CN206033636U - Deamination and retrieve equipment of epoxypropane , propylene in epoxypropane device - Google Patents
Deamination and retrieve equipment of epoxypropane , propylene in epoxypropane device Download PDFInfo
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- CN206033636U CN206033636U CN201621039627.9U CN201621039627U CN206033636U CN 206033636 U CN206033636 U CN 206033636U CN 201621039627 U CN201621039627 U CN 201621039627U CN 206033636 U CN206033636 U CN 206033636U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The utility model discloses a deamination and retrieve equipment of epoxypropane, propylene in epoxypropane device, including deamination adsorption tower, PO rectifying column, condenser, reboiler, propylene recovery tower, tail gas treatment tower, cooler. The utility model discloses equipment structure is simple, has along with the advantage with following away, and the investment is low, and the running cost is low, and product purity is high, is fit for the serialization, semicontinuousization, large -scale production. Be applicable to chloropharin method enterprise and chlorine industry to the tail gas treatment, product processing both can also can be used for liquid phase epoxypropane product to adsorb the deamination as the epoxypropane deamination retrieval and utilization of dropping a hint, and the flow is simple, after will directly discharging atmospheric tail gas originally and passing through device deamination and multistage edulcoration retrieval and utilization, and thorough deamination, it more than 98%, has reduced the pollution of environment to take off inorganic ammonia, and the adoption the utility model discloses can retrieve whole epoxypropane and propylene by -product, economy and energy -conserving benefit are showing very much.
Description
Technical field
This utility model belongs to petrochemical industry, the equipment of the refined removing impurities of the expoxy propane being related in chemical industry for making chlorine and alkali, especially
Which is related to deamination in a kind of propylene oxide unit and reclaims the equipment of expoxy propane, propylene.
Background technology
In recent years, at 3,000,000 tons/year, demand was every year all with 5-10%'s for domestic expoxy propane (PO) production capacity
Rate of increase extends.PO is the third-largest acryloyl derivative in addition to polypropylene and acrylonitrile, is important basic organic chemical industry synthesis
Raw material, mainly for the production of polyethers, Propylene Glycol etc..It is also forth generation detergent nonionic surfactant, oil field demulsifier,
The primary raw material of farm chemical emulgent etc..Synthesis of Propylene Oxide mainly adopts chlorohydrination and conjugated oxidation in the world.Due to chlorine
Alcohol method process is simple, technology maturation, construction scale are flexible, and conjugated oxidation technological process is long, and technical difficulty is larger, unit scale
Can not it is too small and by joint product balance restricted, so more than 95% producer of China using chlorohydrination produce expoxy propane.Chlorine
Alcohol method technique, does not adopt more than high 10,000,000 yuan/year of production cost of carbide slurry technique (40,000 tons of PO unit scales), and adopts
During carbide slurry does the technique of serosity, maximum problem is exactly that system contains ammonia.The presence of ammonia causes the aldehyde value of system cannot be accurate
Really determine, increase system basicity so that product is not up to standard, ammonia can also generate various isopropanolamines with propylene oxide reaction,
And the presence of ammonia can cause downstream product polymerization effect poor, cause performance not up to standard.Ammonia main source be carbide slag from
Band, reaction produce ammonia, the Chinese patent (patent No.：201220362610.2) disclose at raw material calcium carbide dreg slurry by gas
Carry or heat carbide slag slurry and carry out partial removal ammonia, the method there is a problem of can not deamination, heating process high energy consumption completely,
Either heated with hot water heating or steam, with 40,000 tons of expoxy propane/year scale calculating, carbide slurry chlorohydrination technique, the skill
Art heating deamination needs energy consumption 2000kW or so, converts steam energy consumption 3.5t/h.Cai Mingsheng is " carbide slag is applied in expoxy propane
The method ammonia in carbide slag removed using direct-fired method is provided in the method for removing ammonia in production ", by increasing
Carbide slag emulsion head tank, while increase steam heating in carbide slag head tank to realize, using the de- inorganic ammonia effect of the method
Rate 85% or so.But as PO response systems also have ammonia to produce, so can not be taken off completely using above two method
Ammonia is removed, ammonia in system, can be all carried all the time, it is therefore desirable to which, by a large amount of emptying come secondary deamination, emptying can bring about environment
Pollution, the low problem of product yield.
Meanwhile, ammonia can generate various isomery isopropanolamines, isopropanolamine meeting when temperature is less than 30 DEG C with expoxy propane
Solidify and cause rectifying tower top heat exchanger and subsidiary pipeline blocking and stop production, so existing de-light rectification column all can not be at low temperature
Rectification, and ammonia abjection is difficult after raising pressure, and also under high pressure, rectifying column temperature is high, is susceptible to side reaction with asking for being polymerized
Topic.Therefore ammonia is had to be directly discharged in air, due to exhaust system temperature it is higher so that expoxy propane loss is larger.
