CN106608829A - Ammonia recovery method in ethanolamine combined production technology - Google Patents
Ammonia recovery method in ethanolamine combined production technology Download PDFInfo
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Abstract
The invention provides an ammonia recovery method having a high ammonia recovery rate and saving an equipment investment and discloses an ammonia recovery method in an ethanolamine combined production technology. The method comprises (1) mixing reaction products obtained by a liquid ammonia method and an ammonia water method, conveying the mixture into an ammonia recovery tower, and feeding fresh liquid ammonia as a reflux liquid, (2) mixing the tower bottom liquid of the ammonia recovery tower and liquid drops separated by a high-efficiency gas-liquid separator, conveying the mixture into an ammonia flash tank, conveying the liquid phase at the bottom of the ammonia flash tank into a dehydration tower and carrying out dehydration, and (3) conveying the tower bottom liquid of the dehydration tower into an ethanolamine product refining unit. The high-efficiency gas-liquid separator is arranged at a gas phase outlet of the top of the ammonia recovery tower, reduces a gas phase water carrying amount, and prevents reduction of the selectivity and a service life of a liquid ammonia method catalyst. The method does not adopt a low temperature refrigerant and a compressor, saves equipment investment, has a high ammonia recovery rate, can be used for ethanolamine ammonia liquor method and liquid ammonia method combined production and is especially suitable for ammonia liquor method expansion and reformation.
Description
Technical field
The present invention relates to ethanolamine production field, it particularly relates to a kind of Ammonia Process and liquid ammonia process for caustic soda purification co-producing ethanol amine technique
In ammonia recovery method.
Background technology
Ethanolamine is the important derivant of oxirane, it include monoethanolamine (MEA), diethanolamine (DEA),
Three kinds of alcamine compounds of triethanolamine (TEA).It is important fine Organic Chemicals, is widely used in gas
The field such as purification, printing and dyeing, medicine, pesticide, polyurethane and rubber chemicals, is product most with practical value in amino alcohol,
Title with " industrial monosodium glutamate ", its yield account for 90% of amino alcohol total output or so.There are nitrogen-atoms in ethanolamine molecules
With hydroxyl, therefore the chemical property of amine and alcohol is had concurrently.In China, ethanolamine is mainly used in surfactant, insecticide and gathers
The fields such as urethane.Wherein, surfactant and field of pesticides are the maximum consumer fields of ethanolamine, have accounted for Chinese second at present
The 2/3 of hydramine total quantity consumed.India has become the second largest ethanolamine importer in Asia.2011, India's ethanolamine overall consumption
Up to 100,000 tons, monoethanolamine and diethanolamine rely primarily on import to amount..
About 1,850,000 tons of the aggregated capacity of global ethanolamine in 2010, about 1,550,000 tons of annual production, production capacity is mainly intensively
In the U.S., Europe and East Asia, wherein U.S.'s ethanolamine production capacity is maximum, and up to 800,000 tons of annual capacity accounts for global aggregated capacity
43%；European ethanolamine production capacity is only second to the U.S., and up to 550,000 tons of annual capacity accounts for the 27% of global aggregated capacity；The southeast
Sub- ethanolamine production capacity is slightly lower, and annual capacity also has 380,000 tons, accounts for the 30% of global aggregated capacity.Expect 2015, the whole world
Ethanolamine gross annual output can be up to 2,000,000 tons, and demand is also up to 1,850,000 tons.In the economic strong growth of the nations of China and India
Support under, following 3 to five years Asia ethanolamine demand is estimated will also to be continued to increase with average annual 6～7% speedup.
At present, the external relevant enterprise for being engaged in ethanolamine production mainly has Dow chemical, and BASF AG, Huntsman are public
Department, Nippon Shokubai companies etc..According to using raw material in the concentration of ammonia ethanolamine enterprise can be divided into four classes：1)
SD companies of the U.S. adopt the ammonia of low concentration for reaction raw materials, and (ammonia of EO and 20～30wt% is included fresh material
With circulation material), and circulation MEA reacted in fixed bed reactors (with MEA adjust product
Structure), NH3/ EO=10:1,100 DEG C of reaction temperature, system pressure 0.5MPa, after reaction product through separation,
Rectification respectively obtains highly purified MEA, DEA, TEA, and its relative amount is respectively 69wt%, 21wt%, 10wt%,
Excess of ammonia Jing vacuum distillations in reaction system are reclaimed, residual ammonia repetitive cycling in the form of ammonia.As the water in system contains
Amount is high, heats up in reaction high with power consumption in temperature-fall period, and product is soluble in water, and dehydration energy is high.Therefore, although low dense
The ammonia synthesising method reacting condition of degree is gentle, but its energy consumption is too high, gradually will be eliminated.2) Dow Chemical Company is adopted
The ammonia of middle and high concentration is reaction raw materials, and ammonia concn is 35～50wt%, and system pressure is 3.5MPa, and reaction temperature is
115～130 DEG C., first using the method for fine vacuum flash distillation come the ammonia in recovery system, products distribution is by original for Dow Chemical Company
The content of material ammonia comes modulation, and the said firm aborning using EO and the combined production device of ethanolamine.3) BASF AG adopts
The ammonia of high concentration is raw material, and ammonia concn is in more than 90wt%, system pressure 10MPa, NH3/ EO=15～25:1, stop
3～30min of time is stayed, using level Four thermal insulation tubular reactor, EO is in inferior to different nodes in batches and enters reactor, instead
After answering, material reduces pressure in flash column, boils off most of ammonia, and ammonia condensing is returned into liquefied ammonia, and residual ammonia is steamed in 0.4MPa, is used
After the water of dehydrating tower absorbs into weak ammonia, then the participation reaction of 90% strong aqua ammonia is configured to liquefied ammonia.Using high concentration ammonia
Become the trend of Ammonia Process technique, Ammonia Process can obtain reconciliation of inventory composition, but have that product by-product is more, separating difficulty is high,
The problems such as reaction heat cannot be reclaimed.4) Nippon Shokubai companies are with liquefied ammonia as raw material, and the zeolite being modified with La is as catalysis
Agent, the generation diethanolamine of high selectivity, and have been carried out industrial applications.Its process conditions is as follows：In reaction temperature it is
100～110 DEG C, pressure is 12～15MPa, and liquid phase air speed is 8～10h-1When, using fixed bed reactors, diethanolamine
One way weight selectivities 41% or so；By circulating monoethanolamine, the weight selectivities of its diethanolamine can reach 81%,
And oxirane can be realized converting completely.The process selectivity is high, and it is easy that product is separated, reaction heat can centralized recovery utilize,
Energy consumption is low, is the developing direction of ethanolamine technology, but its catalyst on-stream cycle time short (only several days), it is to be badly in need of solving
Problem.
