CN106608833B - Ethanol amine co-production - Google Patents
Ethanol amine co-production Download PDFInfo
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Abstract
The purpose of the present invention is to provide a kind of ammonia recovery height, the high ethanol amine co-productions of product quality.The invention discloses a kind of ethanol amine co-production, (1) is sent after mixing liquid ammonia process for caustic soda purification and Ammonia Process reaction product and fresh liquefied ammonia to recovery ammonia tower, and recovery ammonia tower is equipped with return-flow structure；(2) recovery ammonia tower bottoms is sent to ammonia flash tank, and ammonia flash tank bottom liquid phase is sent to dehydrating tower and is dehydrated；(3) the isolated water part of dehydration tower top returns to Ammonia Process unit as catalyst, and a part dumps wastewater treatment；(4) dehydrating tower kettle liquid is sent to weight-removing column and removes heavy constituent；(5) weight-removing column top mixed ethanol amine product is sent to refined unit, successively isolated monoethanolamine, diethanol amine, triethanolamine product.This method saves equipment investment, and ammonia recovery is high, and product quality is high, can be used in the industrial production of ethanol amine, particularly suitable for Ammonia Process technique capacity expansion revamping.
Description
Technical field
The present invention relates to ethanol amine production fields, are related to a kind of ethanol amine co-production, specifically, a kind of Ammonia Process and
Liquid ammonia process for caustic soda purification Joint Production ethanol amine method.
Background technology
Ethanol amine is the important derivative of ethylene oxide, it includes monoethanolamine (MEA), diethanol amine (DEA), three ethyl alcohol
Three kinds of alcamine compounds of amine (TEA).It is important fine Organic Chemicals, be widely used in gas purification, printing and dyeing,
The fields such as medicine, pesticide, polyurethane and rubber chemicals are products most with practical value in amino alcohol, are had " industrial monosodium glutamate "
Title, yield accounts for about the 90% of amino alcohol total output.There are nitrogen-atoms and hydroxyl in ethanolamine molecules, therefore has the change of amine and alcohol concurrently
Learn property.In China, ethanol amine is mainly used in the fields such as surfactant, insecticide and polyurethane.Wherein, surfactant
It is the maximum consumer field of ethanol amine with field of pesticides, has accounted for the 2/3 of Chinese ethanol amine total quantity consumed at present.India has become
The second largest ethanol amine importer in Asia.2011, India's ethanol amine aggregate consumption was up to 100,000 tons, monoethanolamine and diethanol amine master
Rely on import.、.
It expects 2015, global ethanol amine gross annual output can be up to 2,000,000 tons, and demand is also up to 1,850,000 tons.
Under the support of the economic strong growth of the nations of China and India, following 3 to five years Asia ethanol amine demands are estimated will also be with average annual 6~7%
Speedup continue to increase.
Currently, the external relevant enterprise for being engaged in ethanol amine production mainly has, Dow is chemical, BASF AG, Huntsman companies,
Nippon Shokubai companies etc..External ethanol amine production has following feature：First, comparision of production is concentrated, U.S.'s ethyl alcohol
Amine manufacturer has 4, and aggregated capacity is 640,000 tons/year, and respectively there are 2 manufacturers in Germany and Japan；Second is that production scale is big, U.S.'s second
The hydramine manufacturer production scale that is averaged is up to 160,000 tons/year, about 60,000 tons/year of Germany；Third, concentration is compared in production site, such as
The device of 4 manufacturers in the U.S. all build Texas and Louisiana in, mainly considers raw material supply and product fortune
Defeated convenience reduces logistics cost with this；It build in together with ethylene oxide device fourth, ethanol amine device is substantially all, mainly examines
Consider the particularity of ethylene oxide transport, can guarantee the reduction of the supply stability and cost of primary raw material in addition.
