CN1050351C - Purification of acetonitrile of high purity and rough acetonitrile - Google Patents
Purification of acetonitrile of high purity and rough acetonitrile Download PDFInfo
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- CN1050351C CN1050351C CN93107005A CN93107005A CN1050351C CN 1050351 C CN1050351 C CN 1050351C CN 93107005 A CN93107005 A CN 93107005A CN 93107005 A CN93107005 A CN 93107005A CN 1050351 C CN1050351 C CN 1050351C
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Abstract
The present invention relates to a refining method of acetonitrile, more specifically a simple refining method of crude acetonitrile. Simultaneously, the present invention further relates to a refining method for obtaining high-purity acetonitrile for a mobile phase solvent for carrying out high refining by industrial liquid phase chromatography, particularly to a refining method of high-purity acetonitrile for a mobile phase solvent by high-speed liquid phase chromatography, and the absorption of the high-purity acetonitrile is less in an ultraviolet region with the wave length of 200 to 400 nm.
Description
The present invention relates to the process for purification of acetonitrile of high purity and crude acetonitrile.Specifically, the ultraviolet absorbance that the present invention has disclosed at wavelength 200-400nm place is below 0.05, be used for the acetonitrile of high purity of high speed liquid chromatography mobile phase solvent and the simple process for purification of crude acetonitrile, simultaneously, the present invention relates to obtaining being used to carry out highly refined technical scale liquid phase chromatography mobile phase solvent, especially for high speed liquid chromatography mobile phase solvent, the process for purification of the acetonitrile of high purity that the absorption in the ultraviolet ray range of wavelength 200-400nm is few.
Now, commercially available acetonitrile mainly is the oxidative ammonolysis by propylene or iso-butylene and contacting of ammonia and molecular oxygen are caused usually, reclaim as by product when making vinyl cyanide or methacrylonitrile, and refining obtaining.The acetonitrile that gets by this class by product, owing to have many impurity, thereby relevant purified various methodologies has been proposed.
For example, as the method for removing the vinyl carbinol in the acetonitrile, being disclosed in the spy with the method for carrying out fractionation by distillation behind the sulfuric acid reaction opens in the clear 51-23218 communique, carrying out isolating method by extractive distillation in the presence of water is disclosed in the spy and opens in the clear 55-143949 communique, in addition, the method for reacting with the aqueous solution of hypochlorous an alkali metal salt or alkali earth metal salt is disclosed in the spy and opens in the clear 51-32518 communique.In addition, as from acetonitrile, removing the method remove oxazole, the spy open disclosed in the clear 59-10556 communique with the mol-chloric reaction after carry out isolating method, and open the method for extractive distillation in the presence of the water that disclosed in the clear 55-143950 communique the spy.In addition as the process for purification of acetonitrile, react back distillatory method with basic cpd and be disclosed in the spy and open in the clear 56-5449 communique, be disclosed in the spy and open in the clear 58-124751 communique and carry out the distillatory method by 3 distillation towers.That is to say that the major impurity that contains in the acetonitrile is vinyl carbinol ， oxazole, vinyl cyanide etc., and, need combination disclosed method in the past, make its technology become very complicated like this for removing these impurity.To these methods, present inventors proceed revision test, but can not obtain purpose, and the ultraviolet absorbancy in wavelength 200-400nm place is the acetonitrile below 0.05.
In Deutsches Wirtschafts Patent DD217212A1 communique, disclosed with ozone and contacted the laggard capable distillatory method of processing, disclose and decomposed vinyl carbinol simultaneously, oxazole, propenal etc., and fractionation by distillation is removed the method for the excellence of these materials.But when the present inventor chases after when examination,,, can not obtain the ultraviolet absorbancy in wavelength 200-400nm place and be the acetonitrile below 0.05 in the ultraviolet absorbancy in wavelength 200-400nm place though can reduce the acetonitrile that uses as raw material.Therefore, common commercially available acetonitrile because its absorbancy height in the ultraviolet ray range at 200-400nm place, thereby can not satisfy as the liquid phase chromatography mobile phase solvent that uses in this scope, particularly as the requirement of high speed liquid chromatography mobile phase solvent.But now commercially available, the industrial method for making that is used for the acetonitrile of liquid phase chromatography mobile phase solvent does not disclose as yet, and its technological development waits in expectation.
Recently, be used as the manufacture method of the acetonitrile of high speed liquid chromatography mobile phase solvent, use alkaline substance solution neutral method after in the special 3-199868 of Yuanping City number, having disclosed ozone oxidation, but in this method owing to generate the adhesivity throw out, and need lock out operation, therefore, for continuous operation must carry out blocked operation, there is the shortcoming of running operation complexity.In addition, because this throw out adhesivity height, its difficult treatment not only, and become the material that blocks tower and film in the 3rd operation afterwards.And then the water that adds as alkaline aqueous solution when separating in distillation tower, owing to form azeotrope with acetonitrile, also is being removed except that acetonitrile when anhydrating, thereby is having the low problem of the rate of recovery of acetonitrile.
In addition, in the special 3-214199 of Yuanping City number, disclose and make crude acetonitrile contact the back ozone oxidation with sulfuric acid, and carried out the distillatory method, but in the method, not only needed to contact required contact groove with sulfuric acid, and then, in order to separate the new distillation tower of these sulfuric acid needs.Therefore, will increase by 2 operations in the method, its technology becomes complicated when implementing with technical scale.
Crude acetonitrile contains the impurity that causes from its manufacture method, thereby in the ultraviolet ray range of wavelength 200-400nm absorption is arranged, but the ultraviolet radiation absorption of this scope is mainly owing to two keys of impurity.For example, have the dual key of C=C, C=O carbonyl, COOH carboxyl, CHO aldehyde radical, the dual key of C=N, N=O nitroso-group, NO
2Keys such as nitro or the compound with these functional groups have absorption in this zone, specifically, as vinyl carbinol oxazole, vinyl cyanide, methacrylonitrile, cis and trans vinyl cyanide (propenyl cyanide), vinylformic acid, methyl acrylate, methacrylic acid, methyl methacrylate, acetate, propenal, Methylacrylaldehyde, acetone etc.Remove such compound, and to make the absorbancy at wavelength 200-400nm place be to be unusual difficulty below 0.05.
