CN100415647C - Preparation technology of water soluble metal cyanide salt - Google Patents
Preparation technology of water soluble metal cyanide salt Download PDFInfo
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- CN100415647C CN100415647C CNB2006101279506A CN200610127950A CN100415647C CN 100415647 C CN100415647 C CN 100415647C CN B2006101279506 A CNB2006101279506 A CN B2006101279506A CN 200610127950 A CN200610127950 A CN 200610127950A CN 100415647 C CN100415647 C CN 100415647C
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- prussiate
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Abstract
The present invention discloses preparation process of water soluble metal cyanide salt, and the technological scheme is that the preparation process includes two reaction steps, including the first step of reacting water soluble metal salt and water soluble cyanide to prepare cyanide precipitate and the second step of reacting the cyanide precipitate and water soluble cyanide to prepare water soluble metal cyanide salt. It features the first step including membrane filtering with 0.5-3.5 microns bore membrane resulting in short filtering period and high safety, and the second step including introduction of oxidant to maintain certain oxidant concentration, avoid hydrogen accumulation, raise safety, raise oxidation reaction speed and shorten reaction period.
Description
Technical field
The present invention relates to the bimetallic cyanide complex catalyst field, particularly the technology of preparing of its important source material-water soluble metal cyanide salt.
Background technology
Bimetallic cyanide complex catalyst is as the catalyzer of epoxide, cyclic acid anhydride and episulfide ring-opening polymerization.Bimetallic cyanide complex catalyst is prepared in the presence of organic ligand by water soluble metal cyanide salt and water-soluble metal salt, and the preparation of bimetallic cyanide complex catalyst is referring to US3247258, US4477589, US447256, US5188952, JP03-088821A and EP283148 etc.The water soluble metal cyanide salt example that is suitable for preparing bimetallic cyanide complex catalyst has the sour potassium of six cyano group cobalts (III), the sour potassium of six cyano group iron (II), the sour potassium of six cyano group high ferros (III), the sour calcium of six cyano group cobalts (III), the six sour lithiums of cyano group cobalt (III) and four Potassium Tetracyanonickelates etc., and the most frequently used is six cyano group cobalts acid potassium.
The synthesis technique of the six cyano group cobalts acid potassium of bibliographical information, adopted is that other water soluble metal cyanide salt synthetic methods similarly with cobaltous chloride and potassium cyanide synthetic method more.CA55 rolls up 10187 disclosed preparation methods and 15% excessive slightly cobaltous chloride solution is splashed in 15% potassium cyanide solution reaction generate the inferior cobalt precipitation of cyaniding, again with the inferior cobalt of cyaniding with excessive slightly potassium cyanide reaction, concentrate, crystallization, filter product; Journalof Chemical Eduction, June 1969, Volume46, Number6, the technology in excessive potassium cyanide adding cobaltous chloride solution or the inferior cobalt suspension of cyaniding is adopted in P384～385, explores the reaction mechanism of using cobaltous chloride and the sour potassium of the synthetic six cyano group cobalts of potassium cyanide under aerobic and oxygen free condition.
Adopt the chemical equation of the synthetic six cyano group cobalts acid of cobaltous chloride and potassium cyanide potassium as follows:
The first step: the inferior cobalt of cyaniding is synthetic
CoCl
2+2KCN＝Co(CN)
2↓+2KCl ①
Second step: six cyano group cobalts acid potassium is synthetic
2Co (CN)
2+ 6KCN+O
2=[K
3Co (CN)
5]
2O
2(under the aerobic conditions) 2.
[K
3Co (CN)
5]
2O
2+ 2KCN=2K
3Co (CN)
6+ K
2O
2(under the aerobic conditions) 3.
Co (CN)
2+ 3KCN=K
3Co (CN)
5(under the oxygen free condition) 4.
K
3Co (CN)
5+ 2KCN+2H
2O=K
3Co (CN)
6+ 2KOH+H
2↑ (under the oxygen free condition) 5.
In the first step reaction process, when cobaltous chloride and potassium cyanide reaction generate cyaniding Asia cobalt precipitation, except that the inferior cobalt of cyaniding, also contain Repone K and a small amount of unreacted potassium cyanide that big quantitative response generates in the suspension, must isolate the inferior cobalt of pure cyaniding, just can be further used for synthetic six cyano group cobalts acid potassium.Usually separating technologies such as suction filtration, press filtration and centrifuging all exist filtrate muddiness, the inferior cobalt loss amount of cyaniding to reach problems such as filtration time length greatly; In addition, because all there is stopping property difference problem in separating technologies such as suction filtration, press filtration and centrifuging, personnel easily contact inferior cobalt of hypertoxic cyaniding and filtrate, have bigger potential safety hazard.
