CN105001072A - Propylene-to-acrylic acid oxidation absorption system and method thereof - Google Patents
Propylene-to-acrylic acid oxidation absorption system and method thereof Download PDFInfo
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- CN105001072A CN105001072A CN201510431867.7A CN201510431867A CN105001072A CN 105001072 A CN105001072 A CN 105001072A CN 201510431867 A CN201510431867 A CN 201510431867A CN 105001072 A CN105001072 A CN 105001072A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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Abstract
The present invention discloses a propylene-to-acrylic acid oxidation absorption system and a method thereof. The system is characterized by comprising a propylene vaporization tower, a first oxidation reactor, a second oxidation reactor and a three-in-one tower, wherein the top portion of the propylene vaporization tower is provided with a mixing superheater, the top portion outlet of the mixing superheater, the top portion inlet of the oxidation reactor and the bottom portion outlet of the second oxidation reactor are sequentially connected in series with the lower end inlet of the three-in-one tower, a product steam generator is arranged between the second oxidation reactor and the three-in-one tower, and an upper portion washing water steam stripping section, a middle portion acrylic acid absorption section and a lower portion reactant cooling section are arranged inside the three-in-one tower. The system and the method have the following advantages that the finally obtained acrylic acid solution has characteristics of high concentration and low impurity content, and characteristics of safety, environmental protection, energy saving and effective oxidation catalyst protecting are provided.
Description
Technical field
The present invention relates to the acrylic acid oxidative absorption system and method for a kind of propylene system.
Background technology
Utilizing propylene oxidation to produce vinylformic acid has been ripe technique.Vinylformic acid is produced and is normally reacted obtained by propylene through two-step oxidation.It is the basis of carrying out subsequent propylene acid purification that propylene oxidation absorbs.Whether the effect of oxidative absorption, energy consumption height determines technology advanced.In oxidative absorption process, conventional method is raw material liq propylene through autoclave vaporizer vaporization and then overheated through shell-and-tube superheater, then with after water vapour, air mixed first, second oxidation reactor is entered successively, generate the gas after vinylformic acid through two-stage oxidation reaction and send into quench tower, quench tower tower top sends into quenched water, obtains acrylic acid aqueous solution at the bottom of tower.The absorption waste gas of tower top send emptying after burning disposal.There is following problem in common process:
1, raw material liq propylene feed is directly through the vaporization of autoclave vaporizer, and the polymkeric substance that propylene produces in storage process is not removed, and can be vaporized and bring reactor into, polymkeric substance is attached to catalyst surface, affects the yield of oxidizing reaction, and reduces the life-span of catalyzer.
2, propylene vaporization, overheated, the multiple devices of mixing needs by connecting successively, due to the inflammable and explosive property of propylene, the equipment number of units passed through is more, and tie point is more, and risk of leakage is larger, and danger is also higher.
3, when oxidation products feeding absorption tower absorbs, tower top adopts de-salted water as cooling and absorbing medium, therefore consumes a large amount of de-salted waters, and causes discharging in subsequent propylene acid treating process in a large number containing organic sewage, contaminate environment.
4, the spent air temperture of tower top discharge is low, sends into calorific value when burning low, causes burning cost high.
5, be not applicable to the column internals that vinylformic acid absorbs, conventional column internals causes assimilation effect poor, and easily occurs tower tray liquid flooding problem, is therefore badly in need of the High Efficient Column Internals that exploitation is applicable to vinylformic acid absorption.
6, in order to reduce energy consumption, the gas of oxidative absorption column overhead being returned oxidizing reaction, the steam consumption of system can be reduced like this.But owing to containing multiple organic impurity in oxidative absorption tower top tail gas, direct Returning reactor can reduce the life-span of oxide catalyst, causes production cost to rise.
Effective solution of above problem, all significantly will improve propylene oxidation and produce acrylic acid state of the art, to reduction production cost, improve security of system, reduce energy consumption, reduce environmental pollution all significant.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of safety, environmental protection, energy-conservation and can available protecting catalyzer, the acrylic acid oxidative absorption system and method for propylene system that acrylic acid solution concentration high impurity content is low.
The present invention solves the problems of the technologies described above adopted technical scheme: the acrylic acid oxidative absorption system of a kind of propylene system, comprise propylene vaporization tower, first oxidation reactor, second oxidation reactor and three-in-one tower, the top of described propylene vaporization tower is provided with mixing superheater, the top exit of described mixing superheater is connected with the top inlet of the first described oxidation reactor, the outlet at bottom of the first described oxidation reactor is connected with the top inlet of the second described oxidation reactor, the outlet at bottom of the second described oxidation reactor is connected with the lower end import of described three-in-one tower, the connecting pipeline of described mixing superheater and the first described oxidation reactor is provided with the first entry mixers, the connecting pipeline of the first described oxidation reactor and the second described oxidation reactor is provided with the second entry mixers, the connecting pipeline of the second described oxidation reactor and described three-in-one tower is provided with reaction product vapour generator, upper wash water stripping stage is provided with in described three-in-one tower, middle part vinylformic acid absorber portion and bottom reactant quench zone, the upper end of described three-in-one tower is provided with washing water import, the top of described three-in-one tower is provided with the exhaust port be connected with the first described entry mixers, the pipeline that described exhaust port is connected with the first described entry mixers is provided with tail gas incinerator, the bottom of described three-in-one tower is provided with acrylic acid aqueous solution outlet.
