CN106883142A - A kind of method for being catalyzed hydrogen cyanide and ethylene oxide synthesis 3- hydroxypropionitriles - Google Patents
A kind of method for being catalyzed hydrogen cyanide and ethylene oxide synthesis 3- hydroxypropionitriles Download PDFInfo
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- CN106883142A CN106883142A CN201510945447.0A CN201510945447A CN106883142A CN 106883142 A CN106883142 A CN 106883142A CN 201510945447 A CN201510945447 A CN 201510945447A CN 106883142 A CN106883142 A CN 106883142A
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- reaction
- hydrogen cyanide
- hydroxypropionitriles
- oxirane
- ethylene oxide
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 100
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 title claims description 9
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 229910015900 BF3 Inorganic materials 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000007333 cyanation reaction Methods 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- KJESGYZFVCIMDE-UHFFFAOYSA-N 1-chloroethanol Chemical compound CC(O)Cl KJESGYZFVCIMDE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- CMSMOCZEIVJLDB-UHFFFAOYSA-N Cyclophosphamide Chemical compound ClCCN(CCCl)P1(=O)NCCCO1 CMSMOCZEIVJLDB-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical class NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZQULWKDLLXZZSP-UHFFFAOYSA-N calcium cyanide Chemical compound [Ca+2].N#[C-].N#[C-] ZQULWKDLLXZZSP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- -1 hydrogen cyanide Hydroxypropionitrile Chemical compound 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 208000023275 Autoimmune disease Diseases 0.000 description 1
- 208000019838 Blood disease Diseases 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 208000003170 Bronchiolo-Alveolar Adenocarcinoma Diseases 0.000 description 1
- 206010009944 Colon cancer Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010025323 Lymphomas Diseases 0.000 description 1
- 206010029164 Nephrotic syndrome Diseases 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- WTCBONOLBHEDIL-UHFFFAOYSA-M Sodium iodate Chemical compound [Na+].[O-]I(=O)=O WTCBONOLBHEDIL-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 208000019065 cervical carcinoma Diseases 0.000 description 1
- 208000029742 colonic neoplasm Diseases 0.000 description 1
- 201000001981 dermatomyositis Diseases 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 208000014951 hematologic disease Diseases 0.000 description 1
- 208000018706 hematopoietic system disease Diseases 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002956 necrotizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 208000005987 polymyositis Diseases 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/16—Preparation of carboxylic acid nitriles by reaction of cyanides with lactones or compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
Using the immobilized boron trifluoride of activated alumina and the complex compound of 1,2- pentanediol, by Catalytic Cyanation hydrogen synthesize 3- hydroxypropionitriles with reacting ethylene oxide.Using the method, remove neutralization reaction mixture, also do not produce a large amount of inorganic salts without a large amount of acid in course of reaction, be reaction that Atom economy is 100%；It is easy that reaction scheme is short, operating procedure is few, product is separated, and is reaction easily to operate；Under the conditions of low-temp reaction, hydrogen cyanide, without a large amount of risks overflowed, is the reaction of safe operation in system.
Description
Technical field
A kind of method for being catalyzed hydrogen cyanide and ethylene oxide synthesis 3- hydroxypropionitriles, belong to organic synthesis field and
Organic catalysis field.
Background technology
Endoxan is a kind of alkylating agent, is mainly used in tumour immunity, there is obvious inhibitory action to kinds of tumors.
To different system necrotizing angitis disease, dermatomyositis and polymyositis, chorionitis, there is very strong indication,
Even medication is also preferably maintained after clinical remission for a long time.It is clinically used for malignant lymphoma, Huppert's disease, in vain
Blood disease, breast cancer, oophoroma, cervical carcinoma, prostate cancer, colon cancer, bronchiolar carcinoma, lung cancer etc., there is one
Constant current modulation is imitated.Can also be used for the treatment of rheumatoid arthritis, primary nephrotic syndrome of children and autoimmune disease.Close
An important route into endoxan is low in the mixture that POCl3 reacts with two (2- chloroethyls) amine
Temperature is lower to be added dropwise 3- aminopropanols, and the most green approach for synthesizing 3- aminopropanols surely belongs to the reduction of 3- aminopropionitriles.