In the second step reaction process, inferior cobalt of cyaniding and potassium cyanide further react generation six cyano group cobalts acid potassium and mainly have following two problems:
(1) under oxygen free condition, reaction process produces hydrogen, and there is explosion hazard in system;
(2) to become the trivalent cobalt be that 3. and 5. speed of response is slow for reaction formula to the divalence cobalt oxidation.
Divalence cobalt oxidation technology has two kinds of atmospheric oxidation and cobalt ion autoxidations from reaction principle.These two kinds of reactions often exist simultaneously in the actually operating, usually have hydrogen and superoxide in the system simultaneously, have explosion hazard; Cause the W-response cycle long because of the second step sluggish simultaneously.
Summary of the invention
The technical problem to be solved in the present invention be solve that the filtration time that exists in the water soluble metal cyanide salt building-up process is long, poor stability and oxidation rate problem slowly, a kind of quick, safe preparation technology of water soluble metal cyanide salt is provided.
For solving this technical problem, employing prepares the prussiate precipitation with water-soluble metal salt and water-soluble prussiate and makes product two-step reaction technical scheme with prussiate precipitation and water-soluble prussiate reaction again, it is characterized in that preparing in the prussiate settling step and replace filter plants such as suction filtration, press filtration and centrifuging, shorten filtration cycle, strengthen Personal Safety with membrane filter plant with certain pore size at water-soluble metal salt and water-soluble prussiate; Prepare at prussiate precipitation and water-soluble prussiate and to introduce oxygenant in the water soluble metal cyanide salt step and to keep certain oxidant concentration, avoid the hydrogen accumulation, eliminate safe hidden trouble, also improved second step reaction oxidation rate simultaneously, shorten reaction time.
The inventive method contains following steps:
1. water-soluble metal salt and water-soluble prussiate react in water medium and generate the prussiate precipitation;
2. contain the sedimentary reaction solution of prussiate with the film filter circulating filtration;
3. prussiate is precipitated suspension and add in the complexing stills for air blowing, add water-soluble aqueous cyanide solution and oxygenant, reaction;
4. concentrate, crystallization, filter water soluble metal cyanide salt.
Above-mentioned water-soluble metal salt can be expressed as M ' with general formula
dX
e, wherein M ' is metallic cations such as cobalt, iron, manganese, nickel, chromium, molybdenum, tungsten, palladium, iridium and rhodium; X is negatively charged ion such as chlorion, bromide anion, acetate moiety, sulfate radical or nitrate radical; D, e numerical value are determined by the concrete valency of M ' and X, satisfy the valency balance of system.The water-soluble metal salt such as cobaltous chloride, cobaltous acetate, nickelous chloride, Manganous chloride tetrahydrate, manganous acetate or the Palladous chloride etc. that are suitable for.
Water-soluble prussiate is meant potassium cyanide or sodium cyanide etc.
The prussiate precipitation is meant the inferior cobalt of cyaniding, nickel cyanide, cyaniding manganese or the cyaniding palladium etc. that reaction generates.
Be not that all membrane filter plants all are suitable for the present invention.Through test and Selection, the aperture of the suitable used film of membrane filter plant is 0.5～3.5 μ m, can be film filters such as ceramic membrane, metallic membrane or tunica fibrosa.In addition, adding suitable quantity of water in the circulating filtration process helps Impurity removals such as sodium-chlor or Repone K clean.
The reaction of above-mentioned water-soluble metal salt and water-soluble prussiate can at room temperature be carried out, and water-soluble prussiate add-on is generally excessive 5%～15% than theoretical value, preferably adds in the dropping mode.The actual add-on of water-soluble prussiate is generally also than theoretical value excessive 5%～15% in the reaction of second step.
Oxygenant of the present invention is meant superoxide, permanganate or persulphate etc., and preferred superoxide is as hydrogen peroxide, SPC-D, hydrogen peroxide urea or sodium peroxide etc.
Test shows, use proper amount of oxidant after, the prussiate precipitation can be finished oxidizing reaction at 1-2h with water-soluble prussiate, more oxygenant even can make is reflected at moment and finishes, but excessive oxygenant has nitrone root trend.Therefore, the oxygenant consumption is that 0.7～1.5 times of prussiate precipitation mole number is advisable, and oxidizing reaction is generally at 20～50 ℃ of reaction 1～2h.
It is M that the inventive method is fit to general formula
aM '
b(CN)
cThe preparation of water soluble metal cyanide salt, be particularly suited for the preparation of six cyano group cobalts acid potassium.