Described propylene vaporization tower is that inside is provided with carrying of sieve plate and heats up in a steamer tower.Sieve-plate structure is adopted can effectively to prevent propylene polymerization from blocking internals, and effective polymkeric substance removed propylene and produce in storage process.
Described mixing superheater is tube and shell heat exchanger, and the lower end of described tube and shell heat exchanger is provided with tube sheet.Can make be uniformly distributed from the gas of bottom propylene vaporization tower and water vapour and mix.
The first described entry mixers is provided with propylene water vapour parallel feeding mouth, incineration tail gas import and air intlet, described propylene water vapour parallel feeding mouth, air intlet and incineration tail gas ingress are equipped with under meter, the air intlet of the first described entry mixers is connected air compressor respectively with the air intlet of the second described entry mixers, and the pipeline that described tail gas incinerator is connected with the first described entry mixers is provided with tail-gas compressor.
The first described oxidation reactor is calandria type fixed bed reactor, is provided with epimere reaction zone and hypomere cooling zone in the first described oxidation reactor.Mainly there is the reaction that propylene oxidation generates propenal in epimere reaction zone, the cooling of oxidation products mainly occurs in hypomere cooling zone, to prevent overreaction, reduces the generation of side reaction.
The second described oxidation reactor is calandria type fixed bed reactor, and the first described reaction mixer and the second described reaction mixer are SV type static mixer.This pattern static mixer can effectively hybrid reaction charging.
The top of described three-in-one tower is connected with washing water and adds pipeline, and the middle part of described three-in-one tower is connected with water cooler, the connecting pipeline between described three-in-one tower and described water cooler is connected with stopper and adds pipeline.Intermediate absorption section is provided with water cooler, ensures acrylic acid assimilation effect, adds stopper simultaneously and reduces material polymerization.
Described upper wash water stripping stage and described middle part vinylformic acid absorber portion all adopt efficient random packing or structured packing, some layers of three-dimensional membrane broken bubble column plate is provided with in described bottom reactant cooling section, three-dimensional membrane described in every layer breaks the gas-liquid mass transfer district in lower large little taper type that bubble column plate comprises several horizontal distribution, the bottom in described gas-liquid mass transfer district is provided with the gas rise hole that opening is loudspeaker flared, the top in described gas-liquid mass transfer district is provided with calotte, the sidepiece in described gas-liquid mass transfer district is disposed with the ring diversion plate that several are loudspeaker flared from top to bottom, web plate between neighbouring described ring diversion plate is along the circumferential direction provided with several gas-liquid pod apertures, ring diversion plate described in bottom and be provided with liquid between described gas rise hole and flow into annular space.The gas breaking bubble column plate from the three-dimensional membrane of lower floor enters in gas rise hole, by flow into from liquid annular space flow into lifting liquid membrane after enter in gas-liquid mass transfer district together, gas-liquid two-phase completes gas-liquid mass transfer in gas-liquid mass transfer district, completes the gas-liquid pod apertures that the gas-liquid mixture after gas-liquid mass transfer arranges through gas-liquid mass transfer district sidepiece by the guide functions of top calotte and flows out.Flow through in the process of gas-liquid pod apertures at gas-liquid mixture, by the impact in the oblique Eight characters direction of ring diversion plate, due to the effect of inertia, liquid can be captured and get back on column plate, after gas then flows out from gas-liquid pod apertures, rising enters the three-dimensional membrane in upper strata broken bubble column plate, thus realizes gas-liquid separation.This gas-liquid mass transfer internals commute bubbling system has good their defoaming function, and gas-liquid mass transfer district is lower large little taper type, and this structure can play booster action to the fluid of inside, thus improves gas-liquid mass transfer effect.Three-dimensional drawing-die broken bubble column plate mass-transfer efficiency is high, and treatment capacity is large, and has significant their defoaming function, does not need to add defoamer again.
