CN102786100B - Synthetic method of palladium tetra-ammino sulfate - Google Patents
Synthetic method of palladium tetra-ammino sulfate Download PDFInfo
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Abstract
The invention discloses a synthetic method of palladium tetra-ammino sulfate, comprising the following steps of: (1) adding ammonia water in reagent level palladium chloride in order to dissolve palladium chloride; (2) concentrating and crystallizing the obtained solution, and drying the crystals to obtain orange solids; (3) confecting yellow solids into solution with a certain concentration; (4) flowing the solution through a negative ion exchange resin, exchanging repeatedly till Cl<-> ion cannot be detected in tail solution; (5) concentrating the exchanged solution to a certain concentration, adding sulfuric acid in a quantitative form, keeping on concentrating till crystals are generated; (6) separating out the crystals, re-crystallizing for 2-3 times, obtaining yellow crystals; and (7) drying crystals at a low temperature, so as to obtain faint yellow palladium tetra-ammino sulfate solids. The method has the following characteristics of simple process, few by-products, high product purity, and high product yield of more than 95%.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to the synthetic method of sulfuric acid four ammonia palladiums, affiliated technology is coordination chemistry category.
Background technology
For manufacturing the part of high stable high-wearing feature, conventionally need on coating, deposit one deck precious metal (as gold-plated, rhodium, palladium etc.), along with the development of industrial technology, need to reduce halogens content in plating solution, the consumption of Halogen electroplate liquid is increasing.
Sulfuric acid four ammonia palladiums are a kind of Novel electroplating products, for electron trade plating palladium, are mainly used in coating computer main board and plug, manufacture automobile cat cracker etc. for network.Because its electroplating efficiency is high, and not halogen-containing element, clean environment firendly, can replace traditional Halogen electroplate liquid.At present, domestic open source information there is no sulfuric acid four ammonia palladium synthesis technique introductions, and United States Patent (USP) [US 6346222B1] report is used sulfuric acid to drive the nitric acid in palladium nitrate solution, obtains palladous sulfate solution, then obtains sulfuric acid four ammonia palladiums with ammoniacal liquor complexing.In process, need to use in a large number sulfuric acid to drive away nitric acid, excess sulfuric acid is more, and by product increases, and in complexation process, produce a large amount of ammonium sulfate, mix with sulfuric acid four ammonia palladiums, need the extra product separation operation that increases, technical process is long, and the yield of product and quality be more difficult control all.
Summary of the invention
A kind of method that the object of this invention is to provide synthetic sulfuric acid four ammonia palladiums, the method has the advantages such as technique is simple, by product is few, product purity is high, transformation efficiency is high.
In order to reach above object, embodiment of the present invention are following designs:
1. a synthetic method for sulfuric acid four ammonia palladiums, is characterized in that, according to following steps, completes:
1. with SILVER REAGENT Palladous chloride and SILVER REAGENT ammoniacal liquor, make raw material, with ammoniacal liquor, Palladous chloride is dissolved;
2. the solution 1. step being obtained is concentrated, until there is crystal to separate out, filters to isolate crystal, dries and obtains orange/yellow solid;
3. the solid water dissolution 2. step being obtained;
4. the solution 3. obtaining by anion exchange process step, exchange velocity is 100 ~ 200mL/min, with remaining Cl whether in silver nitrate solution inspection exchange tail washings
-ion, exchange repeatedly, until the inspection of exchange tail washings does not measure Cl
-ion;
The chemical reaction process that said process relates to is:
Pd(NH
3)
4Cl
2?+?2R-OH?→?Pd(NH
3)
4(OH)
2?+?2R-Cl
5. the solution decompression cryoconcentration 4. step being obtained, until the concentration of palladium, to being greater than 10g/L, adds sulfuric acid in solution;
The chemical reaction process relating to is:
Pd(NH
3)
4(OH)
2?+?H
2SO
4?→?Pd(NH
3)
4SO
4?+?2H
2O
6. the solution 5. step being obtained continues concentrated, until there is crystallisate to produce, filters sub-argument and goes out crystallization, and recrystallization 2 ~ 3 times, isolates yellow crystal thing;
7. the crystallization oven drying at low temperature 6. step being obtained, obtains faint yellow sulfuric acid four ammonia palladium solids.
