CN1634860A - Gas distributor in fluidized bed of aniline synthesis and aniline synthesis method - Google Patents
Gas distributor in fluidized bed of aniline synthesis and aniline synthesis method Download PDFInfo
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- CN1634860A CN1634860A CN 200410091353 CN200410091353A CN1634860A CN 1634860 A CN1634860 A CN 1634860A CN 200410091353 CN200410091353 CN 200410091353 CN 200410091353 A CN200410091353 A CN 200410091353A CN 1634860 A CN1634860 A CN 1634860A
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Abstract
The invention discloses a gas distributor and a method for synthesizing aniline in fluidized bed, which belongs to the field of chemical equipment and chemical materials preparing technology. The gas distributor comprises main pipe for transporting gas, branched pipe and ring conduit connected with the same, and nozzle arranged on the ring conduit capable of spraying gas up and down. The invention also discloses a method for vapor hydrogenation preparation of aniline from nitrobenzene by using said equipment, characterized by controlling the quantity of nozzles to adjust the temperature of gas distributor zone for controlling the quality of aniline. The invention can reduce the maximum and average temperature of gas distributor zone, reduce the coking on the catalyst, prolong the using time of catalyst, and improve the purity of aniline.
Description
Technical field
The invention belongs to chemical industry equipment and industrial chemicals technology of preparing scope, gas distributor and aniline synthesis method in particularly a kind of a kind of fluidized bed of aniline synthesis that is equipped with aniline by production by gas phase hydrogenation of nitrobenzene.
Background technology
Aniline is the very important Chemicals of a class.Along with the widespread use of urethane in fields such as construction industry, automobile, electrical equipment and wrapping material, the main raw material methyl vulcabond of urethane (being called for short MDI), the output that is got by the aniline preparation improves rapidly, causes increasing considerably of aniline consumption.Aniline is mainly used in the production of MDI and rubber ingredients at present, also can be used for agricultural chemicals, pigment dyestuff and field of medicaments etc., and the annual requirement in the world is about about 3,000,000 tons.
The method of suitability for industrialized production aniline has four kinds, i.e. oil of mirbane liquid-phase hydrogenatin method, oil of mirbane gas phase hydrogenation method, phenol ammoniation process and iron powder reducing method at present.Wherein the iron powder reducing method is owing to generate the second-rate of aniline, and is eliminated gradually.Phenol ammonification rule depends on the source of phenol strongly, and oil of mirbane liquid-phase hydrogenatin method catalyst system therefor is platinum or palladium catalyst, costs an arm and a leg and reclaims difficulty.And the oil of mirbane gas phase hydrogenation legal system that most of producers all adopt is equipped with aniline.Its ultimate principle is that oil of mirbane and hydrogen are heated to about 200 ℃, feeds fluidized-bed reactor, under the effect of metal load type catalyst (major part is a copper catalyst), generates aniline in the time of 220-320 ℃.After reactant gases goes out reactor, after condensation and dewatering, obtain the aniline crude product.Remove various organic impuritys through the refining operation that is equipped with then, obtain highly purified aniline product.
The key of this process is that requirement oil of mirbane will be transformed as far as possible, and it is little to generate the probability of other by product.The purity of aniline crude product could improve like this, and the load of back refining step reduces.The weight space velocity of oil of mirbane less than 0.3 gram oil of mirbane/gram catalyzer/hour and the mol ratio of hydrogen and oil of mirbane greater than 7 o'clock, temperature of reaction is the key factor that influences the generation and the oil of mirbane conversion of by product.When temperature of reaction was higher than 290 ℃, pyrolysis, coking or the autohemagglutination phenomenon of on-catalytic effect may take place in various organism, generates various impurity, and caused the catalyzer coking and active decline, thereby the transformation efficiency of oil of mirbane reduces.Preparing in the fluidized-bed reactor of aniline at present,,, reacting also the most violent so the concentration with oil of mirbane in the sparger district is the highest in whole reactor because reactor feed gas all is to enter in the fluidized-bed through the gas distributor that is located at reactor bottom.Because hydrogenation of chloronitrobenzene is a strong exothermal reaction (reaction heat is 543KJ/mol), so the heat of reaction that produces in the gas distributor district is huge, the temperature in this zone is the highest in the reactor.Board-like sparger for present employing, pipe distributor or awl hat type sparger, the hole of all jet-stream winds is substantially on same horizontal plane, a large amount of like this oil of mirbane can be sprayed into reactor simultaneously, makes temperature 270-295 ℃ of the sparger district about temperature 250-270 ℃ high 20 ℃ than the catalyzer emulsion zone on its top.When bad operation, the temperature in gas distributor district even can reach 310-330 ℃.At this time can generate many impurity, influence the purity of aniline product, and make catalyst carbon deposition and active decline.And at present these sparger forms of using can not be avoided the phenomenon of the big temperature rise that causes on the structure when bad operation.Prepare in the technology of aniline at the fluidized-bed that uses these spargers, in the bimestrial operational cycle, the content of the tarry material of macromole in the aniline crude product is at 100-300mg/kg, the content of oil of mirbane can surpass 100-200mg/kg, and the content of hexahydroaniline and hexalin can surpass 30-50mg/kg.Coking amount on the catalyzer is greater than 3.5-6%, and in the longer time, coking amount increases rapidly on the catalyzer, and the deactivation rate of catalyzer is accelerated.
