CN107552071A - A kind of preparation method for the Raney's nickel that cobalt salt is modified and the method for synthesizing glufosinate-ammonium - Google Patents
A kind of preparation method for the Raney's nickel that cobalt salt is modified and the method for synthesizing glufosinate-ammonium Download PDFInfo
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- CN107552071A CN107552071A CN201710882050.0A CN201710882050A CN107552071A CN 107552071 A CN107552071 A CN 107552071A CN 201710882050 A CN201710882050 A CN 201710882050A CN 107552071 A CN107552071 A CN 107552071A
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Abstract
A kind of preparation method for the Raney's nickel being modified the invention provides cobalt salt and the method for synthesizing glufosinate-ammonium, the preparation method for the Raney's nickel that cobalt salt is modified comprise the following steps：Nickel alumin(i)um alloy is crushed, at 40~80 DEG C, use 20%~35% 1~2h of sodium hydroxide solution stir process, Raney's nickel is obtained after deionized water is washed, then Raney's nickel is modified with cobalt salt solution again, after processing finally is washed with deionized, the Raney's nickel of cobalt salt modification is obtained, and is stored in water；The method for synthesizing glufosinate-ammonium：The Raney's nickel catalyst that cobalt salt is modified using in the present invention makes reaction temperature can be controlled in 30~75 DEG C, 2.5~6.5Mpa of pressure as the catalyst of reductive amination process；The present invention uses the Raney's nickel that cobalt salt is modified to be catalyzed as reduction amination, reductive amination process is carried out under the conditions of being in relatively mild, reduces the occurrence probability of side reaction, improve the selectivity and yield of glufosinate-ammonium, improve production efficiency, reduce production cost.
Description
Technical field
The present invention relates to field of fine chemical, and in particular to the preparation method and synthesis grass for the Raney's nickel that a kind of cobalt salt is modified
The method of ammonium phosphine.
Background technology
Glufosinate-ammonium is a kind of steriland herbicide, is glutamine synthetase inhibitor, has the non-choosing of part systemic action
Selecting property is tagged wide spectrum steriland herbicide, after dispenser in the short time, in plant ammonium metabolism sinks into disorder, cytotoxic agent ammonium ion
In plant interior accumulation, simultaneously, photosynthesis is seriously suppressed, and reaches the purpose of weeding.Glufosinate-ammonium belongs to phosphoric acid class and removed
Careless agent, it is active high, toxicity is low, environment compatibility is good the features such as.The herbicidal performance of glufosinate-ammonium is less than paraquat, sweet higher than grass
Phosphine.Paraquat aqua in 2016 is forbidden selling at home, and glyphosate, which is reported, carcinogenic analysis, thus glufosinate-ammonium is with extremely wide
Wealthy market, its preparation method turn into the focus of research.
EP0121226A1 reports the method for being carried out reductive amination process using Raney's nickel catalyst and being prepared glufosinate-ammonium, receives
Rate only has 90%, and the purity of product is not also high.Therefore research and development in high yield, the glufosinate-ammonium synthetic method of high-purity, have it is important
Practical significance.
The content of the invention
A kind of preparation method for the Raney's nickel being modified it is an object of the invention to provide salt and the method for synthesizing glufosinate-ammonium, make
It is catalyzed by the use of the Raney's nickel that cobalt salt is modified as reduction amination, reductive amination process is carried out under the conditions of being in relatively mild, reduce
The occurrence probability of side reaction, the selectivity and yield of glufosinate-ammonium are improved, production efficiency is improved, reduces production cost.
To realize object above, the present invention is achieved by the following technical programs：
A kind of preparation method for the Raney's nickel that cobalt salt is modified, comprises the following steps：By the nickel that nickel content is 40%~65%
Aluminium alloy is crushed, and is crushed to 60~120 mesh, at a temperature of 40~80 DEG C, uses 20%~35% sodium hydroxide solution
1~2h of stir process, Raney's nickel is obtained after deionized water is washed, then Raney's nickel is modified with cobalt salt solution again, most
After processing is washed with deionized after, obtain the Raney's nickel of cobalt salt modification, and be stored in water.
Preferably, described cobalt salt is cobalt carbonate, cobaltous sulfate or cobalt nitrate.
Preferably, it is to the specific method that Raney's nickel is modified with cobalt salt solution：With the cobalt salt that concentration is 1~10g/L
The aqueous solution carries out 24~48h of immersion treatment under the conditions of 40~60 DEG C to Raney's nickel.
