CN106883142B - A kind of method for being catalyzed hydrogen cyanide and the hydroxypropionitrile of ethylene oxide synthesis 3 - Google Patents
A kind of method for being catalyzed hydrogen cyanide and the hydroxypropionitrile of ethylene oxide synthesis 3 Download PDFInfo
- Publication number
- CN106883142B CN106883142B CN201510945447.0A CN201510945447A CN106883142B CN 106883142 B CN106883142 B CN 106883142B CN 201510945447 A CN201510945447 A CN 201510945447A CN 106883142 B CN106883142 B CN 106883142B
- Authority
- CN
- China
- Prior art keywords
- reaction
- hydrogen cyanide
- hydroxypropionitriles
- oxirane
- ethylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 103
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 title claims description 16
- 230000015572 biosynthetic process Effects 0.000 title claims description 15
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 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 4
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- 230000035484 reaction time Effects 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
- 238000000926 separation method Methods 0.000 abstract description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 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
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 18
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-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
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- -1 hydrogen cyanide Nitrile Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002585 base Substances 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
- 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
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 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
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 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
- 230000002194 synthesizing effect Effects 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
- 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 1
- 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
- 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 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
- 229920001429 chelating resin Polymers 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
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 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
- 208000014829 head and neck neoplasm Diseases 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
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 208000032839 leukemia Diseases 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
- 206010025482 malaise Diseases 0.000 description 1
- 208000026037 malignant tumor of neck Diseases 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
- 230000001590 oxidative effect Effects 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
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 206010039073 rheumatoid arthritis Diseases 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
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007858 starting material Substances 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
-
- B01J35/19—
Abstract
Using the immobilized boron trifluoride of activated alumina and 1, the complex compound of 2 pentanediols, by Catalytic Cyanation hydrogen 3 hydroxypropionitriles are synthesized with reacting ethylene oxide.Using this method, remove neutralization reaction mixture without a large amount of acid in course of reaction, also do not produce a large amount of inorganic salts, be the reaction that Atom economy is 100%；Reaction scheme is short, operating procedure is few, product separation is easy, is to react easily to operate；Under the conditions of low-temp reaction, hydrogen cyanide is the reaction of safe operation without the risk largely overflowed 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 urge
Change 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 not
Homologous ray necrotizing angitis disease, dermatomyositis and polymyositis, chorionitis, have very strong indication, even after clinical remission
Also medication is preferably maintained for a long time.It is clinically used for malignant lymphoma, Huppert's disease, leukaemia, breast cancer, oophoroma, uterine neck
Cancer, prostate cancer, colon cancer, bronchiolar carcinoma, lung cancer etc., there is certain curative effect.It is comprehensive to can also be used for rheumatoid arthritis, Childhood Nephrotic Syndrome
The treatment of simulator sickness and autoimmune disease.An important route for synthesizing endoxan is POCl3 and two (2- chloroethyls)
3- aminopropanols are added dropwise at low temperature in the mixture of amine reaction, and the most green approach for synthesizing 3- aminopropanols surely belongs to 3- hydroxyls
Base propionitrile reduces.
The method of synthesis 3- hydroxypropionitriles mainly has acrylonitrile hydration, chlorethanol or bromoethanol and hydrogen cyanide reaction, epoxy
Ethane 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 is combined into the high incomes of 3- hydroxypropionitriles up to 98% in the aqueous solution reclaimed water of vulcanized sodium and quaternary ammonium salt.Konstantinov will
Acrylonitrile and concentrated sodium hydroxide reactant aqueous solution, acetaldehyde cyanhydrin yield reach 92%.Sugiyama Kazuo are utilized containing gold
Belong to ambrose alloy and metallic nickel catalysis is lower and water reaction synthesizes 3- hydroxypropionitriles.