Summary of the invention
The objective of the invention is deficiency at sparger technology in the existing preparation aniline device gas distributor and aniline synthesis method in a kind of fluidized bed of aniline synthesis are provided.It is characterized in that: the gas distributor in the described fluidized-bed is the gas distributor with different injection directions, 2 one-tenth direct-connected the connecing of Chui of being in charge of by the air inlet person in charge 1 and right-angled intersection, distribute 3 fens 1-10 circles of circulating line of air-flow and be in charge of 2 UNICOMs, dividing up and down on circulating line 3, both direction connects upward nozzle 4 and downward nozzle 5 respectively; Then, whole gas distributor is installed in the bottom of synthetic fluidized-bed.
Described upward nozzle or downward nozzle respectively are 1-20/m on reactor cross-section
2
Described upward nozzle is 1: 1～1: 8 with the quantity ratio of downward nozzle
The described method of utilizing said apparatus to prepare aniline comprises the steps:
1) will have upward nozzle 4 and the gas distributor of the nozzle 5 downwards fluidized-bed reactor of packing into, at catalyzer emulsion zone 10 inner member 9 and interchanger 11 are set, in the reactor expanding reach 13 on reactor top, cyclone type gas-solid separating device 14 is set, constitutes complete fluidized-bed reactor;
2) with median size be the metal load type catalyst of 45-300 micron from catalyst inlet 17 reactor of packing into, the static loading height of catalyzer be reactor diameter 2-10 doubly;
3) in interchanger 11, feed heating medium (comprising the supersaturation high-temperature steam, high temperature saturation water or high temperature inert gas), or the rare gas element of heat is fed reactor, make that temperature reaches 150-250 ℃ in the reactor; Feed hydrogen then, controlled temperature is reducing catalyst in 150-250 ℃ scope;
4) after the catalyst reduction fully, in reactor, feed the vaporizer of hydrogen and oil of mirbane through gas distributor; The mol ratio of control hydrogen and oil of mirbane is 7: 1～20: 1, the weight space velocity in the reactor be 0.1-0.3 restrain oil of mirbane/gram catalyzer/hour, the absolute pressure of reactor is 0.1-1.0MPa;
5) feed water coolant in the interchanger in being arranged on catalyzer emulsion zone 10 11, the temperature of control catalyst emulsion zone 10 is between 250-260 ℃;
6) the combined feed total feed flow of control hydrogen and oil of mirbane makes the actually operating gas speed in the reactor reach 0.1-0.9m/s; Behind the reactant gases process catalyzer emulsion zone 10, be converted into aniline, reaction product is discharged from reactor outlet 15 through gas-solid separating device 14 backs on reactor top.
Described metal load type catalyst is main active component with copper, and carrier is silicon-dioxide or aluminium sesquioxide, is expressed as Cu-SiO
2Or Cu-Al
2O
3
Behind catalyst deactivation, reclaim in the outlet 8 of reactor bottom, regenerate, add catalyzer continuously from catalyst inlet 17 simultaneously, the assurance process is moved continuously.
