CN203389621U - Segmented rapid cooling fixed bed reactor - Google Patents
Segmented rapid cooling fixed bed reactor Download PDFInfo
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- CN203389621U CN203389621U CN201320273914.6U CN201320273914U CN203389621U CN 203389621 U CN203389621 U CN 203389621U CN 201320273914 U CN201320273914 U CN 201320273914U CN 203389621 U CN203389621 U CN 203389621U
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Abstract
The utility model discloses a segmented rapid cooling fixed bed reactor. The reactor comprises a reactor cylinder body, more than two segments of a catalyst bed, more than two groups of heat exchange tubes, a reaction raw material inlet and a reaction raw material outlet, wherein the more than two segments of the catalyst bed are arranged in the reaction cylinder body along the flowing direction of reactant in a segmented manner; the more than two groups of heat exchange tubes are respectively arranged inside each segment of the catalyst bed; each group of heat exchange tubes comprises a cooling medium inlet and a cooling medium outlet. The reactor disclosed by the utility model can realize excellent heat exchange effect, and is convenient for filling and exchange operations of catalyst.
Description
Technical field
The utility model belongs to petrochemical industry and coal chemical technology, is specifically related to a kind of segmented chilling fixed bed reactors.By catalyst, the form with the bed of segmentation is arranged between shell of reactor and heat exchanger tube reactor of the present utility model, has improved the space utilization efficiency of reactor, increases loaded catalyst, thereby improves reactor production capacity.Meanwhile, the utility model is provided with heat-exchanger rig in each bed, and carries out chilling between each section of beds, has significantly improved overall heat exchange effect.
Background technology
Ethylene glycol is the important source material of PET industry, and the production of China's polyester is in recent years fast-developing, and the demand of ethylene glycol is rapid expanding thereupon also.The main method of industry synthesizing glycol is first through petroleum path, to produce ethene, then ethene is oxidized and produces oxirane, finally oxirane is carried out to non-catalytic hydration reaction and obtains ethylene glycol.Yet along with the minimizing day by day of petroleum resources in world wide, the prospect of the technique that the ethene of take is raw material synthesizing glycol aspect cost of material and reliability of source is increasingly severe.For this reason, people start to pay close attention to the technology path that other produce ethylene glycol, to alleviating the problems referred to above.The carbon monoxide of wherein take has advantages of that through the technique of oxalate intermediate product hydrogenation synthesizing of ethylene glycol step is simple, production efficiency is high as raw material, and its raw material carbon monoxide can derive from the raw material that coal, natural gas, living beings etc. contain carbon, hydrogen resource, can alleviate largely the dependence of ethylene glycol industry to oil.
The technique that the carbon monoxide of take is prepared ethylene glycol as raw material comprises two-step reaction.
First step reaction is to prepare oxalate by carbon monoxide, for example dimethyl oxalate.For example, carbon monoxide, under the effect of catalyst, reacts oxalic dimethyl ester and NO with methyl nitrite, and this reaction is called as coupling reaction, shown in formula specific as follows (I):
2CO+2CH
3ONO=(COOCH
3)
2＋2NO (I)
Coupling reaction generates subsequently NO and methyl alcohol and O
2reaction generates methyl nitrite, is called regenerative response, shown in formula specific as follows (II):
2NO+2CH
3OH+1/2O
2=2CH
3ONO+H
2O (II)
The methyl nitrite generating returns to coupling process and recycles.Therefore, the net reaction of first step reaction is suc as formula shown in (III):
2CO+1/2O
2+2CH
3OH=(COOCH
3)
2+H
2O (III)
In second step reaction, dimethyl oxalate (DMO) is carried out to hydrogenation to prepare ethylene glycol.Specifically, Hydrogenation of Dimethyl Oxalate is a cascade reaction, and first DMO hydrogenation generates intermediate product methyl glycollate (MG), MG repeated hydrogenation generating glycol, and on the whole, it reacts as shown in the formula shown in (IV):
(COOCH
3)
2＋4H
2=(CH
2OH)
2+2CH
3OH (IV)
Above-described two-step reaction carries out respectively in CO synthesis of oxalate reactor and oxalate hydrogenation device.These two reactions are strong exothermal reaction, need in course of reaction, shift out in time reaction heat, prevent that catalysqt deactivation and side reaction from occurring.