For example, in order to make the absorbancy of acetonitrile at wavelength 200nm place is below 0.05, must make the vinyl carbinol in the acetonitrile is that the following ， oxazole of 1.5ppm is below the 0.8ppm, and vinyl cyanide is below the 0.2ppm, methacrylonitrile is below the 0.2ppm, the cis vinyl cyanide is below the 0.2ppm, and vinylformic acid is below the 0.2ppm, below the methyl acrylate 0.2ppm, acetate is below the 30ppm, and also is same requirement to the impurity beyond these.In fact because these compounds nearly all coexist with acetonitrile,, just need the separation and purification technology of height in order to obtain acetonitrile of high purity therefore for the ultimate value that will make each compound further reduces.
It is below 0.05 in the ultraviolet absorbancy in wavelength 200-400nm place that first purpose of the present invention is to disclose a kind of, the acetonitrile of high purity that is used for high speed liquid chromatography mobile phase solvent, and the 2nd purpose of the present invention has been to disclose the simple process for purification of crude acetonitrile and be used for further carrying out highly refined industrial liquid phase chromatography mobile phase solvent, be used for high speed liquid chromatography mobile phase solvent in particular for manufacturing, wavelength 200-400nm place ultraviolet absorbance is lower than the process for purification of 0.05 acetonitrile.
Present inventors at length study for contacting treatment process with ozone, catch by with the processing that contacts of ozone, generate acid and permanganic acid reducing substances, and these contact with solid alkali and/or sorbent material and the fact that is removed, found to reach the object of the invention easy process for purification.Further, surprising is, by after will contacting the fluid handled with ozone and more than one solid alkalis, sorbent material contacting, remove low-boiling compound contained in its acetonitrile and higher-boiling compound, the ultraviolet absorbancy that can obtain wavelength 200-400nm place is lower than 0.05 acetonitrile, and has finished the present invention.
That is, the present invention is the method for refining crude acetonitrile, it is characterized in that, and when making with extra care crude acetonitrile, according to
(1) the 1st operation that the crude acetonitrile of raw material is contacted with the oxygen of status nascendi, and
(2) the 2nd operation that the acetonitrile through the 1st operation is contacted with the compound more than a kind that is selected from solid alkali, sorbent material, and as required,
(3) separate the 3rd operation of removing lower-boiling impurity contained in the acetonitrile of the 2nd operation and high-boiling-point impurity, perhaps
(4) after the 1st operation, carry out the 3rd operation, carry out the refining acetonitrile of order of the 2nd operation then.
In the present invention as the crude acetonitrile of raw material, the ultraviolet absorbance that can use wavelength 200nm place is crude acetonitrile or the propylene more than 0.1, between the iso-butylene or the trimethyl carbinol and ammonia and the molecularity oxygen by contacting the oxidative ammonolysis that causes, during with manufacturing vinyl cyanide or methacrylonitrile, the crude acetonitrile that obtains as by product.
As the raw material crude acetonitrile, though can be crude acetonitrile more than 0.1 with the ultraviolet absorbancy in wavelength 200nm place, but preferably the ultraviolet absorbancy at wavelength 200nm place is more than 0.1, crude acetonitrile below 5, use the ultraviolet absorbancy in wavelength 200nm place more than 0.1 and be more preferably, the crude acetonitrile below 3 is for well.
In addition, the present invention does not have particular determination to the raw material crude acetonitrile, can use the crude acetonitrile of making by other manufacture method to be raw material yet.Particularly, also can use oxidative ammonolysis by aromatics such as saturated hydrocarbon compound such as ethane, propane, butane, Trimethylmethane, pentane, carbon monoxide, toluene, dimethylbenzene etc. and the deutero-crude acetonitrile.
The method according to this invention is that crude acetonitrile more than 0.1 is a raw material with the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy that can obtain wavelength 200-400nm place is the acetonitrile below 0.05.Further, also can use the ultraviolet absorbancy in wavelength 200nm place to be raw material less than 0.1 crude acetonitrile.But, use these raw materials, mainly consider that from economic point of view its effect is little, because of rather than the ideal method.The ultraviolet absorbance of the acetonitrile among the present invention is to be the quartz cell of 10nm with optical length, contrast distilled water in detecting wavelength and the value measured.
The 1st operation of the present invention is the operation that crude acetonitrile is contacted with the oxygen of status nascendi.The purpose of this operation is, with methods such as distillation absorption or reaction, the impurity with two keys that will be difficult to remove, particularly vinyl carbinol, oxazole, vinyl cyanide etc., decompose by contacting, and be transformed into the compound that separate easily is removed in operation after this with the oxygen of status nascendi.
Compound as producing nascent oxygen can use permanganic acid or its salt, for example, and potassium permanganate, superoxide.For example, hydrogen peroxide, sodium peroxide, barium peroxide, oxygen acid or its salt.For example, clorox, potassium hypochlorite, hypoiodous acid sodium, hypoiodous acid potassium, sodium hypobromite, potassium hypobromite, sodium chlorate, Potcrate, sodium iodate, Potassium Iodate, sodium bromate, potassium bromate, sodium perchlorate, potassium perchlorate, perchloric acid, Periodic acid, sodium periodate, potassium periodate, contain ozone gas etc., contain ozone gas but preferably use.Through this operation, can improve significantly afterwards and separate the effect of removing impurity in the operation.
That uses among the present invention contains ozone gas, and by with air or oxygen or oxygen-containing gas, the method for ozone supply producer can obtain, and when contacting with crude acetonitrile, also can be with using behind the gas dilutions such as nitrogen, carbonic acid gas, air.The concentration that contains ozone in the ozone gas is 0.01-5.0Vol%, preferably 0.1-2.0Vol%.If the concentration of ozone is low excessively, the time that needs when contacting with crude acetonitrile is long, and perhaps reactor becomes big, and perhaps the loss of the acetonitrile of carrying secretly owing to air feed increases etc., so its efficient is not high.In addition, ozone concn being increased to more than the 5Vol%, is difficult in the ozonizer performance methodology.
Crude acetonitrile is-40-80 ℃ with the temperature that contacts that contains ozone gas, but preferably 10-40 ℃.If temperature is low excessively, its speed of response is slack-off, perhaps has problems such as separating out microcomponent, if but temperature is too high, then carry out the over-drastic reaction, and make the yield of acetonitrile reduce.