Main improvement of the present invention is that gas distributor has adopted and can compares with existing sparger technology to the nozzle of different directions jet flow stream, has the following advantages and beneficial effect:
(1) adopt simultaneously downwards with former sparger, upwards or simultaneously the nozzle (or jet hole) of side direction jet flow stream is compared simultaneously, the sparger that the present invention adopts has the nozzle downward and jet-stream wind that makes progress simultaneously, like this on the arbitrary cross section in the gas distributor district, particularly close on the cross section of jet orifice, the concentration of oil of mirbane reduces.Temperature in the sparger district is only higher 10～15 ℃ than the temperature in the typical catalyst emulsion zone, can be controlled in substantially below 270 ℃, reduced significantly organic compound thermo-cracking, autohemagglutination coking, benzene ring hydrogenation and with side reaction such as hydroxylation.
(2) since in the reactor temperature in each zone approaching, cause the suffered thermal stresses of catalyzer and improve before compare and reduce, thereby make catalyzer have higher activity and selectivity, transform the nitro benzo and generate aniline.
(3) coking on the catalyzer reduces, and under the overall constant situation of loading of catalyzer, can prolong life of catalyst 5～15%.The operating time that generates high-purity aniline (satisfying the MDI preparation requires) simultaneously prolongs 5～30%.Save the regenerative operation cost relatively, and improved the grade and the added value of product.
(4) temperature contrast of sparger and typical catalyst emulsion zone reduces, reduced the influence of thermal stresses to catalyst strength, it is broken that catalyzer is difficult for, can keep comparatively ideal size-grade distribution, the fluidization operation guarantees good gas-solid contact effect to the requirement of catalyst grain size in the reactor thereby satisfy.Total amount from reactor outlet race granules of catalyst that decrease, very trickle reduces simultaneously, can guarantee all the time that the overall load of catalyst in reactor is constant.After oil of mirbane enters reactor like this, be injected in simultaneously on two or more cross sections in sparger district, and spread and react.The situation that only is injected in a cross section with original all oil of mirbane is compared, nitro phenenyl concentration in the gas distributor zone on arbitrary cross section all decreases, correspondingly the exothermic heat of reaction amount reduces, and reaches the purpose that reduces top temperature and medial temperature in the gas distributor district.This technology has the hot spots temperature and the medial temperature that make in the sparger zone and descends, reduce with the close temperature difference mutually of catalyzer, make the interior temperature of integral reactor even, generate selectivity height, the purity height of aniline, coking reduces advantages such as prolongation in work-ing life on the catalyzer.
Description of drawings
Fig. 1 is the gas distributor form synoptic diagram in the aniline synthesizer: (a) be the vertical view of sparger; (b) be the vertical cross section of sparger; (c) be the vertical cross section of another kind of sparger distortion.
Fig. 2 is for having assembled the fluidized-bed reactor of the preparation aniline of gas distributor shown in Fig. 1 (b).
Fig. 3 is for having assembled the fluidized-bed reactor of the preparation aniline of gas distributor shown in Fig. 1 (c).
Embodiment
The deficiency that The present invention be directed to sparger technology in the existing preparation aniline device provides gas distributor and the aniline synthesis method in a kind of fluidized bed of aniline synthesis.Gas distributor in the described fluidized-bed is the gas distributor with different injection directions, be responsible for 1 and being in charge of 2 one-tenth and vertically being connected of right-angled intersection by air inlet, distribute 3 fens 1-10 circles of circulating line of air-flow and be in charge of 2 UNICOMs, connecting respectively at both direction about the branch on the circulating line 3 respectively is that 1-20 upward nozzle 4 and downward nozzle 5 are arranged on every square metre the cross section, and upward nozzle is 1 with the quantity ratio of downward nozzle: 1-1: 8; Then, whole gas distributor is installed in the bottom of synthetic fluidized-bed.
The oil of mirbane delivery nozzle during with the form rising of bubble and by the gas distributor district, exists the difference of climb like this.Can guarantee that the concentration the when concentration of oil of mirbane on arbitrary level cross-sectionn in gas distributor district all was injected in all oil of mirbane the distribution of same level cross-sectionn more simultaneously reduces.Can effectively reduce the heat of reaction that accumulates on arbitrary level cross-sectionn in the sparger like this, can make the temperature in the sparger district only higher 5～15 ℃ than the temperature in the catalyzer emulsion zone, the medial temperature in the gas distributor is no more than 270 ℃.In order to guarantee above-mentioned effective effect, the outlet of upward nozzle of the present invention is 200-1000mm with the mounting distance of the outlet of nozzle downwards equally.
