A kind of propiolic alcohol, Isosorbide-5-Nitrae-butynediol and urotropine three coproduction continuous production method
Technical field
The present invention relates to technical field of chemistry and chemical engineering, particularly relate to a kind of propiolic alcohol, Isosorbide-5-Nitrae-butynediol and urotropine three coproduction continuous production method.
Background technology
Propiolic alcohol is also known as propargyl alcohol, 2-propine-1-alcohol, and English Propargyl alcohol by name, is called for short PA.It is a kind of important Organic Chemicals, applies very extensive.In pharmaceutical industries, propiolic alcohol be synthesis Fosmicin, fosfomycin sodium, Sulphadiazine Sodium, etc. important intermediate, also for the production of propenal, vinylcarbinol and vitamin A etc.At pesticide industry, propiolic alcohol is mainly for the production of propargite agricultural chemicals, and the latter is a kind of low toxicity, broad spectrum acaricides, for the acarid Be very effective of the various crop such as control vegetables, oranges and tangerines, apple, tea, cotton, flowers.The condenses that propiolic alcohol and the epoxy compounds such as oxyethane or propylene oxide are formed has good Surface flat and bright property, belongs to forth generation nickel plating brightener.Meanwhile, propiolic alcohol and downstream compound thereof, can effectively suppress the acidic substance such as phosphoric acid, acetic acid, hydrochloric acid, sulfuric acid to corrosions of metal such as copper, iron, nickel.Thus propiolic alcohol is widely used as the rust remover of steel industry.Propiolic alcohol can also as the efficient acidification corrosion inhibitor under High Temperature High Pressure, concentrated hydrochloric acid environment in Oil/gas Well during oil production.The application product new along with propiolic alcohol downstream is constantly developed, the positive sustainable growth of its market requirement.
Propiolic alcohol removed hydrogen bromide with 2-bromopropylene alcohol through potassium hydroxide in 1872 by Henuy at first and obtains.There is people subsequently in liquefied ammonia, allow sodium carbide and polyoxymethylene react, obtained equally propiolic alcohol.But these methods are only carried out in the lab, be worth without industrial production.About 1938, Germanization scholar Reppe (thunder pendant) successfully develops the method that formaldehyde reacts under the catalysis of acetylene copper with pressurization acetylene, and then set up main product 1, the Industrial processes of 4-butynediol, by-product propiolic alcohol, the method, also known as Reppe method or alkynes aldehyde method, is also the unique method of current industrial production propiolic alcohol.The concrete reaction process of Reppe method is as follows:
This reaction system is made up of two reactions, belongs to consecutive reaction.The activeconstituents of catalyzer is acetylene copper.First reaction, the formaldehyde in solution and the acetylene of dissolving react at catalyst surface, generate product propiolic alcohol, second reaction, and excessive formaldehyde and propiolic alcohol continue to react and generate Isosorbide-5-Nitrae-butynediol.The feature of this reaction system determines the selectivity improving acetylene pressure and be conducive to improving propiolic alcohol, reduces acetylene pressure then favourable to the selectivity increasing Isosorbide-5-Nitrae-butynediol.
The production technique of current propiolic alcohol mainly contains three kinds: trickle bed production technique, slurry bed production technique and suspension bed production technique.