For this technique, prior art adopts calandria type fixed bed reactor conventionally, loading catalyst in tubulation, and tubulation passes into cooling medium outward, by tubulation wall, shifts out reaction heat.But the defect of this type of reactor is, tubulation inner catalyst filling efficiency is low, and reactor cost is high, is limited by shell-and-tube reactor processing and manufacturing and traffic condition restriction simultaneously, and reactor is difficult to amplify, and the diameter of single reactor is less than 5 meters conventionally.The production capacity of single like this reactor cannot further improve.In the art, by raw materials such as coals, prepare carbon monoxide, and then through the common minimum 200,000 tons of ethylene glycol of annual output that will reach of production scale of above-mentioned technique synthesizing glycol, can realize certain economic benefit by carbon monoxide, ethylene glycol output for such scale, need a plurality of calandria type fixed bed reactors in parallel, significantly improved equipment investment cost, and floor space is very large, operation is also inconvenient.
Meanwhile, every shell-and-tube reactor generally includes ten thousand above tubulations, in these tubulations one by one loading catalyst be a very arduousness job for time and effort consuming, and very high for Catalyst packing quality requirement.If cannot guarantee all tubulation Catalyst packing homogeneous, must make reaction raw materials more by a certain part tubulation, and other tubulation is in non-effective reactiveness, can reduce thus the overall utilization ratio of reactor catalyst.
Therefore, those skilled in the art still wish to develop a kind of reactor, both can improve reactor diameter, increase separate unit reactor production capacity, and Catalyst packing is more convenient again, can shift out in time reaction heat again simultaneously, in realization response device, temperature is controlled.
Utility model content
For the above-mentioned problems in the prior art, the inventor has carried out deeply research widely, has developed a kind of efficient segmentation chilling fixed bed reactors.
The utility model relates to a kind of segmentation chilling fixed bed reactors, and described reactor comprises: reactor shell, the more than two sections beds arranging with the form of segmentation along the direction of reaction stream flow within described reactor shell; Between each beds, on described reactor shell, be provided with at least one chilling agent entrance.
In an embodiment of the present utility model, described reactor comprises 2-10 section beds, preferably includes 2-6 section beds, more preferably comprises 2-3 section beds.
In another embodiment of the present utility model, this reactor also comprises the heat exchanger tube being separately positioned within described every section of beds, and every group of heat exchanger tube comprises respectively cooling medium inlet and cooling medium outlet.
In another embodiment of the present utility model, within described heat exchanger tube is arranged on every section of beds in the following way: heat exchanger tube arranges in triangle bending mode, heat exchanger tube arranges in U-bend folding mode, or heat exchanger tube arranges so that spiral form is crooked, and the above-mentioned combination that form is set.
In another embodiment of the present utility model, each beds bottom of this reactor is provided with sieve plate, is provided with sieve aperture on sieve plate, and sieve diameter is less than the diameter of the catalyst microspheres of filling.
In another embodiment of the present utility model, between adjacent beds, be provided with premix space, by described chilling agent entrance, chilling agent is introduced in this premix space.
In another embodiment of the present utility model, the height in described premix space is reactor diameter 0.05～3.0 times, preferably 0.1～1.0 times.
In another embodiment of the present utility model, chilling agent entrance is connected with outside chilling agent feeding device.
In another embodiment of the present utility model, this reactor also comprises reaction raw materials import, reacting product outlet, the condenser being connected with reacting product outlet, the gas-liquid separator being connected with condenser, and described chilling agent entrance is connected with gas-liquid separator.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that comprises the utility model reactor of three sections of beds.
Fig. 2 is one of the utility model schematic diagram preferred embodiment, and wherein chilling agent is from reaction system itself.