Less for guaranteeing the bubble that initial air inlet forms, and guarantee that better gas contacts effect with solid turbulence state with gas-solid preferably, promote the conversion of oil of mirbane, the gas flow rate in the described main inlet pipe is 5～20m/s, and the pressure drop of pairing gas in main inlet pipe is less.Gas speed by nozzle of the present invention is 60～150m/s.
Below in conjunction with accompanying drawing 1 (a) (b) (c) further be illustrated to 3 couples of the present invention:
When reactant gases enter from the bottom of reactor air inlet be responsible for 1 with right-angled intersection, become Chui direct-connected connect be in charge of 2 after, enter the circulating line 3 (shown in Fig. 1 (a)) that distributes air-flow, then through upwards the nozzle 4 of jet-stream wind and the nozzle 5 of downward jet-stream wind enter reactor (shown in Fig. 1 (b), (c)) simultaneously.Inner member 10 and interchanger 11 are immersed in the catalyzer emulsion zone 9 fully, so just can give full play to the function of interchanger and member.Set up expanding reach 13 and gas solid separation system 14 on the top of reactor, gas solid separation system 14 is fixedly connected with reactor wall, simultaneously with the outlet of gas solid separation system and reactor head limit mutually, as the outlet 15 of reactor.The outlet 8 of setting up catalyst inlet 17 and decaying catalyst respectively in the middle part and the bottom of reactor.Can constitute complete fluidized-bed reactor like this.Catalyzer is entered reactor from catalyst inlet 17.In order to make catalyzer can all enter reactor, when adding catalyzer at reactor bottom reactant gases gas nitrogen or air from being responsible for 1 and be in charge of 2 and feed reactor through gas distributor, down loosening at less nitrogen of airshed or air, granules of catalyst enters reactor from catalyst inlet 17, is accumulated in catalyzer emulsion zone 9 (as Fig. 2, shown in Figure 3) naturally.After packing into catalyzer in the reactor, logical rare gas element is an anaerobic state with the gas displacement in the reactor.Be warming up to 150～250 ℃ during this period gradually, cut hydrogen then and carry out catalyst reduction.Gas speed control during reduction in the reactor guarantees that catalyzer is in fluidized state between 0.05～0.3m/s, avoid the local heap knot of catalyzer overstocked, causes the sintering of catalyst inactivation.Simultaneously 6 feed water coolant in interchanger 11 through entering the mouth, water coolant raises through interchanger 11 back temperature, becomes steam water interface and goes out interchanger 11 from exporting 7.Reduction temperature in the may command reactor is between 150～250 ℃ like this.Recovery time was at 3～40 hours.After reduction finishes, strengthen the inlet amount of hydrogen, reduce the inlet amount of rare gas element gradually, the gas in reactor all is hydrogen.When temperature of reactor is 220～250 ℃, the amount of hydrogen is increased to the process stipulation value.And through the person in charge 1 of reactor be in charge of 2 and in reactor, feed oil of mirbane, it is 7: 1～20: 1 until the mol ratio of hydrogen and oil of mirbane with gas distributor.Regulate the cooling water flow in the interchanger 11, make the medial temperature in the reactor remain on 250～270 ℃.Reactant is converted into aniline through catalyzer emulsion zone 9.Reaction product enters reactor expanding reach 13, enters cyclonic separator 14 from cyclone inlet 16, and goes out reactor from the outlet 15 of cyclonic separator.
In this process, the part catalyzer in the catalyzer emulsion zone 9 is carried by air-flow, enters reactor expanding reach 13, enters cyclonic separator 14 through dipleg 12 return catalizer emulsion zones 9 from cyclone inlet 16.
Behind the catalyzer complete deactivation, can draw off from reactor bottom by catalyst deactivation mouth 8.Catalyzer can be added in suitable period from catalyst inlet 17.
Above-mentioned metal load type catalyst is main active component with copper, and carrier is silicon-dioxide or aluminium sesquioxide, is expressed as Cu-SiO
2Or Cu-Al
2O
3
Exemplifying embodiment is below further specified the present invention.
