CN105061269A - Tin methanesulfonate preparation method - Google Patents
Tin methanesulfonate preparation method Download PDFInfo
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- CN105061269A CN105061269A CN201510474032.XA CN201510474032A CN105061269A CN 105061269 A CN105061269 A CN 105061269A CN 201510474032 A CN201510474032 A CN 201510474032A CN 105061269 A CN105061269 A CN 105061269A
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- methylsulphonic acid
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Abstract
The invention relates to a tin methanesulfonate preparation method and belongs to the technical field of chemical engineering. The preparation method comprises removing a small amount of organic matters in a waste methyl sulfonate catalyst by a two-phase separation method to obtain refined methyl sulfonate solids, dissolving the refined methyl sulfonate solids in water to obtain a methyl sulfonate solution with content of 20-45%, adding 5-10wt% of a methanesulfonic acid solution and 0.25-1wt% of a tin off-color preventing agent into the methyl sulfonate solution, then adding tin into the methyl sulfonate solution so that a displacement reaction occurs, carrying out solid-liquid separation on the product solution, filtering the separated liquid, and concentrating the filtrate to obtain a tin methanesulfonate solution finished product. The tin methanesulfonate preparation method has the advantages of less equipment investment, simple processes, no environmental pollution, high product purity, full utilization of waste methanesulfonate and recycle.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation method of tin methane sulfonate.
Background technology
Tin methane sulfonate is the main raw material of current eleetrotinplate, electroplating tin alloy, chemical plating stannum, chemical plating stannum alloy etc.Metallic surface is zinc-plated is process important during current electronic devices and components, printed circuit plate etc. are manufactured with tin alloy.Along with the fast development of electronic industry, the demand of tin methane sulfonate is day by day vigorous.Tin methane sulfonate and methylsulphonic acid etc. are combined, and are called as methylsulphonic acid plating system, compare, have huge superiority: its electroplating wastewater relatively easily processes with fluoroboric acid system in the past with sulfuric acid system; Quality of coating is reliable and stable; Can high speed electrodeposition be realized, enhance productivity etc.At present, methylsulphonic acid electric plating body ties up to electronics finishing aspect and almost instead of fluoroboric acid system and sulfuric acid system completely.Therefore, the research of the preparation method of methylsulphonic acid and metilsulfate is also very active.
At present, the preparation method of tin methane sulfonate, mainly contains following several:
1) metallic tin and methylsulphonic acid is adopted to carry out replacement(metathesis)reaction.This method will use highly purified metallic tin powder and methylsulphonic acid, and cost is higher; And reaction is at high temperature carried out, the reaction times is longer, and energy consumption is high, has acid tail gas to discharge simultaneously, can cause environmental pollution.
2) tin protochloride and methylsulphonic acid is adopted to carry out replacement(metathesis)reaction preparation.This method will use high-purity tin protochloride and methylsulphonic acid, and tin protochloride production cost is higher, and produces a large amount of chlorions in product, is difficult to remove completely, and has hydrochloric acid tail gas to produce, cause environmental pollution.Because reaction time is long, a large amount of divalent tin ion can be oxidized to tetravalent tin ion, makes the jaundice of coloured product muddiness.
3) methylsulphonic acid and tin protoxide is adopted to prepare tin methane sulfonate.The tin protoxide production cost used in this method is high, and containing a large amount of tetravalent tins in tin protoxide, the tin methane sulfonate muddy stain prepared turns to be yellow, and difficult quality meets the demands.
The above-mentioned method preparing tin methane sulfonate, all there is cost high, quality product is low.Energy consumption is large, the problems such as environmental pollution is larger.
The present invention is directed to metallic tin and can replace comparatively torpescence metal in salt, as metallic tin can replace cupric ion, obtain metallic copper and tin ion.Utilize this character, metallic tin can be utilized to replace metilsulfate, thus obtain tin methane sulfonate, reclaim noble metal.
The methylsulphonic acid salts such as copper methanesulfonate, methylsulphonic acid silver are also a kind of important catalyzer in organic synthesis, as copper methanesulfonate is usually used in catalyzing and synthesizing apple ester etc.The preparation of these catalyzer will use valuable precious metal.They lose activity in use for some time, become refuse, arbitrarily abandon, and can bring serious environmental pollution, waste valuable precious metal simultaneously.How to utilize these to lose the metilsulfate of catalytic activity, turn waste into wealth, have great importance.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect existed in prior art, providing a kind of and utilizing discarded metilsulfate to prepare tin methane sulfonate, reclaiming the method for precious metal simultaneously.