Accompanying drawing number
10 reactor shell 20 reaction raw materials imports
30 reacting product outlet 40 first paragraph beds
50 the 3rd section of second segment beds 60 beds
70 sieve plate 72 Catalyst packing Gao interfaces
80 heat exchanger tube 82 cooling medium inlets
84 cooling mediums export 100 chilling agent entrances
120 premix space 200 condensers
201 gas-liquid separator 202 gaseous products
203 liquid-phase products 204 that reclaim are back to the liquid-phase product of system.
The specific embodiment
" scope " disclosed herein is with the form of lower limit and the upper limit.Can be respectively one or more lower limits, and one or more upper limit.Given range limits by a selected lower limit and a upper limit.Selected lower limit and the upper limit define the border of special scope.All scopes that can limit by this way comprise with capable of being combined, and any lower limit can be combined to form a scope with any upper limit.For example, for special parameter, listed the scope of 60-120 and 80-110, be interpreted as that the scope of 60-110 and 80-120 also expects.In addition, if the minimum zone value 1 and 2 of listing, and if listed maximum magnitude value 3,4 and 5, scope below can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the utility model, unless there are other explanations, number range " a-b " represents that the breviary that a closes to the arbitrary real array between b represents, wherein a and b are real numbers.For example number range " 0-5 " represents all to have listed the whole real numbers between " 0-5 " herein, and " 0-5 " just the breviary of these combinations of values represents.
If do not particularly not pointed out, this description term " two kinds " used refers to " at least two kinds ".
In the utility model, if not special explanation, all embodiments mentioned in this article and preferred embodiment can be combined to form new technical scheme mutually.
In the utility model, if not special explanation, all technical characterictics mentioned in this article and preferred feature can be combined to form new technical scheme mutually.
In the utility model, if not special explanation mentioned in this article can sequentially be carried out in steps, also can carry out at random, but preferably in sequence.For example, described method comprises step (a) and (b), represents that described method can comprise in sequence step (a) and (b), also can comprise in sequence step (b) and (a).For example, describedly mention described method and also can comprise step (c), represent that step (c) can random order join described method, for example, described method can comprise step (a), (b) and (c), also step (a), (c) and (b) be can comprise, step (c), (a) and (b) etc. also can be comprised.
In the utility model, if not special explanation, " comprising " mentioned in this article represents open, can be also closed.For example, described " comprising " can represent to comprise other elements of not listing, also can only comprise the element of listing.
In prior art by Catalyst packing in the many tubulations that are set up in parallel, and make refrigerant circulation flow to remove heat of reaction outward at tubulation.As described above, this kind arranges form and can cause consersion unit to be difficult for amplifying, and production capacity is low, and catalyst is filled time and effort consuming and easily filled the problems such as inhomogeneous.
For above problem, the utility model has adopted following way: within a plurality of beds are set directly to reactor shell in the mode of segmentation successively along reaction logistics flow direction, and within heat exchanger tube is arranged on to each beds, cooling medium is flow through in described heat exchanger tube.By above way, the utility model has saved time and effort consuming and the harsh operation to catalyst filling in tubulation of technological requirement, and reactor of the present utility model can carry out scale amplification as required easily, adapts to different production-scale demands.
As shown in Figure 1, these fixed bed reactors comprise reactor shell 10, reaction raw materials import 20, reacting product outlet 30.In reactor shell 10, be provided with a plurality of beds: first paragraph beds 40, second segment beds 50 and the 3rd section of beds 60, each beds 40,50,60 bottoms are respectively arranged with sieve plate 70, beds inside is respectively arranged with heat exchanger tube 80, and cooling medium entrance 82 and cooling medium outlet 84.Wherein sieve plate 70 has the sieve aperture that diameter is less than 5 millimeters, for example sieve diameter is 1 millimeter, the effect of sieve plate 70 is support catalyst beds, by sieve aperture, gaseous state and liquid material in reactor can be flowed between each beds along logistics direction simultaneously.