Embodiment 1
React at as shown in Figure 2 the fluidizer that production by gas phase hydrogenation of nitrobenzene is equipped with aniline that is used for.The circulating line of a distribution of gas is set, and its diameter is 90% of a main tracheal diameter; Upward nozzle number on the control sparger is 1: 1 with the ratio of downward nozzle number, and the mounting distance of jet exit and upward nozzle outlet downwards is 200mm.Gas speed 5m/s in the main inlet pipe, the gas speed of jet exit is 100m/s.Charging is hydrogen and oil of mirbane, and mol ratio is 20: 1; Working pressure (absolute pressure) is 0.25MPa; Catalyzer (Cu-SiO
2) medial temperature of emulsion zone is 260 ℃, the medial temperature in gas distributor district is 265 ℃; Weight space velocity is 0.2 hour
-1, actual gas speed is 0.1m/s in the catalyzer emulsion zone.The content of oil of mirbane is 0.5mg/kg in the crude benzol amine in two months, and the content of hexalin and hexahydroaniline is respectively 10 and 8mg/kg, and molecular weight is 50mg/kg greater than the content of the tarry matters of oil of mirbane.The coking amount of catalyzer is less than 1.5%.
Embodiment 2
React at as shown in Figure 2 the fluidizer that production by gas phase hydrogenation of nitrobenzene is equipped with aniline that is used for.The circulating line of three distribution of gas is set, and its diameter is respectively 20%, 40%, 60% of a main tracheal diameter; Upward nozzle number on the control sparger is 1: 8 with the ratio of downward nozzle number, and the mounting distance of jet exit and upward nozzle outlet downwards is 500mm.Gas speed 20m/s in the main inlet pipe, the gas speed of jet exit is 150m/s.Charging is hydrogen and oil of mirbane, and mol ratio is 7: 1; Working pressure (absolute pressure) is 0.1MPa; Catalyzer (Cu-Al
2O
3) medial temperature of emulsion zone is 255 ℃, the medial temperature in gas distributor district is 270 ℃; Weight space velocity is 0.1 hour
-1, actual gas speed is 0.9m/s in the catalyzer emulsion zone.In two months, the content of oil of mirbane is 4.5mg/kg in the crude benzol amine, and the content of hexalin and hexahydroaniline is respectively 20 and 13mg/kg.Molecular weight is 80mg/kg greater than the content of the tarry matters of oil of mirbane.The coking amount of catalyzer is less than 2.5%.
Embodiment 3
React at as shown in Figure 3 the fluidizer that production by gas phase hydrogenation of nitrobenzene is equipped with aniline that is used for.The circulating line of four distribution of gas is set, and its diameter is respectively 10,20%, 50%, 80% of a main tracheal diameter; Upward nozzle number on the control sparger is 1: 3 with the ratio of downward nozzle number, and the mounting distance of jet exit and upward nozzle outlet downwards is 1000mm.Gas speed 15m/s in the main inlet pipe, the gas speed of jet exit is 60m/s.Charging is hydrogen and oil of mirbane, and mol ratio is 12: 1; Working pressure (absolute pressure) is 1.0MPa; The medial temperature of catalyzer emulsion zone is 250 ℃, and the medial temperature in gas distributor district is 256 ℃; Weight space velocity is 0.23 hour
-1, catalyzer (Cu-Al
2O
3) actual gas speed is 0.6m/s in the emulsion zone.The content of oil of mirbane is 0.3mg/kg in the crude benzol amine in two months, and the content of hexalin and hexahydroaniline is respectively 6 and 6mg/kg.Molecular weight is 30mg/kg greater than the content of the tarry matters of oil of mirbane.The coking amount of catalyzer is less than 1.2%.