Synthesize the method for 3- hydroxypropionitriles and mainly there is acrylonitrile hydration, chlorethanol or bromoethanol and hydrogen cyanide to react,
Oxirane and hydrogen cyanide reaction and fermentation method etc..
WO200387041 disclose acrylonitrile and sodium carbonate and sodium acid carbonate mixed aqueous solution at 110 degrees Celsius and
Under 0.4MPa, 21% acrylonitrile conversion is 3- hydroxypropionitriles, 65% acrylonitrile conversion 3,3 '-itrile group propyl ether.
Martinetz Dieter reach in the high income that the aqueous solution reclaimed water of vulcanized sodium and quaternary ammonium salt is combined into 3- hydroxypropionitriles
98%.Konstantinov reaches acrylonitrile and concentrated sodium hydroxide reactant aqueous solution, acetaldehyde cyanhydrin yield
92%.Sugiyama Kazuo are utilized containing metal ambrose alloy and metallic nickel catalysis is lower and water is synthesized 3- hydroxyls third
Nitrile.
McGinley chlorethanols react 4 hours in ethanol with potassium cyanide, and the yield of 3- hydroxypropionitriles is 83%；
After ethanol is changed into methyl alcohol, the yield of 3- hydroxypropionitriles brings up to 87%.Song Chunjun report iodate
Sodium is catalyzed chlorethanol and cyaniding nak response, and the yield of 3- hydroxypropionitriles brings up to 90%.Samejiama chloroethenes
Alcohol reacts 10 hours with potassium cyanide at 500 DEG C, and the yield of 3- hydroxypropionitriles is 93%.Cao etc. is reported
In the case where PEG400 coexists, the yield that Cymag is synthesized 3- hydroxypropionitriles with chlorethanol is also 93%.
Oxirane under alkali metal or alkaline earth metal hydroxide effect, can be directly synthesized 3- with hydrogen cyanide
Hydroxypropionitrile.The cost of material of the method is minimum, and synthetic route is most short, also most industrial value.In room
Under temperature, oxirane hardly reacts with hydrogen cyanide；Even if reaction temperature is brought up into 50 DEG C, 3- hydroxyls
The yield of base propionitrile is little；Continuing raising reaction temperature can increase operational danger, while to the receipts of target product
Rate is improved without significant effect.Hydrogen cyanide is obtained corresponding alkali metal with alkali metal hydroxide reaction
Salt, these alkali metal salts react with oxirane under excess alkali metal hydroxide catalysis and generate 3- hydroxyls
Base propionitrile；Content and US1914326 that Terentjew etc. is delivered on Zhurnal Obshchei Khimii
With the method has all been mentioned in DE577686.In order to further improve yield, DE570031 replaces cyanogas
It is used in above-mentioned reaction for Cymag, the dissolubility of the calcium hydroxide of generation in reaction dissolvent is very low, promotes
React is carried out to generation 3- hydroxypropionitriles direction.But, no matter it is reaction from Cymag or cyanogas
Starting material, reaction will remove to neutralize the alkali metal hydroxide for producing after terminating with acid, and generate substantial amounts of inorganic
Salt；Because containing cyanide ion in the raw material of the technique, produced inorganic salts also need to special treatment and just may be used
To discharge or recycle.US2453062 disclose salt that hydrogen cyanide and tertiary amine formed under base catalyst with epoxy
Ethane is synthesized 3- hydroxypropionitriles, is produced in returning to reduce course of reaction through distillation by the tertiary amine of generation after reaction
The amount of raw discarded object.
US2390519 discloses the technique that oxirane and hydrogen cyanide are synthesized 3- hydroxypropionitriles.Using product
The method of part back-mixing, removes the heat produced in course of reaction in time；The raw material of reaction will be had neither part nor lot in product
Distillation reuse, improves the overall utilization of raw material and the yield of product.