Ethanol amine enterprise can be divided into four classes according to the concentration of ammonia in the raw material used：1) SD companies in the U.S. are using low dense
The ammonium hydroxide of degree is reaction raw materials, by the ammonium hydroxide (material for including fresh material and cycle) of EO and 20~30wt%, and is followed
The MEA of ring is reacted (structure that reaction product is adjusted with MEA), NH in fixed bed reactors3/ EO=10:1, reaction temperature
100 DEG C, system pressure 0.5MPa of degree, product respectively obtains MEA, DEA, TEA of high-purity by separation, rectifying after reaction,
Relative amount is respectively 69wt%, 21wt%, 10wt%, and excess of ammonia is recycled through vacuum distillation in reaction system, residual ammonia with
The form repetitive cycling of ammonium hydroxide.It is high in reaction heating and energy consumption in temperature-fall period since the water content in system is high, and product is easy
It is dissolved in water, dehydration energy is high.Therefore, although the ammonium hydroxide synthesising method reacting condition of low concentration is mild, its energy consumption is excessively high, will
Gradually it is eliminated.2) Dow Chemical Company uses the ammonium hydroxide of middle and high concentration for reaction raw materials, and ammonia concn is 35~50wt%, is
System pressure is 3.5MPa, and reaction temperature is 115~130 DEG C.Dow Chemical Company is recycled using the method for high vacuum flash distillation for the first time
Ammonia in system, product is distributed by the content of raw material ammonia come modulation, and the said firm uses the coproduction of EO and ethanol amine in production
Device.3) BASF AG uses the ammonium hydroxide of high concentration for raw material, and ammonia concn is in 90wt% or more, system pressure 10MPa, NH3/
EO=15~25:1,3~30min of residence time, using level Four thermal insulation tubular reactor, EO be inferior in batches different nodes be in into
Enter reactor, reacting rear material is depressurized in flash column, boils off most of ammonia, ammonia condensing is returned at liquefied ammonia, and residual ammonia is in 0.4MPa
It steams, after being absorbed into weak aqua ammonia with the water of dehydrating tower, then is configured to the participation of 90% concentrated ammonia liquor with liquefied ammonia and reacts.Using high concentration
Ammonia has become the trend of Ammonia Process technique, and Ammonia Process can get reconciliation of inventory composition, but there are product by-product is more, and separation is difficult
The problems such as degree is high, and reaction heat can not recycle.4) Nippon Shokubai companies are with the La zeolites being modified using liquefied ammonia as raw material
Catalyst, highly selective generation diethanol amine, and have been carried out industrial applications.Its process conditions is as follows：It is in reaction temperature
100~110 DEG C, pressure is 12~15MPa, and liquid phase air speed is 8~10h-1When, using fixed bed reactors, the list of diethanol amine
Journey weight selectivities are 41% or so；By recycling monoethanolamine, the weight selectivities of diethanol amine can reach 81%, and ring
Oxidative ethane can realize complete conversion.The process selectivity is high, and product separation is easy, reaction heat can centralized recovery utilize, energy consumption
It is low, it is the developing direction of ethanol amine technology, however its catalyst on-stream cycle time is short (only several days), is urgent problem.
The advantages of low ammonia concn technique is that reaction condition is mild, side reaction is few, the disadvantage is that high energy consumption, high ammonia concn work
Skill is then just opposite.No matter which kind of technique, the flow and energy consumption difference of rectification under vacuum separating alcohol amine blends are little, and energy consumption is big
Small difference is mainly reflected in the deamination dewatering process of reactant.Traditional Ammonia Process produces ethanol amine technique, product proportion tune
Section is difficult, and by-product species are more, quantity is big, and the water to be separated as catalyst, and energy consumption is big, and it is competing that economy is unfavorable for market
It strives.
Ethanol amine is important petrochemical materials, even if domestic all production capacity are all opened foot and compared still with demand
There are certain notch, China's ethanol amine still to have larger development potentiality.Change the production status of China's ethanol amine, it is necessary to improve state
Inside more backward production technology, successive optimization process conditions increase high productive capacity plant construction energetically, improve market competition
Power.
