CN101613285A - A kind of oil of mirbane synthetic method and equipment special - Google Patents
A kind of oil of mirbane synthetic method and equipment special Download PDFInfo
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- CN101613285A CN101613285A CN 200810011998 CN200810011998A CN101613285A CN 101613285 A CN101613285 A CN 101613285A CN 200810011998 CN200810011998 CN 200810011998 CN 200810011998 A CN200810011998 A CN 200810011998A CN 101613285 A CN101613285 A CN 101613285A
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Abstract
The present invention relates to a kind of associating nitrofication process of synthesizing nitryl benzene and the associated plant of microreactor and stirring reactor.Building-up process is a starting material with benzene and nitric-sulfuric acid, and benzene and nitration mixture are delivered to two inlets of microreactor respectively by volume pump, carry out pre-mixing in the microchannel, and the part nitration reaction takes place simultaneously; The microreactor outlet is the one-stage nitration product of high dispersion state.The one-stage nitration product continuously flows into the stirring tank nitrator and continues reaction.The present invention's operate continuously under the nitration mixture condition of high-moisture, process safety, the benzene transformation efficiency is 99.85% (mol), product oil of mirbane selectivity 99.8% (mol).
Description
Technical field
The present invention relates to the method for a kind of nitric acid and the nitrated benzene synthesis of high purity of vitriolic mixing acid oil of mirbane, and realize the isolated plant that this method is used, specifically benzene mixed acid nitrification synthesizing nitryl benzene process is united in microreactor and stirring-type nitrator and is finished.Belong to aromatic nitration and novel nitrifying process equipment field.
Background technology
Oil of mirbane is important dyestuff, medicine intermediate, is mainly used in production aniline.Produce at the nitrated benzene of industrial employing low concentration nitre sulphur mixing acid, used nitrator mostly is the mechanical agitation type reactor, and needs many stills serial operation (being generally 3～4).The placed in-line nitration processes of this many stills exists mixing inhomogeneous, is prone to material local superheating phenomenon in the still, and it directly influences and is, the productive rate of product oil of mirbane is not high, generally the highest have only 96～98.5%, or the dinitro by product is many, and its another one shortcoming is that process is dangerous.
It is a very promising nitrated equipment that microreactor is used for the aromatic nitration reaction, and it comprises the not available specific characteristic of some conventional nitrators: scaled microization; Heat and the quality transfering rate construction equipment that routinizes improves 1～3 order of magnitude between fluid; Can realize directly amplifying fast (modular structure, the parallel amplification); Intrinsic safety and process are controlled; Process is continuously with highly integrated; Dispersion and flexible production etc.
Sharpest edges of carrying out aromatic nitration in microreactor are to use the intrinsic speed of reaction of the acid of strong nitrated ability with the raising nitration reaction, and process safety.This is extremely effective for two nitrated reactions as benzene, toluene and chlorobenzene, especially this two nitrated processes generally all allow a spot of single nitro-aromatic to exist, and because be the acid of strong nitrated ability, two nitrated products can't stop up the microchannel, but are dissolved in the strong acid.But use this strong nitrating acid to carry out one when nitrated, equally also since this caloic transmission capacity of microreactor make that two nitrated by products are more and be included in the nitration product, reduced the selectivity of a nitration product; And because the fusing point height of two nitrated products, easily crystallization is gathered and is caused blast, often requires the dinitro production concentration in the product to be lower than 3000ppm for the production of oil of mirbane.
Thereby must reduce nitration acid nitrated ability, main method is to realize by the water content that improves in the nitration mixture.To carry out benzene nitrated but the nitrating acid of high-moisture is used for the microchannel, because residence time of material is short in the microreactor, reacts and be kinetic control, and the benzene per pass conversion is lower.
Although in the nitration mixture of high water concentration, the nitrated transformation efficiency of benzene is low, because microreactor is micro-scaled structures, can promote mixing between organism and nitration mixture, so microreactor outlet product is high dispersing, comprises unreacted benzene.One-stage nitration product this low conversion and good mixing is stirred and the continuation two stage nitration via stirred-tank reactor in the branch phase front, impel benzene to transform fully, can obtain the high purity mononitro-benzene.
Thereby, the present invention propose with novel microreactor with stir the kettle type nitrating reactor associating nitration processes of connecting, because organism and nitration mixture have been realized well blend in microreactor, can significantly improve in the stirred-tank reactor because of mixing the local superheating phenomenon due to bad, avoid potential explosion hazard; Can reduce simultaneously conventional nitrated required tank reactor progression, and eliminate, both guarantee the total conversion rate of benzene, and improved principal product mononitro-benzene selectivity because of the benzene of the residence time in the microreactor due to too short once transforms incomplete problem.