In the formula: M is potassium or sodium etc.;
M ' is cobalt, iron, manganese, nickel, chromium, molybdenum, tungsten, palladium, iridium or rhodium etc.;
A, b and c are determined by the concrete valency of M and M ', should satisfy the valency balance of system.
The water soluble metal cyanide salt of the suitable preparation of present method is the sour potassium of six cyano group cobalts (III), the sour potassium of six cyano group high ferros (III), the sour potassium of six cyano group manganese (III), the six sour potassium of cyano group chromium (III) and four Potassium Tetracyanonickelates etc. for example.Provided the preparation technology of synthetic six cyano group cobalts acid potassium in the specific embodiment of the invention.Other water soluble metal cyanide salts all can adopt similar technology to be prepared, and use corresponding raw material instead and get final product.
Technology of the present invention has following beneficial effect:
1. the employing membrane filtration technique has been simplified technology, has shortened filtration time, has avoided personnel to contact prussiate precipitation and filtrate, has characteristics such as yield height, the cycle is short, security is good;
2. add oxygenant in the oxidising process of the present invention, avoided the hydrogen accumulation, eliminated potential safety hazard, water-soluble cyanide complex yield is higher than atmospheric oxidation simultaneously.
3. the oxidizer oxygen metallization processes shortens reaction time, is the technology that is suitable for producing in batches water soluble metal cyanide salt.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Embodiment is described by the following examples.If no special instructions, described concentration is massfraction.
Embodiment 1
7.2kg six water cobaltous chlorides and 40kg water are added in the inferior cobalt synthesis reactor of 100L cyaniding, stirring and dissolving, at normal temperatures, dropping 34.5kg concentration is 13% the potassium cyanide aqueous solution in 1h, after dripping, stirring reaction 15min generates the inferior cobalt suspension of cyaniding, is the ceramic membrane filter device circulating filtration of 0.5 μ m then with membrane pore size, and add the 250kg pure water continuously, after during 4h, Repone K filters out more than 90% in the inferior cobalt suspension of cyaniding, does not have in the filtrate and wears the filter thing.The inferior cobalt suspension of cyaniding is concentrated into 50kg; suspension is squeezed in the 100L complexing stills for air blowing; under the protection of 50L/min airflow; adding 39kg concentration fast is the 23.1% potassium cyanide aqueous solution; after the inferior cobalt of cyaniding dissolves fully; adding 5kg concentration is 30% hydrogen peroxide; in 25～35 ℃ of reaction 1h; be warmed up to 115 ℃ and be concentrated into 30L; squeeze in the crystallization kettle; be cooled to 0 ℃ of crystallization, filter the 9.6kg light yellow product, the product infrared spectrum is six cyano group cobalts acid potassium by comparing as can be known products obtained therefrom with the standard infrared spectrum.Product purity 96.3%, yield 92.4%.
Embodiment 2
7.2kg six water cobaltous chlorides and 40kg water are added in the inferior cobalt synthesis reactor of 100L cyaniding, stirring and dissolving, at normal temperatures, dropping 33.4kg concentration is 10.2% sodium cyanide solution in 1h, after dropwising, stirring reaction 15min generates the inferior cobalt suspension of cyaniding, and using membrane pore size then is the Fibrous membrane filtration device circulating filtration of 3.5 μ m, and add the 250kg pure water continuously, behind the 4h, sodium-chlor filters out more than 95% in the inferior cobalt suspension of cyaniding, and filtrate nothing is worn the filter thing.To remain the inferior cobalt suspension of cyaniding and be concentrated into 50kg; suspension is squeezed in the 100L complexing stills for air blowing; under the protection of 50L/min airflow; adding 39kg concentration fast is the 23.1% potassium cyanide aqueous solution; after the inferior cobalt of cyaniding dissolves fully; add the 4.5kg30% hydrogen peroxide; in 25～35 ℃ of reaction 2h; be warmed up to 115 ℃ and be concentrated into 30L; squeeze in the crystallization kettle; be cooled to 0 ℃ of crystallization, filter the 9.7kg light yellow product, the product infrared spectrum is six cyano group cobalts acid potassium by comparing as can be known products obtained therefrom with the standard infrared spectrum.Purity 96.4%, yield 92.9%.