In propylene recovery process, Chinese utility model patent application (application number：CN201510961254.4) propose to put
When in air, density of propylene is more than to more than 50%, can directly by washing come Propylene recovery, so that being during washing
In system, expoxy propane of high added value etc. is directly reacted with water and obtains propylene product.The propylene dropped a hint in actual production process
, in 20%wt or so, after density of propylene is too high, tower top temperature is low, now the ammonia and propylene oxide reaction of tower top for general content
Isopropanolamine of generation etc. can block pipeline.And due to wherein also containing the expoxy propane that concentration is higher, using directly washing
Dropping a hint for 50% concentrations above propylene can waste the expoxy propane of a large amount of high added values.So the utility application is carried
For method ratio be more suitable in negative pressure recovery tower after negative pressure multistage condensation at low temperature, density of propylene reaches more than 50%
Fixed gas, but the greatest problem that negative pressure is brought is exactly that system equipment is more, and floor space is very big, high energy consumption, while
Condensation at low temperature is needed to reclaim expoxy propane, during direct condensation at low temperature is reclaimed, the boiling point substance such as harmful substance propionic aldehyde compares ring
Ethylene Oxide is big, can cause in condensation process impurity cannot discharge system and the problem that circulates always, and negative pressure system also needs to
Vacuum equipment and supporting reflux accumulator is equipped with, for inflammable and explosive device negative-pressure operation, once there is the suction of air internal hemorrhage due to trauma, than
It is easier to reach explosion limit and produce explosion danger, so negative pressure device has high demands equipment and pipe-line system.Using negative pressure+
Deep cooling reclaims the technique that brings up to more than 50% directly to wash by density of propylene, as in propylene, organism kinds are more, has
Machine thing different solubility in water, so having high demands to washing flow-control, after not so causing washing, product purity difference is non-
Chang great.
Utility model content
The purpose of this utility model is to overcome the deficiencies in the prior art, there is provided a kind of propylene oxide unit deamination
And the equipment of expoxy propane, propylene is reclaimed, the equipment investment is little, energy consumption is low, by using the equipment deamination and reclaiming epoxy third
Alkane, propylene eliminate original technique environmental pollution, while reclaim having obtained high value-added product.
The purpose of this utility model is achieved through the following technical solutions：
Deamination the equipment of expoxy propane, propylene is reclaimed in a kind of propylene oxide unit, it is smart including deamination adsorption tower 1, PO
Evaporate tower 2, condenser 3, reboiler 4, propylene recovery tower 5, vent gas treatment tower 7；Described 1 tower top of deamination adsorption tower is provided with charging
Mouthful, 1 bottom of towe discharging opening Jing of deamination adsorption tower discharging pipelines 10 are connected with the charging aperture of described PO rectifying columns 2,2 bottom of PO rectifying columns
Portion is provided with PO discharge nozzles 12, and PO discharge nozzles are provided with branch road Jing reboilers 4 and are connected with the reflux inlet of PO rectifying columns 2, PO rectification
Light fraction outlet at the top of tower 2 is connected with condenser 3, and the condensate outlet of condenser 3 is connected with the liquid return hole of PO rectifying columns 2,
The fixed gas outlet of condenser 3 is connected with the charging aperture of described propylene recovery tower 5；Described 5 tower top of propylene recovery tower is provided with
Gas outlet, 5 top of propylene recovery tower be provided with inlet and be connected with absorbent water influent pipeline 14, and 5 bottom of towe of propylene recovery tower goes out
Liquid mouth is connected with absorbent water influent pipeline makes absorbent form circulated sprinkling；The discharging pipeline 10 of described deamination adsorption tower 1 sets
There are tail gas branch road 11 and the air inlet of vent gas treatment tower 7 to be connected, 7 top of vent gas treatment tower is provided with cleaning mixture entrance and is entered with cleaning mixture
Liquid pipe 16 connects, and 7 bottom of towe of vent gas treatment tower is provided with liquid outlet Jing coolers 9 and cleaning mixture entrance and is connected to remove ammonia and is dissolved in water
The heat produced during heat release.
Absorbent circulating pump 6 is provided with described absorbent water influent pipeline 14, in the water outlet end of absorbent circulating pump 6
It is additionally provided with absorbent waste line 15.
Cleaning mixture recycle column 8 is provided with connecting line between 7 liquid outlet of vent gas treatment tower and cooler 9, in washing
The water outlet end of liquid recycle column 8 is additionally provided with cleaning mixture waste line 17.
The number of described deamination adsorption tower 1 is at least one；When having at least two deamination adsorption towers 1, deamination adsorption tower 1
It is arranged in parallel.
Equipment described in the utility model individually can be arranged, it is also possible to which complete skid is used.
Using this utility model equipment deamination and the method that reclaims expoxy propane, propylene, step is as follows：
Step (1), absorption deamination：Raw material is passed through into deamination adsorption tower, raw material passes through adsorbent and adsorbed
Deamination, the material after deamination enter the PO rectifying columns in downstream；Adsorbent carries out parsing regeneration, and the tail gas for parsing is entered at tail gas
Reason tower；
Step (2), the material Jing after step (1) deamination carry out rectification in PO rectifying columns, and the expoxy propane for obtaining is smart from PO
The discharge of tower bottom of towe is evaporated, tower top light component is discharged from tower top, and the condensed rear liquid-phase reflux of tower top light component is to PO rectifying columns, fixed gas
Propylene recovery tower is gone further to process；The main component of described tower top light component is ammonia, propylene, acetylene, oxirane, acetaldehyde
Deng；
Step (3), at operating pressure 0.1-1MPa, temperature 10-50 DEG C, into propylene recovery tower gas using absorb
The impurity such as oxirane, micro expoxy propane, acetaldehyde, propionic aldehyde in agent absorption removing gas, control the matter of absorbent and gas
Amount is 5-200 than (i.e. liquid-gas ratio)：1, obtain the gas that propylene content is not less than 98%；Described absorbent is alcohol-water solution；
The tail gas that step (4), step (1) parsing are obtained enters vent gas treatment tower, after being washed using cleaning mixture circulated sprinkling,
After discharge gas reaches environmental protection standard, air is directly discharged into；Described cleaning mixture is water or alcohol-water solution.