McGinley is reacted 4 hours in ethanol with chlorethanol and potassium cyanide, and the yield of 3- hydroxypropionitriles is 83%；By second
After alcohol is changed to methanol, the yield of 3- hydroxypropionitriles brings up to 87%.Song Chunjun report sodium iodide catalysis chlorethanol with
Cyaniding nak response, the yield of 3- hydroxypropionitriles bring up to 90%.Samejiama is reacted at 500 DEG C with chlorethanol with potassium cyanide
10 hours, the yield of 3- hydroxypropionitriles was 93%.Cao etc. is reported in the case where PEG400 coexists, and Cymag closes with chlorethanol reaction
Yield into 3- hydroxypropionitriles is also 93%.
Oxirane under alkali metal or alkaline earth metal hydroxide effect, can directly synthesize 3- hydroxyls third with hydrogen cyanide
Nitrile.The cost of material of this method is minimum, and synthetic route is most short, also most industrial value.At room temperature, oxirane and hydrogen
Cyanic acid hardly reacts；Even if reaction temperature is brought up into 50 DEG C, the yield of 3- hydroxypropionitriles is little；Continue to improve reaction
Temperature can increase operational danger, while improve no significant effect to the yield of target product.By hydrogen cyanide and alkali metal
Hydroxide reaction is made corresponding alkali metal salt, these alkali metal salts under excess alkali metal hydroxide catalysis with epoxy
Ethane, which reacts, generates 3- hydroxypropionitriles；Content that Terentjew etc. is delivered on Zhurnal Obshchei Khimii and
This method has all been mentioned in US1914326 and DE577686.In order to further improve yield, DE570031 substitutes cyanogas
Cymag is used in above-mentioned reaction, and the dissolubility of the calcium hydroxide of generation in reaction dissolvent is very low, has promoted and has reacted to life
Carried out into 3- hydroxypropionitriles direction.But no matter be start material from Cymag or cyanogas, reaction will after terminating
Gone to neutralize caused alkali metal hydroxide with acid, and generate substantial amounts of inorganic salts；Because contain cyanogen root in the raw material of the technique
Ion, caused inorganic salts, which also need to special processing, just can discharge or recycle.US2453062 disclose hydrogen cyanide with
The salt that tertiary amine is formed synthesizes 3- hydroxypropionitriles under base catalyst with reacting ethylene oxide, by the tertiary amine of generation through distillation after reaction
Return to reduce to produce the amount of discarded object in course of reaction.
The technique that US2390519 discloses oxirane and hydrogen cyanide reaction synthesis 3- hydroxypropionitriles.Using product section
The method of back-mixing, caused heat in course of reaction is removed in time；The raw material that reaction is had neither part nor lot in product is distilled into reuse, improved
The overall utilization of raw material and the yield of product.
US2653162 discloses a kind of anion exchange resin catalyzed hydrogen cyanide of carboxylic acid type containing alkali metal and ring
Oxidative ethane reaction synthesis target product.The amount of generation inorganic salts can be greatly reduced with this method.But utilize amberlite
The basic activated site of fat and the combination of hydrogen cyanide, then generate target product, the operating efficiency of the technique with reacting ethylene oxide
Obviously it is relatively low；In recent years, the patent of German Ying Chuan companies application further discloses the regeneration difficulty of the technique ion exchange resin,
Therefore this method generates the problem of new, i.e. catalyst recovery is difficult.
US2459430 discloses magnesium hydroxide catalysis hydrogen cyanide and 3- hydroxypropionitriles, this method is synthesized with reacting ethylene oxide
Solve 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 are high not enough, it is right
The purification of product improves requirement；Meanwhile hydrogen cyanide participated under conditions of higher than room temperature reaction also there is operating environment hydrogen
Cyanic acid content exceedes the scope of safety.
In summary, the product yield of the hydration method of acrylonitrile is low；Chlorethanol and the method raw material raw material of hydrogen cyanide reaction
It is expensive, product yield is not high, produce substantial amounts of inorganic salts discarded object the problems such as；Although oxirane and hydrogen cyanide reaction road
Line segment, cost are low, but the largely yoke such as inorganic salts discarded object containing hydrogen cyanide will be handled by being also unable to escape.
