CN105001072B - Propylene system acrylic acid oxidative absorption system and method - Google Patents
Propylene system acrylic acid oxidative absorption system and method Download PDFInfo
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- CN105001072B CN105001072B CN201510431867.7A CN201510431867A CN105001072B CN 105001072 B CN105001072 B CN 105001072B CN 201510431867 A CN201510431867 A CN 201510431867A CN 105001072 B CN105001072 B CN 105001072B
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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 invention discloses a kind of propylene system acrylic acid oxidative absorption system and method, feature is to include propylene vaporization tower, first oxidation reactor, second oxidation reactor and three-in-one tower, the top of propylene vaporization tower is provided with mixing superheater, the top exit of mixing superheater, the top inlet of oxidation reactor, the outlet at bottom of the second oxidation reactor is sequentially connected in series with the lower end import of three-in-one tower, product vapor generator it is provided with between second oxidation reactor and three-in-one tower, upper wash water stripping section it is provided with in three-in-one tower, middle part acrylic acid absorber portion and bottom reactant cooling section, the advantage of system and method is that the final acrylic acid solution concentration obtained is high, impurity content is low, safety, environmental protection, energy-conservation and can effectively protect oxidation catalyst.
Description
Technical field
The present invention relates to a kind of propylene system acrylic acid oxidative absorption system and method.
Background technology
Utilizing propylene oxidation to produce acrylic acid has been ripe technique.Acrylic acid produces and is typically to be prepared through two-step oxidation reaction by propylene.Propylene oxidative absorption is by the basis that subsequent propylene acid purifies.It is the most advanced that the effect of oxidative absorption, energy consumption height determines technology.During oxidative absorption, conventional method is that raw material liq propylene is overheated through shell-and-tube superheater the most again through the vaporization of autoclave carburator, then first, second oxidation reactor is sequentially entered with steam, air after mixing, gas after two-stage oxidation reaction generates acrylic acid sends into chilling tower, chilling column overhead sends into chilled water (chw), obtains acrylic acid aqueous solution at the bottom of tower.The absorption waste gas of tower top is vented after sending burning disposal.Common process there is problems in that
1, raw material liq propylene feed directly vaporizes through autoclave carburator, and the polymer that propylene produces during storing is not removed, and can be vaporized and bring reactor into, and polymer is attached to catalyst surface, affects the yield of oxidation reaction, and reduces the life-span of catalyst.
2, propylene vaporization, overheated, mixing need by the multiple devices being sequentially connected with, due to the inflammable and explosive property of propylene, the equipment number of units passed through is the most, and junction point is the most, and risk of leakage is the biggest, and danger is the highest.
3, when oxidation product feeding absorption tower absorbs, tower top uses desalted water as cooling absorbing medium, therefore consumes substantial amounts of desalted water, and can discharge a large amount of containing organic sewage, pollution environment during causing subsequent propylene acid treating.
4, the EGT that tower top is discharged is low, sends into calorific value when burning low, causes burning cost high.
5, not being applicable to the tower internals that acrylic acid absorbs, conventional tower internals causes assimilation effect poor, and tower tray liquid flooding problem easily occurs, is therefore badly in need of exploitation and is suitable for the High Efficient Column Internals that acrylic acid absorbs.
6, in order to reduce energy consumption, the gas of oxidative absorption column overhead is returned oxidation reaction, so can reduce the steam consumption of system.But owing to containing multiple organic impurities in oxidative absorption tower top tail gas, direct Returning reactor can reduce the life-span of oxidation catalyst, causes production cost to rise.
Effective solution of problem above, all will be greatly improved propylene oxidation and produce acrylic acid technical merit, to reduce production cost, improve security of system, to reduce energy consumption, minimizing environmental pollution the most significant.