The preparation method of the tin methane sulfonate that the present invention proposes, comprises the following steps:
The process of step one, methylsulphonic acid salt catalyst
By the organism contained in two-phase laminated flow method removing methylsulphonic acid salt catalyst, subsequent drying process, obtains metilsulfate solid; Above-mentioned methylsulphonic acid salt catalyst is the methylsulphonic acid salt catalyst of metal after being positioned at tin in movable metallic sequence list;
Prepared by step 2, methylsulphonic acid salts solution
By the metilsulfate dissolution of solid of acquisition in water, be configured to the methylsulphonic acid salts solution of 20wt%-45wt%, add the methylsulphonic acid solution of methylsulphonic acid salts solution total mass 5wt%-10wt% and the anti-tin colour-changing agent of 0.25wt%-1wt%, react;
The preparation of step 3, tin methane sulfonate
In above-mentioned metilsulfate solution, add metallic tin, carry out replacement(metathesis)reaction;
Refining of step 4, solution of tin methane sulfonate
Complete for the replacement(metathesis)reaction solution obtained is carried out solid-liquid separation, liquid after filtration, concentrated obtain finished product solution of tin methane sulfonate;
The recovery of step 5, precious metal
The solid that above-mentioned solid-liquid separation obtains is separated, reclaims precious metal wherein.
In technique scheme, in described step one, methylsulphonic acid salt catalyst is the waste losing catalytic activity after using.
In technique scheme, in described step 2, methylsulphonic acid solution allocation becomes saturated solution to add.
In technique scheme, in described step 3, metallic tin adds with the form of tin grain or glass putty.
In technique scheme, in described step 3, the excessive interpolation more than 10% of metallic tin makes replacement(metathesis)reaction fully carry out.
In technique scheme, in described step 2, add methylsulphonic acid solution and anti-tin colour-changing agent simultaneously.
In technique scheme, in described step 2 and step 3, react and carry out under normal pressure or vacuum.
The preparation method of tin methane sulfonate provided by the invention, object is to provide a kind of simple, and the preparation method of the tin methane sulfonate of non-environmental-pollution, realizes turning waste into wealth, and discarded metilsulfate is become available resource.Adopt methylsulphonic acid salt catalyst discarded in organic industry and metallic tin to carry out replacement(metathesis)reaction, obtain tin methane sulfonate and noble metal powder.Because methylsulphonic acid salt catalyst mainly reacts in organic phase, therefore normal containing some organism in metilsulfate, need to carry out refinement treatment.By simple two-phase laminated flow as water-soluble or solvent-extracted method, metilsulfate can be realized and is separated with organic.Selected metilsulfate, should select the metilsulfate being positioned at metallic tin metal below in movable metallic sequence list, as copper methanesulfonate, methylsulphonic acid silver etc.By the metilsulfate dissolution of solid through refining in water, being configured to the solution of 20%-45%, adding the methylsulphonic acid of solution total mass 5%-10% and the anti-tin colour-changing agent of 0.25%-1% simultaneously.Concentrate solution of tin methane sulfonate workload to reduce the later stage and promote that reaction is carried out, augmenting response efficiency, is preferably configured to the saturated solution of higher concentration by metilsulfate.Simultaneously easily be oxidized yellowing due to metal ion or be hydrolyzed, in order to the oxidation of the oxidation or hydrolysis that prevent metal ion, must methylsulphonic acid and anti-blushing agent be added.Wherein the consumption of methylsulphonic acid is too small, and antioxygenation is not obvious, and methylsulphonic acid consumption is excessive, is unfavorable for that replacement(metathesis)reaction is carried out, and is difficult to obtain suitable tin methane sulfonate.In order to abundant displacement, the metallic tin of excessive more than 10% should be added; The replacement(metathesis)reaction of metallic tin is the electrochemical reaction that liquid-solid surface is carried out.Speed of response is relevant to contact area, in order to increase speed of response, metal is made the glass putty that specific surface is larger, but the preparation of glass putty trouble, also can increase cost, also metallic tin can be prepared into metallic tin grain and use.To contact with air to place metal ion deterioration by oxidation occurs, replacement(metathesis)reaction can be carried out under vacuum conditions.