The diameter of the catalyst microspheres of filling is more preferably greater than the diameter of sieve aperture in described beds, be for example 5 millimeters or more than.Preferably, when loading catalyst, on sieve plate, lay the spheroidal particle that one deck diameter is greater than catalyst microspheres, magnetic ball for example, its diameter can for 15 millimeters or more than.The object arranging is like this to prevent that catalyst from dropping out from sieve plate, affects the overall performance of catalyst, or causes the pollution in space.Preferably, inner at beds, in the space between sieve plate 70 and heat exchanger tube 80, magnetic ball and catalyst are laid in the mode of successively separating, one deck magnetic ball and one deck catalyst are arranged alternately.After laying completes, the loading height of beds 40,50,60 (being that sieve plate 70 is to the distance at corresponding Catalyst packing Gao interface 72) is 1 times to 1.5 times of heat exchanger tube height, be preferably 1.05 times to 1.3 times of heat exchanger tube height, most preferably be 1.1 times to 1.2 times of heat exchanger tube height.
Preferably, between two adjacent beds, for example, between the Catalyst packing Gao interface 72 of the sieve plate 70 of first paragraph beds 40 and second segment beds 50, be provided with premix space 120.In premix space 120, be provided with at least one chilling agent entrance 100, be used for spraying into chilling agent in reaction logistics.In premix space 120, the lower chilling agent material higher with the temperature that is passed down through sieve plate 70 outflows by first paragraph beds 40 of temperature spraying into by chilling agent entrance 100 fully mixes, thereby make material have sufficient space to reduce temperature, promote the uniformity of reactor temperature, then make the uniform reaction mass of temperature enter next section of beds to react.The height in premix space 120 is relevant with reactor diameter, is 0.05-3.0 times of reactor diameter, and preferably, the 0.1-1.0 that the height in premix space 120 is reactor diameter doubly.For example, for the tower of 10 meters of diameters, the height in premix space is can be 1-10 rice, and for the tower of 0.1 meter of diameter, the height in premix space can be 10-300 millimeter.One preferred embodiment in, described chilling agent entrance is provided with shower nozzle, described shower nozzle can have arbitrary structures well known in the art, by chilling agent atomization, then sprays in described reactor.
In the embodiment shown in Fig. 1, chilling agent is from outside, its composition is corresponding to participating in the reactant of reaction or product and the accessory substance of reaction generation in reaction or reacting the required components such as solvent, for example, for (i) step reaction by carbon monoxide and nitrous acid dimethyl ester synthesizing dimethyl oxalate, described chilling agent can be the methyl alcohol that additionally provides from outside feeding mechanism or dimethyl oxalate etc.
In the embodiment shown in Fig. 2, chilling agent is from reaction system, specifically as shown in Figure 2, the product that reacting product outlet 30 flows out enters gas-liquid separator 201 after condenser 200, gaseous products 202 is wherein collected or is emptying, and a part of liquid-phase product 203 is used as liquid product and reclaims, and another part liquid-phase product 204 is introduced into chilling agent entrance 100, as chilling agent, reenter in reaction system.
Described heat exchanger tube can wriggle and extend with the form of any appropriate in described beds, and for example triangle bending mode, U-bend are rolled over mode, spirality bending mode etc., and the combination of these shapes.According to factors such as the size of reactor, concrete catalyst type, reaction process condition, reaction scale, in single reactor, can comprise at least two-stage catalytic agent bed, for example can comprise 2-20 section, or 2-10 section, or 2-8 section, or 2-6 section, or 2-3 section beds.In an embodiment of the present utility model, described reactor shell has substantially invariable shape and size along the flow direction of reaction logistics, and the size of each section of beds is also essentially identical, is wherein filled with the catalyst of equivalent.In another embodiment of the present utility model, along the flow direction of reactor stream, the size of described reactor shell reduces gradually or increases gradually, and the height of each section of beds also can reduce gradually or increase gradually.
Reactor of the present utility model can be for the known in the art or reaction that can be undertaken by fixed bed of exploitation in the future arbitrarily, when described reaction is exothermic reaction, cooling matrix flows through in described heat exchanger tube, sprays into chilling agent by chilling agent entrance simultaneously; When carried out reaction is the endothermic reaction, heat medium flows through in described heat exchanger tube, by chilling agent entrance, spray into liquid or the gas stream of heating simultaneously, can also various heaters be set in addition along described reactor shell, such as resistance heating wire, pharoid or inductance coil etc.