In step (1), described raw material is that gaseous expoxy propane is dropped a hint and/or the liquid epoxy third containing inorganic ammonia
Alkane.Expoxy propane middle main component of dropping a hint is as follows：The total ammonia of 50-75wt% expoxy propane, 0.1-3wt% is (including organic amine, nothing
Machine ammonia), 5-30wt% propylene.In liquid epoxy propane containing inorganic ammonia, inorganic ammonia content is in 200-5000ppm.
Described adsorbent is that 3A molecular sieves or 3A load the molecular sieve of reinforcing as adsorbent；During absorption deamination, take off
Adsorptive pressure in ammonia adsorption tower is 0.1-2MPa, and adsorption temp is 5-80 DEG C, and absorption air speed is 0.001-15m/s.Preferably,
Adsorptive pressure in deamination adsorption tower is 0.12-0.5MPa, and adsorption temp is 30-50 DEG C, and absorption air speed is 0.01-5m/s.Enter
One step is preferred, and adsorptive pressure is 0.12-0.16MPa, and adsorption temp is 30-50 DEG C, and absorption air speed is 0.01-1m/s.Through
After absorption deamination, the deamination rate of ammonia can reach more than 98%.
Air speed refers to that (i.e. adsorbent loads layer for the volume flow of material of the stream in adsorption tower and adsorption tower sectional area
Sectional area) ratio, unit m/s.
The pressure of adsorbent parsing regeneration is 0-1.8MPa, and temperature is 120-390 DEG C, and parsing air speed is 0.01-30m/s,
Preferably 0.01-5m/s, parsing medium are the noble gases such as nitrogen.Deamination adsorption tower is passed through the noble gases such as nitrogen to adsorbent
Parsing regeneration is carried out, regenerative process is divided into two steps of Thermal desorption and cold blowing, and, in 120-390 DEG C of Thermal desorption, the later stage is in 10- for early stage
At 40 DEG C, cold blowing is easy to next cycle absorption to the cooling of deamination adsorption tower.In the tail gas that parsing is obtained, main component is nitrogen, together
When also contain substantial amounts of ammonia.
The molecular sieve of described 3A load reinforcings is MgO-3A molecular sieves, SiO2- 3A molecular sieves or MgO-SiO2Modified 3A point
Son sieve；In MgO-3A molecular sieves, the content of MgO is 1-5wt%；SiO2SiO in -3A molecular sieves2Content be 2-10wt%；MgO-
SiO2In modified 3A molecular sieves, the content of MgO is 1-5wt%, SiO2Content be 2-10wt%.
Described MgO-3A molecular sieves are prepared by the following method and obtain：3A molecular sieves are placed in into Mg (NO3)2·6H2O is molten
0.1-10h, wherein Mg (NO is impregnated in liquid at 25-35 DEG C3)2·6H2The concentration of O solution be 0.1-1mol/L, 3A molecular sieves with
Mg(NO3)2·6H2The quality volume of O solution is 1：2-10g/mL；Filter and must precipitate, at being deposited in 25-50 DEG C, be dried 0.1-
24h, 120 DEG C of holding 0.1-4h, at 150-600 DEG C, nitrogen protection constant temperature 0.1-3h obtains MgO-3A molecular sieves.