A kind of method for synthesizing glufosinate-ammonium, the Raney's nickel catalyst that cobalt salt is modified using in the present invention are anti-as reduction amination
The catalyst answered, specifically includes following steps：
(1) 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid, 25% ammoniacal liquor are placed in autoclave, stirring 2~
5h, the Raney's nickel catalyst that cobalt salt is modified then is added into autoclave；
(2) autoclave is evacuated to 1~3Kpa, after 10~30min, be re-filled with hydrogen to kettle, Stress control
In 1.2Mpa, 5~10min is maintained；
(3) after observation autoclave pressure gauge numerical value is unchanged, temperature in the kettle is risen to 30~75 DEG C, pressure rises to
2.5~6.5Mpa, react 3~8h；
(4) hydrogen source is closed after pressure in autoclave is unchanged, temperature of charge in kettle is down to room temperature, opens emptying
Valve, pressure in kettle is down to normal pressure, catalyst is recovered by filtration, produce glufosinate-ammonium solution.
Preferably, in the step (1), mole of the ammoniacal liquor containing ammonia is 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid
3~8 times of mole, the dosage of catalyst are the 1.5%~6% of 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid quality.
Preferably, in the step (3), mixing speed is controlled in 150~300r/min.
Preferably, in the step (4), HPLC analysis glufosinate-ammonium yields are 99%, purity 99%.
Preferably, in the step (4), the renovation process of recovered catalyst is：Catalyst is washed in methyl alcohol
Afterwards, hydrogen presses 5MPa, reacts 5h under the conditions of 60 DEG C.
The beneficial effects of the invention are as follows：
1), the Raney's nickel catalyst that cobalt salt is modified is handled in preparation process without high temperature, high pressure etc., it is only necessary to will be common
Raney's nickel catalyst does immersion and carrying out washing treatment, and simple to operate, safe, cost is low.
2), the Raney's nickel being modified using the cobalt salt in the present invention is can be controlled in as reduction amination catalyst, reaction temperature
30~75 DEG C, 2.5~6.5Mpa of pressure, reaction condition is gentle, advantageously reduces the occurrence probability of side reaction, and glufosinate-ammonium is pure
For degree up to 99%, yield reaches 99%, improves production efficiency, reduces production cost.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1：
A kind of preparation method for the Raney's nickel that cobalt salt is modified, comprises the following steps：
The nickel alumin(i)um alloy that nickel content is 55% is crushed, 100~120 mesh is crushed to, at 60 DEG C, uses 35%
Sodium hydroxide solution stir process 1h, obtains Raney's nickel after deionized water is washed, the cobalt carbonate for being again then 7g/L with concentration
The aqueous solution carries out immersion treatment 32h under the conditions of 50 DEG C to Raney's nickel, after processing finally is washed with deionized, obtains cobalt salt modification
Raney's nickel, and be stored in water.
Embodiment 2：
A kind of preparation method for the Raney's nickel that cobalt salt is modified, comprises the following steps：
The nickel alumin(i)um alloy that nickel content is 40% is crushed, 60~80 mesh is crushed to, at a temperature of 80 DEG C, uses 20%
Sodium hydroxide solution stir process 1.5h, Raney's nickel is obtained after deionized water is washed, the sulphur for being again then 10g/L with concentration
The sour cobalt aqueous solution carries out immersion treatment 24h under the conditions of 50 DEG C to Raney's nickel, after processing finally is washed with deionized, obtains cobalt salt
Modified Raney's nickel, and be stored in water.
Embodiment 3：
A kind of preparation method for the Raney's nickel that cobalt salt is modified, comprises the following steps：
The nickel alumin(i)um alloy that nickel content is 65% is crushed, is crushed to 80~100 mesh, at a temperature of 40 DEG C, is used
28% sodium hydroxide solution stir process 2h, obtains Raney's nickel after deionized water is washed, and with concentration is again then 1g/L's
Cobalt nitrate aqueous solution carries out immersion treatment 48h under the conditions of 60 DEG C to Raney's nickel, after processing finally is washed with deionized, obtains cobalt
The Raney's nickel that salt is modified, and be stored in water.
Embodiment 4：
A kind of method for synthesizing glufosinate-ammonium, including step once：
(1) by 9g 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid, the ammoniacal liquor of 17.5ml 25%, it is added in reactor
2h is stirred, weight in wet base 450mg (substrates (are prepared) in the Raney's nickel catalyst that cobalt salt is modified by the preparation method in embodiment 1
Quality 5%) add in reactor；
(2) autoclave is evacuated to 1~3Kpa, is re-filled with hydrogen to 1.2Mpa after maintaining 30min, maintains
10min；
(3) after pressure gauge numerical value is unchanged on observation autoclave, temperature in the kettle is risen to 75 DEG C, pressure rises to
3.5Mpa, mixing speed 300r/min, react 4h；
(4) hydrogen source is closed after pressure in autoclave is unchanged, is closed after pressure in autoclave is unchanged
Hydrogen source, temperature of charge in kettle is down to room temperature, atmospheric valve is opened, pressure in kettle is down to normal pressure, catalyst is recovered by filtration, produce
Glufosinate-ammonium solution, HPLC analyze glufosinate-ammonium yield up to 99%, purity 99%.