Summary of the invention
The technical problem to be solved is to provide a kind of safe and environment-friendly, energy-conservation and can effectively guard catalyst, propylene system acrylic acid oxidative absorption system and method that acrylic acid solution concentration high impurity content is low.
nullThe present invention solves the technical scheme that above-mentioned technical problem used: a kind of propylene system acrylic acid oxidative absorption system，Including 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，Described mixing superheater is provided with the first entry mixers on the connecting line of the first described oxidation reactor，The first described oxidation reactor is provided with the second entry mixers on the connecting line of the second described oxidation reactor，The second described oxidation reactor is provided with product steam generator on the connecting line of described three-in-one tower，Upper wash water stripping section it is provided with in described three-in-one tower、Middle part acrylic acid absorber portion and bottom reactant quench zone，The upper end of described three-in-one tower is provided with washings import，The top of described three-in-one tower is provided with the exhaust port being connected with the first described entry mixers，It is provided with tail gas incinerator on the pipeline that described exhaust port is connected with the first described entry mixers，The bottom of described three-in-one tower is provided with acrylic acid aqueous solution outlet.
Described propylene vaporization tower is the internally installed stripping tower having sieve plate.Use sieve-plate structure can effectively prevent propylene polymerization from blocking internals, and effectively remove the polymer that propylene produces during storing.
Described mixing superheater is shell-and-tube heat exchanger, and the lower end of described shell-and-tube heat exchanger is provided with tube sheet.The gas of propylene vaporization tower from below can be made and steam is uniformly distributed and mix homogeneously.
Propylene steam mixed feeding mouth, incineration tail gas import and air intlet it is provided with in the first described entry mixers, described propylene steam mixed feeding mouth, air intlet and incineration tail gas import department are equipped with effusion 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.Epimere reaction zone mainly occurs propylene oxidation to generate the reaction of acrylic aldehyde, and hypomere cooling zone mainly occurs the cooling of oxidation product, 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 connects has washings to add pipeline, and the middle part of described three-in-one tower connects cooler, the described connecting line between three-in-one tower and described cooler is connected and has polymerization inhibitor to add pipeline.Intermediate absorption section is provided with cooler, it is ensured that acrylic acid assimilation effect, is simultaneously introduced polymerization inhibitor and reduces material polymerization.
Described upper wash water stripping section and described middle part acrylic acid absorber portion all use efficient random packing or structured packing, if being provided with dried layer solid membrane broken bubble column plate in described bottom reactant cooling section, every layer of described three-dimensional membrane breaks bubble column plate and includes the gas-liquid mass transfer district in lower big little taper type of 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, peripherally disposed on the neighbouring connecting plate between described ring diversion plate have several gas-liquid pod apertures, the ring diversion plate described in bottom and be provided with between described gas rise hole liquid flow into annular space.The gas breaking bubble column plate from lower floor's solid membrane enters in gas rise hole, enter in gas-liquid mass transfer district by flowing into from liquid together after the lifting liquid membrane that annular space flows into, 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 arranged through gas-liquid mass transfer district sidepiece by the guide functions of top calotte and flows out.During gas-liquid mixture flows through gas-liquid pod apertures, being affected by oblique eight word directions of ring diversion plate, due to the effect of inertia, liquid can be captured and return on column plate, gas then ascends into solid membrane broken bubble column plate in upper strata after gas-liquid pod apertures flows out, thus realizes gas-liquid separation.System easy to foaming is had good defoaming function, gas-liquid mass transfer district to be lower big little taper type by this gas-liquid mass transfer internals, and internal fluid can be played acceleration, thus improve gas-liquid mass transfer effect by this structure.Three-dimensional drawing-die broken bubble column plate mass-transfer efficiency is high, and treating capacity is big, and has significant defoaming function, is not required to add defoamer.