Summary of the invention
The present invention takes microreactor and stirring reactor associating nitration processes, realizes benzene mixed acid nitrification synthesizing nitryl benzene.For the oil of mirbane production process provides a kind of technology safely and efficiently, this technology has significantly improved the selectivity of mononitro-benzene.
A kind of oil of mirbane synthetic method, it is the benzene mixed acid nitrification process to be united finish in microreactor and stirred-tank reactor, process is as follows,
1) benzene and nitric acid and vitriolic nitration mixture pump into microreactor simultaneously, carry out pre-mixing in the microchannel, and carry out the one-stage nitration reaction.Wherein the nitration mixture mass concentration is a nitric acid 8～30%, sulfuric acid 50～80%, water 10～25%; The mol ratio of charging nitric acid and benzene is 0.9-1.2.This moment, the benzene transformation efficiency was 15～75%, and the mononitro-benzene selectivity is greater than 99.8%;
2) product from the one-stage nitration reaction directly is delivered to the stirring tank nitrator, stirs down in normal pressure and gets oil of mirbane in 10～30 minutes.
Described nitric acid/vitriolic nitration mixture mass concentration is: nitric acid 13～20%, sulfuric acid 60～70%, water 15～20%.
Described two kinds of fluid benzene and the liquid hourly space velocity of nitration mixture in microreactor are 10
2～10
5h
-1, preferentially 10
3～10
4h
-1Following operation; The working pressure of described microreactor is the pressure that fluid flow produces, and is defined as 0.05～0.5MPa.
The microreactor outlet connects stirred-tank reactor, and described stirred-tank reactor and educt flow are gone into microreactor synchronous operation; The adiabatic operation at normal temperatures of microreactor and stirred-tank reactor, temperature of reaction is by the decision of nitration reaction heat, and stirred-tank reactor need not temperature controlling system.
In order to realize the process of integrated process production oil of mirbane, adopt by a microreactor and the integrated reaction device that stirred-tank reactor is in series.
Wherein, the constitutional features of microreactor is for comprising: 1. two blocks of shroudings and a slice microchannel plate at least; 2. be positioned at least three microchannels on the microchannel plate, wherein at least two intake vents, and at least one reaction channel that links to each other with intake vent; 3. at least one intake vent is in the plane all with reaction; 4. two imports that are connected with intake vent respectively, and an outlet that is connected with reaction channel; 5. be positioned at up and down and can be provided with control and measure the thermocouple jack that temperature is used on the shrouding.
The scale feature of microreactor is that the import microchannel can be consistent with the microchannel characteristic dimension, also can be different; Every intake vent can be provided with branch, and when intake vent was established the branch of one or more, branched bottom linked to each other with the higher level microchannel with arc-shaped structure, and the equivalent diameter size of microchannel can successively decrease step by step, and the amplitude of successively decreasing is 0-80% (0 an expression consistent size); Angle between at least two intake vents that link to each other with reaction channel can be arbitrarily angled, is preferably 0～180 °; The hydraulic diameter scope of reaction channel should be at 0.1～2mm, preferably at 0.3～1.0mm; The microchannel length range is 0.2～50cm, preferred 2～20cm, and wherein intake vent adds that the distance of exit passageway accounts for 1/3～2/3 of total distance between import and outlet.
The described stirring tank nitrator that is connected behind the microreactor adopts known in the art or existing Type of equipment.The material of microreactor can be titanium material, stainless steel or as polymethylmethacrylate macromolecular materials such as (PMMA).
The present invention compares with existing oil of mirbane production technique has following advantage:
1. because microreactor has good transmission characteristic, can realize good pre-mixing between organism and nitration mixture, can improve greatly thus in the stirred-tank reactor because of mixing the hot spot phenomenon due to bad, avoid the potential explosion hazard, improve the security of nitration reaction process.
2. because the pre-mixing of microreactor and the effect of pre-reaction, and be delivered to reaction mass in the stirring tank nitrator and disperse more evenly, can reduce the progression of conventional nitrated required many stills reactor, only need a stirring tank nitrator.
3. liquid hourly space velocity exceeds 3 orders of magnitude of traditional nitration processes in the microreactor, and the space-time yield of reactor is higher.
4. the benzene transformation efficiency in the combination process of the present invention and the selectivity of mononitro-benzene all are higher than existing nitration processes, comprise existing adiabatic method nitration processes.
The starting of process and idle time very short, process reaches stable state very soon, has avoided producing during the start-stop car big technological fluctuation; Reduced the pending product stream that falls short of specifications.