Make crude acetonitrile and contain the pressure that ozone gas contacts, can be in decompression, normal pressure carries out under one of it is any to pressurize, but is preferably the scope of normal pressure and even 10atm.
Crude acetonitrile contacts with ozone gas, can be undertaken by batch mode or continuous mode.Batch mode can perhaps be carried out in foam column having 1 grade or MULTI CONTACT groove of whipping appts, but carries out in order to make gas-to-liquid contact good, to be preferably in the contact groove with whipping appts.And then, contact with containing ozone gas in order to make crude acetonitrile, will contain ozone gas from more than one nozzle, supply in the acetonitrile to well in the small bubbles mode.In addition, supply with below or side that the position contain ozone gas is preferably in agitating vane, behind the whipped state of this acetonitrile of structure observation by groove and blade, can determine only position and quantity.
In batch mode crude acetonitrile with contain contacting of ozone gas, though also depend on impurity level contained in the crude acetonitrile, but contain the volume of ozone gas to the acetonitrile that will contact, be 1-10000 times, when being preferably 10-1000 times gas volume, supply with 1-300 minute, be preferably and supply with 10-120 minute.If its service time is too short, the reaction of ozone and impurity is insufficient, and because gas flow rate is big, existence is carried secretly along with the acetonitrile spittle and the loss that causes becomes problem such as big, and in addition, if service time is long, see there is not advantage from its productivity viewpoint, and can carry out the over-drastic oxidizing reaction.
In addition, contain the service time of ozone gas, also can determine according to the ozone concn of analyzing in the exhaust.Particularly, contain the supply of ozone gas, make it more than 80% of ozone concn that ozone concn in the exhaust reaches supply gas, best is to proceed to more than 90%.In the analysis of ozone concn, can use iodimetry, uItraviolet absorption methods or utilize successive analysis meter of chemoluminescence method etc.
In continuous mode, can use packed tower, wet-wall tower or foam column wait and carry out, and carry out to good but be preferably with packed tower.Filler as packed tower can use Raschig ring, Lessing ring, saddle type filler, square saddle type filler, Tellerette, bohr ring, MeMahon packing, Rod Dixon ring etc.These fillers can use by porcelain system, metal system, the material that materials such as plastics system or carbon system form.Crude acetonitrile with contain contacting of ozone gas, can by adverse current or and stream carry out, but by counter current contact for well.In addition, in packed tower, suitably highly locate liquid grid distributor again is set, also can improve the contact efficiency of gas-liquid.The ratio that contains ozone gas and crude acetonitrile, by volume 1-10000, and be preferably 10-1000 for well, and in conjunction with the characteristic of packed tower, with the value of selecting not take place liquid flooding for well.
The 2nd operation of the present invention be, will through the acetonitrile of the 1st operation be selected from solid alkali, the operation that the material more than a kind in the sorbent material contacts.The order of this operation is will acetonitrile through the 1st operation in contained impurity conversion become segregative compound, perhaps fractionation by adsorption.
This acetonitrile and solid alkali among the present invention, the contact between sorbent material are the temperature at-40-80 ℃, are preferably 5-60 ℃ temperature, carry out and be more preferably under 10-40 ℃ temperature.
As the solid alkali among the present invention, can enumerate anionite-exchange resin, alkali-metal oxyhydroxide, the oxide compound of carbonate or supercarbonate, alkaline-earth metal, oxyhydroxide or carbonate, dissimilar metals hopcalite, upload the material of holding basic metal or alkali earth metallic compound, gac etc. at carrier.
As anionite-exchange resin of the present invention, can use the strongly basic anion exchange resin or the weak base anion-exchange resin of multi-hole type or gel-type.And can use any one resin of aqueous solution spent ion exchange resin or non-aqueous solution spent ion exchange resin.Strongly basic anion exchange resin preferably uses exchange groups such as trimethylammonium ammonium or dimethyl ethanol bases, by manipulation of regeneration, with its ion shape with OH shape or CO
3Shape is used.In addition, weak base anion-exchange resin is preferably with the exchange group of primary-uncle amino etc., with NaOH, NH
4OH etc. carry out using after the manipulation of regeneration.After these anionite-exchange resin carry out the manipulation of regeneration of its exchange group, contact with the acetonitrile of q.s and to clean, and use after contained moisture, the impurity etc. in the deionizing exchange resin to well.
Object lesson as solid alkali except anionite-exchange resin can be enumerated, basic metal Li, Na, K, Rb, the oxyhydroxide of Cs, carbonate or supercarbonate, alkaline-earth metal Mg, Ca, Sr, the oxide compound of Ba, oxyhydroxide or carbonate, and, can use Magnesium Silicate q-agent as the dissimilar metal hopcalite, Calucium Silicate powder, strontium silicate, barium silicate, pure aluminium silicate, and as the compound of basic metal or alkaline-earth metal, can use oxide compound, oxyhydroxide, carbonate or supercarbonate carry the material that is held on the carrier, as carrier, can enumerate gac, silicon-dioxide, aluminum oxide, pure aluminium silicate, titanium oxide or zirconium white, its loading amount is 0.01-50wt%, is preferably 0.1-10wt%.
And then, as solid alkali, can use N
2O, NH
3Perhaps use ZnC
L 2-NH
1Cl-CO
2Come activatory to present the gac of alkalescence.
As sorbent material, can use activated carbon, activated alumina, silica gel, synthetic zeolite, natural zeolite, polymeric adsorbent, natural clay mineral, pure aluminium silicate, Magnesium Silicate q-agent, borosilicate etc.
Solid alkali and or/person's sorbent material can use with powder or particle form, but its size is generally 0.001-100mm, is preferably 0.01-20mm for well.Powder also can be pressed into molding such as cylindric or spherical by compressing tablet forming mill etc. and uses in addition.These solid alkalis and/or sorbent material can be undertaken by continous way or batch-type with contacting of this acetonitrile, but industrial aspect is undertaken to good by continous way when refining.
As continous way, fill the solid alkali of solid state in the part of packed tower or pipe arrangement, and supply with acetonitrile and contact.With air speed SV is 0.001-1000 (rise/minute), is operating as and be preferably 0.01-100 (rise/minute).