One utilizes the acrylic acid oxidative absorption system of aforesaid propylene system to prepare acrylic acid, specifically comprises the following steps:
1) liquid propene is sent into after propylene vaporization tower is vaporizated into propylene gas, propylene gas is mixed in superheater with sending into after 1.6-2.0MPAG vapor mixing, propylene vapor is mixed with water vapour and is superheated to 50-70 DEG C; Wherein the mol ratio of water vapor and propylene is (1.5-1.8): 1; Adopt 10 DEG C of water as heating medium at the bottom of described propylene vaporization tower tower; 10 DEG C of water are used for the cold of Propylene recovery vaporization;
2) by fresh air through air compressor compression after, with the tail gas of the part after catalytic burning after tail-gas compressor pressure-raising from three-in-one tower top, and together send into after the first entry mixers mixes from propylene and the water vapor of mixing superheater, finally send into the epimere reaction zone of the first oxidation reactor, the temperature controlling epimere reaction zone is 300-340 DEG C, pressure is 40-60Kpag, propylene and oxygen carry out oxidizing reaction and generate propenal and a small amount of vinylformic acid under the effect of catalyzer, the propenal generated and a small amount of vinylformic acid enter after hypomere cooling zone is cooled to 260 DEG C, send into the second entry mixers again, the mol ratio of the first oxidation reactor entrance oxygen and propylene is (1.6-1.8): 1, the tail gas sending into the first entry mixers is the 25-40 wt% of incineration tail gas total amount, the transformation efficiency of the first oxidation reactor inner propene is more than 99wt%, and oxidation products acrylic acid content is lower than 1%wt,
3) the second oxidation reactor is sent into after the product of the first oxidation reactor and the air from air compressor being mixed in the second entry mixers, control temperature of reaction is 250-260 DEG C, pressure is 40-60Kpag, and propenal and oxygen carry out oxidizing reaction and generates vinylformic acid under the effect of catalyzer; After reaction product steam-generator temperature is down to 160-170 DEG C, three-in-one tower is sent into containing acrylic acid reaction product; The mol ratio of the second oxidation reactor entrance propenal and oxygen is (0.75-0.85): 1; The acrolein conversion rate of the second oxidation reactor is more than 99.9wt%, effectively can control propenal like this in the polymerization of three-in-one tower and fouling;
4) washing water are sent into downward through upper wash water stripping stage, middle part vinylformic acid absorber portion and bottom reactant cooling section successively from three-in-one column overhead, to send into successively upwards through bottom reactant cooling section, vinylformic acid absorber portion district, middle part and upper wash water stripping stage at the bottom of three-in-one tower tower containing acrylic acid oxidation reaction product, containing acrylic acid reaction product by washing water absorption, chilling, at the bottom of three-in-one tower tower, obtain the acrylic acid aqueous solution that mass concentration is 55-65%.
In the first described oxidation reactor, catalyzer is the composite catalyst containing molybdenum, v element, in the second described oxidation reactor, catalyzer is the composite catalyst containing molybdenum, v element, the first described oxidation reactor and the second described oxidation reactor are calandria type fixed bed reactor, the first described oxidation reactor and the second described oxidation reactor oxidizing reaction liberated heat are taken away by hot melt salt, and hot melt salt enters molten salt cooler to produce 1.6-2.0MPaG steam.
Described washing water adopt the acid-bearing wastewater containing acetic acid and light constituent of acrylic acid aqueous solution lightness-removing column tower top discharge, described acid-bearing wastewater after stripping most of light constituent and acetic acid by stripping to exhaust port.
The tail gas that described three-in-one column overhead is discharged is after catalytic burning removing organism, and a part sends into the first entry mixers through recycle gas compressor pressure-raising, remaining gas row air.
Compared with prior art, the invention has the advantages that: the invention discloses the acrylic acid oxidative absorption system and method for a kind of propylene system, liquid propene is vaporized overheated, then the fixed-bed reactor generation oxidizing reaction through being equipped with catalyzer after mixing with air, water generates vinylformic acid, and through effective chilling, absorption, the acrylic acid aqueous solution of the high acrylic acid concentration of final acquisition, low impurity content, advantage is as follows:
1, adopt propylene vaporization tower integrated mixing superheater to propylene carry out vaporization refine and mix with water vapour overheated: relative to liquid propene autoclave vaporizer and then through superheater, and then with static mixer by water vapor and overheated propylene mixed phase ratio, adopt vaporization tower can refine while propylene vaporization, remove the polymkeric substance and other heavy constituents that store at liquid propene and produce in course of conveying.Mixing superheater not only makes mixed gas overheated, and the orifice-plate type tube sheet of mixing superheater plays and is evenly distributed and mixing effect.Mixing superheater is integrated in propylene evaporator tower top by the propylene after vaporization and vapor mixing overheated, mixing superheater is integrated in tower top, can thermosteresis in minimizing process, reduce connecting tube, (conventional propylene vaporization adopts the autoclave vaporizer of BKU form to reduce occupation area of equipment, floor space is large), reduce costs.Decrease number of devices simultaneously, reduce tie point, reduce leakage point, improve the safety of system.
2, propylene feed, water vapour charging, fresh air charging, circulation gas charging are equipped with under meter, and flow measuring data send DCS Controlling System, beyond blast limit, improve security by material composition in the computing function Controlling System of DCS.