Currently, the liquid ammonia process for caustic soda purification production ethanol amine researched and developed both at home and abroad does not need water as catalyst, and use boiling
Stone molecular sieve reacts as catalyst, ethylene oxide and liquefied ammonia under liquid-phase condition, and reaction is three step consecutive reactions, generates
Three kinds of monoethanolamine (MEA), diethanol amine (DEA) and triethanolamine (TEA) products, reaction equation are as follows：
Since the chemical property of ethylene oxide is extremely active, it is prone to self-polymeric reaction when concentration is higher and generates polyoxy
The high boiling substances such as ethylene or polyethers；Or with the substance containing hydroxyl in molecule, such as water, alcohols etc., hydration reaction life occurs
At high boiling substances such as polyalcohol, polyalcohol ethers, these height boiling substances are referred to as higher ethanol amine (HEA), all enter the three of low value
Among ethanol amine (TEA) seconds.Above-mentioned side reaction is for main reaction-ammonolysis reaction that ethylene oxide and ammonia occur, all
It is harmful side reaction, the high boiling point by-products produced HEA of generation not only reduces the yield of major product, wastes EO raw materials, and
Severely impact the quality of ethanolamine product, it is therefore desirable to it controls bottom temperature in separation process and is no more than 180 DEG C, same to time control
Water content in liquefied ammonia in liquid ammonia process for caustic soda purification technique processed.Ethanol amine is individually produced using liquid ammonia process for caustic soda purification, in liquid ammonia recovery process, needs to use liquid
The ammonia either cryogenic coolants such as freon or compressor increase equipment investment and utility cost.If by liquid ammonia process for caustic soda purification and ammonia
Water law combines, and two kinds of reaction products are sent into a set of piece-rate system simultaneously, can save equipment investment and public work
Expense improves product quality.
Prior art mainly uses tubular reactor to carry out ethanol amine production, and has made many improvement and wound to reaction process
Newly.It is all made of pipe reaction in the patents such as CN101148412A, CN101148413A, CN101613289A, CN101613290A
Device, pipe is outer to remove heat using hot water.Wherein CN101148412A, into EO techniques, reduces the internal circulating load of ammonia, Ke Yiji using multiple spot
The earth saves the energy consumption of reaction product ammonia still process (and removing brought into ammonia water) so that can save ammonia still process dehydration energy 80~
90% or more；The pipe of reaction tube one on earth, is not segmented, is not inserted into heat exchanger in CN101148413A, and reaction tube has water leg,
Water in chuck is reverse with material in pipe and flows, and continuously removes reaction heat, so that the material in pipe is maintained relatively low anti-
It is 6~7MPa to answer temperature (≤100 DEG C), pressure.
In order to reduce the side reaction of EO, process safety is improved, the water content for reducing liquefied ammonia can be taken, reduces reaction zone ring
The concentration of oxidative ethane, it is stringent to control the measures such as reactor temperature liter to improve ethanolamine product yield, reduce the production quantity of by-product.
Liquid ammonia process for caustic soda purification produces ethanol amine technique and uses anhydrous liquid ammonia, can reduce the production quantity of polyethers and polyol ethers；Control ammonia alkane ratio simultaneously
8：1~12：1 (molar ratio) reduces the probability of ethylene oxide autohemagglutination to reduce the concentration of ethylene oxide, improve product yield and
Coloration；Reaction heat is continuously withdrawn by using circulating hot water, control reactor Wen Sheng waits measures in reasonable range, can be improved
Product yield inhibits by-product to generate, and product quality is high, low energy consumption, non-wastewater discharge, safety and environmental protection.
The capacity expansion revamping that ethanol amine technique is produced for Ammonia Process, Ammonia Process and liquid ammonia process for caustic soda purification are combined, can suitably be dropped
Low Ammonia Process production scale reduces equipment investment using the original ammonia still process dehydration device of Ammonia Process and product purification device.
Invention content
The present invention is to be thrown in liquid ammonia process for caustic soda purification and Ammonia Process joint production process to save recovery ammonia and ethanolamine product separation equipment
Money, and during Ammonia Process and the mixing centralized processing of liquid ammonia process for caustic soda purification reaction product, recovery ammonia tower top carries a small amount of liquid phase water secretly, follows
Ring enters liquid ammonia process for caustic soda purification reaction member, and catalyst activity is led to problems such as to reduce, and provides in a kind of new ethanol amine joint production process
Ammonia recovery method when this method is used for the recovery ammonia in ethanol amine joint production process, has equipment investment low, catalyst activity height etc.
Advantage.
In order to solve the above technical problems, technical scheme is as follows：A kind of recovery ammonia in ethanol amine joint production process
Method, which is characterized in that this method follows the steps below：
(1) it is sent to recovery ammonia tower after mixing liquid ammonia process for caustic soda purification and Ammonia Process reaction product and fresh liquefied ammonia, recovery ammonia tower is equipped with
Return-flow structure, gas phase recycle after condensation and are recycled to reactor；
(2) recovery ammonia tower bottoms is sent to ammonia flash tank, is sent to Ammonia Process reaction member after ammonia flash drum overhead vapor condensation
As reaction raw materials, ammonia flash tank bottom liquid phase is sent to dehydrating tower and is dehydrated；
(3) the isolated water part of dehydration tower top returns to Ammonia Process unit as catalyst, and a part, which dumps, gives up
Water process；
(4) dehydrating tower kettle liquid is sent to weight-removing column and removes heavy constituent；
(5) weight-removing column top mixed ethanol amine product is sent to refined unit, successively isolated monoethanolamine, diethanol amine,
Triethanolamine product.