What tradition Reppe method adopted is trickle bed high-pressure process, and use black, spherical copper bismuth catalyst that carrier is SiO2, packed catalyst is in reaction tower.In typical process, reaction raw materials is acetylene and formalin (37%wt), and pressure is 0.5MPa, and temperature is 90 ~ 120 DEG C, and formaldehyde conversion can reach about 95%.Trickle bed production technique catalyzer is fixed on reactor bed, need not be separated with reactor product liquid, and easy and simple to handle, output is high, but there are problems.In trickle-bed reactor, the vapour-liquid ratio of feed stream is comparatively large, and gas phase (acetylene) main manifestations is external phase, and liquid phase (formalin) main manifestations is disperse phase, is flowed through catalyst bed lamellar spacing with drop form by gas phase drive.When a large amount of acetylene gas crosses beds with external phase form percolation, the then easier dry catalyst surface forming local in beds, and carbene reaction will be there is to dry catalyst surface (active ingredient is acetylene copper) in gas phase acetylene into contact, if the bulk that this phenomenon occurs is comparatively large and the time length is longer, then likely there is the cruelly poly-phenomenon of acetylene, thus explosion caused danger.Although add bismuth oxide auxiliary agent in the catalyst to react to suppress carbene, the generation that still cannot carbene be suppressed completely to react when a large amount of acetylene into contact catalyzer desiccated surface, thus cannot avoid explosion hazard.In addition, even if surperficial time shorter initiation that carbene reaction occurs of catalyzer partial drying gathers danger cruelly, but the carbene product produced can be deposited on catalyst surface, cause catalyst deactivation, thus make the acceptable life of whole beds shorter, shorten the catalyst change cycle, increase production cost.Meanwhile, because gas phase is external phase, thermal conductivity is little, and the reaction heat resulting from catalyst reaction surface is not easily derived, and easily causes beds local superheating, even the problem such as temperature runaway.In addition, the carbene product with material outflow reactor also can blocking pipe, shortens the stably manufactured cycle of device.
Slurry bed production technique, be that formalin and catalyst mix form slurry, acetylene imports in catalyst system from liquid level.In typical process, reaction raw materials is acetylene and formalin (37%wt), and temperature of reaction is 95 ~ 100 DEG C, and pressure is 0.04 ~ 0.15MPa, and is filled with a small amount of inert gas dilution, thus minimizing acetylene divides the accumulation be pressed in reactor.In slurry bed reactor, liquid phase is external phase, and pulverous catalyzer is surrounded wetting in most cases by liquid phase, avoid gas phase acetylene and dry catalyst surface contact, and reduce the cruelly poly-danger causing exploding of acetylene, catalyzer also extends work-ing life.But because of stirring intensity skewness in slurry bed reactor, easily form larger bubble at stirring intensity compared with weak-strong test acetylene, if the air pocket hold-time is long, then can cruelly gathers overheated because locally occurring acetylene and produce detonation phenomenon.And follow formalin due to powder catalyst and flow together, the relative movement of liquid-solid is more weak, causes liquid-solid interface mass-and heat-transfer effect poor.In addition, because in this technique, catalyzer is slurry, finally propiolic alcohol and 1 to be obtained, 4-butynediol, must be separated catalyzer with product liquid, compared to trickle bed production technique outside reactor, add catalyst separating link, thus add catalyst attrition and lock out operation expense.
In suspension bed production technique, fresh formaldehyde solution enters reactor bottom after mixing with acetylene in reactor bottom mixing tank with circulation fluid, and formaldehyde and acetylene react under catalyst action, and temperature of reaction is 90 DEG C, and pressure is 0.1 ~ 0.2MPa.Catalyzer in reactor relies on formaldehyde and acetylene momentum upwards and the effect maintenance suspended state of agitator.In this technique, catalyzer is separated in reactor with product.Core sheet glass is loaded onto at the gas inlet place of reactor and reaction solution exit.Acetylene, through core glass distribution, is conducive to mass transfer; Reaction solution leaves system by similar core glass, and catalyzer is left in reactor.Similar with slurry bed production technique, in this technique, acetylene is also easy forms larger bubble at inside reactor, produces detonation phenomenon and bed local superheating phenomenon.And because catalyst particle is in constantly collision and Frotteurism mutually, catalyzer micronization can be produced, thus cause the blockage of the micro orifice exporting core glass, affect the stable operation of reactor.
In three productions technique, formaldehyde all can transform more than 90%, but cannot transform completely, enters in liquid effluent and produces formaldehyde-containing wastewater, be difficult to process, and directly discharge can cause environmental pollution up to the present not yet to have document, patent to propose the effective ways addressed this problem.