Embodiment 3
7.2kg six water cobaltous chlorides and 40kg water are added in the inferior cobalt synthesis reactor of 100L cyaniding, stirring and dissolving, at normal temperatures, in 1h, drip the 34.5kg13% potassium cyanide aqueous solution, after dripping, stirring reaction 15min, generate the inferior cobalt suspension of cyaniding, be the ceramic membrane filter device circulating filtration of 0.5 μ m with membrane pore size then, and add the 250kg pure water continuously, during 4h in the inferior cobalt suspension of cyaniding Repone K filter out more than 90%, do not have in the filtrate and wear the filter thing.The inferior cobalt suspension of cyaniding is concentrated into 50kg; suspension is squeezed in the 100L complexing stills for air blowing; under the protection of 50L/min airflow; add the 37kg23.1% potassium cyanide aqueous solution fast; after the inferior cobalt of cyaniding dissolves fully; adding 4kg concentration is 30% hydrogen peroxide; in 25～35 ℃ of reaction 1h30min; be warmed up to 115 ℃ and be concentrated into 30L; squeeze in the crystallization kettle; be cooled to 0 ℃ of crystallization, filter the 9.7kg light yellow product, the product infrared spectrum is six cyano group cobalts acid potassium by comparing as can be known products obtained therefrom with the standard infrared spectrum.Purity 96.8%, yield 93.3%.
Embodiment 4
7.2kg six water cobaltous chlorides and 40kg water are added in the inferior cobalt synthesis reactor of 100L cyaniding, stirring and dissolving, at normal temperatures, in 1h, drip the 34.5kg13% potassium cyanide aqueous solution, after dripping, stirring reaction 15min, generate the inferior cobalt suspension of cyaniding, be the ceramic membrane filter device circulating filtration of 0.5 μ m with membrane pore size then, and add the 250kg pure water continuously, during 4h in the inferior cobalt suspension of cyaniding Repone K filter out more than 90%, do not have in the filtrate and wear the filter thing.The inferior cobalt suspension of cyaniding is concentrated into 50kg; suspension is squeezed in the 100L complexing stills for air blowing; under the protection of 50L/min airflow; add the 36kg23.1% potassium cyanide aqueous solution fast; after the inferior cobalt of cyaniding dissolves fully; adding 1.5kg concentration is 50% hydrogen peroxide; in 25～35 ℃ of reaction 2h; be warmed up to 115 ℃ and be concentrated into 30L; squeeze in the crystallization kettle; be cooled to 0 ℃ of crystallization, filter the 9.4kg light yellow product, the product infrared spectrum is six cyano group cobalts acid potassium by comparing as can be known products obtained therefrom with the standard infrared spectrum.Purity 97.3%, yield 90.9%.
Comparative Examples 1
7.2kg six water cobaltous chlorides and 40kg water are added in the inferior cobalt synthesis reactor of 100L cyaniding, stirring and dissolving, at normal temperatures, dripping 34.5kg concentration in 1h is the 13% potassium cyanide aqueous solution, after dropwising, stirring reaction 15min generates the inferior cobalt suspension of cyaniding, is the ceramic membrane film filter circulating filtration of 0.5 μ m with the aperture, and add the 250kg pure water continuously, behind the 4h, Repone K filters out more than 90% in the inferior cobalt suspension of cyaniding, does not have in the filtrate and wears the filter thing.The inferior cobalt suspension of cyaniding is concentrated into 50kg, it is squeezed in the 100L complexing stills for air blowing, under the 50L/min airflow, adding 39kg concentration fast is the 23.1% potassium cyanide aqueous solution, after the inferior cobalt of cyaniding dissolves fully, continue with the oxidation of 50L/min airflow the monitoring oxidized tail gas down in 25-35 ℃, there is obvious ammonia to generate, show that potassium cyanide is oxidized, add 1.5kg potassium cyanide, nearly 24h reaction solution consuming time is faint yellow, show that basic oxidation is complete, be warmed up to 115 ℃ and be concentrated into 30L, squeeze in the crystallization kettle, be cooled to 0 ℃ of crystallization, filter 8.6kg orange product, the product infrared spectrum is six cyano group cobalts acid potassium by comparing as can be known products obtained therefrom with the standard infrared spectrum.Purity 95.3%, yield 81.4%.
Comparative Examples 2
0.96kg six water cobaltous chlorides and 5kg water are added in the 10L reactor, stirring and dissolving, at normal temperatures, dripping 3.6kg concentration in 1h is the 16.7% potassium cyanide aqueous solution, after dripping, stirring reaction 15min generates the inferior cobalt suspension of cyaniding, filters with whizzer, nearly 4h consuming time, obtain the about 8kg of little muddy filtrate, the inferior cobalt of cyaniding is worn filter and is measured closely 5%, obtains the inferior cobalt filter cake of 1.4kg cyaniding.The inferior cobalt filter cake of cyaniding is added in the 10L reactor, it is even to add the 4kg water-dispersion, add the 4.2kg 28.6% potassium cyanide aqueous solution then fast, with the oxidation of 5L/min speed blowing air, add 0.3kg potassium cyanide in the oxidising process, oxidation 8h, be concentrated into 3L, be cooled to 0 ℃ of crystallization, filter the 1.1kg light yellow product, the product infrared spectrum is six cyano group cobalts acid potassium by comparing as can be known products obtained therefrom with the standard infrared spectrum.Purity 96.5%, yield 79.1%.