One utilizes aforesaid propylene system acrylic acid oxidative absorption system to prepare acrylic acid, specifically includes 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 steam, propylene vapor is mixed with steam and is superheated to 50-70 DEG C；Wherein water vapour is (1.5-1.8) with the mol ratio of propylene: 1；Use 10 DEG C of water as adding thermal medium at the bottom of described propylene vaporization tower tower；The cold that 10 DEG C of water vaporizes for Propylene recovery；
2) by fresh air after air compressor compresses, with the tail gas after tail-gas compressor pressure-raising of the part after catalytic burning from three-in-one tower top, and together send into after the first entry mixers mixes with water vapour from the propylene 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 oxidation reaction under the effect of catalyst and generate acrylic aldehyde and a small amount of acrylic acid, after the acrylic aldehyde generated and a small amount of acrylic acid entrance hypomere cooling zone are cooled to 260 DEG C, it is re-fed into the second entry mixers, first oxidation reactor inlet oxygen is (1.6-1.8) with the mol ratio of propylene: 1, send into the 25-40 that tail gas is incineration tail gas total amount of the first entry mixers
wt%；The conversion ratio of the first oxidation reactor inner propene is more than 99wt%, and oxidation product acrylic acid content is less than 1%wt；
3) the second oxidation reactor is sent into after being mixed in the second entry mixers with the air from air compressor by the product of the first oxidation reactor, control reaction temperature and be 250-260 DEG C, pressure is 40-60Kpag, and acrylic aldehyde and oxygen carry out oxidation reaction under the effect of catalyst and generates acrylic acid；The reacted product vapor generator temperature containing acrylic acid product sends into three-in-one tower after being down to 160-170 DEG C；Second oxidation reactor entrance acrylic aldehyde is (0.75-0.85) with the mol ratio of oxygen: 1；The acrolein conversion rate of the second oxidation reactor is more than 99.9wt%, so can effectively control acrylic aldehyde in the polymerization of three-in-one tower and fouling；
4) washings are sent into successively down through upper wash water stripping section, middle part acrylic acid absorber portion and bottom reactant cooling section from three-in-one column overhead, acrylic acid oxidation reaction product will be contained and pass upward through bottom reactant cooling section, acrylic acid absorber portion district, middle part and upper wash water stripping section successively from feeding at the bottom of three-in-one tower tower, it is washed water absorption, chilling containing acrylic acid product, at the bottom of three-in-one tower tower, obtains the acrylic acid aqueous solution that mass concentration is 55-65%.
In the first described oxidation reactor, catalyst is containing molybdenum, the composite catalyst of v element, in the second described oxidation reactor, catalyst is 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 oxidation reaction liberated heat are taken away by hot melt salt, and hot melt salt enters molten salt cooler and produces 1.6-2.0MPaG steam.
Described washings use acrylic acid aqueous solution lightness-removing column tower top discharge containing acetic acid and the acid-bearing wastewater of light component, the light component of described acid-bearing wastewater major part after stripping and acetic acid are stripped exhaust port.
The tail gas that described three-in-one column overhead is discharged is after catalytic burning removes Organic substance, and a part sends into the first entry mixers, remaining gas row's air through recycle gas compressor pressure-raising.
Compared with prior art, it is an advantage of the current invention that: the invention discloses a kind of propylene system acrylic acid oxidative absorption system and method, it is overheated to be vaporized by liquid propene, then acrylic acid is generated through the fixed bed reactors generation oxidation reaction equipped with catalyst after mixing with empty gas and water, and through effective chilling, absorption, final acquisition high acrylic acid concentration, the acrylic acid aqueous solution of low impurity content, advantage is as follows:
1, use propylene vaporization tower integrated mixing superheater propylene is vaporized refined and mix with steam overheated: relative to liquid propene autoclave vaporizer the most again through superheater, the most again with static mixer by water vapour and overheated propylene mixed phase ratio, use vaporization tower can refine while propylene is vaporized, remove the polymer and other heavy constituents produced in liquid propene storage and course of conveying.Mixing superheater not only makes mixed gas overheated, and the orifice-plate type tube sheet mixing superheater plays and is evenly distributed and immixture.Mixing superheater is integrated in propylene evaporating column top by propylene and steam after vaporization overheated, mixing superheater is integrated in tower top, heat loss during can reducing, reduce and connect pipeline, reduce occupation area of equipment (the autoclave vaporizer of conventional propylene vaporization employing BKU form, floor space is big), reduce cost.Decrease number of devices simultaneously, reduce junction point, reduce leakage point, improve the safety of system.
2, propylene feed, steam charging, fresh air charging, circulating air charging are equipped with effusion meter, and flow measuring data send DCS control system, beyond blast limit, improve safety by material composition in the computing function control system of DCS.