Described SiO2- 3A molecular sieves are prepared by the following method and obtain：By 3A molecular sieves, non-polar organic solvent and repair
Decorations agent mixing, reacts 0.1-24h at 25-35 DEG C, the wherein mass volume ratio of 3A molecular sieves and non-polar organic solvent is 1：
0.1-100g/mL, preferably 1：The mass volume ratio of 0.1-10g/mL, 3A molecular sieve and dressing agent is 1：0.1-20g/mL, it is excellent
Elect 1 as：0.1-1g/mL；0.1-24h is dried at being deposited in 100-140 DEG C, is warming up to 550 DEG C under nitrogen protection and in the temperature
The lower roasting 0.1-6h of degree, obtains SiO2- 3A molecular sieves.Wherein, described non-polar organic solvent is hexamethylene；Dressing agent is Si
(OCH3)4。
Described MgO-SiO2Modified 3A molecular sieves are prepared by the following method and obtain：3A molecular sieves are placed in into Mg
(NO3)2·6H20.1-10h, wherein Mg (NO is impregnated in O solution at 25-35 DEG C3)2·6H2The concentration of O solution is 0.1-
1mol/L, 3A molecular sieve and Mg (NO3)2·6H2The mass volume ratio of O solution is 1：1-10g/mL；Filter and must precipitate, be deposited in
0.1-24h is dried at 25-50 DEG C, is easy to support structures stable, then 120 DEG C are dried 0.1-4h removing solvents, at 150-600 DEG C
Lower nitrogen protection constant temperature 0.1-3h removes nitrogen oxides and obtains MgO-3A molecular sieves；By MgO-3A molecular sieves, nonpolar organic molten
Agent, wherein dressing agent mixing, the mass volume ratio 1 of MgO-3A molecular sieves and non-polar organic solvent：0.1-100g/mL, preferably
For 1：The mass volume ratio of 0.1-10g/mL, MgO-3A molecular sieve and dressing agent is 1：0.1-20g/mL, preferably 1：0.1-1g/
0.1-24h is reacted at mL, 25-35 DEG C；Be dried 0.1-24h at being deposited in 100-140 DEG C, under nitrogen protection according to 10-60 DEG C/
The speed of 10min is progressively warming up to 550 DEG C and roasting 0.1-6h at such a temperature, obtains MgO-SiO2Modified 3A molecular sieves.Its
In, described non-polar organic solvent is hexamethylene；Dressing agent is Si (OCH3)4。
3A molecular sieves can efficiently remove small-molecule substance such as ammonia, water etc. in PO as adsorbent, but work as PO and ammonia
In the presence of common with water, the acidic site of ammonia and water and its surface that 3A molecular sieves can not only adsorb small molecule is more easy to be catalyzed PO
The by-products such as Propylene Glycol are generated, active sites and the blocking duct of molecular sieve surface is covered, and then is reduced the absorption of 3A molecular sieves
Selectivity and adsorbance.Therefore MgO, SiO are further adopted2Modifying surface and appropriate passivation to 3A molecular sieves, shows
Work improves absorbability and adsorptive selectivity of the 3A molecular sieves to PO small molecular materials.
In step (2), the operating pressure of PO rectifying columns is 0.1-1.5MPa, preferably 0.1-0.5MPa, and tower top temperature is
2-100 DEG C, preferably 6-60 DEG C, reflux ratio is 0.1-300, preferably 50-250, more preferably 140-160.Through step
Suddenly, after (2) rectification, the content of the expoxy propane discharged from bottom of towe is in more than 99.9%wt.
Reflux ratio refers to the ratio of the mass flow of the mass flow and PO rectifying column tower tops discharging being back in PO rectifying columns
Value.
In step (3), in described absorbent, the concentration of alcohol is 1-60wt%；Described alcohol is methanol, ethanol, in propanol
One or more.The mass ratio of absorbent and gas is preferably 100-150：1.
In step (4), the mass ratio (i.e. liquid-gas ratio) of cleaning mixture and tail gas is controlled in 1-100：1.Described cleaning mixture is
The alcohol-water solution of water or determining alcohol for 1-60wt%, described alcohol is methanol, ethanol, one or more in propanol.When with alcohol
Aqueous solution is used as the absorbent waste liquid that can also be discharged using step (3) during cleaning mixture.
During in vent gas treatment tower, cleaning mixture circulated sprinkling washing heel row is deflated, ammonia level reaches environmental protection standard, is emitted into
Air.
This utility model equipment is equally applicable to ethylene oxide device drops a hint and deamination reclaims oxirane.
Using this utility model equipment deamination and expoxy propane, propylene is reclaimed, based on following principle：Expoxy propane is put by this
Air or inorganic ammonia content are passed through deamination adsorption tower in below 200-5000ppm states containing ammoniacal liquor propylene oxide feed, by epoxy
Ammonia gas absorption removing in propane, due to being stripped of ammonia, so as to avoid ammonia and propylene oxide reaction from generating high boiling point, Gao Ning
The isopropanolamine of solid point goes to block pipeline, therefore material can be passed through the PO rectifying columns in downstream, and control tower top low temperature carrys out rectification,
Bottom of towe in PO rectifying columns obtains high-purity product propylene.Even if having micro ammonia to enter PO rectifying columns, due to ammonia
Belong to light component, therefore in PO rectifying columns, the ammonia and expoxy propane of high concentration are enriched with tower top and bottom of towe respectively, are reduced
The probability of heavy constituent isopropanolamine is generated, so as to increase the anti-clogging of PO rectifying columns.Further, since expoxy propane and water meeting
Generation vigorous reaction, is introduced into propylene recovery tower and expoxy propane will be caused directly to be reacted and reduction epoxy with the water in absorbent
Propane recovering rate, thus according to Related product physical property after, it is necessary to first pass through PO rectifying columns, it is after reclaiming expoxy propane, remaining
Micro oxirane, acetaldehyde etc. are dissolved in water or the impurity of alcohol-water solution just removes propylene recovery tower washing Propylene recovery, such that it is able to
Expoxy propane and propylene is reclaimed to greatest extent, reduces the generation of waste water.