3, the transformation efficiency of the first oxidation reactor inner propene is more than 99wt%, and oxidation products acrylic acid content is lower than 1%wt.If transformation efficiency is not up to standard, the second oxidation reactor temperature runaway can be caused, destroy the catalyzer in the second oxidation reactor and equipment.First oxidation reactor is calandria type fixed bed reactor, and reactor is divided into epimere reaction zone and hypomere cooling zone, thus avoids the over oxidation of propenal, improves the yield of target product.
4, acrolein conversion rate more than the control 99.9wt% of the second oxidation reactor, effectively can control propenal in the polymerization of three-in-one tower and fouling.If transformation efficiency is too low, propenal can be caused in the polymerization of three-in-one tower, blocking column internals.And the acrylic acid productive rate of target product can be reduced.Second oxidation reactor reaction product control temperature after product vapour generator producing steam is 160-170 DEG C, not only can efficient recovery heat, and can effectively control acrylic acid polymerization.
5, three-in-one tower is the integrated equipment simultaneously realizing the purification of washing water stripping, vinylformic acid absorption, reaction product cooling combination function.The power waste of effective reduction fluid conveying, reduces equipment and takes up an area and investment.And the washing water that three-in-one column overhead is sent into adopt the acid-bearing wastewater containing acetic acid and light constituent of acrylic acid aqueous solution lightness-removing column tower top discharge, this sewage sends into three-in-one top of tower, emission is first utilized to carry out stripping, in being vented to three-in-one tower top by stripping containing the most of light constituent in sour sewage and acetic acid, which reduce the content of impurity in acid-bearing wastewater, be conducive to acrylic acid absorption, and the burden of emissions reduction sewage disposal.Add the organic content in emission simultaneously, improve the calorific value of burned waste gas.Not only save absorption de-salted water, decrease discharge of wastewater, and reclaim useful organism.
6, by controlling the washing water yield of three-in-one column overhead feeding, the return water temperature of side cooler, the three-in-one column overhead expellant gas temperature of final control is 60-65 DEG C.Corresponding concentration of aqueous solution at the bottom of tower is 55-65%wt.Tower top temperature is high, effectively reduces the content of acetic acid in the aqueous solution at the bottom of tower, reduces the difficulty except acetic acid in follow-up refining vinylformic acid process.Meanwhile, overhead gas temperature is high, more through catalytic burning heat-recoverable.At the bottom of tower, concentration of aqueous solution is high, can reduce energy and the power consumption of follow-up dehydration.
7, three-in-one column overhead expellant gas is after catalytic burning removing organism, and a part sends into the first entry mixers reactor through compressor pressure-raising, remaining gas row air.The 25-40%wt recycle of tail gas after catalytic burning after absorbing.Make full use of the useful organism such as the water vapour in circulation gas.Simultaneously because tail gas after incineration temperature high (about 100 DEG C), water-content are high, the consumption for controlling reactive system water-content steam can be reduced.Three-in-one column overhead expellant gas first carries out Returning reactor after catalytic burning removing detrimental impurity, can available protecting oxide catalyst, reduces poisoning of catalyst, improves catalyst life.The more important thing is the generation that effectively can reduce the by product such as acetone, propionic acid, to improve propenal and acrylic acid yield.
8, three-in-one tower bottom quench zone column internals adopts three-dimensional membrane broken bubble column plate.Column plate mass-transfer efficiency is high, and treatment capacity is large, and has significant their defoaming function, does not need to add defoamer again.Stripping stage and absorber portion adopt efficient random packing or structured packing, can improve stripping and assimilation effect.Be provided with water cooler in the middle of three-in-one tower, ensure acrylic acid assimilation effect.Absorber portion adds stopper, reduces material polymerization.
Accompanying drawing explanation
Fig. 1 is the structural representation of the acrylic acid oxidative absorption system of propylene system of the present invention;
Fig. 2 is the structural representation that three-dimensional membrane breaks bubble column plate.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Specific embodiment one
The acrylic acid oxidative absorption system of a kind of propylene system, as shown in Figure 1, comprise propylene vaporization tower 1, first oxidation reactor 2, second oxidation reactor 3 and three-in-one tower 4, the top of propylene vaporization tower 1 is provided with mixing superheater 5, the top exit of mixing superheater 5 is connected with the top inlet of the first oxidation reactor 2, the outlet at bottom of the first oxidation reactor 2 is connected with the top inlet of the second oxidation reactor 3, the outlet at bottom of the second oxidation reactor 3 is connected with the lower end import of three-in-one tower 4, the connecting pipeline of mixing superheater 5 and the first oxidation reactor 2 is provided with the first entry mixers 6, the connecting pipeline of the first oxidation reactor 2 and the second oxidation reactor 3 is provided with the second entry mixers 7, second oxidation reactor 3 and the connecting pipeline of three-in-one tower 4 are provided with product vapor producer 8, upper wash water stripping stage 9 is provided with in three-in-one tower 4, middle part vinylformic acid absorber portion 10 and bottom reactant cooling section 11, the upper end of three-in-one tower 4 is provided with washing water import 12, the top of three-in-one tower 4 is provided with the exhaust port 13 be connected with the first entry mixers 6, the pipeline that exhaust port 13 is connected with the first entry mixers 6 is provided with tail gas incinerator 22, the bottom of three-in-one tower 4 is provided with acrylic acid aqueous solution outlet 14.