Since liquid ammonia process for caustic soda purification product form depends primarily on NH in charging3With the ratio (NH of EO3/ EO molar ratios, ammonia alkane ratio),
The present invention considers that ammonia alkane ratio is 4 in liquid ammonia process for caustic soda purification technique from product distribution ratio and energy-saving angle：1~16：1 (molar ratio),
Preferably 6：1~12：1, the concentration of ethylene oxide can be reduced, the probability of ethylene oxide autohemagglutination is reduced, obtains a suitable ethyl alcohol
Amine, diethanol amine, triethanolamine product proportion.It can reach adjustment product ratio according to the market demand by adjusting ammonia alkane ratio simultaneously
The purpose of example.
In above-mentioned technical proposal, it is preferable that ammonia content is 50~80% based on mass fraction in liquid ammonia process for caustic soda purification reaction product, also
Contain monoethanolamine, diethanol amine, triethanolamine and heavy constituent.
Result of calculation shows that the ammonia concn in Ammonia Process technique productions ethanol amine has a significant impact to energy consumption, and ammonium hydroxide is dense
Degree is higher, and separating energy consumption is lower, but can not be too low, and water content is too low, and the amount of catalyst is very few, and reacting ethylene oxide is endless
Entirely, water content is controlled 5~20% in ammonium hydroxide.
In above-mentioned technical proposal, it is preferable that ammonia content is 40 based on mass fraction in Ammonia Process reaction product in the present invention
~75%, water content is 1~20% (preferably 5~15%), also contains monoethanolamine, diethanol amine, triethanolamine and recombination
Point.
Simultaneously because ethanol amine is heat-sensitive substance again, during recycling ammonia operation temperature limitation be to be considered it is important
Factor.180 DEG C of recovery ammonia tower bottom temperature, flash tank operation temperature and dehydrating tower bottom temperature ＜ are controlled in the present invention.
It is more than 180 DEG C to avoid bottom temperature due to not aqueous in liquid ammonia process for caustic soda purification, during recovery ammonia tower recycles ammonia, can incites somebody to action
Part ammonia is depressed into tower reactor, and the recovery ammonia of this portion of residual is extremely difficult, and processing method is to flash remaining ammonia or other
Method separate, then with after compressor compresses with cooling water condensation recycle or use cryogenic media such as propylene, freon
Direct condensing recovery, but equipment investment and operating cost will be increased.
Liquid ammonia process for caustic soda purification and Ammonia Process coproduction can change this unfavorable situation, because containing water in reaction product, suitable
Operating pressure under, can more easily control bottom temperature be no more than 180 DEG C, remaining liquefied ammonia dehydration tower top and water together
It separates, catalyst of the water as Ammonia Process technique, liquefied ammonia therein is as raw material.
Recovery ammonia tower is equipped with return-flow structure, and separative efficiency is better than stripper, can reduce in recycling ammonia and contain in water and liquefied ammonia
Impurity content, extend catalyst life.
One section of wire packing is set above recovery ammonia tower upper return mouth, by the big portion of the liquid carried secretly in gas phase especially water
Divide removing.
Recovery ammonia top gaseous phase outlet setting high efficient gas and liquid separator, the preferred high-efficiency blade separation of high efficient gas and liquid separator
Device.High-efficiency blade separator is simultaneously using kinetic collision, the principle of drop absorption coalescence and gravitational settling, to realize higher gas
Liquid separative efficiency, lower pressure drop and broader elastic operation range.The gas of entrained drip efficiently separates leaf once entering
The channel of piece will be immediately split into multiple regions by blade.Gas will be forced to carry out by blade during by each region
Repeatedly quickly flow direction transformation.Gas is in carrying out repeatedly quickly flowing to transition process, and under the influence of centrifugal force, drop will
Kinetic collision is carried out with blade.Effect is coalesced by absorption between drop and is attached to blade surface.It is attached to blade surface coalescence
The liquid of film forming enters the interlayer of blade under the synergy of its own gravity, surface tension of liquid and gas kinetic energy, and is pressing from both sides
Confluence is flowed into the hydrops slot below blade and is collected, finally obtain the gas by purified treatment at stock in layer.