Compared to the prior art, the beneficial effects of the utility model are：
1st, this utility model equipment is applied to chlorohydrination enterprise and chlorine industry to vent gas treatment, Product processing, can both make
Drop a hint deamination reuse for expoxy propane, it is also possible to adsorb deamination for liquid phase epoxidation bromopropane product, and while go for
Ethylene oxide device.This utility model equipment is dropped a hint for expoxy propane, product propylene deamination, and flow process is simple, by original
After directly discharging the tail gas of air by device deamination multistage remove impurity reuse, thorough deamination takes off inorganic ammonia more than 98%,
The pollution of environment is reduced, absorbent low cost, the advantage for easily obtaining, environmental friendliness, material are corrosion-free to equipment, and energy consumption is low,
Have a extensive future.And whole expoxy propane and propylene side-product can be reclaimed using this utility model, according to 40,000 tons/year of PO
Unit scale meter, energy consumption are only 150kW, reclaim expoxy propane and propylene product can bring the side-product of 5,000,000 yuan/year to receive
Enter, economic and energy saving benefit highly significant.Therefore this utility model is for the manufacturing enterprise with chlorohydrination as technique, 40,000 tons of rule
The propylene oxide unit of mould can imitate more than 15,000,000 yuan/year for enterprise's wound every year, make a general survey of domestic 3,000,000 tons/year of production capacity,
Calculate according to 50% ratio, effect more than 500,000,000 can also be created every year.
2nd, this utility model need not increase air stripping deamination apparatus, involved overall skid-mounted device structure letter in system
Single, with the advantage walked, investing low, running cost is low, and product purity is high, is adapted to serialization, semicontinuous, scale metaplasia
Produce.
3rd, this utility model flow process is short, propene feed concentration no requirement (NR), selects using water and alcohol-based mixtures as absorption
Agent, alcohols are big for aldehyde type impurities dissolubility, so circulating load is for the recovery purity of propylene is substantially without impact, be not in because
The problem for causing the propylene for reclaiming not up to standard for Feedstock fluctuation.
Description of the drawings
Fig. 1 is deamination to reclaim the equipment of expoxy propane, propylene in this utility model propylene oxide unit.
In figure, 1- deamination adsorption towers, 2-PO rectifying columns, 3- condensers, 4- reboilers, 5- propylene recovery towers, 6- absorbent
Circulating pump, 7- vent gas treatment towers, 8- detergent circulators, 9- coolers, 10- discharging pipelines, 11- tail gas branch roads, 12-PO dischargings
Pipe, 13- branch roads, 14- absorbent feed tubes, 15- absorbent waste lines, 16- cleaning mixture feed tubes, 17- cleaning mixture waste pipes
Road.
Specific embodiment
With reference to examples of implementation, this utility model is further illustrated, following examples of implementation are illustrative, be not limit
Qualitatively, it is impossible to limit protection domain of the present utility model with following enforcements.
As shown in figure 1, deamination the equipment of expoxy propane, propylene is reclaimed in a kind of expoxy propane, including deamination adsorption tower
1st, PO rectifying columns 2, condenser 3, reboiler 4, propylene recovery tower 5, vent gas treatment tower 7；Described 1 tower top of deamination adsorption tower is provided with
Charging aperture, 1 bottom of towe discharging opening Jing of deamination adsorption tower discharging pipelines 10 are connected with the charging aperture of described PO rectifying columns 2, PO rectification
2 bottom of tower is provided with PO discharge nozzles 12, and PO discharge nozzles are provided with branch road Jing reboilers 4 and are connected with the reflux inlet of PO rectifying columns 2, PO
Light fraction outlet at the top of rectifying column 2 is connected with condenser 3, and the condensate outlet of condenser 3 is connected with the liquid return hole of PO rectifying columns 2
Connect, the fixed gas outlet of condenser 3 is connected with the charging aperture of described propylene recovery tower 5；Described 5 tower top of propylene recovery tower sets
There is gas outlet, 5 top of propylene recovery tower is provided with inlet and is connected with absorbent water influent pipeline 14, in described absorbent feed liquor
Pipeline 14 is provided with absorbent circulating pump 6, is additionally provided with absorbent waste line 15 in the water outlet end of absorbent circulating pump 6, and third
The liquid outlet of 5 bottom of towe of alkene recovery tower is connected with absorbent water influent pipeline makes absorbent form circulated sprinkling, and absorbent saturation absorbs
Effect detects unqualified replacing absorbent later of working off one's feeling vent one's spleen by in-line analyzer；The discharging pipeline of described deamination adsorption tower 1
10 are provided with tail gas branch road 11 is connected with the air inlet of vent gas treatment tower 7, and 7 top of vent gas treatment tower is provided with cleaning mixture entrance and washing
Liquid feed tube 16 connects, 7 bottom of towe of vent gas treatment tower be provided with liquid outlet Jing coolers 9 and cleaning mixture entrance be connected to remove ammonia it is molten
The heat produced during water heat release, is provided with the connecting line between 7 liquid outlet of vent gas treatment tower and cooler 9 and washes
Liquid recycle column 8 is washed, and cleaning mixture waste line 17 is additionally provided with the water outlet end of cleaning mixture recycle column 8.