As batch-type, can in contact groove that has whipping appts or vibrating device etc., carry out.Be 0.1-1000 minute duration of contact, is preferably 1-120 minute.
In the 2nd operation during, can not want separating of solid alkali and/or sorbent material and acetonitrile, and the separation of saving the 3rd operation is removed operation and can be carried out the easy acetonitrile refining of the present invention's the 1st purpose with solid alkali and/or sorbent material.That is to say, the invention discloses without disclosed distillation tower in Deutsches Wirtschafts Patent DD217212A1 number, and the packing layer by forming by solid alkali or sorbent material only, with the simple and easy method of refining acetonitrile.But, obtain the 2nd purpose of the present invention, be acetonitrile below 0.05 in wavelength 200-400nm place ultraviolet absorbancy, just need be after the 1st operation and the 2nd operation processing by the 3rd operation.
The 3rd operation of the present invention is to separate the low-boiling compound remove in the acetonitrile of the 1st or the 2nd operation and the operation of higher-boiling compound.The purpose of this operation is removed in the acetonitrile contained by fractionation by distillation, become the impurity such as compound of ultraviolet radiation absorption reason, and can to obtain wavelength 200-400nm place ultraviolet absorbance be acetonitrile below 0.05.Separate the method for removing, can select in the membrane separation process from distillation method, but as industrial partition method, preferably distillation method.
As distillation tower of the present invention, can use column plate tower or packed tower etc.The example of column plate tower can be enumerated, and has the cross-flow contact-type of upflow tube or does not have counter current contact type of upflow tube etc.In addition, the peristome as column plate can use blister-type, porous template, float valve type etc.As long as the stage number of this distillation tower is that the words more than 10 are just passable, do not limit especially, but 30-80 piece stage number is for well.
As the example of packed tower, can use the filler of filling to be Raschig ring, Lessing ring, bohr ring, the tower of saddle type filler, square saddle type filler, Tellerette, Rod Dixon ring or MeMahon packing etc.The material of filler can be used magnetic system, metal system, plastics system or carbon system etc.And, packed tower liquid grid distributor more suitably highly is set, can improve the contact efficiency of gas-liquid.
In the present invention, separate the method for removing, can enumerate the method for carrying out with 2 distillation towers than low-boiling compound of comparing with acetonitrile and higher-boiling compound.Particularly, in the 1st tower, remove low-boiling compound from the cat head separation, and in the 2nd tower, remove higher-boiling compound from its tower degree separation, and obtained making with extra care the method for acetonitrile from cat head, perhaps separate at the bottom of its tower and remove higher-boiling compound at the 1st tower, its cat head of the 2nd tower separates removes low-boiling compound, from the bottom or its top obtained making with extra care the method for acetonitrile, but in order to improve the quality of acetonitrile, at first separate the azeotrope remove acetonitrile and water, in the 2nd tower from its cat head taking-up acetonitrile for well.Therefore, separate from the 1st column overhead and to remove low-boiling compound, separate at the bottom of the 2nd Tata and remove higher-boiling compound, and the method that makes the purified acetonitrile from cat head is for well.In addition, water be with crude acetonitrile in contained material together, along with the oxidizing reaction with ozone generates.
In addition, remove this low-boiling compound and higher-boiling compound even in 1 distillation tower, also can separate.Be with having, supply with this acetonitrile to the distillation tower middle part, take out low-boiling compound from the top of distillation tower, and take out higher-boiling compound from the bottom of distillation tower, and from the top of the supply position of this acetonitrile or the method that the bottom obtains the purified acetonitrile, the method that preferably obtains the purified acetonitrile from the top of the supply position of this acetonitrile is for well.
In the operation that these separation are removed, the taking-up amount of reflux ratio or low-boiling compound and higher-boiling compound can be used as the condition made from extra care acetonitrile that obtains meeting purpose.For the acetonitrile of supplying with, contain the taking-up amount and taking-up amount at the bottom of the tower that contains higher-boiling compound of the cat head of low-boiling compound, be respectively more than 1%, preferably more than 5%.Under the few situation of taking-up amount at the bottom of cat head and tower, owing to contain the impurity of trace, the ultraviolet absorbance at wavelength 200-400nm place that has does not reach below 0.05 in the acetonitrile that is taken out.
In addition, promptly using the distillation tower more than 3, remove this low-boiling compound and higher-boiling compound though can separate, is not economy and effective means.
These distillation procedures, in decompression, normal pressure adds and depresses all and can implement, but usually its pressure for the 0.5-10atm scope for well.
As mentioned above, the present invention be by the 1st operation that crude acetonitrile will be contacted with the oxygen of status nascendi and be selected from solid alkali, the 2nd operation that material contacts more than a kind in the sorbent material is separated the process for purification of the crude acetonitrile that the 3rd operation chemical combination remove low-boiling compound and higher-boiling compound forms.And making up these operations is the acetonitrile that obtains purpose, need be operating as prerequisite with the order of (1) → (2) → (3) or (1) → (3) → (2).
The present invention compares with the method (the special 3-199868 of Yuanping City number) of the solid alkali of using the liquid that produces coherent substance or the sulfuric acid contact process (the special 3-214199 of Yuanping City number) of its complex process, be that a kind of technology is simple, easy continuous operation, and the loss of acetonitrile is few, the process for purification of crude acetonitrile.
During these 3 operations of running management, when obtaining being used for the acetonitrile of high speed liquid chromatography mobile phase solvent, need running management accurate and height.One of its method, measuring the rerum natura of the raw material of crude acetonitrile and each operation and carry out running management with near-infrared spectroscopy is an effective means.
Enumerate embodiment below and describe the present invention in detail.
Embodiment 1
The raw material acetonitrile, using it is 1.560 in the ultraviolet absorbancy in 200nm place, as impurity, vinyl cyanide 2.8ppm, vinyl carbinol 5.0ppm, sour 1.5ppm is 29% acetonitrile as the permanganic acid percent of decolourization of permanganic acid reducing substances index, carries out following operation.