3, the conversion ratio of the first oxidation reactor inner propene is more than 99wt%, and oxidation product acrylic acid content is less than 1%wt.If conversion ratio is the most up to standard, the second oxidation reactor temperature runaway can be caused, destroy the catalyst 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 acrylic aldehyde, improves the yield of target product.
4, the acrolein conversion rate of the second oxidation reactor controls more than 99.9wt%, can effectively control acrylic aldehyde in the polymerization of three-in-one tower and fouling.If conversion ratio is too low, acrylic aldehyde can be caused in the polymerization of three-in-one tower, block tower internals.And the acrylic acid productivity of target product can be reduced.Second oxidation reactor product controls temperature after product steam generator producing steam and is 160-170 DEG C, not only can efficient recovery heat, and can effectively control acrylic acid polymerization.
5, three-in-one tower is to realize washings stripping purification, acrylic acid absorption, the integrated equipment of product cooling combination function simultaneously.Effectively reduce the power loss of fluid conveying, reduce equipment and take up an area and investment.And the washings that three-in-one column overhead is sent into use acrylic acid aqueous solution lightness-removing column tower top discharge containing acetic acid and the acid-bearing wastewater of light component, this sewage sends into three-in-one top of tower, strip first with emission, it is stripped in three-in-one tower top aerofluxus containing the light component of the major part in acid sewage and acetic acid, which reduce the content of impurity in acid-bearing wastewater, be conducive to acrylic acid absorption, and reduce the burden that sewage effluent processes.Add the content of organics in emission simultaneously, improve the calorific value of burned waste gas.Not only save absorption desalted water, decrease discharge of wastewater, and reclaimed useful Organic substance.
6, by controlling the washing water yield, the return water temperature of intercooler that three-in-one column overhead is sent into, 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 tower bottom water solution, removes the difficulty of acetic acid during reducing follow-up refined acrylic acid.Meanwhile, overhead gas temperature is high, more through catalytic burning heat-recoverable.Tower bottom water solution concentration 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 removes Organic substance, and a part sends into the first entry mixers reactor, remaining gas row's air through compressor pressure-raising.After absorption, tail gas 25-40%wt after catalytic burning recycles.Make full use of the useful Organic substances such as steam in circulating air.Simultaneously because tail gas after incineration temperature high (about 100 DEG C), water content are high, it is possible to reduce for controlling the consumption of response system water content steam.Three-in-one column overhead expellant gas first carries out catalytic burning and removes Returning reactor after objectionable impurities, can effectively protect oxidation catalyst, reduces catalyst poisoning, improves catalyst life.The more important thing is the generation that can effectively reduce the by-product such as acetone, propanoic acid, to improve acrylic aldehyde and acrylic acid yield.
8, three-in-one tower bottom quench zone tower internals uses three-dimensional membrane broken bubble column plate.Column plate mass-transfer efficiency is high, and treating capacity is big, and has significant defoaming function, is not required to add defoamer.Stripping section and absorber portion use efficient random packing or structured packing, can improve stripping and assimilation effect.It is provided with cooler, it is ensured that acrylic acid assimilation effect in the middle of three-in-one tower.Absorber portion adds polymerization inhibitor, reduces material polymerization.
Accompanying drawing explanation
Fig. 1 is the structural representation of propylene system of the present invention acrylic acid oxidative absorption system；
Fig. 2 is the structural representation that three-dimensional membrane breaks bubble column plate.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Specific embodiment one
nullA kind of propylene system acrylic acid oxidative absorption system，As shown in Figure 1，Including 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 and the top inlet of the first oxidation reactor 2 connect，The outlet at bottom of the first oxidation reactor 2 and the top inlet of the second oxidation reactor 3 connect，The outlet at bottom of the second oxidation reactor 3 is connected with the lower end import of three-in-one tower 4，It is provided with the first entry mixers 6 on the connecting line of mixing superheater 5 and the first oxidation reactor 2，It is provided with the second entry mixers 7 on the connecting line of the first oxidation reactor 2 and the second oxidation reactor 3，Second oxidation reactor 3 is provided with product vapor generator 8 on the connecting line of three-in-one tower 4，Upper wash water stripping section 9 it is provided with in three-in-one tower 4、Middle part acrylic acid absorber portion 10 and bottom reactant cooling section 11，The upper end of three-in-one tower 4 is provided with washings import 12，The top of three-in-one tower 4 is provided with the exhaust port 13 being connected with the first entry mixers 6，It is provided with tail gas incinerator 22 on the pipeline that exhaust port 13 is connected with the first entry mixers 6，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 the internally installed stripping tower having sieve plate.Use tower plate structure can effectively prevent propylene polymerization from blocking internals, and effectively remove the polymer that propylene produces during storing.Using 10 DEG C of water as adding thermal 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 shell-and-tube heat exchanger, and the lower end of shell-and-tube heat exchanger is provided with tube sheet, can make the gas of propylene vaporization tower 1 from below and steam is uniformly distributed and mix homogeneously.