Replacement(metathesis)reaction is as follows:
Sn+2RX
+＝XSn
2++R
Obtained solution is carried out solid-liquid separation, containing unreacted tin in solid, can recycle.Liquid obtains finished product solution of tin methane sulfonate after filtration, and namely concentration and evaporation obtains tin methane sulfonate crystal.
The invention has the beneficial effects as follows: equipment investment is few, technique is simple, and non-environmental-pollution, product purity is high, takes full advantage of discarded metilsulfate, realizes the recycle of resource.Noble metal resource can be reclaimed simultaneously and obtain required product.
Accompanying drawing explanation
Fig. 1 utilizes discarded metilsulfate to prepare the schematic flow sheet of tin methane sulfonate in the present invention.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in detail:
Embodiment 1
A preparation method for tin methane sulfonate, as shown in Figure 1, comprises the steps:
Get 200 grams for methylsulphonic acid copper catalyst discarded after apple ester synthesis, repeatedly wash through ethanol, evaporation, obtain not containing organic copper methanesulfonate solid 180 grams.
By above-mentioned 180 grams of copper methanesulfonate dissolution of solids in 655 grams of softening waters, add the methylsulphonic acid solution of 65 grams of 70wt% simultaneously, and add 2.5 grams of Resorcinols, be configured to the methylsulphonic acid copper solutions of 20wt%, the blue-tinted transparent liquid configured is placed in 2000mL anticorrosion container.
200 grams of tin grains are placed in above-mentioned methylsulphonic acid copper solutions.And under vacuumized conditions, constantly stir and replacement(metathesis)reaction is carried out.
React after 24 hours, this blue solution becomes colourless solution, produces dark gray powder at reaction container bottom simultaneously.Filtered by solution, obtain colourless transparent liquid through decompression dehydration, obtaining 408 grams of content is the solution of tin methane sulfonate of 50.2wt%.Analyze indices, all reach the requirement of plating level tin methane sulfonate.Meanwhile, utilize the different melting points of metallic tin and copper, isolate metallic copper and tin, obtain copper powder 43.6 grams.
Embodiment 2
A preparation method for tin methane sulfonate, as shown in Figure 1, comprises the steps:
Get 300 grams for methylsulphonic acid copper catalyst discarded after apple ester synthesis, repeatedly wash through ethanol, evaporation, obtain not containing organic copper methanesulfonate solid 256 grams.
By above-mentioned 256 grams of copper methanesulfonate dissolution of solids in 931 grams of softening waters, add the methylsulphonic acid solution of 90 grams of 70wt% simultaneously, and add 3 grams of Resorcinols, be configured to the methylsulphonic acid copper solutions of 20wt%, the blue-tinted transparent liquid configured is placed in 2000mL anticorrosion container.
300 grams of tin grains are placed in above-mentioned methylsulphonic acid copper solutions.And constantly stirring makes replacement(metathesis)reaction carry out.
React after 20 hours, this blue solution becomes colourless solution.Produce dark gray powder at reaction container bottom, filtered by solution, obtain colourless transparent liquid through decompression dehydration, obtaining 571 grams of content is the solution of tin methane sulfonate of 50.1wt% simultaneously.Analyze indices, all reach the requirement of plating level tin methane sulfonate.Meanwhile, copper powder 72.4 grams is reclaimed.
Embodiment 3
A preparation method for tin methane sulfonate, as shown in Figure 1, comprises the steps:
Get 220 grams of discarded methylsulphonic acid silver catalysts, entered the washings such as ethanol, evaporation, obtain methylsulphonic acid silver solid 205 grams.
Above-mentioned methylsulphonic acid silver is dissolved in 470 grams of softening waters, adds the methylsulphonic acid solution of 95 grams of 70wt% simultaneously, and add 2 grams of Resorcinols.The methylsulphonic acid configured silver solution is placed in 1000ml Glass Containers, stirring reaction.After 18 hours, detect silver ion content in solution and be less than 5ppm.Reaction terminates.Obtain the solution of tin methane sulfonate of 306 grams of 50.2wt%, and recovery obtains 105 grams of silver powder.
