CN107011186A - The method of one kind catalysis S (+) 2 aminobutyric acid hydrogenation synthesis S (+) 2 amino butanol - Google Patents
The method of one kind catalysis S (+) 2 aminobutyric acid hydrogenation synthesis S (+) 2 amino butanol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
The method of one kind catalysis S (+) 2 aminobutyric acid hydrogenation synthesis S (+) 2 amino butanol, it is using the aminobutyric acids of S (+) 2 as raw material, water is solvent, Ru X Y/AC are catalyst, obtain product S (+) 2 amino butanol through catalytic hydrogenation reaction in acid condition；In described Ru X Y/AC catalyst, X is one kind in Pt, Pd, and Y is one kind in Cu, Mn, Fe, and the load capacity of the metal of Ru, X, Y tri- is 3~5wt%, 0.1~1wt%, 0.1~1wt% respectively.The inventive method can obtain higher yield under relatively low pressure and temperature, substantially reduce the reaction time, reduce energy consumption, and catalyst stabilization repeats apply mechanically well.
Description
(1) technical field
S- (+) -2-amino-butyric acid Hydrogenation is catalyzed by the Metal Supported activated-carbon catalyst of Ru bases three the present invention relates to one kind
The method of standby S- (+) -2- amino butanols.
(2) background technology
S- (+) -2- amino butanols are a kind of with chiral amino alcohol.Because N atoms and O atom have good coordination
Ability, is commonly used for medicine, chemical industry and asymmetric syntheses field.S- (+) -2- amino butanols are that synthesis treatment is phthisical
Active compound intermediate, is mainly used in synthesizing ethambutol.Due to the limitation of domestic technique, the purity of S- (+) -2- amino butanols is not
Height, therefore ethambutol depends on import mostly.The import volume of the annual China's ethambutol of data display is entered more than 100 tons
Mouth total value is more than 5,000,000 dollars.If we can obtain the ethambutol of higher degree and yield under the conditions of relatively mild,
There is huge meaning for the price for reducing tuberculosis drugs.
The synthesis of S- (+) -2- amino butanols is main using S- (+) -2-amino-butyric acid cheap and easy to get as raw material, synthetic method
Mainly there are two kinds of chemical resolution method and stereoselective syntheses.Chemical resolution method step is complicated, production cost is high and produces
Pollution problem, therefore commercial Application is more difficult.Stereoselective syntheses mainly have two kinds of " two-step method " and " one-step method ".It is so-called
" two-step method " is exactly to first pass through S- (+) -2-amino-butyric acid to be esterified to be converted into S- (+) -2-amino-butyric acid ester for being relatively easy to hydrogenation,
Then S- (+) -2-amino-butyric acid ester is obtained into S- (+) -2- amino butanols by catalytic hydrogenation, this method second step hydrogenation compared with
Easily, but the first step esterification process operation it is more difficult and be also easy to produce accessory substance, product yield is not high.And " one-step method " is exactly to incite somebody to action
The direct catalytic hydrogenation of S- (+) -2-amino-butyric acid obtains S- (+) -2- amino butanols, although this method hydrogenation difficulty is larger,
It is simple to operate easy, select suitable condition to obtain preferable result.