Domestic generally employing trickle bed explained hereafter propiolic alcohol, and by-product Isosorbide-5-Nitrae-butynediol.Such as: 1. Dongbei Pharmaceutical General Factory centralab. the research of propiolic alcohol synthesis technique and future expectation [J]. Liaoning chemical industry .1978 (6): 6-9; 2. Lv Dong English, Sun Ying. propiolic alcohol Safe production technology innovation [J]. enterprise's technology development .2012,31 (5): 18-19.For alleviating the explosion issues of acetylene, in flow process, change fixed bed into fluidized-bed.In this technique, formaldehyde conversion can reach more than 90%, and the propiolic alcohol product purity obtained can reach 99%.
Reaction raw materials is the formalin of acetylene and 10%wt, and temperature of reaction is 100 DEG C, and pressure is 2MPa.Formaldehyde and acetylene enter first reaction tower respectively from bottom, after the reaction tower reaction of four series connection, obtain the mixture of propiolic alcohol, butynediol, water, methyl alcohol, unreacted formaldehyde and catalyzer.This mixture enters pressure filter, and obtain slurry catalyzer and return reaction tower and reuse, liquid phase discharging enters separation link.First steam propiolic alcohol, water and other low-boiling-point substances by concentration kettle, at the bottom of still, butynediol product can be obtained.The material steamed by primary tower with except methanol column remove portion water and methyl alcohol and other light constituents, obtains the azeotrope of propine alcohol and water successively.Add formaldehyde ester as entrainer, obtain propiolic alcohol product by azeotropic distillation.The recycling of formaldehyde ester is then realized by recovery tower.
Summary of the invention
The invention provides a kind of propiolic alcohol, Isosorbide-5-Nitrae-butynediol and urotropine three coproduction continuous production method.
The present invention adopts following technical scheme:
The concrete steps of propiolic alcohol of the present invention, Isosorbide-5-Nitrae-butynediol and urotropine three coproduction continuous production method are as follows:
(1) formalin and acetylene are added in alkynes aldehyde reaction device, control temperature of reaction is 80-120 DEG C, pressure is 1.0-2.5MPa, control the transformation efficiency of formaldehyde between 20%-90%, reacted liquid phase is containing propiolic alcohol, butynediol, water, methyl alcohol and unreacted formaldehyde, and gas phase is mainly containing acetylene;
(2) reacted liquid phase enters primary tower, and tower bottom passes into water vapor and carries out stripping, obtains the butynediol aqueous solution at the bottom of tower, and tower top obtains the mixture of propiolic alcohol, formaldehyde, water;
(3) discharging of primary tower tower top enters ammoniation of formaldehyde tower, react with ammoniacal liquor and generate urotropine, product enters except ammonia tower, after rectifying, tower top obtains mainly containing the gas phase of ammonia, the mixture of propiolic alcohol, water, methyl alcohol, urotropine is obtained at the bottom of tower, enter urotropine rectifying tower, after being separated, obtain the urotropine aqueous solution at the bottom of tower, tower top obtains the mixture of propiolic alcohol, water and methyl alcohol;
(4) mixture of propiolic alcohol, water and methyl alcohol enters except water tower, obtains highly purified water at the bottom of tower, and tower top obtains the azeotrope of methyl alcohol and propine alcohol and water, after entering methanol rectifying tower removing methyl alcohol, obtains the azeotrope of propine alcohol and water.
In step (1), in formalin, the concentration of formaldehyde is 10%-37%wt, enters the volume ratio of formalin in alkynes aldehyde reaction device and acetylene between 0.05-0.2, reacted gas phase by alkynes aldehyde reaction device top go out purify after reuse.
In step (2), the service temperature of primary tower is 80-120 DEG C, and working pressure is 0.04-0.1MPa (absolute pressure), and tower bottom passes into the weight ratio of liquid phase after the reaction that water vapor and tower top enter between 0.1-0.5.