Of the present utility model one preferred embodiment in, with reactor of the present utility model, carry out the reaction by carbon monoxide synthesizing glycol.As described above, this reaction comprises two strong heat release steps, and these two reactions steps are carried out respectively independently in reactor of the present utility model.For for simplicity, with the reactor of cause carbon monoxide synthesis of oxalate, be denoted as the first reactor, with the reactor of cause oxalate synthesizing glycol, be denoted as the second reactor, for carried out reaction, in these reactors, adopt respectively corresponding catalyst and process conditions setting.According to concrete technique needs, in fact described the first reactor and the second reactor can be respectively the set of reactors that a plurality of reactors described in the utility model are arranged in parallel formation, or also other reaction unit can be set between described the first reactor and the second reactor.As example, the raw material nitrites that the utility model is used is methyl nitrite, synthetic intermediate product oxalate is dimethyl oxalate, but described nitrites can be also nitrous ether (ethyl nitrite), propyl nitrite, butyl nitrite or its mixture, described oxalate can be also diethy-aceto oxalate, dipropyl oxalate, dibutyl oxalate or its mixture.That is to say, being applicable to nitrites of the present utility model is methyl nitrite, nitrous ether (ethyl nitrite), propyl nitrite, butyl nitrite or its mixture, and oxalate described in the utility model comprises dimethyl oxalate, diethy-aceto oxalate, dipropyl oxalate, dibutyl oxalate or its mixture.
Accompanying drawing of the present utility model and following embodiment have shown the reactor that comprises three sections of beds, but in actual operation, can according to circumstances increase arbitrarily or reduce the quantity of beds, or many reactors that are filled with same catalyst bed are together in series and are operated.
The carbon monoxide using as raw material can be derived from various sources, the synthesis gas of for example being prepared by coal, the carbon monoxide producing as accessory substance in coal liquefaction or petroleum cracking refining process, carbon monoxide producing as accessory substance in the carbon monoxide producing from natural gas and biological substance fermentation or oxidation and other industrial synthetic process etc.Different according to the concrete source of carbon monoxide, wherein can also not comprise and can cause to reaction of the present utility model other gas components of negative effect, for example nitrogen, carbon dioxide, methane, rare gas (as argon gas), nitrogen oxide and other micro-gaseous impurities etc., in course of reaction described in the utility model, these so-called other gas components are only to pass through in reaction system, and significant reaction can not occur.Of the present utility model one preferred embodiment in, described carbon monoxide is the synthesis gas prepared by coal, natural gas or biological substance through obtaining except hydrogen, except oxygen and dehydrating operations.
Method of the present utility model comprises three steps: the intermediate product stream that (i) carbon monoxide and methyl nitrite reaction preparation comprise dimethyl oxalate; (ii) from described intermediate product stream separation of dimethyl oxalate; (iii) described dimethyl oxalate is carried out to hydrogenation, thereby make ethylene glycol product.
For described step (i), the admixture of gas that comprises carbon monoxide and methyl nitrite is introduced in the first reactor as shown in Figure 1, it is contacted with the solid catalyst in beds, form the intermediate product stream that comprises dimethyl oxalate.When carrying out above-mentioned reaction, cooling matrix is flow through from described heat exchanger tube, by controlling temperature and the flow velocity of cooling medium, make to keep in the first reactor required temperature.Described cooling matrix can be any cooling fluid known in the art, such as water, freon, liquefied ammonia, various supercritical fluids etc.Of the present utility model one preferred embodiment in, the cumulative volume of the described gaseous mixture that comprises carbon monoxide and nitrites of take is benchmark, in the described gaseous mixture that comprises carbon monoxide and nitrites, the total content of carbon monoxide and nitrites can be 40-100 volume %, wherein the volume ratio of carbon monoxide and nitrites is 20:1 to 1:20, be preferably 10:1 to 1:10, more preferably 5:1 to 1:5.In described gaseous mixture, except carbon monoxide and nitrites, can also not comprise and can cause to reaction other gas components of negative effect, for example nitrogen, carbon dioxide, methane, argon gas, nitrogen oxide and their mixture.Reaction temperature in described the first reactor is 100-155 ℃, and pressure is 0.2-5MPa, preferably 0.3-0.6MPa.In three beds of described the first reactor, use the identical simple substance or the compound that load on inert carrier Shang platinum group metal, described inert carrier be selected from aluminium oxide, kaolin, zeolite, silica, diatomite, activated carbon, bead, and composition thereof, described platinum group metal is selected from ruthenium, rhodium, palladium, platinum, iridium, osmium; More preferably, described platinum group metal is palladium; With the weighing scale of described the first catalyst, wherein the simple substance of platinum group metal or the content of compound are 0.1-5 % by weight.