Direct catalytic hydrogenation S- (+) -2- amino butanols of S- (+) -2-amino-butyric acid are rarely reported in document, it is used here
Its similar amino acid is hydrogenated with to illustrate.The essence of amino acid hydrogenation is the hydrogenation of C=O bond, and conventional catalyst has Ni bases
Catalyst, Ru, Pt even load type catalyst and uses bimetal supported catalyst.Most common of which is cheap Ru support types
Monometallic or modification type bimetallic catalyst.Antons (U.S.Patent5536879,1996.) has investigated different ruthenium-based catalytics
Influence of the agent catalytic amino acid hydrogenation to the optical purity of product amino alcohol.With RuO2It is hydrogenated with for catalyst ALANINE
When, the ee values of L- Propanolamines are 93%, and during with 5wt% Ru/C catalyst, the ee values of L- Propanolamines are 98%, with 5wt%'s
Ru/Al2O3During catalyst, the ee values of L- Propanolamines are 98.5%.Miller(Ind.Eng.Chem.Res.,2004,43,3297-
3303.) in using 5wt% Ru/C as the reaction of catalyst ALANINE hydrogenation synthesis L- Propanolamines, reaction temperature has been investigated
Influence of the consumption (0.07-1.2M) of (363-398K), pressure (1.7-13.7MPa) and phosphoric acid to reaction is spent, when temperature is
398K, Hydrogen Vapor Pressure is 6.9MPa, CH2,liquidFor 0.062kmol/m3, when phosphoric acid is 0.29M, the conversion ratio of ALANINE>
The selectivity of 99%, L- Propanolamine is that 96%, ee values are 90.7%.Appropriate reduction reaction temperature, can improve L- Propanolamines
Ee values, but the conversion ratio of raw material can be reduced substantially, when temperature is down to 363K, the conversion ratio of raw material is down to 63%.Improve anti-
The pressure answered, can improve the conversion ratio of raw material and the yield of product and ee values, but can increase danger and the production of experiment
Cost, while phosphoric acid can cause environmental pollution as auxiliary agent.Pimparkar(Ind.Eng.Chem.Res.,2008,47,7648-
7653.) it is same that catalytic serine, alanine and the corresponding chiral amino of lysine hydrogenation synthesis are distinguished by catalyst of Ru/C
Alcohol, reaction pressure is 7MPa, and temperature is 130 DEG C, and acid used is that the conversion ratio under phosphoric acid, optimal conditions is about 90%.Due to
Monometallic Ru catalyst will just have high activity at higher temperature (>=100 DEG C), while temperature is too high and can make production
Racemization reaction occurs for thing amino alcohol, and then causes selectivity and the optical purity reduction of product.
In order to reduce reaction temperature, reactivity worth is improved, the ruthenium that binary composite metal catalyst and base metal are modified is urged
Agent starts to have reported.Antons (U.S.Patent 6310254,2001.) is with the various amino of Ru-Re/C catalysts
Acid.ALANINE is catalyzed wherein under conditions of 60 DEG C, 200bar to react 7 hours, obtains the ee values of L- Propanolamines>99.9%,
Product yield is 71%.Same Beller (Catalysis today, 2007,121,140-150.) is in the base of Ru/C catalyst
Impregnating metal Re again on plinth, obtains Ru-Re/C bimetallic catalysts, is 20Mpa in reaction pressure, temperature is 80 DEG C, works as m
(Ru):M (Re)=1:When 1, the active highest of catalyst, reaction conversion is complete after L-PROLINE catalytic hydrogenation 13h, optical purity
For 99.5%.Tomishige (Chem.Commun., 2014,50,6656-6659.) report M/C (M=Ru, Rh, Pd, Pt) are urged
Agent is catalyzed the hydrogenation activity of ALANINE Hydrogenation L- Propanolamines, wherein Ru/C active highest, and its conversion ratio is 7.5%；
M-M ' Ox/C (M=Ru, Rh, Pd, Pt are compared again；M ' Ox=MoOx, WOx, ReOx) and M-M ' Ox/SiO2(M=Ru, Rh,
Pd,Pt；M ' Ox=MoOx, WOx, ReOx) catalyst performance, wherein activity and selectivity highest is Rh-MoOx/SiO2,
The conversion ratio of reactant is 46.8%, and yield is 42.2%, and selectivity is 90.2%.Then Mo is adjusted:Rh mass ratioes, work as m
(Mo):M (Rh)=1:When 8, Rh-MoOx/SiO2The performance of catalyst ALANINE Hydrogenation L- Propanolamines is optimal
Reactant is converted completely after value, reaction 12h, and the selectivity of product is close to 90%, and accessory substance has about 12% isopropylamine.In reaction
Acid used is sulfuric acid, and reaction pressure is 8MPa.Although bimetal supported catalyst catalytic amino acid is converted into amino alcohol drop
Low reaction temperature, but the pressure of reaction is of a relatively high, and about 10% accessory substance can increase product separation costs, be unfavorable for industry
Metaplasia is produced.