In step (3), the discharging of primary tower tower top in ammoniation of formaldehyde tower and the weight ratio of the fresh ammoniacal liquor passed between 2-5, temperature of reaction is 50-80 DEG C, working pressure is 0.1-0.3MPa (absolute pressure), except ammonia tower is rectifying tower, service temperature is 80-120 DEG C, and working pressure is 0.1-0.3MPa (absolute pressure); The service temperature of urotropine rectifying tower is 80-110 DEG C, and working pressure is 0.05-0.1MPa (absolute pressure); Except reusing after water absorbs containing ammonia of ammonia column overhead.
In step (4), except water tower is rectifying tower, service temperature is 75-115 DEG C, and working pressure is 0.05-0.1MPa (absolute pressure); The service temperature of methanol rectifying tower is 85-115 DEG C, and working pressure is 0.05-0.1MPa (absolute pressure); Pass into primary tower be used as stripping except the high-purity water part obtained at the bottom of water tower tower is heated into steam, all the other can be used as technique soft water and use.
The azeotrope of the propine alcohol and water obtained in step (4) enters propiolic alcohol knockout tower, add entrainer, propiolic alcohol product is obtained at the bottom of tower, tower top discharging decant is aqueous phase and oil phase, enter entrainer knockout tower A and entrainer knockout tower B respectively, obtain the entrainer that can be recycled and the high-purity water that can be used as the use of technique soft water.
Propiolic alcohol knockout tower is rectifying tower, and service temperature is 70-120 DEG C, and working pressure is 0.015-0.1MPa (absolute pressure); Entrainer knockout tower A and B is rectifying tower, and service temperature is 80-110 DEG C, and working pressure is 0.05-0.1MPa (absolute pressure).
Described entrainer is the one in n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, entrainer is disposable feed intake and enter propiolic alcohol knockout tower the weight ratio of liquid phase to be separated between 6-7, during system cloud gray model entrainer recyclable after reuse.
Propiolic alcohol of the present invention, 1,4-butynediol and urotropine three coproduction continuous production device comprise alkynes aldehyde reaction device, primary tower, ammoniation of formaldehyde tower, except ammonia tower, urotropine rectifying tower, except water tower, methanol rectifying tower, propiolic alcohol knockout tower and entrainer knockout tower A, B, they are connected by pipeline successively.
Wherein alkynes aldehyde reaction device is packed bed Oscillatory Flow Reactor (our company's patent, be in the open stage, application number is 201310238138.0), be applicable to the industrial gas-liquid reaction based on liquid phase, liquid-liquid reaction or the gas-liquid-solid phase reaction system containing solid catalyst, can the steady running of serialization for a long time.In packed bed Oscillatory Flow Reactor, liquid phase (formalin) is external phase, gas phase (acetylene) is disperse phase, oscillating flow is while being dispersed into smaller bubble by acetylene, catalyst surface can be kept to be soaked by liquid all the time, thus avoid gaseous state acetylene to do at catalyzer surface generating carbene and cause catalyst activity to reduce and explosion hazard.By regulating oscillation intensity, make acetylene bubble in filled section, obtain optimum form and distribution of sizes, increase the contact area of itself and formalin and granules of catalyst bed, the surface making gas, liquid, solid three alternate is constantly updated, strengthening transfer process, can not only speed of reaction be improved, the problems such as beds is overheated, temperature runaway can also be avoided.In addition, copper bismuth catalyst is fixing in the reactor with the form of similar fixed bed, and solid can not suspend or flow away with fluid, particle loss and efflorescence degree all greatly lower, and the mixing of material relies on vibration to realize in reactor, inside containing dynamic component, does not decrease the wearing and tearing of catalyzer.
The present invention with formalin and acetylene for Material synthesis propiolic alcohol, coproduction 1,4-butynediol and urotropine, temperature of reaction is 80-120 DEG C, pressure is 1.0-2.5MPa, can obtain the propiolic alcohol of purity more than 99.5%, the butynediol aqueous solution and the urotropine aqueous solution, the transformation efficiency of whole technique formaldehyde can reach 100%.