In above-mentioned technical proposal, it is preferable that catalyst is adhesiveless ZSM-5 zeolite molecular sieve in liquid ammonia process for caustic soda purification technique, point
Son sieve has strict demand to water, it is desirable that water content is no more than 200ppm in liquefied ammonia.Therefore, it is set in the outlet of recovery ammonia top gaseous phase
High efficient gas and liquid separator is set, further down to 50ppm (mainly water), the liquid of separation is straight for removing by the liquid carried secretly in gas phase
It picks to Ammonia Process unit as catalyst.
In above-mentioned technical proposal, it is preferable that recovery ammonia tower theoretical cam curve be 10~30, tower top operating pressure be 1.0~
3.0MPaG, tower top operation temperature are 30~80 DEG C.
In above-mentioned technical proposal, it is preferable that ammonia flash tank operating pressure be 0.3~1.0MPaG, operation temperature be 130~
175℃。
In above-mentioned technical proposal, it is preferable that dehydration column overhead operating pressure is -0.1~0.3MPaG, tower top operation temperature
It is 60~120 DEG C.
It is dehydrated the isolated water part of tower top and returns to Ammonia Process unit as catalyst, a part dumps at waste water
Reason, main purpose are that hydro carbons, boiling point in system are less than to the light component impurity such as ethylene oxide polymer etc. of ethanolamine mixtures
It dumps, reduces it and side reaction occurs with product in subsequent separation process, improve product coloration and triethanolamine product top grade product
Yield.
Weight-removing column tower top operating pressure is 0~1kPaA, and tower top operation temperature is 100~150 DEG C.
Therefore, technique of the invention can significantly save equipment investment, reduce production cost, improve product quality,
Technical process environmental protection, achieves preferable technique effect.
Description of the drawings
Fig. 1 is present invention process flow diagram.
In Fig. 1, R101 is Ammonia Process long-tube reactor, and R102 is liquid ammonia process for caustic soda purification shell and tube reactor, and R103 is liquid ammonia process for caustic soda purification
Heat-insulating fixed bed reactors, T101 are recovery ammonia tower, and T102 is dehydrating tower, and T103 is weight-removing column, and S101 is high efficient gas and liquid point
From device, V101 is ammonia flash tank, and E101 is recovery ammonia tower condenser, and E102 is secondary condenser.1 feeds for ethylene oxide, and 2 are
Liquid ammonia process for caustic soda purification ethylene oxide is fed, and 3 feed for fresh liquefied ammonia, and 4 be liquid ammonia process for caustic soda purification shell and tube reactor R102 reaction products, and 5 be liquefied ammonia
Method heat-insulating fixed bed reactors R103 reaction products, 6 feed for Ammonia Process ethylene oxide, and 7 be Ammonia Process long-tube reactor
R101 reaction products, 8 be the T101 chargings of recovery ammonia tower, and 9 be recovery ammonia tower T101 kettle liquids, and 10 be fixed gas, and 11 be secondary recovery
Liquid, 12 be flash tank bottom liquid, and 13 be outer draining, and 14 be recovery ammonia tower overhead gas, and 15 be reclaim liquid phase, and 16 be high efficient gas and liquid separator
S101 top gas phases, 17 be recovery ammonia tower T101 phegmas, and 18 is remove Ammonia Process reactor R101 liquefied ammonia, and 19 be supplement fresh water
(Ammonia Process catalyst), 20 be ammonium hydroxide (Ammonia Process reaction raw materials), and 21 is remove liquid ammonia process for caustic soda purification reactor R102 liquefied ammonia, and 22 be liquid ammonia process for caustic soda purification
Charging, 23 be dehydrating tower kettle liquid, and 24 be that (alcohol ethers compound, amino alcohol ethers compound, i.e. boiling point are more than three to weight-removing column kettle liquid
The heavy constituents such as the high-boiling components of ethanol amine).
Ammonia Process long-tube reactor R101 removes heat, liquid ammonia process for caustic soda purification shell and tube reactor R102 using chuck long tube hot water circuit
Shell side is passed through hot water circuit and removes heat, and hot water can be used to preheat liquefied ammonia charging.