Step 1. in the ratio of Palladous chloride and ammoniacal liquor be 100g:160 ~ 400mL, solvent temperature is controlled at 40 ~ 90 ℃; The step 2. middle thickening temperature of controlling is no more than 90 ℃, and crystal bake out temperature is 90 ~ 120 ℃; The step 3. middle concentration of controlling palladium is 1 ~ 50 g/L; Step 4. in resin anion(R.A) used be 201 * 2,201 * 4,201 * 7, a kind of in D290, D296, D371, D382 resin; Step 5. middle pressure is 0.01 ~ 0.07Mpa, and temperature is 50 ~ 80 ℃, and palladium and sulfuric acid ratio are 100g:70 ~ 150g; Step 6. middle thickening temperature should remain on 50 ~ 80 ℃, and crystalline mother solution can be incorporated to next batch and use; Step 7. middle drying temperature should remain on 80 ~ 120 ℃, is incubated more than 6 hours.
It is raw material that the present invention adopts Palladous chloride and ammoniacal liquor, obtains pure Pd (NH
3)
4cl
2after solution, adopt the mode of ion-exchange to remove chlorion, obtain intermediate product Pd (NH
3)
4(OH)
2, then add sulfuric acid, obtain Pd (NH
3)
4sO
4solution, purifies through periodic crystallisation, obtains pure Pd (NH
3)
4sO
4solid.
The present invention adopts ion exchange technique separating chlorine ion, and selectivity is good, and exchange capacity is large, and the regenerative operation of absorption, backwash and resin is simple, and flow process is short, and side reaction is few, and product yield is high, can reach more than 95%.
Accompanying drawing explanation
Accompanying drawing 1 is for realizing process flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Example 1
Get reagent Palladous chloride 200g in flask, add SILVER REAGENT ammoniacal liquor 600mL, heating in water bath, homo(io)thermism is 50 ℃, stirs 30 minutes, solid all dissolves, and obtains light yellow transparent solution.Adjusting temperature is 85 ℃, is incubated 3 hours, separates out a large amount of solids in flask.Filter to isolate solid, use pure water rinsing solid, filtrate and wash water are collected pending, and solid proceeds in baking oven, control 100 ℃ of temperature, and constant temperature 2 hours, obtains orange/yellow solid.
Solid is dissolved in water, and the concentration of adjusting palladium in solution is 5g/L.The volume of ion exchange resin pipe is 10L, loads the about 7L of 201 * 7 anionite-exchange resin, and the solution of preparation slowly flows through resin, and flow velocity is 50mL/min, gets exchange tail washings and detect Cl in process
-, as found Cl
-, stop exchange, the sodium hydroxide solution regenerating resin with 10%, then continue exchange, so repeatedly, until the whole exchanges of all solution are complete, the solution after exchange, again by resin, is guaranteed in solution without Cl
-exist.
Exchange tail washings is proceeded to decompression evaporator, and reactor pressure is 0.02 ~ 0.04Mpa, and temperature is 60 ℃, and solution is concentrated into the about 10L of volume, adds SILVER REAGENT sulfuric acid 80mL.Continue to concentrate, have faint yellow solid to separate out, reactant is shifted out, subcooling, obtains a large amount of yellow needle crystal, leaches crystallization, with a small amount of water, rinses, and wash water and crystalline mother solution merge, and collect pending.Crystallisate recrystallization 3 times, each mother liquor and wash water are all collected.
The pure crystallisate obtaining is put into loft drier, and 90 ℃ are incubated 8 hours.Obtain faint yellow crystallisate and be product sulfuric acid four ammonia palladiums, quality is 269.11g, and product compositional analysis is in Table 1, and the distribution of palladium in product, mother liquor, intermediate product is in Table 2.
Table 1 product compositional analysis
| Element | Pd | N | S | O | H | Cl | Fe | Na |
| Theoretical content % | 39.35 | 20.71 | 11.83 | 23.67 | 4.44 | 0 | 0 | 0 |
| Analyze content % | 39.08 | 20.66 | 11.92 | 23.88 | 4.46 | 0.005 | ＜0.005 | ＜0.003 |
The distribution of table 2 palladium
| Quality g | Distribution proportion % | |
| Palladium in raw material | 120 | 100% |
| Palladium in product | 105.17 | 87.64% |
| Palladium in crystalline mother solution | 4.63 | 3.86% |
| The middle palladium of intermediate product | 10.07 | 8.39% |
| The palladium of loss | 0.13 | 0.11% |
Example 2
Get reagent Palladous chloride 200g in flask, add SILVER REAGENT ammoniacal liquor 500mL, heating in water bath, homo(io)thermism is 50 ℃, stirs 30 minutes, solid all dissolves, and obtains light yellow transparent solution.Adjusting temperature is 85 ℃, is incubated 3 hours, separates out a large amount of solids in flask.Suction filtration is isolated solid, with a small amount of water, rinses solid, and filtrate and wash water are collected pending, and solid proceeds in baking oven, controls 100 ℃ of temperature, and constant temperature 2 hours, obtains orange/yellow solid.