In this particular embodiment, the structure of propylene vaporization tower 1 is that inside is provided with carrying of sieve plate and heats up in a steamer tower.Tower plate structure is adopted can effectively to prevent propylene polymerization from blocking internals, and effective polymkeric substance removed propylene and produce in storage process.Adopt 10 DEG C of water as heating medium at the bottom of propylene vaporization tower 1 tower, 10 DEG C of water are used for the cold of Propylene recovery gasification; Mixing superheater 5 is tube and shell heat exchanger, and the lower end of tube and shell heat exchanger is provided with tube sheet, can make be uniformly distributed from the gas of bottom propylene vaporization tower 1 and water vapour and mix.
In this particular embodiment, as shown in Figure 1, propylene water vapour parallel feeding mouth, inlet exhaust gas and air intlet in first entry mixers 6, propylene water vapour parallel feeding mouth, air intlet and inlet exhaust gas place are equipped with under meter, and the air intlet of the first entry mixers 6 is connected air compressor 15 respectively with the air intlet of the second entry mixers 7.The pipeline that tail gas incinerator 22 is connected with the first entry mixers 6 is provided with tail-gas compressor 16.
In this particular embodiment, the first oxidation reactor 2 is calandria type fixed bed reactor, is provided with epimere reaction zone 17 and hypomere cooling zone 18 in the first oxidation reactor 2.Second oxidation reactor 3 is calandria type fixed bed reactor, and the first reaction mixer 6 and the second reaction mixer 7 are as SV type static mixer.The top of three-in-one tower 4 connects washing water and adds pipeline 19, and the middle part of three-in-one tower 4 is connected with water cooler 20, the connecting pipeline between three-in-one tower 4 and water cooler 20 is connected with stopper and adds pipeline 21.Upper wash water stripping stage 9 and middle part vinylformic acid absorber portion 10 adopt efficient random packing or structured packing, some layers of three-dimensional membrane broken bubble column plate 23 is provided with in bottom reactant cooling section 11, every layer of three-dimensional membrane breaks the gas-liquid mass transfer district 24 in lower large little taper type of steeping column plate 23 and comprising several horizontal distribution, the bottom in gas-liquid mass transfer district 24 is provided with the gas rise hole 25 that opening is loudspeaker flared, the top in gas-liquid mass transfer district 24 is provided with calotte 26, the sidepiece in gas-liquid mass transfer district 24 is disposed with the ring diversion plate 27 that several are loudspeaker flared from top to bottom, web plate between neighbouring ring diversion plate 27 is along the circumferential direction provided with some gas-liquid pod apertures 28, between ring diversion plate 27 bottom and gas rise hole 25, form liquid flow into annular space 29.The gas breaking bubble column plate 23 from the three-dimensional membrane of lower floor enters in gas rise hole 25, enter in gas-liquid mass transfer district 24 together by flow into lifting liquid membrane that annular space 29 flows into from liquid after, after gas-liquid two-phase completes gas-liquid mass transfer in gas-liquid mass transfer district 24, the gas-liquid pod apertures 28 that gas-liquid mixture is arranged through gas-liquid mass transfer tower 24 sidepiece by the guide functions of top calotte 26 flows out.Flow through in the process of gas-liquid pod apertures 28 at gas-liquid mixture, by the impact in the oblique Eight characters direction of ring diversion plate 27, due to the effect of inertia, liquid can be captured and get back on column plate, gas then flows out rear rising from gas-liquid pod apertures 28 and enters the three-dimensional membrane in upper strata broken bubble column plate, thus realizes gas-liquid separation.