As the 1st operation, using external diameter 5mm, internal diameter 2mm, in the ozone contact tower of Raschig ring of height 5mm with the highly-filled diameter 30mm of 410mm, under atmospheric pressure, under 20 ℃ the temperature, supply with acetonitrile from cat head with the flow velocity of 300ml/Hr, supply with at the bottom of the tower and contain 0.24Vol% (5.1g/Nm
3" Nm
3" be illustrated in 0 ℃, at 1 atmospheric m
3(cubic meter)) ozone gas of ozone, its feed speed is 180NL/Hr (0 ℃ of " NL " expression, 1 in 1 air pressure (liter)) (gas/liquid ratio=600).At the bottom of the tower of this ozone contact tower, take out and the contacted acetonitrile of ozone.To the vinyl cyanide in the acetonitrile of this taking-up, though vinyl carbinol does not detect, acid concentration increases to 105ppm, and the permanganic acid percent of decolourization rises to 100%.
Then,, in the post of the diameter 20mm that has filled non-water system multi-hole type weak base anion-exchange resin (trade(brand)name A Mubalisite A-21) 50ml, continue to supply with acetonitrile, under 20 ℃ of temperature, contact through the 1st operation in the 2nd operation.The ultraviolet absorbance of the acetonitrile that finally obtains at the 200nm place is 1.620, and when analyzing by vapor-phase chromatography, its vinyl cyanide, vinyl carbinol is detecting below the boundary.And acid is 0.9ppm, and the permanganic acid percent of decolourization is 0%.In addition, as obviously finding out from the result, by the processing of the 1st operation, though decompose vinyl cyanide, vinyl carbinol increases acid and permanganic acid reducing substances.Clearly, handle, removed acid and permanganic acid reducing substances by the 2nd operation.Also have, this operation, though carried out continuously 200 hours, simple to operate, and can runs steadily.In addition, this moment refining acetonitrile the rate of recovery reach 90% the high yield of supplying with acetonitrile.The mensuration of ultra-violet absorption spectrum is to use the quartz cell of optical length 10mm, and the distilled water that will be used for liquid chromatography thing in contrast, measures with the system spectrophotometer 288A of Hitachi.In addition, the analysis of gas-chromatography is with Yokogawa system gas chromatograph HP-5890, weighting agent is silicon OV-1's, capillary column internal diameter 0.25mm* length 50mm, the temperature that makes post at first 40 ℃ keep 5 minutes after, be warming up to 200 ℃ with 10 ℃/minute heat-up rates, keep carrying out in 10 minutes in this temperature at last.The oxygen analysis is measured by 5.6 (1) of JISK8001 then.In addition, the permanganic acid reducing substances is with reference to the method for JISK8032 record, mix adding 0.1N peracid potassium 0.1ml vibration among the sample 10g, after sombre dark place is placed 30 minutes, with the UV2000 type of Shimadzu Seisakusho Ltd., measure the permanganic acid percent of decolourization, with this index as the permanganic acid reducing substances.
Permanganic acid percent of decolourization=(1-(A/B) * 100
Absorbancy after A:30 minute
B: the absorbancy after just having begun
Wavelength: 545nm
Embodiment 2
Except in the 2nd operation of embodiment 1, use the atomic ratio of aluminum nitrate and silica gel with Al: Si=1 as sorbent material: after the material evaporation drying of 1 mixed, 500 ℃ carry out agglomerating pure aluminium silicate 35g beyond, other are operated equally by embodiment 1 and obtain the purified acetonitrile.The ultraviolet absorbancy of this acetonitrile at wavelength 20nm place is 1.480, and acid is 1.0ppm, and the permanganic acid percent of decolourization is 7%.
Embodiment 3
Except in the 2nd operation of embodiment 1, with beyond the gac 50ml, operate obtaining the purified acetonitrile similarly to Example 1 as sorbent material.The ultraviolet absorbancy of this acetonitrile at wavelength 200nm place is 1.500, and acid is 1.2ppm, and the permanganic acid percent of decolourization is 5%.
Embodiment 4
As the raw material acetonitrile, using in the ultraviolet absorbancy in 200nm place is 1.703, impure vinyl cyanide 3.5ppm, and methacrylonitrile 8ppm, vinyl carbinol 8ppm, the acetonitrile of oxazole 2ppm carries out following operation.
As the 1st operation, with external diameter 5mm, internal diameter 2mm, in the ozone contact tower of the magnetic system Raschig ring of height 5mm with the diameter 30mm of the filling of 410mm height, under the normal atmosphere, 20 ℃ of temperature, supply with this acetonitrile from cat head with the 300ml/Hr flow velocity, supply with at the bottom of the tower and contain 0.24Vol% ozone (5.1g/Nm
3) gas, its flow velocity is 180Nl/Hr (gas/liquid ratio=600).At the bottom of the tower of this ozone contact tower, take out and the contacted acetonitrile of ozone.
In the 2nd operation, in the post of the diameter 20mm that has filled non-water system multi-hole type weak base anion-exchange resin (trade(brand)name A Mubalisite A-21) 50ml, supply with acetonitrile continuously, and under 20 ℃ of temperature, contact through the 1st operation.
Then, in the 3rd operation, use diameter 40mm, multiaperture-type, total stage number is 65 a water distilling apparatus, supplies with the acetonitrile through the 2nd operation in the 10th block of column plate continuously, making tower top pressure is normal atmosphere, with reflux ratio is to operate for 16 times, takes out the acetonitrile that contains low-boiling compound from cat head with 20% of feed rate, takes out the acetonitrile that contains higher-boiling compound at the bottom of tower, its amount is 10% of feed rate, and obtains the purified acetonitrile from 40 blocks of column plates with 70% of feed rate.
The ultraviolet absorbance of this acetonitrile at wavelength 200nm place is 0.021, is below 0.013 at 210-400nm place ultraviolet absorbance.And, by gas phase form and aspect chromatography analysis, its vinyl cyanide, methacrylonitrile, vinyl carbinol, oxazole are for detecting below the boundary.
In addition, though this operation has been carried out 200 hours continuously, do not find that special problem can stably turn round.And,, and carry out running management with society of NIR system 6500 type near infrared optical splitter on-line analysis raw material crude acetonitrile and the 1st operation, the 2nd operation and the 3rd operations as running management, can obtain stable product.
The ultra-violet absorption spectrum of this purified acetonitrile and the acetonitrile that uses as raw material is shown in respectively among Fig. 1 and Fig. 2.