In reaction, also by described chilling agent entrance 100, chilling agent is sprayed in described the first reactor, it is mixed, to control better the temperature of described reaction system with reacting logistics.One preferred embodiment in, product, accessory substance or the solvent etc. that generate in the first reactor are depended in the chilling agent of using in described the first reactor, for example, can be dimethyl oxalate, diethy-aceto oxalate, dipropyl oxalate, dibutyl oxalate, methyl alcohol, ethanol, propyl alcohol, butanols or its mixture, prerequisite be can not cause negative effect to reaction.Described chilling agent can also can need only its cryogenic temperature higher than the freezing point of this chilling agent in the freezing state lower than zero degree in normal temperature state, makes described chilling agent keep being in a liquid state.One preferred embodiment in, use liquid dimethyl oxalate as chilling agent.
After synthesizing dimethyl oxalate, carry out step (ii), the intermediate product stream that comprises dimethyl oxalate is drawn from described the first reactor, by condensation separation, obtain dimethyl oxalate.Reaction end gas after separated dimethyl oxalate can further be regenerated and reclaimer operation, thereby recovery methyl nitrite, imported in described the first reactor and recycle, remaining gas drains in atmosphere after directly discharging or be further processed as waste gas as components such as nitrogen, methane, argon gas, carbon monoxide, nitric oxides.
In step (iii), the dimethyl oxalate that above step (ii) separation is obtained is sent in the second reactor together with hydrogen, described the second reactor equally as shown in Figure 1, comprise three sections of beds, under the effect of described catalyst, by the hydrogenation of dimethyl oxalate, prepare ethylene glycol product.In reaction, cooling matrix is flow through from heat exchanger tube, the second reactor is remained on to required reaction temperature.Described cooling medium can be identical with the cooling medium that above the first reactor is used, and also can use different cooling matrix, and need to carry out concrete selection to the temperature of cooling medium and flow velocity according to concrete technique.The catalyst of filling in described beds is the metal component loading on inert carrier, described inert carrier be selected from aluminium oxide, kaolin, zeolite, silica, diatomite, activated carbon, bead, and composition thereof, described metal component is selected from metallic copper, cuprous oxide, mantoquita, silver salt, ruthenium salt, chromic salts and their mixture; The liquid hourly space velocity (LHSV) of described oxalate is 0.2-0.7g/mlh, and the pressure in described the second reactor is 0.8-3.0 MPa, and temperature is 200-250 ℃, and hydrogen gas space velocity is 4000-8000 hour
-1.
In reaction, also by described chilling agent entrance 100, chilling agent is sprayed in described the second reactor, it is mixed, to control better the temperature of described reaction system with reacting logistics.One preferred embodiment in, product, accessory substance or the solvent etc. that generate in the second reactor are depended in the chilling agent of using in described the second reactor, for example, can be ethylene glycol, oxalate, methyl alcohol, ethanol, propyl alcohol, butanols, and composition thereof, prerequisite is can not cause negative effect to reaction.Described chilling agent can also can need only its cryogenic temperature higher than the freezing point of this chilling agent in the freezing state lower than zero degree in normal temperature state, makes described chilling agent keep being in a liquid state.One preferred embodiment in, use the methyl alcohol of normal temperature as chilling agent.
In the mode of example, describe preferred embodiment more of the present utility model in the following embodiments.But those skilled in the art can carry out suitable change or combination to it, thereby implement the utility model.