In this particular embodiment, as shown in Figure 1, propylene steam mixed feeding mouth, inlet exhaust gas and air intlet in first entry mixers 6, being equipped with effusion meter at propylene steam mixed feeding mouth, air intlet and inlet exhaust gas, the air intlet of the first entry mixers 6 and the air intlet of the second entry mixers 7 connect air compressor 15 respectively.It is provided with tail-gas compressor 16 on the pipeline that tail gas incinerator 22 is connected with the first entry mixers 6.
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 washings and adds pipeline 19, and the middle part of three-in-one tower 4 connects cooler 20, the connecting line between three-in-one tower 4 and cooler 20 is connected and has polymerization inhibitor to add pipeline 21.Upper wash water stripping section 9 and middle part acrylic acid absorber portion 10 use efficient random packing or structured packing, if being provided with dried layer solid membrane broken bubble column plate 23 in bottom reactant cooling section 11, every layer of three-dimensional membrane breaks bubble column plate 23 and includes the gas-liquid mass transfer district 24 in lower big little taper type of 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, peripherally disposed on the neighbouring connecting plate between ring diversion plate 27 have some gas-liquid pod apertures 28, between the ring diversion plate 27 and gas rise hole 25 of bottom, form liquid flow into annular space 29.The gas breaking bubble column plate 23 from lower floor's solid membrane enters in gas rise hole 25, enter in gas-liquid mass transfer district 24 by flowing into from liquid together after the lifting liquid membrane that annular space 29 flows into, 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.During gas-liquid mixture flows through gas-liquid pod apertures 28, being affected by oblique eight word directions of ring diversion plate 27, due to the effect of inertia, liquid can be captured and return on column plate, gas then ascends into solid membrane broken bubble column plate in upper strata after gas-liquid pod apertures 28 flows out, thus realizes gas-liquid separation.
Specific embodiment two
One utilizes above-mentioned specific embodiment one propylene system acrylic acid oxidative absorption system to prepare acrylic acid, specifically includes following steps:
1) liquid propene is sent into propylene vaporization tower 1 be vaporizated into propylene gas and refined after, propylene gas is mixed in superheater 5 with feeding after 1.6MPAG steam, propylene vapor is mixed with steam and is superheated to 50-70 DEG C；Wherein water vapour is (1.5-1.8) with the mol ratio of propylene: 1；
2) by fresh air after air compressor 15 compresses, (back amount is the 25-40 of total incineration tail gas amount with the tail gas after tail-gas compressor 16 pressure-raising of the part after catalytic burning from three-in-one tower 4
Wt%), and together send into after the first entry mixers 6 mixes with water vapor mixture from the propylene of mixing superheater 5, it is re-fed into the epimere reaction zone of the first oxidation reactor 2, control epimere reaction zone 17 temperature and be 300-340 DEG C, pressure is 40-60Kpag, after propylene and oxygen carry out oxidation reaction generation acrylic aldehyde and a small amount of acrylic acid under the effect of catalyst, product is entered after people's hypomere cooling zone 18 is cooled to 260 DEG C, being re-fed into the second entry mixers 7, the first oxidation reactor inlet oxygen is (1.6-1.8) with the mol ratio of propylene: 1；
3) the second oxidation reactor 3 is sent into after the product from hypomere cooling zone 18 being mixed in the second entry mixers 7 with the air from air compressor 15, control reaction temperature and be 250-260 DEG C, pressure is 40-60Kpag, acrylic aldehyde and oxygen carry out oxidation reaction under the effect of catalyst and generate acrylic acid, send into three-in-one tower 4 containing acrylic acid product after product steam generator 8 is down to 160-170 DEG C；Second oxidation reactor entrance acrylic aldehyde is (0.75-0.85) with the mol ratio of oxygen: 1；