In this technical process, the main gas containing acetylene that alkynes aldehyde reaction device top obtains, reuse after major part purification, only has emptying on a small quantity; The ammonia-containing gas technique soft water absorption Posterior circle obtained except ammonia top of tower uses; The methanol purity that methanol rectification top of tower obtains is 97%, can be used as industrial goods and sells; The entrainer obtained bottom entrainer knockout tower A can be recycled; The water purity obtained except water tower and entrainer knockout tower B is very high, and a part can be heat vaporized rear as stripped vapor use, and all the other can be used as technique soft water and use.Therefore, this technique produces without other pollutents except catalyst waste slag and a small amount of emptying gas.Meanwhile, in alkynes aldehyde reaction device, unreacted formaldehyde is converted into urotropine by reacting with ammoniacal liquor, solves the emission problem of formaldehyde waste water.
Reduce the transformation efficiency of reactor outlet formaldehyde, the selectivity of propiolic alcohol can be made to improve, thus the mass ratio of propiolic alcohol and butynediol in raising product, therefore by regulating the flow of liquid phase feeding, change its residence time in reactor, regulate the temperature and pressure in reactor also can change level of response in addition, thus control the transformation efficiency of reactor outlet formaldehyde, and final change propiolic alcohol in product, 1,4-butynediol and urotropine ratio.
Propiolic alcohol of the present invention, Isosorbide-5-Nitrae-butynediol and urotropine three coproduction continuous production method are the production technique of a kind of safety, environmental protection, compared with the prior art, have the following advantages:
(1) by coproduction urotropine, raw material formaldehyde is transformed completely, has both avoided the waste of raw material, eliminate again the formaldehyde in raffinate, fundamentally solve the formaldehyde waste water emission problem in original technique.What obtain in this technique is heat vaporized rear as stripped vapor without an aldehyde water part simultaneously, all the other can be used as technique soft water and recycle, decrease the discharge of waste water, this technique is produced without other pollutents except catalyst waste slag and a small amount of emptying gas, becomes the production technique of clean a, environmental protection.
(2) patented technology packed bed Oscillatory Flow Reactor is used to carry out alkynes aldehyde reaction.Oscillating flow, while acetylene is dispersed into smaller bubble, can keep catalyst surface to be soaked by liquid all the time, thus avoids gaseous state acetylene to do at catalyzer surface generating carbene and cause catalyst activity to reduce and explosion hazard.By regulating oscillation intensity, make acetylene bubble in filled section, obtain optimum form and distribution of sizes, increase the contact area of itself and formalin and granules of catalyst bed, the surface making gas, liquid, solid three alternate is constantly updated, strengthening transfer process, can not only speed of reaction be improved, the problems such as beds is overheated, temperature runaway can also be avoided.
(3) by regulating the transformation efficiency of reactor outlet formaldehyde, controlling the ratio of propiolic alcohol, butynediol and urotropine, to adapt to the changes in market demand of three kinds of products, making this technique have high economy and market adaptability.
(4) compare with suspension bed production technique with slurry bed production technique, catalyzer is fixing in the reactor with the form of similar fixed bed, solid can not suspend or flow away with fluid, particle loss and efflorescence degree all greatly lower, packed bed Oscillatory Flow Reactor is inner without dynamic component simultaneously, and decrease the wearing and tearing of catalyzer, this technique is without the need to the separation link of catalyzer in addition, reduce process cost, eventually reduce production cost.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of embodiment 1;
1 alkynes aldehyde reaction device, 2 primary towers, 3 ammoniation of formaldehyde towers, 4 are except ammonia tower, 5 urotropine rectifying tower, 6 are except water tower, 7 methanol rectifying towers, 8 propiolic alcohol knockout towers, 9 phase separators, 10 entrainer knockout tower A, 11 entrainer knockout tower B.
Embodiment
Design embodiments below describes in further detail of the present invention.