Specific embodiment two
One utilizes the acrylic acid oxidative absorption system of above-mentioned specific embodiment one propylene system to prepare acrylic acid, specifically comprises the following steps:
1) liquid propene is sent into propylene vaporization tower 1 be vaporizated into propylene gas and refining after, propylene gas is mixed in superheater 5 with sending into after 1.6MPAG vapor mixing, propylene vapor is mixed with water vapour and is superheated to 50-70 DEG C; Wherein the mol ratio of water vapor and propylene is (1.5-1.8): 1;
2) by fresh air after air compressor 15 compresses, with the tail gas of the part after catalytic burning after tail-gas compressor 16 pressure-raising (back amount is the 25-40 wt% of total incineration tail gas amount) from three-in-one tower 4, and together send into after the first entry mixers 6 mixes from propylene and the water vapor mixture of mixing superheater 5, send into the epimere reaction zone of the first oxidation reactor 2 again, controlling epimere reaction zone 17 temperature is 300-340 DEG C, pressure is 40-60Kpag, propylene and oxygen carry out after oxidizing reaction generates propenal and a small amount of vinylformic acid under the effect of catalyzer, reaction product is entered after people's hypomere cooling zone 18 is cooled to 260 DEG C, send into the second entry mixers 7 again, the mol ratio of the first oxidation reactor entrance oxygen and propylene is (1.6-1.8): 1,
3) the second oxidation reactor 3 is sent into after the reaction product from hypomere cooling zone 18 and the air from air compressor 15 being mixed in the second entry mixers 7, control temperature of reaction is 250-260 DEG C, pressure is 40-60Kpag, propenal and oxygen carry out oxidizing reaction and generate vinylformic acid under the effect of catalyzer, send into three-in-one tower 4 containing acrylic acid reaction product after product vapour generator 8 is down to 160-170 DEG C; The mol ratio of the second oxidation reactor entrance propenal and oxygen is (0.75-0.85): 1;
4) washing water are sent into downward through upper wash water stripping stage 9 successively from three-in-one tower 4 tower top, middle part vinylformic acid absorber portion 10 and bottom reactant cooling section 11, to send into successively upwards through bottom reactant cooling section 11 at the bottom of three-in-one tower 4 tower containing acrylic acid reaction product, middle part vinylformic acid absorber portion 10 and upper wash water stripping stage 9, absorbed by washing water containing acrylic acid reaction product, chilling, the acrylic acid aqueous solution that mass concentration is 55-65% is obtained at the bottom of three-in-one tower 4 tower, the tail gas that three-in-one tower 4 tower top obtains returns the first oxidation reactor 2 recycle through catalytic burning 22 rear section, other incineration tail gas emptying.
In this particular embodiment, the first catalyst for oxidation reaction is the composite catalyst containing molybdenum, bismuth element, and the second catalyst for oxidation reaction is the composite catalyst containing molybdenum, v element.First oxidation reactor 2 and the second oxidation reactor 3 are calandria type fixed bed reactor, and the first oxidation reactor 2 and the second oxidation reactor 3 liberated heat are taken away, for generation of steam by hot melt salt.Washing water adopt the acid-bearing wastewater containing acetic acid and light constituent of acrylic acid aqueous solution lightness-removing column tower top discharge, acid-bearing wastewater after three-in-one tower 4 stripping most of light constituent and acetic acid by stripping to exhaust port; The tail gas that three-in-one column overhead is discharged is after catalytic burning removing organism, and a part sends into the first entry mixers 6 recycle through recycle gas compressor 16 pressure-raising, remaining gas row air.
Specific embodiment three
Be 99%wt by propylene content, oligopolymer and heavy constituent content are that the liquid propene of 0.5%wt is sent into propylene vaporization tower 1 to carry out propylene gasification refining, the mixing superheater 5 at propylene vaporization tower 1 top is entered together with after the top sending into propylene vaporization tower 1 from the 2.0MPAG steam of oxidation reactor by-product mixes with the propylene after vaporization, by controlling heating steam flow, controlling mixing superheater 5 outlet mass temperatures is 60 DEG C.
Tail gas after incineration consists of: nitrogen: 77.4%wt, water: 13.7%wt, carbonic acid gas: 6.5%, oxygen: 2.4%.
Control the fresh air inlet amount of feeding first entry mixers 6, ensure propylene in the mixture that the first entry mixers 6 exports: oxygen: water (mol ratio)=1:1.7:1.The gas mixture meeting composition requirement sends into the first oxidation reactor.
In first oxidation reactor 2, conversion zone is equipped with containing molybdenum, secret composite catalyst.After the first oxidizing reaction, outlet mass temperatures is 260 DEG C, pressure 50KPAG.Consist of: nitrogen: 67.4%wt, water: 10.2%wt, propenal: 14.0%wt, vinylformic acid: 0.7%wt, propylene: 0.08%wt.
In second oxidation reactor 3, conversion zone is equipped with the composite catalyst containing molybdenum, vanadium.Consist of through the second oxidizing reaction after product: nitrogen: 68.9%wt, water: 8.7%wt, propenal: 0.1%wt, vinylformic acid: 14.8%wt, propylene: 0.05%wt, acetic acid: 0.38%wt
Second oxidation reactor 3 outlets products sends into three-in-one tower 4 after product vapour generator 8 is down to 170 DEG C.
The washing water that three-in-one tower 4 tower top is sent into consist of: water: 96.5%wt, acetic acid: 2.6%wt, vinylformic acid: 0.7%wt, other organism: 0.2%wt.
Carry out after washing water stripping, vinylformic acid absorption, reactant cooling through three-in-one tower 4, the acrylic acid aqueous solution of discharging at the bottom of tower consists of: vinylformic acid: 60.2%wt, water: 37.9%wt, acetic acid: 1.3%wt, other: 0.6%.Tower top expellant gas consists of: nitrogen: 78.9%wt, water: 12.6%wt, oxygen: 4.7%wt, acetic acid: 0.45%wt.