US2653162 discloses a kind of anion exchange resin catalyzed hydrogen cyanogen of carboxylic acid type containing alkali metal
Acid synthesizes target product with reacting ethylene oxide.The amount of generation inorganic salts can be greatly reduced with the method.But,
Basic activated site and the combination of hydrogen cyanide using ion exchange resin, then generate target with reacting ethylene oxide
Product, the operating efficiency of the technique is obviously relatively low；In recent years, the patent of German Ying Chuan companies application is further disclosed
The regeneration of the technique ion exchange resin is difficult, therefore the method generates new problem, i.e. catalyst and reclaims
It is difficult.
US2459430 discloses magnesium hydroxide catalysis hydrogen cyanide and synthesizes 3- hydroxypropionitriles with reacting ethylene oxide, should
Method solves the problems, such as to produce a large amount of inorganic salts discarded objects in above-mentioned technique, but the selectivity of product and yield
High not enough, the purification to product improves requirement；Meanwhile, hydrogen cyanide is participated in instead under conditions of higher than room temperature
The scope that operating environment hydrogen cyanide content exceedes safety should also be there is.
In sum, the product yield of the hydration method of acrylonitrile is low；The method raw material that chlorethanol reacts with hydrogen cyanide
Expensive raw material price, product yield be high, the problems such as produce substantial amounts of inorganic salts discarded object；Oxirane and hydrogen
Although cyanic acid reaction route segment, low cost, be also unable to escape to process the substantial amounts of inorganic salts containing hydrogen cyanide give up
The yokes such as gurry.
The content of the invention
[problem for intending to solve]
The present invention intend to solve oxirane and hydrogen cyanide be synthesized in 3- hydroxypropionitrile techniques produce it is a large amount of inorganic
The problem of salt discarded object；
The present invention intends to solve that oxirane there may be environment during 3- hydroxypropionitrile techniques are synthesized with hydrogen cyanide
Middle hydrogen cyanide content exceedes the problem of safe range；
The present invention intend to solve hydrogen cyanide reacted at ambient temperature with oxirane 3- hydroxypropionitriles yield it is not high
Problem.
[technical scheme]
Technical solutions according to the invention are to be divided into following several steps：
(1) oxirane and hydrogen cyanide are added in the reactor with refrigerating plant and are well mixed, and controlled
System temperature processed is between -20 DEG C -5 DEG C；
(2) by BF3/1,2 pentanediols/activated alumina catalyst is added in reactant mixture；
(3) in -20 DEG C~15 DEG C stirring reactions 2~72 hours；Or in -20 DEG C~0 DEG C stirring reaction 8h,
Again in 0 DEG C of -20 DEG C of stirring reaction 24h；
(4) after should terminating, Filtration of catalyst obtains 3- hydroxypropionitrile yields；
(5) catalyst is directly used in the reaction of catalytic epoxyethane and hydrogen cyanide without further treatment.
[beneficial effects of the present invention]
With having seen the hydrogen cyanide of document report compared with the method for reacting ethylene oxide synthesis 3- hydroxypropionitriles, this
Invention has following obvious beneficial effect.
(1) with the cyanide of alkali metal or alkaline-earth metal be initiation material synthesize 3- hydroxypropionitriles method phase
Than the alkali metal or alkaline earth gold of neutralization reaction generation need not be removed after present invention reaction with substantial amounts of inorganic acid
The hydroxide of category, also not producing largely needs inorganic salts to be processed；
(2) with hydrogen cyanide with the salt that tertiary amine is formed be initiation material synthesize 3- hydroxypropionitriles method compared with,
The present invention need not significantly simplify synthesis by distilling the trimethylamine recycling by generation is reacted
Technique.
(3) with magnesium hydroxide catalysis hydrogen cyanide compared with the method for ethylene oxide synthesis 3- hydroxypropionitriles, this hair
The steam of bright hydrogen cyanide at the reaction temperatures is forced down, and operational danger is small.