Solid is dissolved in water, and the concentration of adjusting palladium in solution is 10g/L.The volume of ion exchange resin pipe is 10L, loads the about 7L of 201 * 7 anionite-exchange resin, and the solution of preparation slowly flows through resin, and flow velocity is 50mL/min, gets exchange tail washings and detect whether contain Cl in process
-, as found Cl
-, stop exchange, the sodium hydroxide solution regenerating resin with 10%, then continue exchange, so repeatedly, until the whole exchanges of all solution are complete, the solution after exchange, again by resin, is guaranteed in solution without Cl
-exist.
Exchange tail washings is proceeded to decompression evaporator, and maintenance pressure is 0.02 ~ 0.04Mpa, and temperature is 60 ℃, and solution is concentrated into the about 10L of volume, adds SILVER REAGENT sulfuric acid 70mL.Continue to concentrate, have faint yellow solid to separate out, reactant is shifted out, subcooling, obtains a large amount of yellow needle crystal, leaches crystallization, with a small amount of water, rinses, and wash water and crystalline mother solution merge, and collect pending.Crystallisate recrystallization 2 times, each mother liquor and wash water are all collected.
The pure crystallisate obtaining is put into loft drier, and 90 ℃ are incubated 8 hours.Obtain faint yellow crystallisate and be product sulfuric acid four ammonia palladiums, quality is 288.63g, and product compositional analysis is in Table 3, and the distribution of palladium in product, mother liquor, intermediate product is in Table 4.The transformation efficiency of palladium is 94.28%, and in product, foreign matter content is very low.
Table 3 product compositional analysis
| Element | Pd | N | S | O | H | Cl | Fe | Na |
| Theoretical content % | 39.35 | 20.71 | 11.83 | 23.67 | 4.44 | 0 | 0 | 0 |
| Analyze content % | 39.20 | 20.83 | 11.60 | 23.48 | 4.82 | ＜0.002 | ＜0.005 | ＜0.003 |
The distribution of table 4 palladium
| Quality g | Distribution proportion % | |
| Palladium in raw material | 120 | 100% |
| Palladium in product | 113.14 | 94.28% |
| Palladium in crystalline mother solution | 4.30 | 3.58% |
| The middle palladium of intermediate product | 2.47 | 2.06% |
| The palladium of loss | 0.09 | 0.08% |
Example 3
Get reagent Palladous chloride 1000g in flask, add SILVER REAGENT ammoniacal liquor 2000mL, heating in water bath, homo(io)thermism is 60 ℃, stirs 30 minutes, solid all dissolves, and obtains light yellow transparent solution.Adjusting temperature is 85 ℃, is incubated 5 hours, separates out a large amount of solids in flask.Suction filtration is isolated solid, and water rinses solid, and filtrate and wash water are collected pending, and solid proceeds in baking oven, controls 100 ℃ of temperature, and constant temperature 4 hours, obtains orange/yellow solid.
Solid is dissolved in water, and the concentration of adjusting palladium in solution is about 20g/L.The volume of ion exchange resin pipe is 10L, loads the about 7L of 201 * 7 anionite-exchange resin, and the solution of preparation slowly flows through resin, and flow velocity is 200mL/min, gets exchange tail washings and detect whether contain Cl in process
-, as found Cl
-, stop exchange, the sodium hydroxide solution regenerating resin with 10%, then continue exchange, so repeatedly, until the whole exchanges of all solution are complete, the solution after exchange, again by resin, is guaranteed in solution without Cl
-exist.
Exchange tail washings is proceeded to decompression evaporator, and keeping pressure is ~ 0.04Mpa that temperature is 70 ℃, and solution is concentrated into the about 20L of volume, adds SILVER REAGENT sulfuric acid 320mL.Continue to concentrate, have faint yellow solid to separate out, reactant is shifted out, subcooling, obtains a large amount of yellow needle crystal, leaches crystallization, with a small amount of water, rinses, and wash water and crystalline mother solution merge, and collect pending.Crystallisate recrystallization 2 times, each mother liquor and wash water are all collected.
The pure crystallisate obtaining is put into loft drier, and 90 ℃ are incubated 8 hours.Obtain faint yellow crystallisate and be product sulfuric acid four ammonia palladiums, quality is 1453.58g, and product compositional analysis is in Table 5, and the distribution of palladium in product, mother liquor, intermediate product is in Table 6.