4) washings are sent into successively down through upper wash water stripping section 9 from three-in-one tower 4 tower top, middle part acrylic acid absorber portion 10 and bottom reactant cooling section 11, acrylic acid product will be contained and pass upward through bottom reactant cooling section 11 successively from feeding at the bottom of three-in-one tower 4 tower, middle part acrylic acid absorber portion 10 and upper wash water stripping section 9, it is washed water containing acrylic acid product to absorb, chilling, obtain, at the bottom of three-in-one tower 4 tower, the acrylic acid aqueous solution that mass concentration is 55-65%, the tail gas that three-in-one tower 4 tower top obtains returns the first oxidation reactor 2 through catalytic burning 22 rear section and recycles, other incineration tail gas are vented.
In this particular embodiment, the first oxidation reaction catalyst is containing molybdenum, the composite catalyst of bismuth element, and the second oxidation reaction catalyst is containing molybdenum, the composite catalyst of 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 by hot melt salt, are used for producing steam.Washings use acrylic acid aqueous solution lightness-removing column tower top discharge containing acetic acid and the acid-bearing wastewater of light component, the light component of acid-bearing wastewater major part after three-in-one tower 4 strips and acetic acid are stripped exhaust port；The tail gas that three-in-one column overhead is discharged is after catalytic burning removes Organic substance, and a part is sent into the first entry mixers 6 through recycle gas compressor 16 pressure-raising and recycled, remaining gas row's air.
Specific embodiment three
It is 99%wt by propylene content, it is refined that oligomer and the liquid propene feeding propylene vaporization tower 1 that heavy constituent content is 0.5%wt carry out propylene gasification, from the 2.0MPAG steam of oxidation reactor by-product send into after the top of propylene vaporization tower 1 mixes with the propylene after vaporization together with enter the mixing superheater 5 at propylene vaporization tower 1 top, 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, carbon dioxide: 6.5%, oxygen: 2.4%.
Control to send into the fresh air inlet amount of the first entry mixers 6, it is ensured that propylene in the mixture of the first entry mixers 6 outlet: oxygen: water (mol ratio)=1:1.7:1.The gaseous 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 oxidation reaction, outlet mass temperatures is 260 DEG C, pressure 50KPAG.Consist of: nitrogen: 67.4%wt, water: 10.2%wt, acrylic aldehyde: 14.0%wt, acrylic acid: 0.7%wt, propylene: 0.08%wt.
In second oxidation reactor 3, conversion zone is equipped with containing molybdenum, the composite catalyst of vanadium.Consist of through the second oxidation reaction afterproduct: nitrogen: 68.9%wt, water: 8.7%wt, acrylic aldehyde: 0.1%wt, acrylic 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 steam generator 8 is down to 170 DEG C.
The washings that three-in-one tower 4 tower top is sent into consist of: water: 96.5%wt, acetic acid: 2.6%wt, acrylic acid: 0.7%wt, other Organic substances: 0.2%wt.
After three-in-one tower 4 carries out washings stripping, acrylic acid absorption, reactant cooling, the acrylic acid aqueous solution discharged at the bottom of tower consists of: acrylic 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) absorbing the content of acetic acid in emission after oxidative absorption is 0.45%wt, and is substantially free of acetic acid in tower top discharge tail gas in common process.
3) result using this patented technology to run shows, in the case of three-in-one tower 4 not being used defoamer, three-in-one tower operates steadily, the problem not occurring causing tower liquid flooding because froth breaking is not thorough.The most three-dimensional membrane breaks bubble plate and has good in vitro mechanical property and defoaming function.