In Fig. 1, it is two parts that ethylene oxide, which feeds 1 point, is entered after a part of (logistics 6) and ammonium hydroxide (logistics 20) mixing
R101, reaction product are logistics 7, and logistics 6 and 20 hybrid position of logistics are as close as possible from reactor R101 entrances, a part of (object
2) stream is mixed with recovery ammonia column overhead liquefied ammonia (logistics 21) after, logistics 22 enters reactor R102, and reaction product (logistics 4) enters
Reactor R103, after reaction product (logistics 5) is mixed with fresh liquefied ammonia (logistics 3), logistics 7, logistics 8 is sent to recovery ammonia tower
T101, recovery ammonia tower overhead gas 14 after the drop (logistics 15) of high efficient gas and liquid separator S101 separation entrainment, logistics 15 send to
Reactor R101, ammonia (logistics 16) liquefied ammonia after the E101 condensations of recovery ammonia tower condenser are divided into two parts, logistics 18 and object
Stream 19 is recycled to Ammonia Process and liquid ammonia process for caustic soda purification reaction member as reaction raw materials respectively, and recovery ammonia tower bottoms (logistics 9), which is sent to ammonia, to be dodged
Steaming pot V101, after vacuum flashing, gas phase is after E102 is secondary condenser partial condensation, the liquefied ammonia (logistics 11) containing a small amount of water
It send to Ammonia Process unit as reaction raw materials, fixed gas (logistics 10) is used as ammonia after sending to ammonia absorber (Fig. 1 is not marked) absorption
Water law unit catalyst, flash tank bottom liquid (logistics 12) are sent to dehydrating tower T102, and liquid of top of the tower mainly contains water, micro ammonia send to
For Ammonia Process unit as catalyst, sub-fraction (logistics 13) dumps wastewater treatment, and dehydrating tower kettle liquid (logistics 23) is sent to de-
Weight tower T103, removes alcohol ethers compound, and amino alcohol ethers compound, i.e. boiling point are more than the heavy constituents such as the high-boiling components of triethanolamine
(logistics 24), tower top are mixed ethanol amine product, and monoethanolamine, diethanol amine, three second are obtained successively by later separation unit
Alcohol amine product (it is I type that triethanolamine, which detaches overhead product, and tower reactor is II type).
The present invention will be further described below by way of examples, but these embodiments are not anyway to this hair
Bright range is construed as limiting.
Specific implementation mode
【Embodiment 1】
In Fig. 1, it is two parts that ethylene oxide, which feeds 1 point, is entered after a part of (logistics 6) and ammonium hydroxide (logistics 20) mixing
R101, reaction product are logistics 7, and logistics 6 and 20 hybrid position of logistics are as close as possible from reactor R101 entrances, a part of (object
2) stream is mixed with recovery ammonia column overhead liquefied ammonia (logistics 21) after, logistics 22 enters reactor R102, and reaction product (logistics 4) enters
Reactor R103, after reaction product (logistics 5) is mixed with fresh liquefied ammonia (logistics 3), logistics 7, logistics 8 is sent to recovery ammonia tower
T101, recovery ammonia tower overhead gas 14 after the drop (logistics 15) of high efficient gas and liquid separator S101 separation entrainment, logistics 15 send to
Reactor R101, ammonia (logistics 16) liquefied ammonia after the E101 condensations of recovery ammonia tower condenser are divided into two parts, logistics 18 and object
Stream 19 is recycled to Ammonia Process and liquid ammonia process for caustic soda purification reaction member as reaction raw materials respectively, and recovery ammonia tower bottoms (logistics 9), which is sent to ammonia, to be dodged
Steaming pot V101, after vacuum flashing, gas phase is after E102 is secondary condenser partial condensation, the liquefied ammonia (logistics 11) containing a small amount of water
It send to Ammonia Process unit as reaction raw materials, fixed gas (logistics 10) is used as ammonia after sending to ammonia absorber (Fig. 1 is not marked) absorption
Water law unit catalyst, flash tank bottom liquid (logistics 12) are sent to dehydrating tower T102, and liquid of top of the tower mainly contains water, micro ammonia send to
For Ammonia Process unit as catalyst, sub-fraction (logistics 13) dumps wastewater treatment, and dehydrating tower kettle liquid (logistics 23) is sent to de-
Weight tower T103, removes alcohol ethers compound, and amino alcohol ethers compound, i.e. boiling point are more than the heavy constituents such as the high-boiling components of triethanolamine
(logistics 24), tower top are mixed ethanol amine product, and monoethanolamine, diethanol amine, three second are obtained successively by later separation unit
Alcohol amine product (top grade product and Grade A).