Compared with common process:
1) the acrylic acid aqueous solution concentration that oxidative absorption obtains reaches 60.2%wt, far above the 50%wt of common process.
2) content absorbing acetic acid in emission after oxidative absorption is 0.45%wt, and does not substantially contain acetic acid in tower top discharge tail gas in common process.
3) result adopting this patented technology to run shows, when not using defoamer to three-in-one tower 4, three-in-one tower operates steadily, and does not occur because froth breaking does not thoroughly cause the problem of tower liquid flooding.Also as can be seen here three-dimensional membrane break bubble plate there is good in vitro mechanical property and their defoaming function.
Above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned citing.Those skilled in the art are in essential scope of the present invention, and the change made, remodeling, interpolation or replacement, also should belong to protection scope of the present invention.
Claims (10)
1. the acrylic acid oxidative absorption system of propylene system, it is characterized in that: comprise propylene vaporization tower, first oxidation reactor, second oxidation reactor and three-in-one tower, the top of described propylene vaporization tower is provided with mixing superheater, the top exit of described mixing superheater is connected with the top inlet of the first described oxidation reactor, the outlet at bottom of the first described oxidation reactor is connected with the top inlet of the second described oxidation reactor, the outlet at bottom of the second described oxidation reactor is connected with the lower end import of described three-in-one tower, the connecting pipeline of described mixing superheater and the first described oxidation reactor is provided with the first entry mixers, the connecting pipeline of the first described oxidation reactor and the second described oxidation reactor is provided with the second entry mixers, the connecting pipeline of the second described oxidation reactor and described three-in-one tower is provided with reaction product vapour generator, upper wash water stripping stage is provided with in described three-in-one tower, middle part vinylformic acid absorber portion and bottom reactant quench zone, the upper end of described three-in-one tower is provided with washing water import, the top of described three-in-one tower is provided with the exhaust port be connected with the first described entry mixers, the pipeline that described exhaust port is connected with the first described entry mixers is provided with tail gas incinerator, the bottom of described three-in-one tower is provided with acrylic acid aqueous solution outlet.
2. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 1, it is characterized in that: described propylene vaporization tower is that inside is provided with carrying of sieve plate and heats up in a steamer tower, described mixing superheater is tube and shell heat exchanger, and the lower end of described tube and shell heat exchanger is provided with tube sheet.
3. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 1, it is characterized in that: the first described entry mixers is provided with propylene water vapour parallel feeding mouth, incineration tail gas import and air intlet, described propylene water vapour parallel feeding mouth, air intlet and incineration tail gas ingress are equipped with under meter, the air intlet of the first described entry mixers is connected air compressor respectively with the air intlet of the second described entry mixers, the pipeline that described tail gas incinerator is connected with the first described entry mixers is provided with tail-gas compressor.
4. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 1, is characterized in that: the first described oxidation reactor is calandria type fixed bed reactor, is provided with epimere reaction zone and hypomere cooling zone in the first described oxidation reactor.
5. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 1, it is characterized in that: the second described oxidation reactor is calandria type fixed bed reactor, the first described reaction mixer and the second described reaction mixer are as SV pattern static mixer.
6. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 1, it is characterized in that: the top of described three-in-one tower is connected with washing water and adds pipeline, the middle part of described three-in-one tower is connected with water cooler, the connecting pipeline between described three-in-one tower and described water cooler is connected with stopper and adds pipeline.
7. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 1, it is characterized in that: described upper wash water stripping stage and described middle part vinylformic acid absorber portion all adopt efficient random packing or structured packing, some layers of three-dimensional membrane broken bubble column plate is provided with in described bottom reactant cooling section, three-dimensional membrane described in every layer breaks the gas-liquid mass transfer district in lower large little taper type that bubble column plate comprises several horizontal distribution, the bottom in described gas-liquid mass transfer district is provided with the gas rise hole that opening is loudspeaker flared, the top in described gas-liquid mass transfer district is provided with calotte, the sidepiece in described gas-liquid mass transfer district is disposed with the ring diversion plate that several are loudspeaker flared from top to bottom, web plate between neighbouring described ring diversion plate is along the circumferential direction provided with several gas-liquid pod apertures, ring diversion plate described in bottom and be provided with liquid between described gas rise hole and flow into annular space.