Table 5 product compositional analysis
| Element | Pd | N | S | O | H | Cl | Fe | Na |
| Theoretical content % | 39.35 | 20.71 | 11.83 | 23.67 | 4.44 | 0 | 0 | 0 |
| Analyze content % | 39.23 | 20.80 | 11.74 | 23.40 | 4.83 | ＜0.002 | ＜0.002 | ＜0.005 |
The distribution of table 6 palladium
| Quality g | Distribution proportion % | |
| Palladium in raw material | 600 | 100% |
| Palladium in product | 570.24 | 95.04% |
| Palladium in crystalline mother solution | 18.32 | 3.05% |
| The middle palladium of intermediate product | 11.06 | 1.84% |
| The palladium of loss | 0.38 | 0.06% |
Claims (7)
1. a synthetic method for sulfuric acid four ammonia palladiums, is characterized in that according to following steps, carrying out successively:
1. with SILVER REAGENT Palladous chloride and SILVER REAGENT ammoniacal liquor, make raw material, extremely limpid with ammonia solvent Palladous chloride;
2. the solution 1. step being obtained is concentrated, until crystal is separated out, filters to isolate crystal, dries and obtains orange/yellow solid;
3. the solid water dissolution 2. step being obtained;
4. the solution 3. obtaining by anion exchange process step, exchange velocity is 100～200mL/min, with remaining Cl whether in silver nitrate solution inspection exchange tail washings
-ion, exchange repeatedly, until inspection does not measure Cl
-ion, resin anion(R.A) used is 201 * 2,201 * 4,201 * 7, one or more the mixture in D290, D296, D371, D382 resin;
5. the solution decompression cryoconcentration 4. step being obtained, until the concentration to 20 of palladium～50g/L in solution adds sulfuric acid;
6. the solution 5. step being obtained continues concentrated, until there is crystallisate to produce, filters to isolate crystallization, and recrystallization 2～3 times, isolates yellow crystal thing;
7. the yellow crystal thing oven drying at low temperature 6. step being obtained, obtains faint yellow sulfuric acid four ammonia palladium solids.
2. the synthetic method of a kind of sulfuric acid four ammonia palladiums as described in right 1, is characterized in that, described step 1. in the ratio of Palladous chloride and ammoniacal liquor be 100g:160～300mL, solvent temperature is controlled at 40～90 ℃;
3. as described in right 1, the step 2. middle thickening temperature of controlling is no more than 90 ℃, and crystal bake out temperature is 90～120 ℃;
4. the synthetic method of a kind of sulfuric acid four ammonia palladiums as described in right 1, is characterized in that, the described step 3. middle concentration of controlling palladium is 1～50g/L;
5. the synthetic method of a kind of sulfuric acid four ammonia palladiums as described in right 1, is characterized in that, described step 5. in concentrated pressure be 0.01～0.07MPa, temperature is 40～80 ℃, palladium and sulfuric acid ratio are 100g:70～150g;
6. the synthetic method of a kind of sulfuric acid four ammonia palladiums as described in right 1, is characterized in that, described step 6. middle thickening temperature should remain on 50 ℃;
7. the synthetic method of a kind of sulfuric acid four ammonia palladiums as described in right 1, is characterized in that, described step 7. middle oven drying at low temperature temperature should remain on 90～120 ℃.
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| CN105712411A (en) * | 2016-03-22 | 2016-06-29 | 云南铁坦新材料科技股份有限公司 | Method for synthesizing tetrammineplatinum sulfate (II) |
| CN105836814B (en) * | 2016-03-22 | 2017-12-12 | 云南铁坦新材料科技股份有限公司 | The method of one kind synthesis ammino palladium (II) of sulfuric acid four |
| CN107176625A (en) * | 2017-04-19 | 2017-09-19 | 乐山东承新材料有限公司 | A kind of production method of the ammonia palladium of sulfuric acid four |
| CN108823554B (en) * | 2018-07-12 | 2020-09-04 | 深圳市化讯半导体材料有限公司 | Chemical palladium plating solution, preparation method, use method and application thereof |
| CN108946829A (en) * | 2018-08-06 | 2018-12-07 | 金川集团股份有限公司 | A kind of electrodialysis preparation method of four ammonia palladium of sulfuric acid |
| CN110482620B (en) * | 2019-08-27 | 2021-10-22 | 贵研铂业股份有限公司 | Refining method of tetraammine palladium sulfate capable of realizing mass production |
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| CN101838830B (en) * | 2010-05-07 | 2012-08-15 | 厦门大学 | Electrolyte of electroplating palladium-nickel alloy |
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