Using the said equipment deamination and the method that reclaims expoxy propane, propylene, step is as follows：
Step (1), absorption deamination：Raw material is passed through into deamination adsorption tower 1, raw material passes through adsorbent and adsorbed
Deamination, the material after deamination enter the PO rectifying columns 2 in downstream；Adsorbent carries out parsing regeneration, and the tail gas for parsing enters tail gas
Treating column 7；
Step (2), the material Jing after deamination in step (1) carry out rectification in PO rectifying columns 2, and the expoxy propane for obtaining is from PO
2 bottom of towe of rectifying column is discharged, and tower top light component is discharged from tower top, and after the condensed device 3 of tower top light component is condensed, liquid-phase reflux is smart to PO
Tower 2 is evaporated, fixed gas goes propylene recovery tower 5 further to process；
Step (3), at operating pressure 0.1-1MPa, temperature 10-50 DEG C, into propylene recovery tower 5 gas using inhale
Impurity, control absorbent and the gases such as oxirane, micro expoxy propane, acetaldehyde, propionic aldehyde in receipts agent absorption removing gas
Mass ratio (i.e. liquid-gas ratio) is 5-200：1, obtain the gas that propylene content is not less than 98%；
The tail gas that step (4), step (1) parsing are obtained enters vent gas treatment tower 7, is washed using cleaning mixture circulated sprinkling
Afterwards, after discharge gas reaches environmental protection standard, it is directly discharged into air.
Embodiment 1
Expoxy propane mixed gas (i.e. expoxy propane is dropped a hint) are taken, main component is as follows：Expoxy propane 75wt%, propylene
22wt%, ammonia 3wt%, with flow 2m3/ h is passed through deamination adsorption tower 1, and through 3A molecular sieves, (3A molecular sieves are loaded from top to bottom
The diameter of layer is a diameter of 200mm of deamination adsorption tower, and length is 1000mm) carry out absorption deamination, 40 DEG C of adsorption temp, absorption
Pressure 0.12MPa, the Gaseous materials after deamination are discharged from deamination adsorption tower bottom discharge mouth, and in material, ammonia concentration is reduced to
308ppm, deamination rate are 98.9%.
Embodiment 2
Expoxy propane mixed gas are taken, main component is as follows：Expoxy propane 75%wt, propylene 22%wt, ammonia 3%wt,
With flow 2m3/ h is passed through deamination adsorption tower 1, MgO-3A molecular sieves (the molecular sieve filling diameter being modified through MgO from top to bottom
200mm, length 1000mm) carry out absorption deamination, 40 DEG C of adsorption temp, adsorptive pressure 0.12MPa, the Gaseous materials after deamination from
Deamination adsorption tower bottom discharge mouth is discharged, and in material, ammonia concentration is reduced to 153ppm, and deamination rate is 99.49%.
Wherein, in MgO-3A molecular sieves, content of MgO is 5wt%, and MgO-3A molecular sieves are obtained by following methods：Take 3A molecules
Sieve 10g, the Mg (NO of 0.4mol/L3)2·6H23A molecular sieves are immersed in Mg (NO at 35 DEG C of temperature by O solution 35mL3)2·
6H2In O solution, sonic oscillation 2h is filtered, is deposited at 50 DEG C and is dried 24h, then 120 DEG C of holding 2h, finally at 280 DEG C
Nitrogen protection constant temperature 1h obtains the MgO-3A molecular sieves of content of MgO 5wt%.
Embodiment 3
Expoxy propane mixed gas are taken, main component is as follows：Expoxy propane 75wt%, propylene 22wt%, ammonia 3wt%,
With flow 2m3/ h is passed through deamination adsorption tower 1, from top to bottom through SiO2(molecular sieve loads diameter 200mm, length to -3A molecular sieves
Absorption deamination carried out 1000mm), 40 DEG C of adsorption temp, adsorptive pressure 0.12MPa, the Gaseous materials after deamination are from deamination adsorption tower
Bottom discharge mouth is discharged, and in material, ammonia concentration is reduced to 112ppm, and deamination rate is 99.63%.
Wherein, SiO2SiO in -3A molecular sieves2Content is 5wt%, SiO2- 3A molecular sieves are obtained by following methods：Take 3A point
Son sieve 10g, adds hexamethylene 55mL at 35 DEG C, adds the Si (OCH of 5mL3)4Impregnate at 35 DEG C, sonic oscillation 2h, filter,
24h is dried below at 120 DEG C, is warming up to 550 DEG C under nitrogen protection and roasting 1h at such a temperature, is obtained the SiO of 5%wt2-
3A molecular sieves.
Embodiment 4
Expoxy propane mixed gas are taken, main component is as follows：Expoxy propane 75wt%, propylene 22wt%, ammonia wt 3%,
With flow 2m3/ h is passed through deamination adsorption tower 1, from top to bottom through MgO-SiO2(molecular sieve loads diameter to modified 3A molecular sieves
200mm, length 1000mm) carry out absorption deamination, 40 DEG C of adsorption temp, adsorptive pressure 0.12MPa, the Gaseous materials after deamination from
Deamination adsorption tower bottom discharge mouth is discharged, and in material, ammonia concentration is reduced to 45ppm, and deamination rate is 99.85%.