Embodiment 5
Except with the solid alkali in the 2nd operation of embodiment 4, be that all the other are operated equally with embodiment 4, obtain the purified acetonitrile beyond the material 50ml of OH shape with making the ion shape of gel type strong basic anion exchange resin (trade(brand)name IRA-400).The ultraviolet absorbance of this acetonitrile at wavelength 200nm place is 0.040, and the ultraviolet absorbance at 210-400nm place is below 0.025.
Embodiment 6
Except using granulous Ca-CO at the solid alkali in the 2nd operation of embodiment 4
3Beyond the 30g, all the other are operated equally with embodiment 4, obtain the purified acetonitrile.This acetonitrile is 0.034 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.021.
Embodiment 7
Except using to carry and hold beyond the silicon-dioxide 40g of 5.0wt% MgO at the solid alkali in the 2nd operation of embodiment 4, all the other are operated equally with embodiment 4, obtain the purified acetonitrile.This acetonitrile is 0.030 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.019.
Embodiment 8
To use and carry the gac 50g that holds 2.0wt%KOH at the solid alkali in the 2nd operation of embodiment 4, till the 2nd operation, operate similarly to Example 4.As the 3rd operation, use diameter 32mm, multiaperture-type, and column plate adds up to 2 towers of water distilling apparatus of 60, the 40th block of column plate to the 1st tower, supplying with acetonitrile through the 2nd operation with 250ml/Hr, is normal atmosphere with the tower top pressure, and reflux ratio is 12 to operate, take out 80% acetonitrile of feed rate at the bottom of the tower, and with its 20th block of column plate supplying with the 2nd tower, operate with reflux ratio 3, take overhead out 70% refining acetonitrile of feed rate.This acetonitrile is 0.043 at the ultraviolet luminosity in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.026.
Embodiment 9
Except in the 2nd operation of embodiment 4 as sorbent material, with making aluminum nitrate and silica gel with atomic ratio Al: Si=1: 1 carries out the blended material carries out after evaporation drying solidifies, 500 ℃ carry out agglomerating pure aluminium silicate 35g beyond, all the other are operated equally with embodiment 4, obtain the purified acetonitrile.This acetonitrile is 0.039 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.024.
Comparative example 1
In embodiment 4, will join through the acetonitrile 2000ml of the 1st operation in the round-bottomed flask as 3 liters band stirrer of the 2nd operation, and add the 50wt%NaOH aqueous solution down at 20 ℃, behind the 15.0g, stirred 20 minutes.At this moment, owing to separate out white coherent substance in flask, separate by filtration, but be stranded this material adhesivity height, it handles very difficulty.
To acetonitrile through the 2nd operation, carrying out the 2nd operation of embodiment 4 operates equally, take overhead out the acetonitrile that contains low-boiling compound, its amount is 25% of feed rate, at the bottom of tower, take out the acetonitrile that contains higher-boiling compound, its taking-up amount is 11% of a feed rate, and obtains the purified acetonitrile from the 40th block of column plate, and the gained amount is 64% of a feed rate.Resulting acetonitrile is 0.022 in the ultraviolet photoabsorption in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.014, and, when analyzing according to vapor-phase chromatography, vinyl cyanide, methacrylonitrile all detecting below the boundary, do not have qualitative problem.But the yield of acetonitrile is than embodiment 4 low 6%.
Further, when proceeding the distillation of the 3rd operation,, check when it is inner, find from all being attached with white adhesiveness material to the 10th block of column plate supplying with section at the bottom of the tower because the pressure reduction of distillation tower increases gradually, thereby shuts down after 20 hours.
Can know that from this comparative example as the method that aqueous solution solid alkali contacts with acetonitrile, because the generation of its adhesiveness material and the loss of acetonitrile, its industrializing implementation is difficult.
Comparative example 2
Remove in embodiment 4, do not carry out its 1st operation with the contacting of ozone beyond, all the other are operated equally and obtain acetonitrile.This acetonitrile is 1.601 in the ultraviolet absorbancy in wavelength 200nm place.
Comparative example 3
Except in embodiment 4, do not carry out its 2nd operation with the contacting of solid alkali beyond, all the other are operated equally and obtain acetonitrile.This acetonitrile is 0.157 in the ultraviolet absorbancy in wavelength 200nm place.
Comparative example 4
In embodiment 4, except not carrying out the distillation of its 3rd operation, all the other are operated equally and obtain acetonitrile.This acetonitrile is 1.451 in the ultraviolet absorbancy in wavelength 200nm place.
Like that, even remove wherein 1 operation in 32 prefaces, all can not obtain at wavelength 200nm place ultraviolet absorbance is acetonitrile below 0.05 known to from 3 examples of comparative example 2-4.
Comparative example 5
In embodiment 4, operate by the order of the 2nd operation, the 3rd operation, the 1st operation, obtain acetonitrile.This acetonitrile is 1.655 in the ultraviolet absorbancy in wavelength 200nm place.
Comparative example 6
In embodiment 4, operate by the order of the 2nd operation, the 1st operation, the 3rd operation, obtain acetonitrile.This acetonitrile is 0.219 in the ultraviolet absorbancy in wavelength 200nm place.
Comparative example 7
In embodiment 4, operate by the order of the 3rd operation, the 1st operation, the 2nd operation, obtain acetonitrile.The ultraviolet absorbancy of this acetonitrile at wavelength 200nm place is 1.552.
Comparative example 8
In embodiment 4, operate by the order of the 3rd operation, the 2nd operation, the 1st operation, obtain acetonitrile, this acetonitrile is 1.550 in the ultraviolet absorbancy in wavelength 200nm place.
Embodiment 10
Be added in acetonitrile 2 weight parts that obtain among the embodiment 4 in raw material acetonitrile 8 weight parts that will in embodiment 1, use, the ultraviolet absorbancy in preparation wavelength 200nm place is 1.4 acetonitrile, and in the round-bottomed flask of 2 liters band stirrer, add this acetonitrile 1500ml, under 25 ℃ of temperature, supply with the gas that contains 0.5Vol% ozone, its speed is 3 liters/min, makes it to contact 240 minutes.To this acetonitrile with the identical device of the 2nd and the 3rd operation of embodiment 4, operate obtaining the purified acetonitrile equally.This acetonitrile is 0.045 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is 0.028.