The content of the invention
[the problem of intending to solve]
The present invention intends to solve that oxirane gives up with producing a large amount of inorganic salts in hydrogen cyanide reaction synthesis 3- hydroxypropionitrile techniques
The problem of gurry；
The present invention intends to solve oxirane with there may be hydrogen in environment in hydrogen cyanide reaction synthesis 3- hydroxypropionitrile techniques
Cyanic acid content exceedes the problem of safe range；
The present invention intends to solve that hydrogen cyanide reacts the yields of 3- hydroxypropionitriles with oxirane and not high asked at ambient temperature
Topic.
[technical scheme]
Technical solutions according to the invention are to be divided into the following steps：
(1) oxirane and hydrogen cyanide are added in the reactor with refrigerating plant and are well mixed, and control system
Temperature is between -20 DEG C -5 DEG C；
(2) by BF3/ 1,2- pentanediol/activated alumina catalyst are 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, then at 0 DEG C -20
DEG C stirring reaction 24h；
(4) after reaction terminates, Filtration of catalyst obtains 3- hydroxypropionitrile products；
(5) catalyst is directly used in the reaction of catalytic epoxyethane and hydrogen cyanide without further processing.
[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, present invention tool
There is following obvious beneficial effect.
(1) compared with the cyanide of alkali metal or alkaline-earth metal being the method for initiation material synthesis 3- hydroxypropionitriles, this
The alkali metal of neutralization reaction generation or the hydroxide of alkaline-earth metal need not be removed after invention reaction with substantial amounts of inorganic acid, also not
Generation largely needs inorganic salts to be processed；
(2) with hydrogen cyanide with the salt that tertiary amine is formed be initiation material synthesis 3- hydroxypropionitriles method compared with, the present invention
The trimethylamine recycling of generation need not will be reacted by distilling, simplify synthesis technique significantly.
(3) hydrogen cyanide is catalyzed compared with the method for ethylene oxide synthesis 3- hydroxypropionitriles with magnesium hydroxide, the present invention is anti-
The steam of hydrogen cyanide at a temperature of answering forces down, and operational danger is small.
(4) compared with these methods for having seen document report, do not make in the reaction of hydrogen cyanide and oxirane in the present invention
With solvent, the ability that solvent separates with product is greatly reduced；
(5) compared with these methods for having seen document report, the separation of product rear catalyst of the invention and product is easy,
Separation of solid and liquid can is only needed to separate target product with catalyst.
(6) compared with these methods for having seen document report, catalyst of the invention can be substantially increased with direct reuse
The Atom economy of course of reaction.
Embodiment
Embodiment 1
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirred
The stirring reaction 24h at 10 DEG C afterwards.The content of 3- hydroxypropionitriles is detected after the hydrogen cyanide for having neither part nor lot in reaction through sodium hypochlorite processing.
As a result show that under this condition, hydrogen cyanide hardly reacts with oxirane.
Embodiment 2
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirred
After add 4.0g sodium hydroxides, the stirring reaction 24h at 10 DEG C.After reaction terminates, handled through sodium hypochlorite and have neither part nor lot in reaction
Hydrogen cyanide after detect 3- hydroxypropionitriles content.As a result show under this condition, hydrogen cyanide is also hardly sent out with oxirane
Raw reaction.
Embodiment 3
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirred
After add 0.2g boron trifluoride etherates, the stirring reaction 4h at -20 DEG C.After reaction terminates, handled through sodium hypochlorite
Have neither part nor lot in the content that 3- hydroxypropionitriles are detected after the hydrogen cyanide of reaction.As a result show under this condition, the yield of 3- hydroxypropionitriles
For 9.8%.