Embodiment
In following embodiment, unless otherwise indicated, the various reagent that use are for analyzing alcohol.The CO unstripped gas using carries out routine except hydrogen, except obtaining after oxygen and dehydration to industrial synthesis gas, wherein the volume content of CO is 98%, surplus is that nitrogen, carbon dioxide, methane and argon gas etc. can not affect the component of reaction, in described CO unstripped gas, the content of objectionable impurities is as follows: sulfide≤1.15ppm, NH
3≤ 200ppm, H
2≤ 100ppm, O
2≤ 1000ppm, H
2o≤100ppm.
Synthesizing of embodiment 1 dimethyl oxalate
Use in this embodiment reactor as shown in Figure 1, this reactor diameter 0.1m, high 2.5m, wherein arranges three sections of beds, according to order from top to bottom, each section of bed height is respectively 0.5m, 0.5m, 1m, wherein fills the palladium catalyst of 9.38 kilograms of alumina loads, in described catalyst, the content of palladium is 1%, and granularity is 5mm.Interval between each section of beds (being the height in premix space) 300mm.CO unstripped gas and nitrites is mixed with the volume ratio of 2:1, with 3000hr
-1air speed from the reactant entrance of reactor head, introduce, successively by described three sections of beds.Pressure in described reactor is 0.4MPag.Between described three sections of beds, be provided with two chilling agent entrances, in course of reaction respectively with the flow of 0.04l/min to the dimethyl oxalate that sprays into normal temperature in reactor, the described dimethyl oxalate using as chilling agent is to be provided by the dimethyl oxalate feeding mechanism beyond reaction system.Three groups of heat exchanger tubes arrange with U-shaped structure, and conventional condensed water flows through therein, are used for removing the heat that reaction produces, and it is 150 ℃ that reaction system is remained on to reaction temperature.Gas stream after reaction is derived from the reactor product outlet of reactor bottom.Sample with GC-MS and characterize herein, calculate methyl nitrite (conversion ratio be 60%, the concentration of dimethyl oxalate is 6.3%, is selectively 99.5%.
The separation of embodiment 2 dimethyl oxalates
In this embodiment, gas stream that embodiment 1 is made imports condensation separation tower, in temperature, is to isolate liquid dimethyl oxalate under 75 ℃, the pressure condition that is 0.4Mpag.
The hydrogenation of embodiment 3 dimethyl oxalates
In this embodiment, use reactor as shown in Figure 1, this reactor diameter 0.1m, high 2.5m, wherein arranges three sections of beds, according to order from top to bottom, each section of bed height is respectively 0.5m, 0.5m, 1m, wherein fill the cuprous oxide catalysis agent of 5.966 kilograms of alumina loads, described catalyst grain size is 5mm.Interval between each section of beds (being the height in premix space) 300mm.The dimethyl oxalate that embodiment 2 is obtained is dissolved in methanol solution, obtains the methanol solution that concentration is 50 % by weight.Use high-pressure metering pump that this methanol solution is injected to gasifier, then the gaseous matter of gained is inputted described reactor from the reactant entrance of reactor head.The liquid hourly space velocity (LHSV) of wherein said dimethyl oxalate is 0.5g/mlh.Meanwhile, by hydrogen with 5000hr
-1air speed from the reactant entrance of reactor head, input described reactor.Make described reactant dimethyl oxalate and hydrogen successively by described three sections of beds.Pressure in described reactor is 2.5MPag.Between described three sections of beds, be provided with two chilling agent entrances, in course of reaction respectively with the flow of 0.05l/min to the methyl alcohol that sprays into normal temperature in reactor, the described methyl alcohol as chilling agent is that the methyl alcohol feeding mechanism by reaction system outside provides.Three groups of heat exchanger tubes arrange with U-shaped structure, and conventional condensed water flows through therein, are used for removing the heat that reaction produces, and it is 210 ℃ that reaction system is remained on to reaction temperature.Gas stream after reaction is derived from the reactor product outlet of reactor bottom.Sample with GC-MS and characterize herein, the conversion ratio that calculates dimethyl oxalate is 99.5%, and the concentration of ethylene glycol is 1.7%, is selectively 92%.