The content be not described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (7)
1. a preparation method for tin methane sulfonate, is characterized in that, comprises the following steps:
The process of step one, methylsulphonic acid salt catalyst
By the organism contained in two-phase laminated flow method removing methylsulphonic acid salt catalyst, subsequent drying process, obtains metilsulfate solid; Above-mentioned methylsulphonic acid salt catalyst is the methylsulphonic acid salt catalyst of metal after being positioned at tin in movable metallic sequence list;
Prepared by step 2, methylsulphonic acid salts solution
By the metilsulfate dissolution of solid of acquisition in water, be configured to the methylsulphonic acid salts solution of 20wt%-45wt%, add the methylsulphonic acid solution of methylsulphonic acid salts solution total mass 5wt%-10wt% and the anti-tin colour-changing agent of 0.25wt%-1wt%, react;
The preparation of step 3, tin methane sulfonate
In above-mentioned metilsulfate solution, add metallic tin, carry out replacement(metathesis)reaction;
Refining of step 4, solution of tin methane sulfonate
Complete for the replacement(metathesis)reaction solution obtained is carried out solid-liquid separation, liquid after filtration, concentrated obtain finished product solution of tin methane sulfonate;
The recovery of step 5, precious metal
The solid that above-mentioned solid-liquid separation obtains is separated, reclaims precious metal wherein.
2. the preparation method of tin methane sulfonate according to claim 1, is characterized in that: in described step one, and methylsulphonic acid salt catalyst is the waste losing catalytic activity after using.
3. the preparation method of tin methane sulfonate according to claim 2, it is characterized in that: in described step 2, methylsulphonic acid solution allocation becomes saturated solution to add.
4. the preparation method of tin methane sulfonate according to claim 3, is characterized in that: in described step 3, and metallic tin adds with the form of tin grain or glass putty.
5. the preparation method of tin methane sulfonate according to claim 4, it is characterized in that: in described step 3, the excessive interpolation more than 10% of metallic tin makes replacement(metathesis)reaction fully carry out.
6. the preparation method of tin methane sulfonate according to claim 5, is characterized in that: in described step 2, adds methylsulphonic acid solution and anti-tin colour-changing agent simultaneously.
7. the preparation method of tin methane sulfonate according to claim 6, is characterized in that: in described step 2 and step 3, react and carry out under normal pressure or vacuum.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083663A (en) * | 2016-05-30 | 2016-11-09 | 柳州百韧特先进材料有限公司 | A kind of method improving stannous methanesulfonate product clarity |
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| CN1124231A (en) * | 1995-05-11 | 1996-06-12 | 福建师范大学 | Producing method for stinnous sulfate |
| US6187169B1 (en) * | 1996-09-16 | 2001-02-13 | Atofina Chemicals, Inc. | Generation of organosulfonic acid from its salts |
| CN1657520A (en) * | 2004-12-08 | 2005-08-24 | 云南锡业集团有限责任公司研究设计院 | Process for preparing methyl stannous sulfonate using tin powder |
| CN101218359A (en) * | 2005-07-06 | 2008-07-09 | 株式会社神钢环境舒立净 | Process for recovery of metals and equipment therefor |
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2015
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Patent Citations (5)
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| US4152143A (en) * | 1977-09-08 | 1979-05-01 | Klockner-Humboldt-Deutz Aktiengesellschaft | Method and apparatus for precipitating metal cement |
| CN1124231A (en) * | 1995-05-11 | 1996-06-12 | 福建师范大学 | Producing method for stinnous sulfate |
| US6187169B1 (en) * | 1996-09-16 | 2001-02-13 | Atofina Chemicals, Inc. | Generation of organosulfonic acid from its salts |
| CN1657520A (en) * | 2004-12-08 | 2005-08-24 | 云南锡业集团有限责任公司研究设计院 | Process for preparing methyl stannous sulfonate using tin powder |
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Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083663A (en) * | 2016-05-30 | 2016-11-09 | 柳州百韧特先进材料有限公司 | A kind of method improving stannous methanesulfonate product clarity |
| CN106083663B (en) * | 2016-05-30 | 2018-01-09 | 柳州百韧特先进材料有限公司 | A kind of method for improving stannous methanesulfonate product clarity |
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Application publication date: 20151118 |