In summary, the method shortcoming of document report mainly has：(1) conversion ratio and yield that reached, cause reaction
Time is long, and temperature is high, catalyst easy in inactivation；(2) use phosphoric acid as auxiliary agent, cost is high, causes environmental pollution.
The present invention is, using the activated carbon of high-specific surface area as carrier, using ruthenium base as major catalyst, to connect in the preparation of catalyst
Introducing other two metal promoter, H is activated using ruthenium in reaction2, other two metal, which is cooperateed with, to be activated and polarization C=O double bonds, reduction
The temperature and pressure of reaction, substantially reduces the time of reaction, the selectivity and yield of product are all higher.Three gold medals are utilized simultaneously
Interaction between category reduces the loss of active component in reaction, catalyst is circulated efficient utilization.I.e.：With new
The Metal Supported activated carbons of Ru-X-Y tri- be catalyst, a step catalysis S- (+) -2-amino-butyric acid hydrogenation synthesis S- (+) -2- amino
Butanol.
(3) content of the invention
It is an object of the invention to provide a kind of catalytic hydrogenation synthesis side of efficient, new S- (+) -2- amino butanols
Method, higher yield can be obtained under relatively low pressure and temperature, the reaction time is substantially reduced, energy consumption is reduced, and
Catalyst stabilization repeats apply mechanically well.
For achieving the above object, the present invention is adopted the following technical scheme that：
The method of one kind catalysis S- (+) -2-amino-butyric acid hydrogenation synthesis S- (+) -2- amino butanols, with S- (+) -2- amino
Butyric acid is raw material, and water is solvent, and Ru-X-Y/AC is catalyst, obtains product S- through catalytic hydrogenation reaction in acid condition
(+) -2- amino butanols；In described Ru-X-Y/AC catalyst, X is one kind in Pt, Pd, and Y is one kind in Cu, Mn, Fe,
And the load capacity of the metal of Ru, X, Y tri- is 3~5wt%, 0.1~1wt%, 0.1~1wt% respectively；Reaction equation is as follows：
Methods described includes：
First, the preparation of Ru-X-Y/AC catalyst：
(a) take activated carbon to be placed in reaction vessel, ruthenium saline solution is added dropwise dropwise, drop finishes is warming up to 60~80 under stirring
DEG C, continue to stir 2~4 hours, then adjust pH ＞ 12.5, continue to stir 1~2 hour, cooling and standings are depressurized after 1~2 hour
Suction filtration, filter cake is washed with deionized to filtrate in neutrality, and vacuum drying obtains loading the activated carbon of ruthenium salt；
(b) ruthenium salt is replaced with to the combination of X soluble-salt and Y soluble-salt, according to the operation of step (a) by X's
Soluble-salt and Y soluble-salt are loaded on the activated carbon of load ruthenium salt, and obtain loading ruthenium salt, X soluble-salt and Y can
The activated carbon of soluble；
(c) activated carbon and deionized water that will load ruthenium salt, X soluble-salt and Y soluble-salt are mixed, and are added dropwise
Excessive formalin, in 60~80 DEG C of reductase 12~3 hour, then obtains Ru-X-Y/AC and urges through filtering, washing, vacuum drying
Agent；
2nd, reactions steps：
(1) it is 1 according to mass ratio by S- (+) -2-amino-butyric acid, deionized water, acid, Ru-X-Y/AC catalyst：20~
70：0.8~1.5：0.1~0.5 is added sequentially in autoclave, detects reactor air-tightness, uses nitrogen displacement reactor
Interior air, then hydrogen displacement nitrogen is passed through, it is 5~10MPa with pressure that the temperature for setting reaction system, which is 70 DEG C~120 DEG C,
Carry out hydrogenation reaction；Described acid is the phosphoric acid of mass concentration >=85% or the concentrated sulfuric acid of mass concentration 95~98%；
(2) after reaction certain time, the catalyst stopped when pressure gauge registration is constant in reaction, reaction solution passes through decompression
It is filtered to remove；
(3) filtrate decompression is boiled off into part water, then revolving liquid is adjusted to neutrality, then added ethanol, shake up and be filtered under diminished pressure
Insoluble matter is removed, finally by filtrate decompression rectifying, product S- (+) -2- amino butanols are obtained.