Claims (12)
1. segmentation chilling fixed bed reactors, described reactor comprises: reactor shell (10), it is characterized in that, the more than two sections beds (40 arranging with the form of segmentation along the direction of reaction stream flow within described reactor shell (10), 50,60); Between each beds, on described reactor shell (10), be provided with at least one chilling agent entrance (100).
2. segmentation chilling fixed bed reactors as claimed in claim 1, is characterized in that, described reactor comprises 2-10 section beds.
3. segmentation chilling fixed bed reactors as claimed in claim 1, is characterized in that, described reactor comprises 2-6 section beds.
4. segmentation chilling fixed bed reactors as claimed in claim 1, is characterized in that, described reactor comprises 2-3 section beds.
5. segmentation chilling fixed bed reactors as claimed in claim 1, it is characterized in that, this reactor also comprises and is separately positioned on described every section of beds (40,50,60) heat exchanger tube within (80), every group of heat exchanger tube comprises respectively cooling medium inlet (82) and cooling medium outlet (84).
6. segmentation chilling fixed bed reactors as claimed in claim 5, it is characterized in that, within described heat exchanger tube (80) is arranged on every section of beds in the following way: heat exchanger tube arranges in triangle bending mode, heat exchanger tube arranges in U-bend folding mode, or heat exchanger tube arranges so that spiral form is crooked, and the above-mentioned combination that form is set.
7. segmentation chilling fixed bed reactors as claimed in claim 1, is characterized in that, each beds bottom of this reactor is provided with sieve plate (70), is provided with sieve aperture on sieve plate, and sieve diameter is less than the diameter of the catalyst microspheres of filling.
8. segmentation chilling fixed bed reactors as claimed in claim 1, it is characterized in that, between adjacent beds, be provided with premix space (120), by described chilling agent entrance (100), chilling agent is introduced in this premix space (120).
9. segmentation chilling fixed bed reactors as claimed in claim 8, is characterized in that, the height in described premix space (120) is reactor diameter 0.05～3.0 times.
10. segmentation chilling fixed bed reactors as claimed in claim 8, is characterized in that, the height in described premix space (120) is reactor diameter 0.1～1.0 times.
11. segmentation chilling fixed bed reactors as claimed in claim 1, is characterized in that, chilling agent entrance (100) is connected with outside chilling agent feeding device.
12. segmentation chilling fixed bed reactors as claimed in claim 1, it is characterized in that, this reactor also comprises reaction raw materials import (20), reacting product outlet (30), the condenser (200) being connected with reacting product outlet, the gas-liquid separator (201) being connected with condenser, and described chilling agent entrance (100) is connected with gas-liquid separator (201).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098422A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Method for isomerizing 5-vinyl-2-norbornylene to produce 5-ethylene-2-norbornylene |
| CN104162383A (en) * | 2013-05-17 | 2014-11-26 | 上海碧科清洁能源技术有限公司 | Sectionalized quenching fixed bed reactor and application method thereof |
| CN104324671A (en) * | 2014-09-23 | 2015-02-04 | 中国科学院广州能源研究所 | Modularly designed fixed bed reaction unit and assembly method thereof |
| CN106179149A (en) * | 2016-08-22 | 2016-12-07 | 中国神华能源股份有限公司 | The reaction unit of methanol-to-olefins |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104162383A (en) * | 2013-05-17 | 2014-11-26 | 上海碧科清洁能源技术有限公司 | Sectionalized quenching fixed bed reactor and application method thereof |
| CN104098422A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Method for isomerizing 5-vinyl-2-norbornylene to produce 5-ethylene-2-norbornylene |
| CN104324671A (en) * | 2014-09-23 | 2015-02-04 | 中国科学院广州能源研究所 | Modularly designed fixed bed reaction unit and assembly method thereof |
| CN106179149A (en) * | 2016-08-22 | 2016-12-07 | 中国神华能源股份有限公司 | The reaction unit of methanol-to-olefins |
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