8. utilize the acrylic acid oxidative absorption system of the propylene system described in claim 1 to prepare an acrylic acid, it is characterized in that specifically comprising the following steps:
1) liquid propene is sent into after propylene vaporization tower is vaporizated into propylene gas, propylene gas is mixed in superheater with sending into after 1.6-2.0MPAG vapor mixing, propylene vapor is mixed with water vapour and is superheated to 50-70 DEG C; Wherein the mol ratio of water vapor and propylene is (1.5-1.8): 1;
2) by fresh air through air compressor compression after, with the tail gas of the part after catalytic burning after tail-gas compressor pressure-raising from three-in-one tower top, and together send into after the first entry mixers mixes from propylene and the water vapor of mixing superheater, finally send into the epimere reaction zone of the first oxidation reactor, the temperature controlling epimere reaction zone is 300-340 DEG C, pressure is 40-60Kpag, propylene and oxygen carry out oxidizing reaction and generate propenal and a small amount of vinylformic acid under the effect of catalyzer, the propenal generated and a small amount of vinylformic acid enter after hypomere cooling zone is cooled to 260 DEG C, send into the second entry mixers again, the mol ratio of the first oxidation reactor entrance oxygen and propylene is (1.6-1.8): 1, the tail gas sending into the first entry mixers is the 25-40wt% of incineration tail gas total amount,
3) the second oxidation reactor is sent into after the product of the first oxidation reactor and the air from air compressor being mixed in the second entry mixers, control temperature of reaction is 250-260 DEG C, pressure is 40-60Kpag, and propenal and oxygen carry out oxidizing reaction and generates vinylformic acid under the effect of catalyzer; After reaction product steam-generator temperature is down to 160-170 DEG C, three-in-one tower is sent into containing acrylic acid reaction product; The mol ratio of the second oxidation reactor entrance propenal and oxygen is (0.75-0.85): 1;
4) washing water are sent into downward through upper wash water stripping stage, middle part vinylformic acid absorber portion and bottom reactant cooling section successively from three-in-one column overhead, to send into successively upwards through bottom reactant cooling section, vinylformic acid absorber portion district, middle part and upper wash water stripping stage at the bottom of three-in-one tower tower containing acrylic acid reaction product, containing acrylic acid reaction product by washing water absorption, chilling, at the bottom of three-in-one tower tower, obtain the acrylic acid aqueous solution that mass concentration is 55-65%.
9. one according to claim 8 utilizes the acrylic acid oxidative absorption system of propylene system to prepare acrylic acid, it is characterized in that: in the first described oxidation reactor, catalyzer is for containing molybdenum, the composite catalyst of v element, in the second described oxidation reactor, catalyzer is for containing molybdenum, the composite catalyst of v element, the first described oxidation reactor and the second described oxidation reactor are calandria type fixed bed reactor, the first described oxidation reactor and the second described oxidation reactor liberated heat are taken away by hot melt salt, hot melt salt enters molten salt cooler to produce 1.6-2.0MPaG steam, adopt 10 DEG C of water as heating medium at the bottom of described propylene vaporization tower tower.
10. the acrylic acid oxidative absorption system of a kind of propylene system according to claim 8 prepares acrylic acid, it is characterized in that: described washing water adopt the acid-bearing wastewater containing acetic acid and light constituent of acrylic acid aqueous solution lightness-removing column tower top discharge, described acid-bearing wastewater after stripping most of light constituent and acetic acid by stripping to exhaust port; The tail gas that described three-in-one column overhead is discharged is after catalytic burning removing organism, and a part sends into the first entry mixers through recycle gas compressor pressure-raising, remaining gas row air.
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| CN110551008A (en) * | 2018-05-30 | 2019-12-10 | 中国石油集团东北炼化工程有限公司吉林设计院 | tail gas recycling method in acrolein production process |
| CN112439300A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Tail gas treatment system and tail gas treatment method for preparing acrylic acid |
| CN112441905A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Process for preparing acrylic acid by propylene oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105402742A (en) * | 2015-12-01 | 2016-03-16 | 中国天辰工程有限公司 | Feed-in hazardous waste diluting device for incinerator and method of device |
| CN106631759A (en) * | 2016-12-09 | 2017-05-10 | 中国化学赛鼎宁波工程有限公司 | System and method for simultaneously producing methacrylic acid and methacrolein |
| CN106631759B (en) * | 2016-12-09 | 2019-02-15 | 中国化学赛鼎宁波工程有限公司 | A kind of system and method producing methacrylic acid coproducing methyl methacrylaldehyde |
| CN106731501A (en) * | 2016-12-28 | 2017-05-31 | 山东丰元化学股份有限公司 | The method on acid tail gas absorption tower and absorption oxalic acid tail gas in oxalic acid production |
| CN110551008A (en) * | 2018-05-30 | 2019-12-10 | 中国石油集团东北炼化工程有限公司吉林设计院 | tail gas recycling method in acrolein production process |
| CN110551008B (en) * | 2018-05-30 | 2022-07-19 | 中石油吉林化工工程有限公司 | Tail gas recycling method in acrolein production process |
| CN112439300A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Tail gas treatment system and tail gas treatment method for preparing acrylic acid |
| CN112441905A (en) * | 2019-09-05 | 2021-03-05 | 中石油吉林化工工程有限公司 | Process for preparing acrylic acid by propylene oxidation |
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