Design embodiments 1
The concrete steps of propiolic alcohol of the present invention, Isosorbide-5-Nitrae-butynediol and urotropine three coproduction continuous production method are as follows:
(1) formalin enters alkynes aldehyde reaction device 1 with acetylene gas after preheating from bottom, wherein the mass rate of formaldehyde solution is 1157.7kg/hr, the mass rate of acetylene is 166.7kg/hr, both 100.0 DEG C, there is ethynylation under 2.0MPa condition, the transformation efficiency of formaldehyde is 50%.Reuse after reacted gas phase purification, liquid phase enters primary tower 2, carries out separating-purifying.
(2) primary tower 2 is atmospheric operation, service temperature is 110.9 DEG C, tower bottom passes into water vapor and carries out stripping, steam quality flow is 433.3kg/hr, and heavy constituent at the bottom of tower is directly as Isosorbide-5-Nitrae-butynediol product extraction, mass rate is 355.8kg/hr, wherein Isosorbide-5-Nitrae-butynediol mass content is 60.0%, and tower top light constituent enters ammoniation of formaldehyde tower 3.
(3) discharging of primary tower 2 tower top enters ammoniation of formaldehyde tower 3 together with ammoniacal liquor, 60 DEG C, generate urotropine, the mass rate 423.5kg/hr of ammoniacal liquor under condition of normal pressure, formaldehyde conversion is 100%, and product enters except ammonia tower 4.
(4) except ammonia tower 4 is atmospheric operation, service temperature is 98.4 DEG C, and top gaseous phase absorbs through water to be become ammoniacal liquor Posterior circle and return ammoniation of formaldehyde tower 3 and reuse, and discharging at the bottom of tower enters urotropine rectifying tower 5.
(5) urotropine rectifying tower 5 is atmospheric operation, and service temperature is 104.9 DEG C, and after being separated, at the bottom of tower, discharging is directly as product extraction, and mass rate is 432.2kg/hr, and wherein the mass content of urotropine is 40.1%, and tower top discharging enters except water tower 6.
(6) except water tower 6 is atmospheric operation, service temperature is 103.7 DEG C, the propiolic alcohol aqueous solution that top extraction forms close to azeotropic point, wherein also containing the methyl alcohol carried secretly in system, enters methanol rectifying tower 7.Obtain highly purified water except at the bottom of water tower 6 tower, mass rate is 1118.8kg/hr, and wherein the mass content of water is 99.9%, and reuse is to primary tower as stripped vapor use after heat vaporized for a part, and a part can directly use as technique soft water.
(7) methanol rectifying tower 7 is atmospheric operation, and service temperature is 97.2 DEG C, and overhead product is methyl alcohol, and mass rate is 11.9kg/hr, and wherein the mass content of methyl alcohol is 97.0%, is the mixture of propiolic alcohol, water, enters propiolic alcohol knockout tower 8 at the bottom of tower.
(8) alkynol knockout tower 8 is normal pressure azeotropy rectification column, and service temperature is 114.0 DEG C, and entrainer is n-propyl acetate, and mass rate is 2002.0kg/hr.Obtain propiolic alcohol product at the bottom of tower, mass rate is 138.5kg/hr, and wherein the mass content of propiolic alcohol is 99.9%, and tower top obtains the mixed solution of n-propyl acetate and water, in phase separator 9, be divided into oil phase and aqueous phase after cooling.
(9) oil phase obtained in phase separator 9 enters entrainer knockout tower A10, and operational condition is 103.2 DEG C, normal pressure, obtains the n-propyl acetate that can be recycled at the bottom of tower, and mass content is 99.9%, and tower top discharging loops back phase separator 9 and processes.The aqueous phase obtained in phase separator 9 enters entrainer knockout tower B11, operational condition is 101.6 DEG C, normal pressure, and tower top discharging loops back phase separator 9 and processes, and obtains highly purified water at the bottom of tower, mass rate is 184.8kg/hr, and wherein the mass content of water is 99.9%.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.