In the preparation of Ru-X-Y/AC catalyst of the present invention, ruthenium salt can be RuCl3·nH2O, acetic acid ruthenium.X soluble-salt
Can be PdCl2、Pd(NO3)2、H2PtCl6、Pt(NO2)2(NH3)2.Y soluble-salt can be FeCl3、Fe(NO3)3、Cu
(NO3)2、Cu(CH3COO)2·H2O、MnCl2、Mn(CH3COO)2。
In the preparation of Ru-X-Y/AC catalyst of the present invention, preferably pH value is adjusted with sodium hydroxide solution.
In the present invention, described Ru-X-Y/AC catalyst is preferably Ru-Pt-Fe/AC catalyst, Ru-Pt-Mn/AC catalysis
Agent, Ru-Pt-Cu/AC catalyst, Ru-Pd-Fe/AC catalyst or Ru-Pd-Mn/AC catalyst, most preferably Ru-Pt-Fe/AC are urged
Agent.In the Ru-X-Y/AC catalyst, the load capacity of the metal of Ru, X, Y tri- is respectively preferably 5wt%, 1wt%, 1wt%.
In reactions steps of the present invention, described sour preferably sulfuric acid.
In reactions steps of the present invention, reaction temperature is preferably 80 DEG C~110 DEG C, particularly preferably 90 DEG C~105 DEG C, optimal
Select 90 DEG C.
In reactions steps of the present invention, reaction pressure is preferably 6~8MPa, most preferably 7MPa.
In reactions steps of the present invention, described S- (+) -2-amino-butyric acid, water, acid, the mass ratio of catalyst are preferably 1：
40~60：1~1.25：0.1~0.3.
In reactions steps (2) of the present invention, reaction certain time refers to since reaction to pressure gauge registration and no longer changes this section
Time.
In reactions steps (3) of the present invention, the pH value for rotating liquid is adjusted with alkali lye, alkali used is NaOH or KOH, preferably
NaOH。
In reactions steps (3) of the present invention, ethanol used is the absolute ethyl alcohol of content >=99.7%, and its each consumption exists
0.5mL ethanol/mL revolvings liquid~2mL ethanol/mL revolving liquid.
The method that the present invention specifically recommends the catalysis S- (+) -2-amino-butyric acid hydrogenation synthesis S- (+) -2- amino butanols
Carry out in accordance with the following steps：
(1) it is 1 according to mass ratio by S- (+) -2-amino-butyric acid, deionized water, acid, catalyst：40~60：1~1.25：
0.1~0.3 is added sequentially in autoclave, detects reactor air-tightness, with the air in nitrogen displacement reactor, then leads to
Enter hydrogen displacement nitrogen, it is 6~8MPa with pressure that the temperature for setting reaction system, which is 90 DEG C~105 DEG C, carries out hydrogenation reaction；Institute
Catalyst is stated for Ru-Pt-Fe/AC catalyst；Described acid is the phosphoric acid or mass concentration 95~98% of mass concentration >=85%
The concentrated sulfuric acid；
(2) after reaction certain time, the catalyst stopped when pressure gauge registration is constant in reaction, reaction solution passes through decompression
It is filtered to remove；
(3) filtrate decompression is boiled off into part water, then revolving liquid is adjusted to neutrality, then added ethanol, shake up and be filtered under diminished pressure
Insoluble matter is removed, finally by filtrate decompression rectifying, product S- (+) -2- amino butanols are obtained.
Compared with prior art, the advantage of the invention is that：Using S- (+) -2-amino-butyric acid cheap and easy to get as raw material, adopt
It is hydrogenated with one-step method, reduces production cost；Catalyst used is urged for a kind of new three metal load types of Ru-X-Y/AC simultaneously
Agent, H is activated using ruthenium2, other two metal, which is cooperateed with, to be activated and polarization C=O double bonds, can be in relatively low pressure and temperature
Under obtain higher yield, substantially reduce the reaction time, reduce energy consumption, its effect be significantly better than Ru/AC catalyst；Simultaneously
Interaction between three metals can reduce the loss of active component, reuse 20 times, the yield and purity of product all do not have
There is obvious reduction, beneficial to the industrialized production for realizing S- (+) -2- amino butanols.