Described above not limitation of the present invention, the present invention is also not limited to the example above.Those skilled in the art, in the essential scope of the present invention, the change made, retrofit, add or replace, and also should belong to protection scope of the present invention.
Claims (9)
1. utilize propylene system acrylic acid oxidative absorption system to prepare an acrylic acid, described propylene
Make acrylic acid oxidative absorption system include propylene vaporization tower, the first oxidation reactor, the second oxidation reactor and
Three-in-one tower, the top of described propylene vaporization tower is provided with mixing superheater, the top of described mixing superheater
Portion's outlet is connected with the top inlet of the first described oxidation reactor, the bottom of the first described oxidation reactor
Outlet is connected with the top inlet of the second described oxidation reactor, and the bottom of the second described oxidation reactor goes out
Mouth is connected with the lower end import of described three-in-one tower, described mixing superheater and the first described oxidation reaction
The first entry mixers, the first described oxidation reactor and the second described oxygen it is provided with on the connecting line of device
Changing and be provided with the second entry mixers on the connecting line of reactor, the second described oxidation reactor is with described
It is provided with product steam generator on the connecting line of three-in-one tower, is provided with in described three-in-one tower
Portion's washings stripping section, middle part acrylic acid absorber portion and bottom reactant quench zone, described three-in-one tower upper
End is provided with washings import, and the top of described three-in-one tower is provided with the first described entry mixers even
The exhaust port connect, the pipeline that described exhaust port is connected with the first described entry mixers is arranged
Tail gas incinerator, the bottom of described three-in-one tower is had to be provided with acrylic acid aqueous solution outlet, it is characterised in that tool
Body comprises the following steps:
1) liquid propene is sent into after propylene vaporization tower is vaporizated into propylene gas, by propylene gas and 1.6-2.0MPaG
Send into after steam in mixing superheater, propylene vapor is mixed with steam and is superheated to 50-70 DEG C；Its
Middle steam is (1.5-1.8) with the mol ratio of propylene: 1；
2) by fresh air after air compressor compresses, with the part after catalytic burning from three-in-one tower top
Tail gas after tail-gas compressor pressure-raising, and together send into first with steam enter from the propylene of mixing superheater
After feed mixer mixing, finally send into the epimere reaction zone of the first oxidation reactor, control the temperature of epimere reaction zone
Degree is for 300-340 DEG C, and pressure is 40-60KPaG, and propylene aoxidizes under the effect of catalyst with oxygen
Reaction generates acrylic aldehyde and a small amount of acrylic acid, the acrylic aldehyde of generation and a small amount of acrylic acid and enters the cooling of hypomere cooling zone
After 260 DEG C, it is re-fed into the mol ratio of the second entry mixers, the first oxidation reactor inlet oxygen and propylene
For (1.6-1.8): 1, send into the 25-40wt% that tail gas is incineration tail gas total amount of the first entry mixers；
3) product of the first oxidation reactor is mixed in the second entry mixers with the air from air compressor
Rear feeding the second oxidation reactor, controls reaction temperature and is 250-260 DEG C, and pressure is 40-60KPaG, propylene
Aldehyde and oxygen carry out oxidation reaction under the effect of catalyst and generate acrylic acid；Containing acrylic acid product through anti-
Product vapor generator temperature is answered to send into three-in-one tower after being down to 160-170 DEG C；Second oxidation reactor entrance third
Olefine aldehydr is (0.75-0.85) with the mol ratio of oxygen: 1；
4) washings are sent into successively down through upper wash water stripping section, middle part acrylic acid from three-in-one column overhead
Absorber portion and bottom reactant cooling section, will contain acrylic acid product from the bottom of three-in-one tower tower send into successively to
On through bottom reactant cooling section, acrylic acid absorber portion district, middle part and upper wash water stripping section, containing acrylic acid
Product be washed water absorb, chilling, obtain the propylene that mass concentration is 55-65% at the bottom of three-in-one tower tower
Aqueous acid.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: described propylene vaporization tower is the internally installed stripping tower having sieve plate, described mixing
Superheater is shell-and-tube heat exchanger, and the lower end of described shell-and-tube heat exchanger is provided with tube sheet.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: it is provided with propylene steam mixed feeding mouth in the first described entry mixers, burns