Embodiment 4
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirred
After add 0.2g boron trifluoride etherates, 0.16g1,2- pentanediols, the stirring reaction 4h at -20 DEG C.Reaction terminates
Afterwards, the content of 3- hydroxypropionitriles is detected after the hydrogen cyanide for having neither part nor lot in reaction through sodium hypochlorite processing.As a result show under this condition,
The yield of 3- hydroxypropionitriles is 52%.
Embodiment 5
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirred
After add 0.2g boron trifluoride etherates, 0.16g1,2- pentanediols, 1.0g activated aluminas, stirred at -10 DEG C anti-
Answer 4h.After reaction terminates, the content of 3- hydroxypropionitriles is detected after the hydrogen cyanide for having neither part nor lot in reaction through sodium hypochlorite processing.As a result table
It is bright under this condition, the yields of 3- hydroxypropionitriles is 70%.
Embodiment 6
By 0.2g boron trifluoride etherates, 0.16g1,2- pentanediols, 1.0g activated aluminas and 20mL dry diethyl ethers add
Enter into the closed reactor with agitating device, white solid is filtered to obtain after 24h is stirred at room temperature.
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirring is equal
It is even；Then the above-mentioned white solids of 1.0g, the stirring reaction 4h at -10 DEG C are added.After reaction terminates, handled with a small amount of sodium hypochlorite
Have neither part nor lot in the content that 3- hydroxypropionitriles are detected after the hydrogen cyanide of reaction.As a result show under this condition, the yield of 3- hydroxypropionitriles
Up to 86%.
Embodiment 7
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirring is equal
It is even；Then the white solid added in 1.0g embodiments 6, the stirring reaction 4h at -10 DEG C, then the stirring reaction 4h at 10 DEG C.
After reaction terminates, the content of detection 3- hydroxypropionitriles after the hydrogen cyanide for having neither part nor lot in reaction is handled with a small amount of sodium hypochlorite.As a result table
It is bright under this condition, the high incomes of 3- hydroxypropionitriles is up to 93%.
Embodiment 8
2.70g hydrogen cyanide and 4.40g oxirane are put into the closed reactor with cooling device, stirring is equal
It is even；Then the white solid added in 1.0g embodiments 6, the stirring reaction 4h at -10 DEG C, then the stirring reaction 24h at 10 DEG C.
After reaction terminates, the content of detection 3- hydroxypropionitriles after the hydrogen cyanide for having neither part nor lot in reaction is handled with a small amount of sodium hypochlorite.As a result table
It is bright under this condition, the high incomes of 3- hydroxypropionitriles is up to 97.3%.
Embodiment 9
2.70g hydrogen cyanide and 5.00g oxirane are put into the closed reactor with cooling device, stirring is equal
It is even；Then the white solid added in 1.0g embodiments 6, the stirring reaction 4h at -10 DEG C, then the stirring reaction 24h at 10 DEG C.
After reaction terminates, the hydrogen cyanide for having neither part nor lot in reaction is determined after adding appropriate sodium hydroxide solution.As a result show under this condition,
As a result show the high conversion rate of hydrogen cyanide in 99%.
Claims (5)
- A kind of 1. method for being catalyzed hydrogen cyanide and ethylene oxide synthesis 3- hydroxypropionitriles, it is characterised in that hydrogen cyanide and oxirane In BF3The lower synthesis 3- hydroxypropionitriles of/1,2- pentanediol/activated alumina composite catalyst catalysis.
- 2. according to the method described in right 1, between wherein the amount of substance ratio of hydrogen cyanide and oxirane is 1: 1 to 1: 1.5.
- 3. according to the method described in right 1, the wherein ratio of the amount of substance of catalyst BF3 and 1,2- pentanediol is 1: 0.6 to 1: 3 Between；Catalyst BF3With the gross mass of 1,2- pentanediols and the gross mass ratio of activated alumina between 0.02 to 0.3.
- 4. according to the method described in right 1, the wherein ratio of the quality of catalyst and raw material hydrogen cyanide between 0.001 to 0.2.