Description of drawings:
Fig. 1 is microreactor and stirred-tank reactor composite reaction artwork;
Fig. 2 is a hyperchannel microreactor channel plate front view.
Embodiment
The present invention realizes the technology (accompanying drawing 1) of the nitrated synthesizing nitryl benzene of whole process adiabatic benzene, requirement has conveying equipment for fluid substances, 2～3 fluid transferpumps for example, with a microreactor, a stirred-tank reactor, and fluid-transporting tubing, for example can adopt external diameter in the laboratory is 3 millimeters stainless steel tube or polytetrafluoroethylene (PTFE) pipe, can select the subsidiary conduit of suitable dimension in the commercial run according to industrial scale.
The core of microreactor is at least one titanium or stainless steel flat plate 5 (accompanying drawing 2) with multi-channel structure, 1 and outlet 4 of two inlets is arranged on it, each inlet is provided with some branches intake vent 2, and two inlets should have branch's intake vent of equal amts, the point of branch's intake vent enters reaction channel 3, so the quantity of reaction channel is identical with the branches of intake vent.Two inlets of channel plate are when the homonymy at plate, branched bottom is overlapping, when the heteropleural of plate, then have only the inlet of a raw material and reaction channel to be in the plane, the end of branch's intake vent of another raw material must be by micropore turn back reaction channel side and last mixing of materials so.The design consideration benzene of inlet microchannel and the flow of nitration mixture are determined, fall close with the flowing pressure that guarantees two fluid streams.
Each side-entrance passage in the channel plate shown in Figure 2 is provided with 16 branches, also can be arranged to other number as 2
n(n is the intake vent branches, can be 0 i.e. branch not), link to each other with the semicircular arc microchannel between higher level microchannel and the subordinate microchannel, and the equivalent diameter size of microchannel is successively decreased step by step, the amplitude of successively decreasing is 50%, also can be decided at the higher level but not officially announced in 0～80% scope (0 expression is not successively decreased).Thereby the reaction two-phase is distributed in 16 reaction channels and finishes mixing, mass transfer and reaction process, be equivalent to 16 tubular reactors and carry out nitration reaction synchronously, wherein the equivalent diameter of every reaction channel is 0.3mm, also can between 0.1～2.0mm, choose wantonly, every long 60mm of passage, or between 2～500mm, appoint and decide.
Nitration processes of the present invention contains from the effusive one-stage nitration product in microreactor exit (organic product) still that unreacted benzene is 25%～85%, and high dispersing in mineral acid mutually in.The one-stage nitration product of microreactor outlet is high dispersion state, and has certain temperature (thermal insulation warming), this be by benzene in the microreactor partly transform produce; Temperature rise is formed relevant, also relevant with liquid hourly space velocity with nitrating acid.Under nitration mixture of the present invention and air speed condition, product, helps unreacted reactant benzene and realizes transforming fully in the stirring tank nitrator between 30～60 ℃ in exit, microchannel temperature.
One-stage nitration product this good mixing and that be high dispersion state is flowed into by short as far as possible connecting tube and proceeds reaction in the stirring tank nitrator that has started whipping appts, product after reaction is finished separates and can carry out in equipment known in the art, or carry out by means of means known in the art, for example separate and can finish in static separation device or cyclonic separator, spent acid concentrates can take the low pressure flash mode to finish.
Conventional stirring tank nitrator used in the present invention, its size, scale and stirring velocity and churning time should adapt to the liquid hourly space velocity in the microreactor.
The liquid hourly space velocity that microreactor of the present invention uses is 10
2～10
5h
-1, more fortunately 10
3～10
4h
-1Following operation, more preferably 1 * 10
3～1 * 10
4h
-1Full airspeed is defined as nitrating acid and benzene flows into the maximum space speed that the interior generation of microreactor is not higher than the 0.5MPa resistance drop, and full airspeed is relevant with structure of reactor and yardstick.
For guaranteeing that the benzene total conversion rate reaches more than 99.85%, the residence time in the stirring tank nitrator was at 10～30 minutes.
The design of stirring-type nitrator should according to the microreactor size, the operation air speed and reaction time the three, plant-scale stirring tank nitrator also can design or choose according to actual scale.For example, the microreactor effective volume is by 75 microlitres, and liquid hourly space velocity is 5000h
-1The time, about 6 ml/min of the semi-invariant of product.Therefore, in a reaction time (30 minutes meters), 180 milliliters of the product total amounts that need stir, promptly the quiet liquid volume of stirring-type nitrator is only 0.2 liter; Stirring can conventional stirring velocity promptly 150～300 rev/mins carry out.