MgO-SiO2Content of MgO 3wt% in modified 3A molecular sieves, SiO2Content 5wt%, MgO-SiO2Modified 3A molecular sieves
It is obtained by following methods：3A molecular sieve 10g are taken, at 35 DEG C below using the Mg (NO of 0.4mol/L3)2·6H2In O solution 19mL
Dipping, sonic oscillation 2h；Filter, be deposited in 50 DEG C and be dried 24h below, then 2h is dried at 120 DEG C, finally at 280 DEG C
Nitrogen protection constant temperature 1h obtains the MgO-3A molecular sieves of 3wt%；Add in the MgO-3A molecular sieves strengthened toward the 10.3g of above-mentioned acquisition
Enter hexamethylene 55mL, add the Si (OCH of 5mL3)4Impregnate at 35 DEG C, sonic oscillation 2h, filter, be dried at 120 DEG C below
24h, the programming rate for automatically controlling 50 DEG C/10min under nitrogen protection in Muffle furnace are warming up to 550 DEG C and at 550 DEG C
Roasting 1h, that is, obtain 3%wtMgO-5%wtSiO2Modified 3A molecular sieves.
Embodiment 5
Expoxy propane mixed gas are taken, main component is as follows：Expoxy propane 75wt%, propylene 22wt%, ammonia 3wt%,
With flow 2m3/ h is passed through deamination adsorption tower 1, from top to bottom through MgO-SiO2(molecular sieve loads diameter to modified 3A molecular sieves
200mm, length 1000mm) carry out absorption deamination, 40 DEG C of adsorption temp, adsorptive pressure 0.12MPa, the Gaseous materials after deamination from
Deamination adsorption tower bottom discharge mouth is discharged, and in material, ammonia concentration is reduced to 28ppm, and deamination rate is 99.91%.
MgO-SiO2In modified 3A molecular sieves, content of MgO is 5wt%, SiO2Content is 5wt%, MgO-SiO2Modified 3A point
Son sieve is obtained by following methods：3A molecular sieve 10g are taken, at 35 DEG C below using the Mg (NO of 0.4mol/L3)2·6H2O solution
Impregnate in 35mL, sonic oscillation 2h；Filter, be deposited in 50 DEG C and be dried 24h below, then 2h is dried at 120 DEG C, is finally existed
At 280 DEG C, nitrogen protection constant temperature 1h obtains the MgO-3A molecular sieves of 5wt%；Toward the 10.5g MgO-3A molecular sieves of above-mentioned acquisition
Hexamethylene 55mL is added, the Si (OCH of 5mL are added3)4Impregnate at 35 DEG C, sonic oscillation 2h, filter, be dried at 120 DEG C below
24h, the programming rate for automatically controlling 50 DEG C/10min under nitrogen protection in Muffle furnace are warming up to 550 DEG C and at 550 DEG C
Roasting 1h, that is, obtain 5%wtMgO-5%wtSiO2Modified 3A molecular sieves.
Embodiment 6
Expoxy propane mixed gas are taken, main component is as follows：Expoxy propane 74wt%, propylene 20.4wt%, acetylene
2.5wt%, ammonia 2.5wt%, acetaldehyde 0.2wt%, propionic aldehyde 0.1wt%, oxirane 0.3wt%, with flow 2.5m3/ h is passed through
Deamination adsorption tower 1, carries out absorption deamination through 3A molecular sieves (molecular sieve loads diameter 200mm, length 1000mm) from top to bottom,
30 DEG C of adsorption temp, adsorptive pressure 0.16MPa, the Gaseous materials after deamination are discharged from 1 bottom discharge mouth of deamination adsorption tower, material
Middle ammonia concentration 223ppm；The material of Jing deaminations sends into PO rectifying columns 2, pressure 0.14MPa, 6 DEG C of tower top temperature, control of reflux ratio
150, rectification is obtained qualified PO products, discharges from 2 bottom discharge mouth of PO rectifying columns, and PO product purities 99.98wt%, ammonia contain
Amount 30ppm；2 tower overhead gas flow of PO rectifying columns is 0.51m3/ h, mass flow are 2.4kg/h, into propylene recovery tower, with
The ethanol water washing of 5wt%, spray flux control 0.4m3/ h (350kg/h), ethanol water can circulated sprinkling always,
Changed after absorbent saturation again, 5 tower top of propylene recovery tower obtains the gaseous mixture of 98wt% propylene and 2wt% acetylene.
Adsorbent in deamination adsorption tower 1 adopts nitrogen for parsing medium, regenerates at pressure 0.2MPa, 220 DEG C of temperature
3h, nitrogen flow are controlled to 400Nm3/h(366m3/ h), then it is standby to cool to 35 DEG C of cooling 1h next cycles.The tail gas for parsing
Vent gas treatment tower 7 is passed through with 550kg/h, under 35 DEG C of temperature, pressure 0.18MPa, the methanol-water of the 3wt% of 850kg/h is passed through
Except ammonia, in the passing nitrogen of vent gas treatment tower top discharge, ammonia concentration is 46ppm, and wherein, the methanol of 3wt% is water-soluble for solution washing
Liquid circulated sprinkling is used, and is changed after cleaning mixture saturation again.