(4) compared with these methods for having seen document report, the reaction of hydrogen cyanide and oxirane in the present invention
In be not used solvent, greatly reduce the ability that solvent with product separate；
(5) compared with these methods for having seen document report, product rear catalyst of the invention divides with product
From easy, it is only necessary to which separation of solid and liquid can just separate target product with catalyst.
(6) compared with these methods for having seen document report, catalyst of the invention can be with direct reuse, greatly
The big Atom economy that improve course of reaction.
Specific embodiment
Embodiment 1
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
After stirring at 10 DEG C stirring reaction 24h.Processed through sodium hypochlorite and examined after having neither part nor lot in the hydrogen cyanide of reaction
Survey the content of 3- hydroxypropionitriles.Result shows that under this condition hydrogen cyanide hardly occurs instead with oxirane
Should.
Embodiment 2
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
4.0g NaOH is added after stirring, the stirring reaction 24h at 10 DEG C.After reaction terminates, warp
Sodium hypochlorite treatment has neither part nor lot in the content of detection 3- hydroxypropionitriles after the hydrogen cyanide of reaction.Result shows at this
Under part, hydrogen cyanide also hardly reacts with oxirane.
Embodiment 3
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
0.2g boron trifluoride etherates are added after stirring, the stirring reaction 4h at -20 DEG C.Reaction knot
Shu Hou, the content that 3- hydroxypropionitriles are detected after having neither part nor lot in the hydrogen cyanide of reaction is processed through sodium hypochlorite.As a result table
It is bright under this condition, the yield of 3- hydroxypropionitriles is 9.8%.
Embodiment 4
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
0.2g boron trifluoride etherates, 0.16g1,2- pentanediols, at -20 DEG C are added after stirring
Stirring reaction 4h.After reaction terminates, to be processed through sodium hypochlorite and detect 3- hydroxyls after having neither part nor lot in the hydrogen cyanide of reaction
The content of propionitrile.Result shows that under this condition the yield of 3- hydroxypropionitriles is 52%.
Embodiment 5
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
0.2g boron trifluoride etherates, 0.16g1,2- pentanediols, 1.0g activity are added after stirring
Aluminum oxide, the stirring reaction 4h at -10 DEG C.After reaction terminates, processed through sodium hypochlorite and have neither part nor lot in reaction
The content of 3- hydroxypropionitriles is detected after hydrogen cyanide.Result shows that under this condition the yield of 3- hydroxypropionitriles is
70%.
Embodiment 5
By 0.2g boron trifluoride etherates, 0.16g1,2- pentanediols, 1.0g activated aluminas and 20mL
Dry diethyl ether is added in the closed reactor with agitating device, and suction filtration obtains white solid after 24h is stirred at room temperature
Body.
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
Stir；The above-mentioned white solids of 1.0g are subsequently adding, the stirring reaction 4h at -10 DEG C.After reaction terminates,
The content of detection 3- hydroxypropionitriles after the hydrogen cyanide of reaction is had neither part nor lot in the treatment of a small amount of sodium hypochlorite.Result shows
Under this condition, the high income of 3- hydroxypropionitriles is up to 86%.
Embodiment 6
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
Stir；The white solid in 1.0g embodiments 5 is subsequently adding, the stirring reaction 4h at -10 DEG C,
The stirring reaction 4h at 10 DEG C again.After reaction terminates, the cyanogen for having neither part nor lot in reaction is processed with a small amount of sodium hypochlorite
The content of 3- hydroxypropionitriles is detected after change hydrogen.Result shows that under this condition the high income of 3- hydroxypropionitriles reaches
93%.
Embodiment 7
During 2.70g hydrogen cyanide and 4.40g oxirane put into the closed reactor with cooling device,
Stir；The white solid in 1.0g embodiments 5 is subsequently adding, the stirring reaction 4h at -10 DEG C,
The stirring reaction 24h at 10 DEG C again.After reaction terminates, the cyanogen for having neither part nor lot in reaction is processed with a small amount of sodium hypochlorite
The content of 3- hydroxypropionitriles is detected after change hydrogen.Result shows that under this condition the high income of 3- hydroxypropionitriles reaches
97.3%.