The present invention uses nitric acid and vitriolic mixing acid as nitrating agent, preparation nitric acid of nitration mixture and vitriolic concentration can be used as 65～68% concentrated nitric acid with greater than 95% the vitriol oil, both require not have cotton-shaped or particulate contamination, and are mobile unobstructed to guarantee in the microreactor.
The nitration mixture of preparation should contain the water of higher proportion, to reduce benzene two nitrated speed, but be lower than certain value, because reaction mass residence time in microreactor is short, nitration reaction is subjected to kinetic control under high water-content condition, thereby nitration acid water content should have a reasonable threshold value, to guarantee that certain benzene transformation efficiency is arranged in microreactor, in next stage stirring tank reaction unit benzene transformed fully or reaches a degree that almost completely transforms.Nitrating acid used in the present invention can mix in conventional Preparation tank in advance, can be introduced separately into also in the micro mixer that on-line mixing is laggard goes into microreactor (as accompanying drawing 1).
The mass concentration of sulfuric acid/nitric acid/water mixing acid that the present invention uses is: nitric acid 8～30%, better use 13～20%, and sulfuric acid 50～80% better uses 60～70%, and water 10～25% better uses 15～20%.
In the nitration processes of the present invention, the mol ratio of nitric acid and benzene is 0.9～1.2, and benzene is total to be transformed fully in order to make, and the middle mutually nitric acid amount of spent acid is the least possible, and the mol ratio of nitric acid and benzene is preferably 1.0～1.05.
The organic product that nitration processes of the present invention obtained, wherein, the selectivity of oil of mirbane is greater than 99.8mol%, and the transformation efficiency of benzene in microreactor is 15～75mol%, and the total conversion rate of benzene reaches 99.85%.
More than described the present invention, the illustrative explanation the invention process of following examples effect can not be interpreted as it is limiting the scope of the invention.Except as otherwise noted, all percentage ratios are mass percent among the embodiment.
Take the nitration processes shown in the accompanying drawing 1, nitration mixture is pumped into micro mixer preparation mixed acid nitration, prepares a kind of sulfuric acid of 68.5wt% sulfuric acid, 13.2wt% nitric acid and 18.3wt% water and mixing acid of nitric acid of containing, and mixing acid flows into microreactor with benzene.The microreactor channel volume is 154 microlitres, and nitric acid is 1.04 with the amount ratio of benzene, is that the liquid hourly space velocity of benchmark is 2400h with benzene and mixing acid total amount
-1Since the heat release of nitration reaction process, 39.8 ℃ of microreactor outlet product temperature; The logistics of one-stage nitration product enters stirring reactor, stirs 30 minutes under normal pressure, 200 rev/mins of speed, and microreactor here and agitator be operation at normal temperatures all.Organic phase is through washing, alkali cleaning be washed to neutral oil of mirbane product in the product, and spent acid is the water of sulfur acid about 75% and 25% mutually, removes concentrating part.
Total conversion rate based on benzene is 99.74mol%, and the selectivity of oil of mirbane is 99.61mol%.
Process and technology are with embodiment 1.The mol ratio that only changes committed step material nitric acid and benzene is 1.16.Pump operation 10 minutes stirred 30 minutes.Because the nitric acid amount is high slightly than embodiment 1, a nitration product of high dispersive is 51 ℃ of the temperature in microreactor exit.
The benzene total conversion rate that obtains is 99.92mol%, and the oil of mirbane selectivity is 99.85mol%.
Comparative example 1
In the nitration reaction device shown in the accompanying drawing 1, remove the stirring-type nitrator, other process is constant.Microreactor is operated under normal temperature and 80 ℃ of two temperature, and the quality of mixed acid nitration is formed identical with embodiment 1 and 2, and nitric acid is respectively 0.97 and 1.03 with the amount ratio of benzene, and liquid hourly space velocity is respectively 2875h
-1And 2474h
-1, the reacting product outlet temperature reaches 21 ℃ and 107 ℃ respectively.
The transformation efficiency of benzene is respectively 16.3mol% and 75.4mol% under two conditions, and the oil of mirbane selectivity under two conditions is respectively 99.7mol% and 98.7mol%.
Illustrate that high water concentration mixed acid nitrification ability reduces, benzene under normal temperature condition once transforms very incomplete, also explanation improves temperature when improving a nitration reaction speed, also improved two nitrated speed of response, thereby the selectivity of purpose product mononitro-benzene reduces.