(4) illustrate
Fig. 1 is product S- (+) -2- amino butanols1H NMR spectras.
(5) embodiment
Embodiment illustrates technical scheme, but protection scope of the present invention not limited to this in detail below.
Catalyst Preparation Example 1：The preparation of 5wt%Ru-1wt%Pt-1wt%Fe/AC catalyst：
(1) weigh 5g activated carbons to be placed in 100mL three neck round bottom flask, it is 0.01022g/ that 24.5mL concentration is added dropwise dropwise
ML RuCl3·nH2O solution (concentration is in terms of metal, similarly hereinafter), adds magneton stirring, is warming up to 80 DEG C, continues to stir 4h.
(2) NaOH solution for being added dropwise 20% is adjusted to pH ＞ 12.5, continues to stir 2h.
(3) liquid in cooling and standings 1h, decompression suction filtration three-necked flask, is washed with deionized during filter cake is in cleaning solution
Property, filter cake is dried in vacuo 9h under the conditions of 120 DEG C.
(4) filter cake of step (3) is transferred in 100mL three neck round bottom flask, adds 20mL deionized waters, stirring.According to
The secondary concentration of dropwise addition dropwise is 0.00752g/mL platinum acid chloride solutions 6.6mL and concentration is 0.005014g/mLFeCl3Solution 10mL,
80 DEG C are warming up to, continues to stir 4h.
(5) NaOH solution for being added dropwise 20% is adjusted to pH ＞ 12.5, continues to stir 2h.
(6) liquid in cooling and standings 1h, decompression filtered off with suction three-necked flask, filter cake to filtrate, which is washed with deionized, is in
(detected in neutrality, and filtrate without chlorion with silver nitrate solution), filter cake is dried in vacuo 9h under the conditions of 120 DEG C.(7) will
The filter cake of step (6) is transferred in 100mL three neck round bottom flask, adds 20mL deionized waters, stirring.Excessive 37wt% is added dropwise
Formalin, reductase 12 h under the conditions of 80 DEG C, filtering, washing (number of times at least 5 times) filter cake, then by filter cake in 120 DEG C of conditions
Lower vacuum drying 9h, obtains 5wt%Ru-1wt%Pt-1wt%Fe/AC catalyst.
The preparation method of remaining catalyst is ibid.
Embodiment 1
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 8.5h, pressure gauge registration is constant to stop reaction, by the catalyst in reaction solution by being filtered under diminished pressure
Remove；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.62g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 99.6%, and product quality yield is 93.7%.Production
Thing1H NMR spectras are shown in accompanying drawing 1, and data are as follows：1H NMR(500MHz,D2O) δ 3.59 (dd, J=12.3,3.3Hz, 1H),
3.41 (dd, J=12.3,6.8Hz, 1H), 3.02 (dd, J=6.5,3.3Hz, 1H), 1.53-1.29 (m, 2H), 0.74 (dt, J
=14.8,7.5Hz, 3H).
Embodiment 2
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Mn/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 15h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.53g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 95.2%,1H NMR product purities are 99.2%, and product quality yield is 88.5%.
Embodiment 3
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Cu/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 14h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go, obtain S- (+) -2-amino-butyric acid salt；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.58g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 98.1%,1H NMR product purities are 99.4%, and product quality yield is 91.4%.
Embodiment 4
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pd-1wt%Cu/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 17h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.23g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 80.8%,1H NMR product purities are 98.3%, and product quality yield is 71.4%.
Embodiment 5
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pd-1wt%Mn/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 16.5h, pressure gauge registration is constant to stop reaction, by the catalyst in reaction solution by being filtered under diminished pressure
Remove；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.41g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 87.3%,1H NMR product purities are 99.4%, and product quality yield is 81.6%.
Embodiment 6
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pd-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 18h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.42g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 89.8%,1H NMR product purities are 99.6%, and product quality yield is 82.1%.
Embodiment 7 (control experiment)
The preparation of 5wt%Ru/AC catalyst：
(1) weigh 5g activated carbons to be placed in 100mL three neck round bottom flask, it is 0.01022g/ that 24.5mL concentration is added dropwise dropwise
ML RuCl3·nH2O solution (concentration is in terms of metal, similarly hereinafter), adds magneton stirring, is warming up to 80 DEG C, continues to stir 4h.
(2) NaOH solution for being added dropwise 20% is adjusted to pH ＞ 12.5, continues to stir 2h.
(3) liquid in cooling and standings 1h, decompression suction filtration three-necked flask, is washed with deionized during filter cake is in cleaning solution
Property, filter cake is dried in vacuo 9h under the conditions of 120 DEG C.
(4) filter cake of step (3) is transferred in 100mL three neck round bottom flask, adds 20mL deionized waters, stirring.Drop
Plus excessive 37wt% formalin, reductase 12 h under the conditions of 80 DEG C, filtering, washing (number of times at least 5 times) filter cake then will filters
Cake is dried in vacuo 9h under the conditions of 120 DEG C, obtains 5wt%Ru/AC catalyst.
Reactions steps：
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru/AC
Catalyst is added sequentially in autoclave, detects reactor air-tightness, with the air three times in nitrogen displacement reactor, then
It is passed through hydrogen to replace three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 100 DEG C, is filled with H2It is 7Mpa to pressure, is added
Hydrogen reacts；
(2)：React after 23h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.23g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 79.6.%,1H NMR product purities are 99.3%, and product quality yield is 71.1%.
Embodiment 8
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.05g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 12h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.57g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 98.2%,1H NMR product purities are 99.4%, and product quality yield is 90.9%.
Embodiment 9
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.6g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 11h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.60g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 99.1%, and product quality yield is 92.6%.
Embodiment 10
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.6g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 6h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.59g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 99.6%, and product quality yield is 92.0.%.
Embodiment 11
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 8Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 7h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.56g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 99.0%, and product quality yield is 90.3%.
Embodiment 12
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 6Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 10h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.51g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 95%,1H NMR product purities are 99.6%, and product quality yield is 87.4%.
Embodiment 13
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 105 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 5.5h, pressure gauge registration is constant to stop reaction, by the catalyst in reaction solution by being filtered under diminished pressure
Remove；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.52g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 96.8%, and product quality yield is 88.0%.
Embodiment 14
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 100 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 6.5h, pressure gauge registration is constant to stop reaction, by the catalyst in reaction solution by being filtered under diminished pressure
Remove；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.56g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 98.3%, and product quality yield is 90.3%.
Embodiment 15
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g85% phosphoric acid, 0.4g5wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 100 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 8h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.60g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 100%,1H NMR product purities are 99.2%, and product quality yield is 92.6%.
Embodiment 16
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g3wt%Ru-
1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, detects reactor air-tightness, anti-with nitrogen displacement
The air three times in kettle is answered, then is passed through hydrogen and is replaced three times, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with H2
It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 14h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.60g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 99.4%,1H NMR product purities are 99.8%, and product quality yield is 92.6%.
Embodiment 17
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-0.1wt%Fe/AC catalyst is added sequentially in autoclave, is detected reactor air-tightness, is used nitrogen displacement
Air in reactor three times, then hydrogen displacement three times is passed through, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with
H2It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 10.5h, pressure gauge registration is constant to stop reaction, by the catalyst in reaction solution by being filtered under diminished pressure
Remove；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.57g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 97.6%,1H NMR product purities are 99.5%, and product quality yield is 90.8%.
Embodiment 18
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
1wt%Pt-0.5wt%Fe/AC catalyst is added sequentially in autoclave, is detected reactor air-tightness, is used nitrogen displacement
Air in reactor three times, then hydrogen displacement three times is passed through, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with
H2It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 9h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.58g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 98.2%,1H NMR product purities are 99.8%, and product quality yield is 91.4%.
Embodiment 19
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
0.1wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, is detected reactor air-tightness, is used nitrogen displacement
Air in reactor three times, then hydrogen displacement three times is passed through, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with
H2It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 12h, pressure gauge registration is constant to stop reaction, and the catalyst in reaction solution is removed by being filtered under diminished pressure
Go；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.55g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 96.6%,1H NMR product purities are 99.3%, and product quality yield is 89.7%.