Embodiment 11
As the raw material acetonitrile, be when making vinyl cyanide by the oxidative ammonolysis of propylene, reclaim, make with extra care and get as its by product, is the round-bottomed flask that 0.360 acetonitrile is put into 3 liters band stirrer with 2000ml in the ultraviolet absorbancy in wavelength 200nm place, and under 20 ℃, speed supply with 3Nl/min contains ozone 0.24Vol% gas, when the concentration of the ozone in its exhaust reaches 0.20Vol%, stops supply and contains ozone gas.This moment the ozone concn in the exhaust be in the supply gas ozone concn 83%.This acetonitrile is used the identical device of the 2nd and the 3rd operation with embodiment 4, operate equally, obtain the purified acetonitrile.This acetonitrile is 0.040 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet photoabsorption in 210-400nm place is below 0.026.
Embodiment 12
Except in the 2nd operation of embodiment 11, (trade(brand)name: zeolite-4a) beyond the 50ml, all the other are operated equally with embodiment 11, obtain the purified acetonitrile to use synthetic zeolite as sorbent material.This acetonitrile is 0.011 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.005.
Use this acetonitrile to carry out lipid analysis.When the phospholipid with physiologically active being studied, need analyze with HIGH SENSITIVITY AND HIGH PRECISION the lipid of the trace in the panoramic living body sample, and, need high purity being used for the acetonitrile of high-speed liquid chromatography mobile phase with the molecule spirit-leveling instrument.But, the commercially available acetonitrile that is used for liquid phase chromatography and according to Deutsches Wirtschafts Patent DD217212A1 communique the acetonitrile of purified comparative example 3, its foreign matter content height is not suitable for lipid analysis.Yet wavelength is the acetonitrile of 0.011 present embodiment in the ultraviolet photoabsorption in 200nm place, and its foreign matter content is very low, is suitable for lipid analysis.
In addition, the acetonitrile with present embodiment has carried out the refining of peptide.Be used for refining the dividing equally of peptide and need high purity with liquid phase chromatography mobile phase acetonitrile.But, the commercially available acetonitrile that is used for liquid phase chromatography and by Deutsches Wirtschafts Patent DD217212A1 communique the acetonitrile of purified comparative example 3, its foreign matter content height is not suitable for the refining of peptide.Yet, in the ultraviolet photoabsorption in wavelength 200nm place the acetonitrile of 0.011 present embodiment, its foreign matter content is low significantly, is suitable for the refining of peptide.
Embodiment 13
Except in the 2nd operation of embodiment 11, beyond sorbent material use gac 50ml, operate equally with embodiment 10, obtain the purified acetonitrile, this acetonitrile is 0.013 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.006.
Embodiment 14
As the 1st operation of embodiment 4, in the round-bottomed flask of 2 liters band stirrers, put into 1 liter of this acetonitrile, and in base, add and the superfine potassium permanganate 1.09g of the pure system of light, with compound, 60 ℃ of stirrings 2 hours as the generation nascent oxygen.After this carry out the unit distillation, do not contained the acetonitrile of potassium permanganate.Then, its 2nd operation and the 2nd operation are operated similarly to Example 4, obtain the purified acetonitrile.This acetonitrile is 0.045 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.027.
Embodiment 15
In embodiment 4, operate by the order of the 1st operation, the 3rd operation, the 2nd operation, obtain the purified acetonitrile.This acetonitrile is 0.048 in the ultraviolet absorbancy in wavelength 200nm place, and the ultraviolet absorbancy in 210-400nm place is below 0.028.Shown in embodiment 4-15, same simple operation, can obtain in the ultraviolet absorbancy in 200nm place with high yield is acetonitrile of high purity below 0.05.
The present invention makes crude acetonitrile contact with nascent oxygen, only makes it then by having filled the packed tower that is selected from more than one materials in solid alkali and/or the sorbent material, just can produce acid and the few acetonitrile of permanganic acid reducing substances.This method is compared with disclosed distillation method in Deutsches Wirtschafts Patent DD217212A1 number, does not need water cooler, and the temperature treatment technology of thermal source and height is a kind of method of extremely simply refining acetonitrile.And then, make and to be used for high speed liquid chromatography mobile phase solvent, when the ultraviolet absorbancy in wavelength 200-400nm place is acetonitrile below 0.05, crude acetonitrile is contacted with the oxygen of status nascendi, make it then with make from solid alkali with or sorbent material in material more than a kind contact, continue to separate attached low-boiling compound and the higher-boiling compound of going, crude acetonitrile is contacted with the oxygen of status nascendi, continue to separate and remove low-boiling compound and higher-boiling compound, make it then be selected from solid alkali and/or sorbent material in material more than a kind contact, can be manufactured on the ultraviolet absorbancy in 200-400nm place and be the acetonitrile below 0.05, the method of the solid alkali of the liquid of this method and use generation adhesiveness material, perhaps the sulfuric acid contact process of its process complications relatively, technology is simple, continuous operation, and efficient height easily.
Fig. 1 is the ultra-violet absorption spectrum of purified acetonitrile.
Fig. 2 is the ultra-violet absorption spectrum of raw material acetonitrile.
Claims (25)
1. the process for purification of a crude acetonitrile, when it is characterized in that refining crude acetonitrile, according to
(1) the 1st operation that the crude acetonitrile of raw material is contacted with the oxygen of status nascendi, this raw material crude acetonitrile is more than 0.1 in the ultraviolet absorbancy in wavelength 200nm place, and
(2) make through the acetonitrile of the 1st operation be selected from solid alkali, the 2nd operation that material contacts more than a kind in the sorbent material and
(3) separate the 3rd operation of removing low-boiling compound contained in the acetonitrile of the 2nd operation and higher-boiling compound, perhaps carry out the 3rd operation after the 1st operation, carry out the refining crude acetonitrile of order of the 2nd operation then.
2. as the method for claim 1 record, it is characterized in that be below 0.05 through the refining acetonitrile that obtains in the ultraviolet absorbancy in wavelength 200-400nm place.
3. as the method for claim 1 record, it is characterized in that wherein said raw material crude acetonitrile is by propylene, contact oxidative ammonolysis between the iso-butylene or the trimethyl carbinol and ammonia and the molecular oxygen, when making vinyl cyanide or methacrylonitrile, the acetonitrile that obtains as by product.
4. as the methods of claim 2 or 3 records, the compound of generation nascent oxygen that it is characterized in that wherein being used for the 1st operation is for being selected from permanganic acid or its salt, oxygen acid or its salt, and superoxide contains a kind or above compound in the ozone gas.