Embodiment 7
Expoxy propane mixed gas are taken, main component is as follows：Expoxy propane 74wt%, propylene 20.4wt%, acetylene
2.5wt%, ammonia 2.5wt%, acetaldehyde 0.2wt%, propionic aldehyde 0.1wt%, oxirane 0.3w t%, with flow 2.5m3/ h leads to
Enter deamination adsorption tower 1, from top to bottom through MgO-SiO2(molecular sieve loads diameter 200mm, length to modified 3A molecular sieves
5) 1000mm, molecular sieve carry out absorption deamination, 30 DEG C of adsorption temp, adsorptive pressure 0.16MPa, the gaseous state after deamination with embodiment
Material is discharged from 1 bottom discharge mouth of deamination adsorption tower, ammonia concentration 185ppm in material；Material through deamination is sent into into PO smart
Tower 2 is evaporated, 6.5 DEG C of tower top temperature, pressure 0.14MPa, control of reflux ratio 150, rectification are obtained qualified PO products, from PO rectifying columns
2 bottom discharge mouths are discharged, PO product purities 99.99wt%, ammonia level 9ppm；2 tower overhead gas flow of PO rectifying columns is 0.5m3/
H, mass flow are 2.37kg/h, into propylene recovery tower, are washed with the ethanol water of 5wt%, spray flux control 0.4m3/h
(350kg/h), the top of propylene recovery tower 5 obtains the gaseous mixture of 98wt% propylene and 2wt% acetylene.
Adsorbent in deamination adsorption tower 1 adopts nitrogen for parsing medium, regenerates at pressure 0.2MPa, 220 DEG C of temperature
3h, nitrogen flow are controlled to 400Nm3/h(366m3/ h), then it is standby to cool to 35 DEG C of cooling 1h next cycles.The tail gas for parsing
Vent gas treatment tower 7 is passed through with 553kg/h, under 35 DEG C of temperature, pressure 0.18MPa, the methanol-water of the 3wt% of 850kg/h is passed through
Except ammonia, in the passing nitrogen of vent gas treatment tower top discharge, ammonia concentration is 33ppm for solution washing.
Above-mentioned raw materials gas is repeatedly adsorbed into -10 cycles of parsing under identical adsorption conditionses, adsorbent is according to the present embodiment
Renovation process regeneration.The material through deamination after the 10th cycle is taken, now the later tail gas ammonia content of deamination is sent for 22ppm
Enter PO rectifying columns 2,6.5 DEG C of tower top temperature, pressure 0.14MPa, control of reflux ratio 150, tower reactor obtain PO product purities 99.99%
Containing ammonia in 10ppm in wt, PO product.PO rectifying column tower tops throughput is 0.49m3/ h, mass flow are 2.34kg/h, are passed through
After 5% ethanol water washing, spray flux control 0.4m3/ h (350kg/h), propylene recovery tower top obtain 98wt% propylene
With the gaseous mixture of 2wt% acetylene.
Claims (5)
1. deamination the equipment of expoxy propane, propylene is reclaimed in a kind of propylene oxide unit, it is characterised in that adsorb including deamination
Tower, PO rectifying columns, condenser, reboiler, propylene recovery tower, vent gas treatment tower, cooler；Described deamination absorption column overhead sets
There is charging aperture, deamination adsorption tower bottom of towe discharging opening Jing discharging pipelines are connected with the charging aperture of described PO rectifying columns, PO rectifying columns
Bottom is provided with PO discharge nozzles, and PO discharge nozzles are provided with branch road Jing reboilers and are connected with the reflux inlet of PO rectifying columns, PO rectifying columns
The light fraction outlet at top is connected with condenser, and the condensate outlet of condenser is connected with the liquid return hole of PO rectifying columns, condenser
Fixed gas outlet be connected with the charging aperture of described propylene recovery tower；Described propylene recovery column overhead is provided with gas outlet,
Propylene recovery tower top is provided with inlet and is connected with absorbent water influent pipeline, and the liquid outlet of propylene recovery tower bottom of towe is entered with absorbent
Liquid pipeline connection makes absorbent form circulated sprinkling；The discharging pipeline of described deamination adsorption tower is provided with tail gas branch road and tail gas
The air inlet connection of reason tower, vent gas treatment tower top are provided with cleaning mixture entrance and are connected with cleaning mixture feed tube, vent gas treatment tower tower
Bottom is provided with liquid outlet Jing coolers and is connected to remove the heat produced during ammonia is dissolved in water heat release with cleaning mixture entrance.
2. deamination the equipment of expoxy propane, propylene is reclaimed in propylene oxide unit according to claim 1, its feature exists
In absorbent circulating pump being provided with described absorbent water influent pipeline, be additionally provided with absorption in the water outlet end of absorbent circulating pump
Agent waste line；
3. deamination the equipment of expoxy propane, propylene is reclaimed in propylene oxide unit according to claim 1, its feature exists
Cleaning mixture recycle column is provided with the connecting line between vent gas treatment tower liquid outlet and cooler, in cleaning mixture recycle column
Water outlet end is additionally provided with cleaning mixture waste line.
4. deamination the equipment of expoxy propane, propylene is reclaimed in propylene oxide unit according to claim 1, its feature exists
In described deamination adsorption tower number be at least one.
5. deamination the equipment of expoxy propane, propylene is reclaimed in propylene oxide unit according to claim 4, its feature exists
When having at least two deamination adsorption towers, deamination adsorption tower is arranged in parallel.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110422950A (en) * | 2019-06-05 | 2019-11-08 | 南京化工园博瑞德水务有限公司 | A kind of processing unit and method for production of propylene oxide waste water |
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2016
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110422950A (en) * | 2019-06-05 | 2019-11-08 | 南京化工园博瑞德水务有限公司 | A kind of processing unit and method for production of propylene oxide waste water |
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