Liquid ammonia process for caustic soda purification reaction product 1, based on mass fraction, ammonia content 50% also contain monoethanolamine, diethanol amine, and three
Ethanol amine and heavy constituent.
Ammonia Process reaction product 2, based on mass fraction, ammonia content 75%, water content 5% also contain monoethanolamine,
Diethanol amine, triethanolamine and heavy constituent.
Recovery ammonia tower theoretical cam curve is 10, operating pressure 1.45MPaG, and operation temperature is 40 DEG C.
Ammonia flash tank operating pressure is 0.3MPaG, and operation temperature is 155 DEG C.
Dehydrating tower operating pressure is -0.08MPaG, and operation temperature is 65 DEG C.
Weight-removing column tower top operating pressure is 0.1kPaA, and tower top operation temperature is 115 DEG C.
Monoethanolamine product quality score >=99.9%, moisture≤0.1%, coloration≤10；Diethanol amine product quality point
Number >=99.9%, moisture≤0.1%, coloration≤15；Triethanolamine product (I type) mass fraction >=99.5%, moisture≤
0.1%, coloration≤15；Triethanolamine product (II type) mass fraction >=98.0%, coloration≤50.
In the present embodiment, 180 DEG C of recovery ammonia tower bottom temperature, flash tank operation temperature and the equal ＜ of dehydrating tower bottom temperature.
【Embodiment 2】
Liquid ammonia process for caustic soda purification reaction product 1, based on mass fraction, ammonia content 75% also contain monoethanolamine, diethanol amine, and three
Ethanol amine and heavy constituent.
Ammonia Process reaction product 2, based on mass fraction, ammonia content 65%, water content 10% also contain an ethyl alcohol
Amine, diethanol amine, triethanolamine and heavy constituent.
Recovery ammonia tower theoretical cam curve is 20, operating pressure 1.6MPaG, and operation temperature is 45 DEG C.
Ammonia flash tank operating pressure is 0.45MPaG, and operation temperature is 160 DEG C.
Dehydrating tower operating pressure is -0.05MPaG, and operation temperature is 68 DEG C.
Weight-removing column tower top operating pressure is 0.2kPaA, and tower top operation temperature is 124 DEG C.
Monoethanolamine product quality score >=99.9%, moisture≤0.1%, coloration≤10；Diethanol amine product quality point
Number >=99.9%, moisture≤0.1%, coloration≤15；Triethanolamine product (I type) mass fraction >=99.5%, moisture≤
0.1%, coloration≤15；Triethanolamine product (II type) mass fraction >=98.0%, coloration≤50.
In the present embodiment, 180 DEG C of recovery ammonia tower bottom temperature, flash tank operation temperature and the equal ＜ of dehydrating tower bottom temperature.
【Embodiment 3】
Liquid ammonia process for caustic soda purification reaction product 1, based on mass fraction, ammonia content 80% also contain monoethanolamine, diethanol amine, and three
Ethanol amine and heavy constituent.
Ammonia Process reaction product 2, based on mass fraction, ammonia content 50%, water content 15% also contain an ethyl alcohol
Amine, diethanol amine, triethanolamine and heavy constituent.
Recovery ammonia tower theoretical cam curve is 30, operating pressure 1.8MPaG, and operation temperature is 48 DEG C.
Ammonia flash tank operating pressure is 0.65MPaG, and operation temperature is 170 DEG C.
Dehydrating tower operating pressure is 0.15MPaG, and operation temperature is 75 DEG C.
Weight-removing column tower top operating pressure is 0.3kPaA, and tower top operation temperature is 138 DEG C.
Monoethanolamine product quality score >=99.9%, moisture≤0.1%, coloration≤10；Diethanol amine product quality point
Number >=99.9%, moisture≤0.1%, coloration≤15；Triethanolamine product (I type) mass fraction >=99.5%, moisture≤
0.1%, coloration≤15；Triethanolamine product (II type) mass fraction >=98.0%, coloration≤50.
In the present embodiment, 180 DEG C of recovery ammonia tower bottom temperature, flash tank operation temperature and the equal ＜ of dehydrating tower bottom temperature.