Embodiment 5：
The catalyst reclaimed to embodiment 2 carries out repeating experiment, observes the catalytic activity of catalyst, its result such as institute of table 1
Show：
Table 1：
| Reuse number | 2 | 3 | 4 | 5 | 6 | 7 | 8…..15 |
| Glufosinate-ammonium yield | 99 | 99 | 98 | 98 | 98 | 98 | 97….95 |
| Glufosinate-ammonium purity | 99 | 99 | 99 | 99 | 99 | 99 | 98….98 |
When cycle-index reaches 15 times, the yield of glufosinate-ammonium is reduced to 95%, and purity is reduced to 98%, and now reply is urged
Agent is regenerated.
Catalyst recovery process：After catalyst is washed in methyl alcohol, hydrogen presses 5MPa, reacts 5h under the conditions of 60 DEG C.
Reacted using the catalyst after regeneration, the purity and yield of glufosinate-ammonium increase.
Embodiment 6：
(1) by 9g 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid, 17.5 25%ml ammoniacal liquor, it is added in reactor
2h is stirred, weight in wet base 225mg (substrates (are prepared) in the Raney's nickel catalyst of the cobalt salt property by the preparation method in embodiment 1
Quality 2.5%) add in reactor；
(2) 1~3Kpa is evacuated to autoclave, hydrogen is re-filled with to 1.2Mpa after maintaining 20min, maintains
8min；
(3) after pressure gauge numerical value is unchanged on observation autoclave, temperature in the kettle is risen to 30 DEG C, pressure rises to
6.5Mpa, mixing speed 300r/min, react 8h；
(4) hydrogen source is closed after pressure in autoclave is unchanged, temperature of charge in kettle is down to room temperature, opens emptying
Valve, pressure in kettle is down to normal pressure, catalyst is recovered by filtration, produce glufosinate-ammonium solution, HPLC analyzes glufosinate-ammonium yield up to 99%,
Purity is 99%.
Embodiment 7：
(1) by 18g 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid, the ammoniacal liquor of 35ml 25%, it is added in reactor
2h is stirred, weight in wet base 900mg (substrates (are prepared) in the Raney's nickel catalyst of the cobalt salt property by the preparation method in embodiment 2
Quality 5%) add in reactor；
(2) 1~3Kpa is evacuated to autoclave, hydrogen is re-filled with to 1.2Mpa after maintaining 30min, maintains
10min；
(3) after pressure gauge numerical value is unchanged on observation autoclave, temperature in the kettle is risen to 50 DEG C, pressure rises to
3.5Mpa, mixing speed 200r/min, react 5h；
(4) hydrogen source is closed after pressure in autoclave is unchanged, temperature of charge in kettle is down to room temperature, opens emptying
Valve, pressure in kettle is down to normal pressure, catalyst is recovered by filtration, produce glufosinate-ammonium solution, HPLC analyzes glufosinate-ammonium yield up to 99%,
Purity is 99%.
Embodiment 8：
(1) by 18g 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid, the ammoniacal liquor of 45ml 25%, it is added in reactor
2h is stirred, weight in wet base 1080mg (substrates (are prepared) in the Raney's nickel catalyst of the cobalt salt property by the preparation method in embodiment 3
Quality 6%) add in reactor；
(2) 1~3Kpa is evacuated to autoclave, hydrogen is re-filled with to 1.2Mpa after maintaining 30min, maintains
5min；
(3) after pressure gauge numerical value is unchanged on observation autoclave, temperature in the kettle is risen to 70 DEG C, pressure is extremely
2.5Mpa, mixing speed 150r/min, react 3h；
(4) hydrogen source is closed after pressure in autoclave is unchanged, temperature of charge in kettle is down to room temperature, opens emptying
Valve, pressure in kettle is down to normal pressure, catalyst is recovered by filtration, produce glufosinate-ammonium solution, HPLC analyzes glufosinate-ammonium yield up to 99%,
Purity is 99%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (9)
1. the preparation method for the Raney's nickel that a kind of cobalt salt is modified, it is characterised in that comprise the following steps：By nickel content be 40%~
65% nickel alumin(i)um alloy is crushed, and is crushed to 60~120 mesh, at a temperature of 40~80 DEG C, uses 20%~35% hydrogen-oxygen
Change sodium solution 1~2h of stir process, Raney's nickel is obtained after deionized water is washed, then Raney's nickel is carried out with cobalt salt solution again
It is modified, after processing finally is washed with deionized, the Raney's nickel of cobalt salt modification is obtained, and be stored in water.
