returns evaporation concentration and crystallisation by cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007103038087A CN100528740C (en) | 2007-12-25 | 2007-12-25 | Method for producing amido nickel sulphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007103038087A CN100528740C (en) | 2007-12-25 | 2007-12-25 | Method for producing amido nickel sulphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101195479A CN101195479A (en) | 2008-06-11 |
| CN100528740C true CN100528740C (en) | 2009-08-19 |
Family
ID=39546138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007103038087A Active CN100528740C (en) | 2007-12-25 | 2007-12-25 | Method for producing amido nickel sulphonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100528740C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704517B (en) * | 2009-10-28 | 2011-05-18 | 广东光华科技股份有限公司 | Preparation method of electronic grade high-purity nickel sulfamic acid solution |
| CN103950905B (en) * | 2014-04-30 | 2016-04-13 | 金川集团股份有限公司 | A kind of crystallization method of nickel sulfamic acid product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1181994A1 (en) * | 1983-12-21 | 1985-09-30 | Физико-химический институт АН УССР | Method of producing solution of sulfaminoacid nickel |
| RO91732A2 (en) * | 1985-04-26 | 1987-05-15 | Centrul De Chimie,Ro | PROCESS FOR OBTAINING NICKEL SULFAMATE |
| EP1328471A1 (en) * | 2000-10-05 | 2003-07-23 | Honeywell Specialty Chemicals Seelze GmbH | Method and device for producing nickel sulphamate |
| CN1583718A (en) * | 2004-06-11 | 2005-02-23 | 上海光铧科技有限公司 | Preparation of nickel sulphamate |
-
2007
- 2007-12-25 CN CNB2007103038087A patent/CN100528740C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1181994A1 (en) * | 1983-12-21 | 1985-09-30 | Физико-химический институт АН УССР | Method of producing solution of sulfaminoacid nickel |
| RO91732A2 (en) * | 1985-04-26 | 1987-05-15 | Centrul De Chimie,Ro | PROCESS FOR OBTAINING NICKEL SULFAMATE |
| EP1328471A1 (en) * | 2000-10-05 | 2003-07-23 | Honeywell Specialty Chemicals Seelze GmbH | Method and device for producing nickel sulphamate |
| CN1583718A (en) * | 2004-06-11 | 2005-02-23 | 上海光铧科技有限公司 | Preparation of nickel sulphamate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101195479A (en) | 2008-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7376862B2 (en) | Wet synthesis method of NCMA high nickel quaternary precursor | |
| CN106276988B (en) | A kind of method that battery-level lithium carbonate is prepared using potassium carbonate as precipitating reagent | |
| CN102127657B (en) | Comprehensive recovery method for extracting ferrovanadium from stone coal acid immersion liquid | |
| CN106315625A (en) | Method for composite production of high-purity lithium hydroxide monohydrate, high-purity lithium carbonate and battery grade lithium carbonate | |
| CN113336246B (en) | Resource treatment method of waste salt | |
| CN101580464B (en) | Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct | |
| CN114105172B (en) | Method for producing high-purity lithium carbonate by causticizing and carbonizing crude lithium carbonate lime | |
| CN114436297B (en) | Method for preparing sodium carbonate from mirabilite | |
| CN109534365B (en) | Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride | |
| CN107739040A (en) | Waste material containing lithium produces the production technology of high-purity lithium carbonate | |
| CN105803199B (en) | A kind of method that hydroxide precipitation method prepares low-sulfur rare earth oxide | |
| CN112225235A (en) | Method for preparing sodium bicarbonate and sodium bisulfate from sodium sulfate | |
| WO2023169432A1 (en) | Method and system for preparing battery-grade lithium hydroxide and lithium carbonate | |
| CN216662498U (en) | System for preparing battery-grade lithium hydroxide and lithium carbonate | |
| CN110078099A (en) | A method of scavenging solution, which is leached, from lepidolite prepares lithium carbonate | |
| CN109592699A (en) | The preparation method of LITHIUM BATTERY lithium hydroxide | |
| CN109809440B (en) | Method for preparing high-purity lithium chloride, high-purity lithium formate and high-purity lithium carbonate | |
| CN102020316B (en) | Method for preparing chromic anhydride from potassium chromate | |
| CN115893749A (en) | Resource utilization method for lithium battery anode ternary precursor production wastewater | |
| CN109824064B (en) | Method for recovering sodium carbonate from sodium tungstate leaching solution | |
| CN101704517B (en) | Preparation method of electronic grade high-purity nickel sulfamic acid solution | |
| CN100528740C (en) | Method for producing amido nickel sulphonic acid | |
| CN103044239A (en) | Production method of sodium citrate | |
| CN113277572B (en) | Low-sodium-sulfur-nickel-cobalt composite hydroxide precursor and preparation method thereof | |
| CN114538471A (en) | Method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: JINCHUAN GROUP CO., LTD. Free format text: FORMER NAME: JINCHUAN GROUP CORP., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 737103 Jinchuan Road, Gansu, China, No. 98, No. Patentee after: Jinchuan Group Co., Ltd. Address before: 737103 Jinchuan Road, Gansu, China, No. 98, No. Patentee before: Jinchuan Group Corp., Ltd. |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20080611 Assignee: Lanzhou Jinchuan precious metal materials Limited by Share Ltd Assignor: Jinchuan Group Co., Ltd. Contract record no.: 2014620000027 Denomination of invention: Method for producing amido nickel sulphonic acid Granted publication date: 20090819 License type: Exclusive License Record date: 20140930 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |