CN107245066B - A kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine - Google Patents
A kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine Download PDFInfo
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- CN107245066B CN107245066B CN201710494558.3A CN201710494558A CN107245066B CN 107245066 B CN107245066 B CN 107245066B CN 201710494558 A CN201710494558 A CN 201710494558A CN 107245066 B CN107245066 B CN 107245066B
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- amine
- tetrahydrofurfuryl
- chaff
- furfuryl alcohol
- selectivity
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- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 150000001412 amines Chemical class 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 25
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 153
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 23
- 238000005576 amination reaction Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 92
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 55
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 229910021529 ammonia Inorganic materials 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 18
- 229910000564 Raney nickel Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- 238000010926 purge Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YXDXXGXWFJCXEB-UHFFFAOYSA-N 2-furonitrile Chemical compound N#CC1=CC=CO1 YXDXXGXWFJCXEB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 125000000174 L-prolyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])[C@@]1([H])C(*)=O 0.000 description 1
- 229910003218 Ni3N Inorganic materials 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 208000004880 Polyuria Diseases 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- -1 Tetrahydrofurfuryl amine Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000035619 diuresis Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- UTVVREMVDJTZAC-UHFFFAOYSA-N furan-2-amine Chemical compound NC1=CC=CO1 UTVVREMVDJTZAC-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229960003883 furosemide Drugs 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002171 loop diuretic Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- FNKQXYHWGSIFBK-RPDRRWSUSA-N sapropterin Chemical compound N1=C(N)NC(=O)C2=C1NC[C@H]([C@@H](O)[C@@H](O)C)N2 FNKQXYHWGSIFBK-RPDRRWSUSA-N 0.000 description 1
- 229960004617 sapropterin Drugs 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a kind of methods that selectivity prepares chaff amine or tetrahydrofurfuryl amine, and using furfuryl alcohol as raw material, using metallic nickel as catalyst, under the conditions of no hydrogen, chaff amine is prepared through reduction amination；Under hydrogen atmosphere, tetrahydrofurfuryl amine is prepared through reduction amination.The present invention provides a kind of methods that selectivity prepares chaff amine or tetrahydrofurfuryl amine, using furfuryl alcohol as raw material, using heterogeneous catalysis, under identical raw material, catalyst system and essentially identical process conditions, change the selectivity of product by introducing hydrogen.
Description
Technical field
The present invention relates to organic synthesis fields, and in particular to a kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine.
Background technique
Chaff amine is also known as 2- furylamine, chemical formula C5H7NO, structural formula areChaff amine is a kind of important
Organic synthesis intermediate and chemical products, chaff amine and its derivative be widely used in medical industry, such as with the chloro- 5- ammonia of 2,4- bis-
Sulfonephthalein yl benzoic acid condensation, loop diuretic " furosemide " can be made, diuresis is strong and effect is fast, be treat Severe edema must
Need drug；In addition, chaff amine also serves as corrosion inhibitor, scaling powder etc..
As general primary amine, chaff amine can be prepared under the action of metallic catalyst by furfural reduction amination, but by
Active in furfural property, usually what reaction obtained is all the mixture of primary amine, secondary amine and tertiary amine, and the selectivity of primary amine is lower,
And using furfuryl alcohol as raw material, the selectivity of purpose product chaff amine is higher, but prepared at present by furfuryl alcohol reduction amination the report of chaff amine compared with
It is few, and only homogeneous metal complex catalysts are used for this reaction.
It such as the United States Patent (USP) of Publication No. WO 2010018570, uses Ru- acridine complex for catalyst, is catalyzed furfuryl alcohol
Directly and NH3Reaction prepares chaff amine, furfuryl alcohol 10mmol, and ammonia presses 7.5atm, solvent toluene 3ml, back flow reaction 12h, furfuryl alcohol conversion
Rate reaches 100%, and product chaff amine yield reaches 94.8%.
For another example the United States Patent (USP) of Publication No. WO 2012076560 uses Ru3(CO)12It is catalyst with pyrrole ligand, urges
Change furfuryl alcohol and NH3Reaction prepares chaff amine, reacts under an argon atmosphere, by raw material furfuryl alcohol 0.098g, ruthenium 0.0128g, pyrroles
Ligand 0.0204g, solvent 2- methyl -2- butanol 1ml be added 50ml reactor in, 20bar argon pressure purge three times,
Then 0.6g ammonia is added, is reacted 20 hours at 150 DEG C, conversion ratio reaches 99%, and the yield of chaff amine reaches 71%.
But since homogeneous system is expensive, and it is difficult to separate, therefore, develops a kind of heterogeneous catalystic converter system
With important practical value.
Tetrahydrofurfuryl amine is also known as 2- tetrahydrofurfuryl amine, molecular formula C5H11NO, structural formula areTetrahydrofurfuryl amine conduct
The important intermediate of the chemical products such as synthetic drug, rubber and perfume.Currently, the preparation of tetrahydrofurfuryl amine is mainly original with furfural
Material first passes through reduction amination and prepares chaff amine and then further add hydrogen or hydrogen is first added to prepare tetrahydrofurfuryl alcohol then ammonification, additionally
There is the method for 2- cyanofuran catalytic hydrogenation.
If the Japan Patent of Publication No. JP 60178877 is using the hydrogenation products tetrahydrofurfuryl alcohol of furfural as raw material, urged with Ni
Agent catalysis tetrahydrofurfuryl alcohol reduction amination prepares tetrahydrofurfuryl amine, and 10.2g tetrahydrofurfuryl alcohol, 3.4g liquid are added in 50ml reaction kettle
Ammonia, Ni catalyst 1.0g, at 200 DEG C, 100kg/cm2Pressure under react 5 hours, tetrahydrofurfuryl alcohol conversion ratio 15.4%, tetrahydro
Chaff amine selectivity 98.3%.
For another example hydrogen is added to prepare tetrahydrofurfuryl amine using 2- cyanofuran in the Japan Patent of Publication No. JP 2008143832,
Raw material 30g, the Rh/Al of solvent 2- (dimethyl amine) ethyl alcohol 120g, 5wt% are added in 500ml reaction kettle2O3Catalyst 0.3g,
5wt%Pd/Al2O3Catalyst 1.5g, nitrogen are passed through 2MPa H after purging2, 60 DEG C are reacted 9 hours.Then reaction temperature is risen
It to 110 DEG C, then reacts 5 hours, feed stock conversion reaches 100%, and tetrahydrofurfuryl amine yield reaches 92%.
Also there is the report that tetrahydrofurfuryl amine is directly prepared by furfural, if the United States Patent (USP) of Publication No. US 4598159 is with thunder Buddhist nun
Nickel catalysis furfural reduction amination prepares tetrahydrofurfuryl amine, and reaction carries out in the reaction kettle of 50cc, and 0.5g Raney's nickel catalyst is added,
Solvent dioxane 5.0g, liquefied ammonia 1.1g, and 10.12g tetrahydrofurfuryl amine is added, it is reacted 6 hours at 150 DEG C, conversion ratio reaches
100%, tetrahydrofurfuryl amine yield reaches 89%.And using tetrahydrofurfuryl amine as solvent in reacting, inevitably introduce secondary amine and tertiary amine
By-product.
Although the preparation of chaff amine and tetrahydrofurfuryl amine can be using furfural as raw material, the preparation of tetrahydrofurfuryl amine is usually first led to
Crossing furfural tetrahydrobiopterin synthesis chaff amine, perhaps tetrahydrofurfuryl alcohol then further plus hydrogen or ammonification, the reaction condition of two steps and is urged
Change system is often different, and is directly prepared tetrahydrofurfuryl amine by the reduction amination of furfural and then needed to be added product tetrahydrofurfuryl amine work
For solvent, the selectivity of primary amine is not also high.
Summary of the invention
The present invention provides a kind of methods that selectivity prepares chaff amine or tetrahydrofurfuryl amine, using furfuryl alcohol as raw material, using non-equal
Phase catalyst changes product by introducing hydrogen under identical raw material, catalyst system and essentially identical process conditions
Selectivity.
Specific technical solution is as follows:
A kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine, using furfuryl alcohol as raw material, using metallic nickel as catalyst, in nothing
Under hydrogen atmosphere, chaff amine is prepared through reduction amination；Under hydrogen atmosphere, tetrahydro is prepared through reduction amination
Chaff amine.
Technological core of the invention is that using metallic nickel as catalyst, under the conditions of ammonia reduction amination occurs for catalysis furfuryl alcohol
Reaction prepares chaff amine, is passed through the selectivity reacted after hydrogen and changes, and target product is changed into tetrahydrofurfuryl amine by chaff amine, and two
The process conditions of reaction are essentially identical, but the generation of the selective different products of control may be implemented.
Specifically:
Furfuryl alcohol, catalyst are mixed with organic solvent, are passed through ammonia or ammonia/hydrogen blending gas to reactor
Interior pressure reaches 0.1~2.0MPa, is again heated to 120~220 DEG C, and after reduction amination, then post-treated selectivity obtains
To the chaff amine or tetrahydrofurfuryl amine.
Preferably, the organic solvent is selected from tetrahydrofuran, dioxane, methanol or ethyl alcohol；
The mass ratio that feeds intake of the furfuryl alcohol and catalyst is 1:0.05~0.8；
The volume mass ratio of the organic solvent and furfuryl alcohol is 15~50mL/g.
If when using chaff amine as target product, preferably, be passed through ammonia to reactor pressure reach 0.1~
0.4MPa is again heated to 140~200 DEG C, carries out reduction amination.
Further preferably, it is passed through ammonia to reactor pressure and reaches 0.3~0.4MPa, be again heated to 160~180 DEG C,
Chaff amine is prepared after 48~60h of reaction.The conversion ratio and target product chaff amine of furfuryl alcohol can be improved under preferred processing condition
Selectivity.
If when using tetrahydrofurfuryl amine as target product, preferably, be first passed through ammonia to reactor pressure reach 0.1~
0.4MPa, then be passed through hydrogen to reactor pressure and reach 0.5~2.0MPa, 140~200 DEG C are heated to, reduction amination is carried out
Reaction.
Further preferably, it is first passed through ammonia to reactor pressure and reaches 0.3~0.4MPa, then be passed through hydrogen to reactor
Interior pressure reaches 0.8~1.5MPa, is heated to 160~180 DEG C, and tetrahydrofurfuryl amine is prepared after reacting 48~60h.Selection process
Under the conditions of the conversion ratio of furfuryl alcohol and the selectivity of target product tetrahydrofurfuryl amine can be improved.
Under the above-described reaction conditions, further preferably:
The organic solvent is selected from tetrahydrofuran；
The quality that feeds intake of the furfuryl alcohol and catalyst is 1:0.5；
The volume mass ratio of the organic solvent and furfuryl alcohol is 30mL/g.
Preferably, the post-processing are as follows:
Reaction solution is filtered, filter cake can be recycled after rinsing and obtain catalyst；Filtrate is finally produced after being evaporated under reduced pressure
Object.
Compared with prior art, the present invention has the advantage that
1, the present invention is using furfuryl alcohol as raw material, under the action of metalNicatalyst, changes product by introducing hydrogen
Selectivity, after hydrogen is added, target product is changed into tetrahydrofurfuryl amine by chaff amine, and the process conditions of two reactions are essentially identical, but
But the generation of the selective different products of control may be implemented；
2, the present invention is simple and easy to get using furfuryl alcohol as raw material, low in cost；
3, the present invention is using heterogeneous catalysis-metallic nickel, it can be achieved that the recycling of catalyst.
Detailed description of the invention
Fig. 1 is the method schematic diagram that furfuryl alcohol selectively prepares chaff amine or tetrahydrofurfuryl amine in the present invention.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Embodiment 1
(1) preparation of chaff amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, is warming up to 160 DEG C, and the reaction time, for 24 hours, after reaction, reaction kettle was cooled to room temperature, sample into
Row gas chromatographic detection, furfuryl alcohol conversion ratio 24.0%, chaff amine selectivity 92.5%.
(2) preparation of tetrahydrofurfuryl amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, and then leading to hydrogen makes reactor pressure reach 1.0MPa, is warming up to 160 DEG C, the reaction time for 24 hours, reacts
After, reaction kettle is cooled to room temperature, sampling carries out gas chromatographic detection, furfuryl alcohol conversion ratio 27.5%, tetrahydrofurfuryl amine selection
Property 40%.
Embodiment 2
(1) preparation of chaff amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, is warming up to 180 DEG C, and the reaction time, for 24 hours, after reaction, reaction kettle was cooled to room temperature, sample into
Row gas chromatographic detection, furfuryl alcohol conversion ratio 52.0%, chaff amine selectivity 91.7%.
(2) preparation of tetrahydrofurfuryl amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, and then leading to hydrogen makes reactor pressure reach 1.0MPa, is warming up to 180 DEG C, the reaction time for 24 hours, reacts
After, reaction kettle is cooled to room temperature, sampling carries out gas chromatographic detection, furfuryl alcohol conversion ratio 67.8%, tetrahydrofurfuryl amine selection
Property 68.1%.
Embodiment 3
(1) preparation of chaff amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, is warming up to 200 DEG C, and the reaction time, for 24 hours, after reaction, reaction kettle was cooled to room temperature, sample into
Row gas chromatographic detection, furfuryl alcohol conversion ratio 52.8%, chaff amine selectivity 57.6%.
(2) preparation of tetrahydrofurfuryl amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, and then leading to hydrogen makes reactor pressure reach 1.0MPa, is warming up to 200 DEG C, the reaction time for 24 hours, reacts
After, reaction kettle is cooled to room temperature, sampling carries out gas chromatographic detection, furfuryl alcohol conversion ratio 98.5%, tetrahydrofurfuryl amine selection
Property 66.4%.
Embodiment 4
The preparation of tetrahydrofurfuryl amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, and then leading to hydrogen makes reactor pressure reach 0.5MPa, is warming up to 160 DEG C, the reaction time for 24 hours, reacts
After, reaction kettle is cooled to room temperature, sampling carries out gas chromatographic detection, furfuryl alcohol conversion ratio 27.8%, the choosing of tetrahydrofurfuryl amine
Selecting property 27.0%.
Embodiment 5
The preparation of tetrahydrofurfuryl amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, and then leading to hydrogen makes reactor pressure reach 2.0MPa, is warming up to 160 DEG C, the reaction time for 24 hours, reacts
After, reaction kettle is cooled to room temperature, sampling carries out gas chromatographic detection, furfuryl alcohol conversion ratio 69.3%, the choosing of tetrahydrofurfuryl amine
Selecting property 10.8%.
Embodiment 6
(1) preparation of chaff amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, is warming up to 180 DEG C, and reaction kettle is cooled to room temperature by reaction time 60h after reaction, sample into
Row gas chromatographic detection, furfuryl alcohol conversion ratio 81.8%, chaff amine selectivity 96.3%.
(2) preparation of tetrahydrofurfuryl amine
0.5g furfuryl alcohol is added in 25ml reaction kettle, 15ml THF solvent, 0.25g Raney's nickel catalyst, closing are added
Lead to nitrogen after reaction kettle and purge the air displaced in reaction kettle, then leading to ammonia makes reactor pressure reach 0.35MPa, room temperature
Lower stirring balances 20min, and then leading to hydrogen makes reactor pressure reach 1.0MPa, is warming up to 180 DEG C, reaction time 48h, reaction
After, reaction kettle is cooled to room temperature, sampling carries out gas chromatographic detection, furfuryl alcohol conversion ratio 98.2%, the choosing of tetrahydrofurfuryl amine
Selecting property 95.7%.
Embodiment 7~11
The reaction condition for preparing tetrahydrofurfuryl amine is identical as in embodiment 2, and difference is only that the Raney's nickel catalyst of use
For the catalyst of recycling, the time of reaction is for 24 hours.The recycling number of catalyst and the test result of acquisition arrange respectively
In the following table 1.
Embodiment 12~13
The reaction condition for preparing chaff amine is identical as in embodiment 2, and difference is only that the time of reaction is 48h, and uses
Raney's nickel catalyst be recycling catalyst.The recycling number of catalyst and the test result of acquisition are listed in respectively
In the following table 1.
Table 1
| Embodiment | Catalyst number of repetition | Furfuryl alcohol conversion ratio (%) | Tetrahydrofurfuryl amine selectivity (%) | Chaff amine selectivity (%) |
| 7 | 1 | 66.2 | 68.1 | - |
| 8 | 2 | 67.6 | 69.1 | - |
| 9 | 3 | 64.5 | 67.6 | - |
| 10 | 4 | 64.4 | 67.6 | - |
| 11 | 5 | 63.9 | 69.0 | - |
| 12 | 1 | 78.5 | - | 97.5 |
| 13 | 2 | 53.4 | - | 98.7 |
As shown in Table 1, in 1MPa H2Under the conditions of furfuryl alcohol reduction amination prepare in the reaction of tetrahydrofurfuryl amine, raney ni catalysis
Agent is reused 5 times, and activity does not change substantially, and reduction amination is prepared in the reaction of chaff amine under the conditions of no hydrogen, thunder Buddhist nun
Raney nickel uses primary sharp fall active later, through showing in the reaction under hydrogen-free condition, raney ni catalysis
Agent and NH3Reaction generates Ni3N is so as to cause catalyst activity reduction.
Comparative example 1~5
The reaction condition for preparing chaff amine is identical as in embodiment 1, and difference is only that replaces catalyst Raney's nickel respectively
For Pd/C, Pt/C, Ru/C, Rh/C, Raney Co.Test result is listed in the table below in 2 respectively.
Comparative example 6~10
The reaction condition for preparing tetrahydrofurfuryl amine is identical as in embodiment 1, and difference, which is only that, distinguishes catalyst Raney's nickel
Replace with Pd/C, Pt/C, Ru/C, Rh/C, Raney Co.Test result is listed in the table below in 2 respectively.
Table 2
It is known compared with comparative example through the embodiment of the present invention: preparing chaff amine or tetrahydrofurfuryl amine in selective catalysis furfuryl alcohol
Technique in, Raney's nickel shows higher activity than thunder Buddhist nun cobalt and noble metal, and noble metal is under the conditions of reduction amination, surface
Active sites are easier by NH3Absorption occupies, and does not have activity substantially so as to cause catalyst.
Claims (9)
1. a kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that be to urge with metallic nickel using furfuryl alcohol as raw material
Chaff amine is prepared through reduction amination under the conditions of no hydrogen in agent；Under hydrogen atmosphere, through reduction amination system
It is standby to obtain tetrahydrofurfuryl amine.
2. the method that selectivity according to claim 1 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that specifically:
Furfuryl alcohol, catalyst are mixed with organic solvent, are passed through ammonia or ammonia/hydrogen blending gas to reactor internal pressure
Power reaches 0.1~2.0MPa, is again heated to 120~220 DEG C, and after reduction amination, then post-treated selectivity obtains institute
The chaff amine or tetrahydrofurfuryl amine stated.
3. the method that selectivity according to claim 2 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that described is organic
Solvent is selected from tetrahydrofuran, dioxane, methanol or ethyl alcohol；
The mass ratio that feeds intake of the furfuryl alcohol and catalyst is 1:0.05~0.8；
The volume mass ratio of the organic solvent and furfuryl alcohol is 15~50mL/g.
4. the method that selectivity according to claim 2 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that be passed through ammonia extremely
Reactor pressure reaches 0.1~0.4MPa, is again heated to 140~200 DEG C, and chaff is selectively prepared through reduction amination
Amine.
5. the method that selectivity according to claim 4 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that be passed through ammonia extremely
Reactor pressure reaches 0.3~0.4MPa, is again heated to 160~180 DEG C, and chaff amine is prepared after reacting 48~60h.
6. the method that selectivity according to claim 2 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that be first passed through ammonia
Reach 0.1~0.4MPa to reactor pressure, then be passed through hydrogen to reactor pressure and reach 0.5~2.0MPa, is heated to
140~200 DEG C, tetrahydrofurfuryl amine is selectively prepared through reduction amination.
7. the method that selectivity according to claim 6 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that be first passed through ammonia
Reach 0.3~0.4MPa to reactor pressure, then be passed through hydrogen to reactor pressure and reach 0.8~1.5MPa, is heated to
160~180 DEG C, tetrahydrofurfuryl amine is prepared after reacting 48~60h.
8. the method that the selectivity according to claim 5 or 7 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that described
Organic solvent is selected from tetrahydrofuran；
The quality that feeds intake of the furfuryl alcohol and catalyst is 1:0.5；
The volume mass ratio of the organic solvent and furfuryl alcohol is 30mL/g.
9. the method that selectivity according to claim 2 prepares chaff amine or tetrahydrofurfuryl amine, which is characterized in that the rear place
Reason are as follows:
Reaction solution is filtered, filter cake can be recycled after rinsing and obtain catalyst；Filtrate obtains final product after being evaporated under reduced pressure.
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| WO2010018570A1 (en) * | 2008-08-10 | 2010-02-18 | Yeda Research And Development Co. Ltd. | Process for preparing amines from alcohols and ammonia |
| WO2012076560A1 (en) * | 2010-12-08 | 2012-06-14 | Evonik Degussa Gmbh | Process for homogeneously catalyzed, highly selective direct amination of primary alcohols with ammonia to primary amines with a high volume ratio of liquid phase to gas phase and/or high pressures |
| CN104508138A (en) * | 2012-07-03 | 2015-04-08 | 希乐克公司 | Conversion of biomass |
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| WO2010018570A1 (en) * | 2008-08-10 | 2010-02-18 | Yeda Research And Development Co. Ltd. | Process for preparing amines from alcohols and ammonia |
| WO2012076560A1 (en) * | 2010-12-08 | 2012-06-14 | Evonik Degussa Gmbh | Process for homogeneously catalyzed, highly selective direct amination of primary alcohols with ammonia to primary amines with a high volume ratio of liquid phase to gas phase and/or high pressures |
| CN104508138A (en) * | 2012-07-03 | 2015-04-08 | 希乐克公司 | Conversion of biomass |
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