【Comparative example 1】
Embodiment is identical as Examples 1 to 3, the difference is that fresh liquefied ammonia is directly entered reactor, the service life of catalyst
Shorten at least 1/10th than Examples 1 to 3, ethanolamine product moisture increases to 0.20%, and triethanolamine coloration increases to 10
~30.
【Comparative example 2】
In comparative example 2 coproduction mode is not used to liquid ammonia process for caustic soda purification and Ammonia Process technique, a set of ammonia recovery unit, liquid is respectively adopted
Ammonia process technique needs low-grade cryogen such as propylene, freon to cool down medium as liquefied ammonia or need to increase compressor, need
Increase by a recovery ammonia tower, a flash tank increases equipment investment expense.
【Comparative example 3】
Embodiment is identical as Examples 1 to 3, is reacted the difference is that dehydration overhead product is all returned as catalyst
Device, ethanolamine product coloration increase by 10~35, and triethanolamine Grade A yield reduces >=1%.
【Comparative example 4】
Embodiment is identical as Examples 1 to 3, the difference is that dehydrating tower kettle product is directly separated without de- processing again,
Monoethanolamine, diethanol amine product, triethanolamine product (I type) coloration is constant, triethanolamine product (II type) mass fraction drop
Down to 97%, coloration increases by 10~50.
Claims (9)
1. a kind of ethanol amine co-production, which is characterized in that this method follows the steps below：
(1) it is sent after mixing liquid ammonia process for caustic soda purification and Ammonia Process reaction product and fresh liquefied ammonia to recovery ammonia tower, recovery ammonia tower is equipped with reflux
Structure, gas phase recycle after condensation and are recycled to reactor；
(2) recovery ammonia tower bottoms is sent to ammonia flash tank, is sent to Ammonia Process reaction member conduct after ammonia flash drum overhead vapor condensation
Reaction raw materials, ammonia flash tank bottom liquid phase are sent to dehydrating tower and are dehydrated；
(3) the isolated water part of dehydration tower top returns to Ammonia Process unit as catalyst, and a part dumps at waste water
Reason；
(4) dehydrating tower kettle liquid is sent to weight-removing column and removes heavy constituent；
(5) weight-removing column top mixed ethanol amine product is sent to refined unit, successively isolated monoethanolamine, diethanol amine, three second
Alcohol amine product；
Wherein, one section of wire packing is set above recovery ammonia tower upper return mouth；It is efficient in recovery ammonia top gaseous phase outlet setting
Gas-liquid separator.
2. ethanol amine co-production according to claim 1, it is characterised in that liquid ammonia process for caustic soda purification reaction product based on mass fraction, ammonia
Content is 50~80%, also contains monoethanolamine, diethanol amine, triethanolamine and heavy constituent.
3. ethanol amine co-production according to claim 1, it is characterised in that Ammonia Process reaction product ammonia based on mass fraction
Content is 40~75%, and water content is 1~20%, also contains monoethanolamine, diethanol amine, triethanolamine and heavy constituent.
4. ethanol amine co-production according to claim 1, it is characterised in that efficient in recovery ammonia top gaseous phase outlet setting
Blade separator.
5. according to the ethanol amine co-production of claim 1 or 4, it is characterised in that high efficient gas and liquid separator bottom liquid phases are direct
Ammonia Process reactor is returned as catalyst.
6. ethanol amine co-production according to claim 1, it is characterised in that recovery ammonia tower theoretical cam curve is 10~30, tower
Top operating pressure is 1.0~3.0MPaG, and tower top operation temperature is 30~80 DEG C.
7. ethanol amine co-production according to claim 1, it is characterised in that ammonia flash tank operating pressure be 0.3~
1.0MPaG, operation temperature are 130~175 DEG C.
8. ethanol amine co-production according to claim 1, it is characterised in that dehydration column overhead operating pressure be -0.1~
0.3MPaG, tower top operation temperature are 60~120 DEG C.
9. ethanol amine co-production according to claim 1, it is characterised in that weight-removing column tower top operating pressure is 0~1kPaA,
Tower top operation temperature is 100~150 DEG C.
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| CN114478274A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Method for preparing monoethanolamine and coproducing diglycol |
| CN115724753A (en) * | 2021-08-25 | 2023-03-03 | 中国石油化工股份有限公司 | Preparation method and system of ethanolamine |
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