Embodiment 20
(1)：By 2g S- (+) -2-amino-butyric acid, 100mL deionized waters, 2.5g98% sulfuric acid, 0.4g5wt%Ru-
0.5wt%Pt-1wt%Fe/AC catalyst is added sequentially in autoclave, is detected reactor air-tightness, is used nitrogen displacement
Air in reactor three times, then hydrogen displacement three times is passed through, it is 0.5Mpa to make reacting kettle inner pressure, is warming up to 90 DEG C, is filled with
H2It is 7Mpa to pressure, carries out hydrogenation reaction；
(2)：React after 9.5h, pressure gauge registration is constant to stop reaction, by the catalyst in reaction solution by being filtered under diminished pressure
Remove；
(3)：Filtrate is boiled off into about 1/2 water, then the hydroxide for being 20% with self-control concentration in decompression on Rotary Evaporators
It is about 7 that sodium, which will rotate liquid and be adjusted to pH, then adds the absolute ethyl alcohol of 50mL >=99.7%, shakes up and be filtered under diminished pressure removing insoluble matter,
Finally by filtrate decompression rectifying, 172 DEG C~174 DEG C of cut is collected, 1.58g products S- (+) -2- amino butanols are obtained.
HPLC feed stock conversions are 98.9%,1H NMR product purities are 99.6%, and product quality yield is 91.4%.
Embodiment 21
Catalyst is applied mechanically：By taking the catalyst of embodiment 15 as an example, the condition one of evaluation and post-treatment condition and embodiment 15
Cause.Catalyst obtained by filtering puts into next secondary response, and 0.02 gram of 5wt%Ru-1wt%Pt-1wt%Fe/AC is added every time
Fresh catalyst, is applied mechanically 20 times altogether, and the result such as following table of gained, the yield of S- (+) -2- amino butanols is good, it was demonstrated that this is urged
Agent has outstanding stability and activity.
| Number of times | 1 | 2 | 3 | 3 | 5 | 6 | 7 | 8 | 9 | 10 |
| Yield | 92.5 | 93.2 | 93.6 | 92.9 | 92.7 | 93.0 | 92.5 | 92.7 | 93.7 | 91.9 |
| Number of times | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| Yield | 93.2 | 93.1 | 92.1 | 92.6 | 92.9 | 92.1 | 91.8 | 91.2 | 90.6 | 89.5 |
Claims (10)
1. the method for one kind catalysis S- (+) -2-amino-butyric acid hydrogenation synthesis S- (+) -2- amino butanols, with S- (+) -2- amino fourths
Acid be raw material, water is solvent, and Ru-X-Y/AC is catalyst, in acid condition through catalytic hydrogenation reaction obtain product S- (+)-
2- amino butanols；In described Ru-X-Y/AC catalyst, X be Pt, Pd in one kind, Y be Cu, Mn, Fe in one kind, and Ru,
The load capacity of the metal of X, Y tri- is 3~5wt%, 0.1~1wt%, 0.1~1wt% respectively；Reaction equation is as follows：
Methods described includes：
First, the preparation of Ru-X-Y/AC catalyst：
(a) take activated carbon to be placed in reaction vessel, ruthenium saline solution is added dropwise dropwise, drop finishes is warming up to 60~80 DEG C under stirring, after
Continuous stirring 2~4 hours, then adjusts pH ＞ 12.5, continues to stir 1~2 hour, cooling and standings depressurize suction filtration after 1~2 hour,
Filter cake is washed with deionized to filtrate in neutrality, and vacuum drying obtains loading the activated carbon of ruthenium salt；
(b) ruthenium salt is replaced with to the combination of X soluble-salt and Y soluble-salt, according to the operation of step (a) by the solvable of X
Property salt and Y soluble-salt load on the activated carbon of load ruthenium salt, obtain loading ruthenium salt, X soluble-salt and Y solubility
The activated carbon of salt；
(c) activated carbon and deionized water that will load ruthenium salt, X soluble-salt and Y soluble-salt are mixed, and are added dropwise excessive
Formalin, in 60~80 DEG C of reductase 12~3 hour, then obtain Ru-X-Y/AC catalysis through filtering, washing, vacuum drying