Burn inlet exhaust gas and air intlet, described propylene steam mixed feeding mouth, air intlet and incineration tail gas
Import department is equipped with effusion meter, and the air intlet of the first described entry mixers mixes with the described second charging
The air intlet of device connects air compressor, described tail gas incinerator and the first described entry mixers respectively
It is provided with tail-gas compressor on the pipeline connected.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: the first described oxidation reactor is calandria type fixed bed reactor, described first
Epimere reaction zone and hypomere cooling zone it is provided with in oxidation reactor.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: the second described oxidation reactor is calandria type fixed bed reactor, described first
Entry mixers and the second described entry mixers are SV pattern static mixer.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: the top of described three-in-one tower connects has washings to add pipeline, three described conjunctions
The middle part of one tower connects cooler, and the described connecting line between three-in-one tower and described cooler connects
It is connected to polymerization inhibitor and adds pipeline.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: described upper wash water stripping section and described middle part acrylic acid absorber portion all use
Efficiently random packing or structured packing, breaks if being provided with dried layer solid membrane in described bottom reactant cooling section
Bubble column plate, every layer of described three-dimensional membrane break bubble column plate include several horizontal distribution in lower big little taper type
Gas-liquid mass transfer district, the bottom in described gas-liquid mass transfer district be provided with opening be loudspeaker flared gas rise
Hole, the top in described gas-liquid mass transfer district is provided with calotte, and the sidepiece in described gas-liquid mass transfer district depends on from top to bottom
Secondary it is provided with the ring diversion plate that several are loudspeaker flared, between neighbouring described ring diversion plate
Connecting plate on peripherally disposed have several gas-liquid pod apertures, be positioned at the described annular water conservancy diversion of bottom
It is provided with liquid between plate and described gas rise hole and flows into annular space.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: in the first described oxidation reactor, catalyst is containing molybdenum, the composite catalyzing of v element
Agent, in the second described oxidation reactor, catalyst is containing molybdenum, the composite catalyst of v element, described first
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, and it is cold that hot melt salt enters fused salt
But device produces 1.6-2.0MPaG steam, uses 10 DEG C of water to be situated between as heating at the bottom of described propylene vaporization tower tower
Matter.
One the most according to claim 1 utilizes propylene system acrylic acid oxidative absorption system to prepare acrylic acid
Method, it is characterised in that: described washings use acrylic acid aqueous solution lightness-removing column tower top discharge containing acetic acid and
The acid-bearing wastewater of light component, the light component of described acid-bearing wastewater major part after stripping and acetic acid are stripped tail gas
Floss hole；The tail gas that described three-in-one column overhead is discharged is after catalytic burning removes Organic substance, and a part is through following
Ring air compressor pressure-raising sends into the first entry mixers, remaining gas row's air.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510431867.7A CN105001072B (en) | 2015-07-21 | 2015-07-21 | Propylene system acrylic acid oxidative absorption system and method |
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| CN201510431867.7A CN105001072B (en) | 2015-07-21 | 2015-07-21 | Propylene system acrylic acid oxidative absorption system and method |
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| CN105001072B true CN105001072B (en) | 2016-08-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105402742B (en) * | 2015-12-01 | 2017-10-17 | 中国天辰工程有限公司 | A kind of incinerator charging danger wastes diluent facilities and its method |
| 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 |
| 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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Inventor after: Gu Xinchun Inventor after: Wang Yuguang Inventor after: Yu Zhi Inventor after: Wu Lijuan Inventor after: Wei Weijian Inventor after: Zhang Zhiming Inventor after: Liu Ying Inventor after: Li Quan Inventor after: Hu Xiaozheng Inventor after: Wang Aifang Inventor after: Miao Yanjun Inventor before: Gu Xinchun Inventor before: Wu Lijuan Inventor before: Wei Weijian Inventor before: Li Quan Inventor before: Hu Xiaozheng Inventor before: Wang Aifang Inventor before: Miao Yanjun Inventor before: Wang Yuguang |
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