2. the preparation method for the Raney's nickel catalyst that cobalt salt according to claim 1 is modified, it is characterised in that described cobalt
Salt is cobalt carbonate, cobaltous sulfate or cobalt nitrate.
3. the preparation method for the Raney's nickel catalyst that cobalt salt according to claim 1 is modified, it is characterised in that molten with cobalt salt
Liquid is to the specific method that Raney's nickel is modified：With concentration be 1~10g/L cobalt saline solution under the conditions of 40~60 DEG C it is right
Raney's nickel carries out 24~48h of immersion treatment.
A kind of 4. method for synthesizing glufosinate-ammonium, it is characterised in that being modified using the cobalt salt as described in claim any one of 1-3
Catalyst of the Raney's nickel catalyst as reductive amination process.
5. the method for synthesis glufosinate-ammonium as claimed in claim 4, it is characterised in that comprise the following steps：
(1) 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid, 25% ammoniacal liquor are placed in autoclave, stir 2~5h, so
The Raney's nickel catalyst that cobalt salt is modified is added in backward autoclave；
(2) autoclave is evacuated to 1~3Kpa, after 10~30min, be re-filled with hydrogen to kettle, Stress control exists
1.2Mpa, maintain 5~10min；
(3) observe autoclave pressure gauge numerical value it is unchanged after, temperature in the kettle is risen to 30~75 DEG C, pressure rises to 2.5~
6.5Mpa, react 3~8h；
(4) hydrogen source is closed after pressure in autoclave is unchanged, temperature of charge in kettle is down to room temperature, opens atmospheric valve,
Pressure in kettle is down to normal pressure, catalyst is recovered by filtration, produce glufosinate-ammonium solution.
6. synthesis glufosinate-ammonium method according to claim 5, it is characterised in that in the step (1), ammoniacal liquor rubbing containing ammonia
Your amount is 3~8 times of 4- (methylhydroxy phosphoryl) -2- carbonyls-butyric acid mole, and the dosage of catalyst is 4- (methylhydroxies
Phosphoryl) -2- carbonyls-butyric acid quality 1.5%~6%.
7. synthesis glufosinate-ammonium method according to claim 5, it is characterised in that in the step (3), mixing speed control
In 150~300r/min.
8. synthesis glufosinate-ammonium method according to claim 5, it is characterised in that in the step (4), HPLC analyzes careless ammonium
Phosphine yield is 99%, purity 99%.
9. synthesis glufosinate-ammonium method according to claim 5, it is characterised in that in the step (4), recovered catalysis
The renovation process of agent is：After catalyst is washed in methyl alcohol, hydrogen presses 5MPa, reacts 5h under the conditions of 60 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114749187A (en) * | 2022-04-24 | 2022-07-15 | 河南尤尼特化工新材料有限公司 | Metal framework catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121226A1 (en) * | 1983-04-02 | 1984-10-10 | Hoechst Aktiengesellschaft | Process for preparing phosphinothricin |
| US5105015A (en) * | 1991-06-04 | 1992-04-14 | W. R. Grace & Co.-Conn. | Synthesis of non-cyclic aliphatic polyamines |
| CN1802212A (en) * | 2003-04-07 | 2006-07-12 | 格雷斯公司 | Nickel and cobalt plated sponge catalysts |
| CN102417161A (en) * | 2011-08-25 | 2012-04-18 | 天津大学 | Method for producing CO-free hydrogen by steam reformation based on biomass alcohol as raw material |
| CN103665032A (en) * | 2013-12-09 | 2014-03-26 | 江苏七洲绿色化工股份有限公司 | Preparation method of glufosinate |
-
2017
- 2017-09-26 CN CN201710882050.0A patent/CN107552071A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121226A1 (en) * | 1983-04-02 | 1984-10-10 | Hoechst Aktiengesellschaft | Process for preparing phosphinothricin |
| US5105015A (en) * | 1991-06-04 | 1992-04-14 | W. R. Grace & Co.-Conn. | Synthesis of non-cyclic aliphatic polyamines |
| CN1802212A (en) * | 2003-04-07 | 2006-07-12 | 格雷斯公司 | Nickel and cobalt plated sponge catalysts |
| CN102417161A (en) * | 2011-08-25 | 2012-04-18 | 天津大学 | Method for producing CO-free hydrogen by steam reformation based on biomass alcohol as raw material |
| CN103665032A (en) * | 2013-12-09 | 2014-03-26 | 江苏七洲绿色化工股份有限公司 | Preparation method of glufosinate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114749187A (en) * | 2022-04-24 | 2022-07-15 | 河南尤尼特化工新材料有限公司 | Metal framework catalyst and preparation method and application thereof |
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Application publication date: 20180109 |