Claims (5)
1. preparation technology of water soluble metal cyanide salt, comprise two steps: first water-soluble metal salt and water-soluble prussiate prepare the prussiate precipitation, it two is that prussiate precipitation and water-soluble prussiate react and make product, it is characterized in that in first step adopting the aperture is that the membrane filter plant of 0.5～3.5 μ m filters, in second step, add the oxygenant oxidation, wherein:
Water soluble metal cyanide salt is meant that being fit to general formula is M
aM '
b(CN)
CWater soluble metal cyanide, M is potassium or sodium in the formula, M ' is cobalt, iron, manganese, nickel, chromium, molybdenum, tungsten, palladium, iridium or rhodium, a, b and c are determined by the concrete valency of M and M ', should satisfy the valency balance of system;
Water-soluble metal salt is meant that general formula is M '
dX
eCompound, wherein M ' is cobalt, iron, manganese, nickel, chromium, molybdenum, tungsten, palladium, iridium or rhodium, X is chlorion, bromide anion, acetate moiety, sulfate radical or nitrate radical, d, e numerical value satisfy the valency balance of system by the concrete valency decision of M ' and X;
Water-soluble prussiate is meant potassium cyanide or sodium cyanide;
The oxygenant consumption is 0.7～1.5 times of prussiate precipitation mole number, and oxidizing reaction is carried out 1～2h at 20 ℃～50 ℃.
2. according to the described preparation technology of claim 1, it is characterized in that:
Oxygenant is meant superoxide, permanganate or persulphate;
Membrane filter plant is meant ceramic membrane filter device, metal membrane filter device or Fibrous membrane filtration device.
3. according to the described preparation technology of claim 2, it is characterized in that oxygenant is hydrogen peroxide, SPC-D, hydrogen peroxide urea or sodium peroxide, membrane filter plant is the ceramic membrane filter device.
4. according to the described preparation technology of claim 2, it is characterized in that water-soluble prussiate add-on is than theoretical value all excessive 5%～15% in the two-step reaction.
5. according to the described preparation technology of one of claim 1～4, it is characterized in that water-soluble metal salt is a cobaltous chloride, water-soluble prussiate is a potassium cyanide, and oxygenant is a hydrogen peroxide.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277236A (en) * | 1987-02-26 | 1988-11-15 | アルコ・ケミカル・カンパニー | Production of double metal cyanide composite catalyst |
| US4843054A (en) * | 1987-02-26 | 1989-06-27 | Arco Chemical Technology, Inc. | Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization |
| SU1708760A1 (en) * | 1989-12-12 | 1992-01-30 | Украинский научно-исследовательский углехимический институт | Method for preparation monovalent copper thiocyanate |
| CN1494946A (en) * | 2002-09-20 | 2004-05-12 | Bimetallic cyanide catalyst for preparing polybasic alcohol and its related method | |
| CN1662303A (en) * | 2002-06-14 | 2005-08-31 | 国际壳牌研究有限公司 | Preparation of a double metal cyanide catalyst |
-
2006
- 2006-09-05 CN CNB2006101279506A patent/CN100415647C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277236A (en) * | 1987-02-26 | 1988-11-15 | アルコ・ケミカル・カンパニー | Production of double metal cyanide composite catalyst |
| US4843054A (en) * | 1987-02-26 | 1989-06-27 | Arco Chemical Technology, Inc. | Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization |
| SU1708760A1 (en) * | 1989-12-12 | 1992-01-30 | Украинский научно-исследовательский углехимический институт | Method for preparation monovalent copper thiocyanate |
| CN1662303A (en) * | 2002-06-14 | 2005-08-31 | 国际壳牌研究有限公司 | Preparation of a double metal cyanide catalyst |
| CN1494946A (en) * | 2002-09-20 | 2004-05-12 | Bimetallic cyanide catalyst for preparing polybasic alcohol and its related method |
Non-Patent Citations (2)
| Title |
|---|
| 氰化银钾的合成技术. 刘伟平.贵金属，第19卷第3期. 1998 |
| 氰化银钾的合成技术. 刘伟平.贵金属，第19卷第3期. 1998 * |
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