Agent；
2nd, reactions steps：
(1) it is 1 according to mass ratio by S- (+) -2-amino-butyric acid, deionized water, acid, Ru-X-Y/AC catalyst：20~70：0.8
~1.5：0.1~0.5 is added sequentially in autoclave, reactor air-tightness is detected, with the sky in nitrogen displacement reactor
Gas, then hydrogen displacement nitrogen is passed through, it is 5~10MPa with pressure that the temperature for setting reaction system, which is 70 DEG C~120 DEG C, is added
Hydrogen reacts；Described acid is the phosphoric acid of mass concentration >=85% or the concentrated sulfuric acid of mass concentration 95~98%；
(2) after reaction certain time, the catalyst in reaction, reaction solution is stopped when pressure gauge registration is constant by being filtered under diminished pressure
Remove；
(3) filtrate decompression is boiled off into part water, then revolving liquid is adjusted to neutrality, then added ethanol, shake up and be filtered under diminished pressure removing
Insoluble matter, finally by filtrate decompression rectifying, obtains product S- (+) -2- amino butanols.
2. the method as described in claim 1, it is characterised in that：Described Ru-X-Y/AC catalyst is catalyzed for Ru-Pt-Fe/AC
Agent, Ru-Pt-Mn/AC catalyst, Ru-Pt-Cu/AC catalyst, Ru-Pd-Fe/AC catalyst or Ru-Pd-Mn/AC catalyst.
3. method as claimed in claim 1 or 2, it is characterised in that：In the Ru-X-Y/AC catalyst, the metal of Ru, X, Y tri-
Load capacity be respectively 5wt%, 1wt%, 1wt%.
4. the method as described in one of claims 1 to 3, it is characterised in that：In step (1), described acid is sulfuric acid.
5. the method as described in one of claims 1 to 3, it is characterised in that：In step (1), reaction temperature is 80 DEG C~110
DEG C, reaction pressure is 6~8MPa.
6. method as claimed in claim 5, it is characterised in that：In step (1), reaction temperature is 90 DEG C~105 DEG C.
7. method as claimed in claim 6, it is characterised in that：In step (1), reaction temperature is 90 DEG C, and reaction pressure is
7MPa。
8. the method as described in one of claims 1 to 3, it is characterised in that：In step (1), described S- (+) -2- amino fourths
Acid, water, acid, the mass ratio of catalyst are 1：40~60：1~1.25：0.1~0.3.
9. the method as described in one of claims 1 to 3, it is characterised in that：In step (3), each consumption of ethanol is in 0.5mL second
Alcohol/mL revolvings liquid~2mL ethanol/mL revolving liquid.
10. the method as described in claim 1, it is characterised in that：The catalysis S- (+) -2-amino-butyric acid hydrogenation synthesis S-
The method of (+) -2- amino butanols is carried out in accordance with the following steps：
(1) it is 1 according to mass ratio by S- (+) -2-amino-butyric acid, deionized water, acid, catalyst：40~60：1~1.25：0.1
~0.3 is added sequentially in autoclave, detects reactor air-tightness, with the air in nitrogen displacement reactor, then is passed through
Hydrogen replaces nitrogen, and it is 6~8MPa with pressure that the temperature for setting reaction system, which is 90 DEG C~105 DEG C, carries out hydrogenation reaction；It is described
Catalyst is Ru-Pt-Fe/AC catalyst；Described acid is the phosphoric acid or mass concentration 95~98% of mass concentration >=85%
The concentrated sulfuric acid；
(2) after reaction certain time, the catalyst in reaction, reaction solution is stopped when pressure gauge registration is constant by being filtered under diminished pressure
Remove；
(3) filtrate decompression is boiled off into part water, then revolving liquid is adjusted to neutrality, then added ethanol, shake up and be filtered under diminished pressure removing
Insoluble matter, finally by filtrate decompression rectifying, obtains product S- (+) -2- amino butanols.
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