5. as the method for claim 4 record, it is characterized in that wherein said superoxide is a kind or the above compound that is selected from hydrogen peroxide, sodium peroxide, the barium peroxide.
6. as the method for claim 4 record, it is characterized in that wherein oxygen acid or its salt are for being selected from clorox, potassium hypochlorite, hypoiodous acid sodium, hypoiodous acid potassium, sodium hypobromite, potassium hypobromite, sodium chlorate, Potcrate, sodium iodate, Potassium Iodate, sodium bromate, potassium bromate, sodium perchlorate, potassium perchlorate, perchloric acid, Periodic acid, sodium periodate, a kind or above oxygen acid or its salt in the potassium periodate.
7. as the method for claim 1 record, it is characterized in that wherein that in the 1st operation the contacting of oxygen with status nascendi is under-40 ℃ of-80 ℃ of temperature, carry out with batch-type or continous way.
8. as the method for claim 7 record, the oxygen that it is characterized in that the status nascendi in the 1st operation wherein is for containing ozone gas, and it contains ozone amount is 0.01-5.0 volume %.
9. as the method for claim 8 record, it is characterized in that the ozone gas of wherein supplying with batch-type that contains is, for the volume of the crude acetonitrile that should contact, 1-10000 gas volume is doubly supplied with 1-300 minute by 1 or above nozzle in the acetonitrile of liquid phase.
10. as the method for claim 8 record, it is characterized in that wherein with batch-type supply with contain ozone gas be make contain in the exhaust ozone concn reach the supply gas ozone concn 80% or more than supply with.
11. the method for claim 8 record, it is characterized in that making the gas-to-liquid contact that contains ozone gas and crude acetonitrile with continous way in the 1st operation wherein, be in packed tower or column plate tower, to carry out, supply with crude acetonitrile from its cat head, supply with at the bottom of the tower and contain ozone gas, and be that 1-10000 operates with the gas/liquid volumetric ratio.
12. as the method for claim 1 record, it is characterized in that wherein making in the 2nd operation this acetonitrile with solid alkali or/and contacting between the sorbent material is to carry out under-40 ℃-80 ℃ temperature.
13. the method as claim 12 record is characterized in that solid alkali wherein is an anionite-exchange resin.
14. as the method for claim 13 record, it is characterized in that anionite-exchange resin wherein is multi-hole type or gel-type, ionic is OH type or CO
3The strongly basic anion exchange resin of type or exchange group are primary, secondary, the amino weak base anion-exchange resin of uncle.
15. method as claim 12 record, it is characterized in that wherein solid alkali is for being selected from alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, alkaline-earth metals oxide, alkaline-earth metal oxyhydroxide, alkaline earth metals carbonate, Magnesium Silicate q-agent, Calucium Silicate powder, strontium silicate, a kind or above material among the barium silicate.
16., it is characterized in that wherein solid alkali is for to upload the material of having held basic metal or alkali earth metallic compound at carrier as the method for claim 12 record.
17. the method as claim 16 record is characterized in that wherein basic metal or alkali earth metallic compound are oxide compound, oxyhydroxide, carbonate or supercarbonate.
18. the method as claim 17 record is characterized in that wherein carrier is for being selected from gac, silicon-dioxide, aluminum oxide, the material among titanium oxide or the zirconium white.
19. the method as claim 12 record is characterized in that solid alkali wherein is N
2O, NH
2Perhaps ZnCl
2-NH
4Cl-CO
2The activatory gac.
20., it is characterized in that the sorbent material in the 2nd operation wherein is a kind or the above compound that is selected among gac, activated alumina, silica gel, synthetic zeolite, natural zeolite, polymeric adsorbent, natural clay mineral, pure aluminium silicate, Magnesium Silicate q-agent, the borosilicate as the method for claim 1 record.
21., wherein in the 3rd operation, separate and remove the method for low-boiling compound and higher-boiling compound for being selected from distillation method, a kind or above method among the membrane separation process as the method for claim 1 record.
22., it is characterized in that the distillation tower in the 3rd operation wherein is column plate tower or packed tower, and in 0.5-10atm pressure, operate as the method for claim 21 record.
23. method as claim 21 record, it is characterized in that separation in the 3rd operation wherein removes the operation that is in a ratio of low-boiling compound and higher-boiling compound with acetonitrile and formed by 2 towers, separate in the 1st at it and to remove low-boiling compound, in the 2nd tower, separate and remove higher-boiling compound.
24. method as claim 21 record, it is characterized in that separating in the 3rd operation wherein and remove the operation that is in a ratio of low-boiling compound and higher-boiling compound with acetonitrile and form by 1 tower, supply with acetonitrile to its tower pars intermedia, take overhead out low-boiling compound, at the bottom of tower, take out higher-boiling compound, and on this second supply position, obtain the purified acetonitrile.
25. the method for claim 1 record is characterized in that wherein carrying out process management with near-infrared spectroscopy.
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| CN93107005A CN1050351C (en) | 1993-05-14 | 1993-05-14 | Purification of acetonitrile of high purity and rough acetonitrile |
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| CN93107005A CN1050351C (en) | 1993-05-14 | 1993-05-14 | Purification of acetonitrile of high purity and rough acetonitrile |
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| CN111960966B (en) * | 2020-09-14 | 2022-03-08 | 永华化学股份有限公司 | Preparation method of chromatographic grade acetonitrile |
| CN113956179B (en) * | 2021-12-20 | 2022-03-29 | 潍坊中汇化工有限公司 | Acetonitrile refining method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2051803A (en) * | 1979-06-14 | 1981-01-21 | Du Pont | Removal of acrylonitrile from acetonitrile |
| EP0429057A1 (en) * | 1989-11-20 | 1991-05-29 | Digital Equipment Corporation | Text-to-speech system having a lexicon residing on the host processor |
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1993
- 1993-05-14 CN CN93107005A patent/CN1050351C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2051803A (en) * | 1979-06-14 | 1981-01-21 | Du Pont | Removal of acrylonitrile from acetonitrile |
| EP0429057A1 (en) * | 1989-11-20 | 1991-05-29 | Digital Equipment Corporation | Text-to-speech system having a lexicon residing on the host processor |
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