Comparative example 2
Process and technology are with embodiment 1, and the charge ratio of nitration mixture composition, liquid hourly space velocity and nitric acid and benzene is with embodiment 1.The microreactor service temperature is 80 ℃, and microreactor exit product temperature is 107 ℃.A product that is high dispersion state of 107 ℃ flows in the stirring-type nitrator again and reacted 30 minutes, takes out the product compartment analysis.
This benzene total conversion rate of implementing to be obtained is 98.93mol%, and the selectivity of oil of mirbane is 99.43mol%.
Relatively can learn with the result of embodiment 1 and 2, under near the stoichiometric reaction condition, the microreactor service temperature is increased to 80 ℃, part nitric acid may decompose, the available nitric acid quantity not sufficient of benzene causes the transformation efficiency of benzene that reduction is arranged slightly, but total influence and not very big, synthetic high-purity product oil of mirbane in this combination nitration processes method, need not the reactor temperature control, can start and the realization adiabatic nitration at normal temperature.
Although in above illustrating, stated the present invention and result of implementation thereof in detail; but be to be understood that; described details only is used to illustrate; this area professional and technical personnel is in the disclosed technical scope of the present invention; can understand conversion or the replacement expected; all should be encompassed in of the present invention comprising within the scope, therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. oil of mirbane synthetic method is characterized in that: the benzene mixed acid nitrification process is united in microreactor and stirring reactor and is finished, and process is as follows,
1) benzene and nitric acid and vitriolic nitration mixture pump into microreactor simultaneously, carry out pre-mixing in the microchannel, and carry out the one-stage nitration reaction.Wherein the nitration mixture mass concentration is a nitric acid 8～30%, sulfuric acid 50～80%, water 10～25%; The mol ratio of charging nitric acid and benzene is 0.9-1.2.This moment, the benzene transformation efficiency was 15～75%, and the mononitro-benzene selectivity is greater than 99.8%;
2) product from one-stage nitration reaction flows directly into the stirring tank nitrator, stirs 10～30 minutes down in normal pressure, finish react oil of mirbane.
2. according to the described synthetic method of claim 1, it is characterized in that: described nitration mixture mass concentration is a nitric acid 13～20%, sulfuric acid 60～70%, water 15～20%
3. according to the described synthetic method of claim 1, it is characterized in that: the mol ratio of described charging nitric acid and benzene is 1.0-1.05.
4. according to the described synthetic method of claim 1, it is characterized in that: the liquid hourly space velocity LHSV of described microreactor is 10
2～10
5h
-1Following operation, working pressure is 0.05～0.5MPa.
5. according to the described synthetic method of claim 1, it is characterized in that: the liquid hourly space velocity LHSV of described microreactor is 10
3～10
4h
-1Following operation.
6. according to the described synthetic method of claim 1, it is characterized in that: the thermal insulation at normal temperatures of mixed acid nitrification process is carried out, and temperature of reaction is by the decision of nitration reaction heat, and stirred-tank reactor does not have temperature control unit.
7. one kind in order to realize the isolated plant of the described method of claim 1, and it is made of microreactor polyphone stirred-tank reactor, it is characterized in that:
Described microreactor comprises, 1. two blocks of shroudings and a slice microchannel plate at least; 2. be positioned at least three microchannels on the microchannel plate, wherein at least two intake vents, and at least one reaction channel that links to each other with intake vent; 3. at least one intake vent and reaction channel are in the plane; 4. two imports that are connected with intake vent respectively, and an outlet that is connected with reaction channel; 5. be positioned at up and down and can be provided with control and measure the thermocouple jack that temperature is used on the shrouding.
8. according to the described isolated plant of claim 7, it is characterized in that: the import microchannel of described microreactor can be consistent with the microchannel characteristic dimension, also can be different; Every intake vent can be provided with branch, and when intake vent was established the branch of one or more, branched bottom linked to each other with the higher level microchannel with arc-shaped structure, and the equivalent diameter size of microchannel can successively decrease step by step, and the amplitude of successively decreasing is 0-80%, 0 expression consistent size; Angle between at least two intake vents that link to each other with reaction channel can be arbitrarily angled; Hydraulic diameter 0.1～the 2mm of reaction channel, length 0.2～50cm, intake vent add that the distance of exit passageway accounts for 1/3～2/3 of total distance between import and outlet.
9. according to the described isolated plant of claim 8, it is characterized in that: the angle between described at least two intake vents that link to each other with reaction channel is 0～180 °; Hydraulic diameter 0.3～the 1.0mm of reaction channel, length 2～20cm.
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|---|---|---|---|
| CN 200810011998 CN101613285B (en) | 2008-06-25 | 2008-06-25 | Synthetic method and special equipment for nitrobenzene |
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