Embodiment 4
React at as shown in Figure 3 the fluidizer that production by gas phase hydrogenation of nitrobenzene is equipped with aniline that is used for.The circulating line of two distribution of gas is set, and its diameter is respectively 20%, 60% of a main tracheal diameter; Upward nozzle number on the control sparger is 1: 5 with the ratio of downward nozzle number, and the mounting distance of jet exit and upward nozzle outlet downwards is 600mm.Gas speed 18m/s in the main inlet pipe, the gas speed of jet exit is 130m/s.Charging is hydrogen and oil of mirbane, and mol ratio is 10: 1; Working pressure (absolute pressure) is 0.3MPa; Catalyzer (Cu-Al
2O
3) medial temperature of emulsion zone is 258 ℃, the medial temperature in gas distributor district is 267 ℃; Weight space velocity is 0.3 hour
-1, actual gas speed is 0.5m/s in the catalyzer emulsion zone.The content of oil of mirbane is 3mg/kg in the crude benzol amine in two months, and the content of hexalin and hexahydroaniline is respectively 10 and 12mg/kg.Molecular weight is 90mg/kg greater than the content of the tarry matters of oil of mirbane.Catalyzer coking amount is less than 2.8%.
Claims (8)
1. the gas distributor in the fluidized bed of aniline synthesis, it is characterized in that: the gas distributor in the described fluidized-bed is the gas distributor with different injection directions, the intersection center of being in charge of (2) that (1) is vertically connected on right-angled intersection is responsible in its air inlet, distribute the circulating line (3) of air-flow to divide 1～10 circle and be in charge of (2) UNICOM, upward dividing up and down at circulating line (3), both direction connects upward nozzle (4) and downward nozzle (5) respectively; Then, whole gas distributor is installed in the bottom of synthetic fluidized-bed.
2. according to the gas distributor in the described fluidized bed of aniline synthesis of claim 1, it is characterized in that: described upward nozzle or downward nozzle respectively are 1～20/m on the gas distributor cross section
2
3. according to the gas distributor in the described fluidized bed of aniline synthesis of claim 1, it is characterized in that: described circulating line (3) divides to enclose the land and passes being in charge of (2) and being in charge of (2) connection of right-angled intersection, or is connected and is in charge of (2) two ends.
4. according to the gas distributor in the described fluidized bed of aniline synthesis of claim 1, it is characterized in that: described air inlet is responsible for (1) or is connected with becoming the T font single being in charge of (2).
5. according to the gas distributor in the described fluidized bed of aniline synthesis of claim 1, it is characterized in that: described upward nozzle is 1: 1～1: 8 with the quantity ratio of downward nozzle.
6. aniline synthesis method, it is characterized in that: the described method of utilizing said apparatus to prepare aniline comprises the steps:
1) will have upward nozzle (4) and the downward gas distributor of nozzle (5) fluidized-bed reactor of packing into, at catalyzer emulsion zone (9) inner member (10) and interchanger (11) are set, in the reactor expanding reach (13) on reactor top, cyclone type gas-solid separating device (14) is set, constitutes complete fluidized-bed reactor;
2) with median size be the metal load type catalyst of 45-300 micron from catalyst inlet (17) reactor of packing into, the static loading height of catalyzer is 2～10 times of reactor diameter;
3) in interchanger (11), feed heating medium, or the inert nitrogen gas of heat is fed reactor, make that temperature reaches 150～250 ℃ in the reactor; Feed hydrogen then, controlled temperature is reducing catalyst in 150～250 ℃ scope;
4) after the catalyst reduction fully, in reactor, feed the vaporizer of hydrogen and oil of mirbane through gas distributor; The mol ratio of control hydrogen and oil of mirbane is 7: 1～20: 1, the weight space velocity in the reactor be 0.1～0.3 restrain oil of mirbane/gram catalyzer/hour, the absolute pressure of reactor is 0.1～1.0MPa;
5) feed water coolant in the interchanger (11) in being arranged on catalyzer emulsion zone (9), the temperature of control catalyst emulsion zone (9) is between 250～260 ℃;
6) the combined feed total feed flow of control hydrogen and oil of mirbane makes the actually operating gas speed in the reactor reach 0.1～0.9m/s; Behind the reactant gases process catalyzer emulsion zone (9), be converted into aniline, reaction product is discharged from reactor outlet (15) through gas-solid separating device (14) back on reactor top.
7. according to the described aniline synthesis method of claim 6, it is characterized in that: described metal load type catalyst is main active component with copper, and carrier is silicon-dioxide or aluminium sesquioxide, is expressed as Cu-SiO
2Or Cu-Al
2O
3
8. according to the described aniline synthesis method of claim 6, it is characterized in that: described to feed heating medium in interchanger (11) be saturated high-temperature steam, high temperature saturation water or high temperature inert gas.
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