Embodiment 8
During 2.70g hydrogen cyanide and 5.00g oxirane put into the closed reactor with cooling device,
Stir；The white solid in 1.0g embodiments 5 is subsequently adding, the stirring reaction 4h at -10 DEG C,
The stirring reaction 24h at 10 DEG C again.After reaction terminates, determined after the appropriate sodium hydroxide solution of addition and do not joined
With the hydrogen cyanide of reaction.Result shows under this condition, as a result shows the high conversion rate of hydrogen cyanide in 99%.
Claims (5)
1. a kind of method for being catalyzed hydrogen cyanide and ethylene oxide synthesis 3- hydroxypropionitriles, it is characterised in that hydrogen cyanide with oxirane in BF3/1,2 penta
The lower synthesis 3- hydroxypropionitriles of glycol/activated alumina composite catalyst catalysis.
2. the hydrogen cyanide and oxirane described in right 1, its rate of charge is characterised by the ratio of massless between 1: 1 to 1: 1.5.
3. the catalyst described in right 2 is characterised by, BF3With 1, the ratio of the amount of substance of 2 pentanediols is between 1: 0.6 to 1: 3；BF3
With the gross mass of 1,2- pentanediols and the gross mass ratio of Mars aluminum oxide between 0.02 to 0.3, mass ratio preferably 0.05 to 0.1
Between.
4. the addition catalytic amount described in right 1 is characterised by, the quality of catalyst and the ratio of raw material hydrogen cyanide between 0.001 to 0.2,
Between the preferred 0.05-0.1 of the ratio.
5. reaction temperature and reaction time described in right 1 be characterised by, 24h to 120h is reacted between -20 DEG C to 0 DEG C, or -20
DEG C to react between 0 DEG C after 1-8h again by temperature be increased to 0 to 20 DEG C between react 8-48h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498740A (en) * | 2019-09-18 | 2019-11-26 | 重庆医药高等专科学校 | A method of producing 3- hydracrylic acid |
| CN110577467A (en) * | 2019-09-18 | 2019-12-17 | 重庆医药高等专科学校 | Synthetic method of 3-hydroxypropionic acid |
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|---|---|---|---|---|
| US2453062A (en) * | 1946-06-04 | 1948-11-02 | American Cyanamid Co | Production of alkylene cyanohydrins |
| US2459430A (en) * | 1946-05-04 | 1949-01-18 | American Cyanamid Co | Production of ethylene cyanohydrin |
| US2653162A (en) * | 1951-08-22 | 1953-09-22 | Rohm & Haas | Synthesis of alkylene cyanohydrins |
| US3395172A (en) * | 1964-08-01 | 1968-07-30 | Basf Ag | Continuous production of ethylene cyanohydrin |
| CN101472882A (en) * | 2006-06-14 | 2009-07-01 | 赢创罗姆有限责任公司 | Apparatus and process for continuously preparing ethylene cyanohydrin |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2459430A (en) * | 1946-05-04 | 1949-01-18 | American Cyanamid Co | Production of ethylene cyanohydrin |
| US2453062A (en) * | 1946-06-04 | 1948-11-02 | American Cyanamid Co | Production of alkylene cyanohydrins |
| US2653162A (en) * | 1951-08-22 | 1953-09-22 | Rohm & Haas | Synthesis of alkylene cyanohydrins |
| US3395172A (en) * | 1964-08-01 | 1968-07-30 | Basf Ag | Continuous production of ethylene cyanohydrin |
| CN101472882A (en) * | 2006-06-14 | 2009-07-01 | 赢创罗姆有限责任公司 | Apparatus and process for continuously preparing ethylene cyanohydrin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498740A (en) * | 2019-09-18 | 2019-11-26 | 重庆医药高等专科学校 | A method of producing 3- hydracrylic acid |
| CN110577467A (en) * | 2019-09-18 | 2019-12-17 | 重庆医药高等专科学校 | Synthetic method of 3-hydroxypropionic acid |
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