- 5. according to the method described in right 1, wherein reaction temperature and reaction time is characterised by, anti-between -20 DEG C to 0 DEG C 24h to 120h is answered, or 8-48h is reacted between temperature is increased into 0 to 20 DEG C again after reaction 1-8h between -20 DEG C to 0 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945447.0A CN106883142B (en) | 2015-12-16 | 2015-12-16 | A kind of method for being catalyzed hydrogen cyanide and the hydroxypropionitrile of ethylene oxide synthesis 3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510945447.0A CN106883142B (en) | 2015-12-16 | 2015-12-16 | A kind of method for being catalyzed hydrogen cyanide and the hydroxypropionitrile of ethylene oxide synthesis 3 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106883142A CN106883142A (en) | 2017-06-23 |
| CN106883142B true CN106883142B (en) | 2018-03-20 |
Family
ID=59175600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510945447.0A Active CN106883142B (en) | 2015-12-16 | 2015-12-16 | A kind of method for being catalyzed hydrogen cyanide and the hydroxypropionitrile of ethylene oxide synthesis 3 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883142B (en) |
Families Citing this family (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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-12-16 CN CN201510945447.0A patent/CN106883142B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106883142A (en) | 2017-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5744031B2 (en) | Continuous production method of aliphatic polycarbonate using carbon dioxide and epoxide compound | |
| CN106883142B (en) | A kind of method for being catalyzed hydrogen cyanide and the hydroxypropionitrile of ethylene oxide synthesis 3 | |
| CN103242139B (en) | Method for preparing 2-methyl allyl alcohol by esterification and hydrolysis | |
| CN106008413A (en) | Environment-friendly synthesis method of D-calcium pantothenate intermediate D, L-pantoyl lactone | |
| JPWO2014046250A1 (en) | Process for producing 1,2-dichloro-3,3,3-trifluoropropene | |
| CN106631776A (en) | Green preparation process for synthesizing 12-carbon alcohol ester by double catalytic system | |
| CN100506768C (en) | 2,4-di-(1-phenylisopropyl) phenol preparation method | |
| JPWO2016194983A1 (en) | Method for producing conjugated diene | |
| CN104628991B (en) | Method for synthesizing o-cresol formaldehyde epoxy resin by using cosolvent and recovering cosolvent | |
| CN1239449C (en) | Catalytic process for producing an alkylene glycol with reactor-output recycle | |
| CN100491315C (en) | Process for preparing 2,4-dicumyl phenol | |
| CN104876786B (en) | The technology of olefine aldehydr preparing isoprene through liquid phase method | |
| CN108530301B (en) | Synthetic method of 2,4, 6-trifluorobenzylamine | |
| CN103360262A (en) | Method for preparing tributylamine by utilizing tetrabutylammonium bromide crystallization mother liquor | |
| CN103739506A (en) | Method for preparing aminoacetaldehyde dimethyl acetal | |
| CN103702987B (en) | The manufacture method of alkyl diol list glycidyl ether | |
| US3079446A (en) | Production of haloprenes | |
| JP2016527289A (en) | Method for producing trisaziridinomethane | |
| CN104910021A (en) | Preparation technology of 2-methyl-6-ethylaniline | |
| TWI644893B (en) | Polyol-ether compound and method for producing the same | |
| US2477573A (en) | Synthesis of 1,4-dicyano-2-butene | |
| CN102659162B (en) | Method for preparing calcium bromide through using tetrabutylammonium bromide crystallization mother solution | |
| JPS6133180A (en) | Production of epoxy compound | |
| US3557179A (en) | Preparation of orthosilicic acid tetramethyl esters | |
| CN110563586A (en) | Method for preparing dimethyl carbonate in one pot under low pressure condition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200824 Address after: 113000, 52 urban-rural Road, Dongzhou District, Liaoning, Fushun Patentee after: FUSHUN SHUNTE CHEMICAL Co.,Ltd. Address before: 1800 No. 214122 Jiangsu city of Wuxi Province Li Lake Avenue Patentee before: Jiangnan University |