The advantage of low ammonia concn technique is that reaction condition is gentle, side reaction is few, has the disadvantage high energy consumption, high ammonia concn technique
It is then just contrary.No matter which kind of technique, less, energy consumption is big for the flow process and energy consumption difference of rectification under vacuum separating alcohol amine blends
Little difference is mainly reflected in the deamination dewatering process of reactant.Traditional Ammonia Process production ethanolamine technique, product proportion are adjusted
Section is difficult, and by-product species are more, quantity big, and the water as catalyst to be separated, and energy consumption is big, and economy is unfavorable for market
Competition.
Ethanolamine is important petrochemical materials, even if domestic all production capacity all open foot, comparing with demand still has one
Determine breach, China's ethanolamine still has larger development potentiality.The production status changed by China's ethanolamine, it is necessary to improve domestic
More backward production technology, successive optimization process conditions increase high productive capacity plant construction energetically, improve the market competition
Power.
At present, the liquid ammonia process for caustic soda purification production ethanolamine for researching and developing both at home and abroad does not need water as catalyst, and adopts zeolite point
Son sieve reacts under liquid-phase condition as catalyst, oxirane and liquefied ammonia, and reaction is three step consecutive reactions, generates one
Ethanolamine (MEA), three kinds of products of diethanolamine (DEA) and triethanolamine (TEA), reaction equation are as follows：
As the chemical property of oxirane is extremely active, self-polymeric reaction is prone to when concentration is higher and generates Polyethylene oxide
Or the high boiling substance such as polyethers；Or with the material containing hydroxyl in molecule, such as water, alcohols etc., occur hydration etc. reaction life
Into high boiling substances such as polyhydric alcohol, polyalcohol ethers, these height boiling materials are referred to as higher ethanol amine (HEA), all into low value
Triethanolamine (TEA) seconds among.Primary response-ammonolysis reaction that above-mentioned side reaction is occurred with ammonia for oxirane
For, 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 impacted the quality of ethanolamine product, it is therefore desirable in controlling separation process, bottom temperature does not surpass
180 DEG C are crossed, while water content in liquefied ammonia in controlling liquid ammonia process for caustic soda purification technique.Ethanolamine is produced using liquid ammonia process for caustic soda purification individually, liquefied ammonia is reclaimed
During, need, using the cryogenic coolants such as liquefied ammonia or freon or compressor, to increase equipment investment and utility cost.
At present, it is difficult to Ammonia Process to be all changed to a step liquid ammonia process for caustic soda purification, liquid ammonia process for caustic soda purification and Ammonia Process are exactly combined by best scheme,
Two kinds of product are sent into into a set of piece-rate system simultaneously, equipment investment and utility cost can be saved, improve product
Quality.
Existing process mainly carries out ethanolamine production using tubular reactor, and has made many improvement and innovation to reaction process.
Tubular type is adopted in the patents such as CN101148412A, CN101148413A, CN101613289A, CN101613290A
Reactor, pipe is outer to remove heat using hot water.Wherein CN101148412A clicks through EO techniques using more, reduces the circulation of ammonia
Amount, can greatly save the energy consumption of product ammonia still process (water of ammonia entrainment), so that ammonia still process dehydration energy can be saved
More than 80～90%；In CN101148413A, reaction tube one is managed on earth, is not segmented, is not inserted into heat exchanger, its reaction tube peripheral hardware
Water leg, the water in chuck are inversely flowed with material in pipe, are continuously removed reaction heat, are allow the material in pipe to maintain ratio
Relatively low reaction temperature (≤100 DEG C), pressure are 6～7MPa.
In order to reduce the side reaction of EO, process safety is improved, can take reduces the water content of liquefied ammonia, reduce reaction zone ring
The concentration of oxidative ethane, it is strict to control the measures such as reactor temperature rise to improve ethanolamine product yield, reduce the growing amount of by-product.
Liquid ammonia process for caustic soda purification production ethanolamine technique adopts anhydrous liquid ammonia, reduces the generation probability and content of polyethers and polyol ethers；Improve simultaneously
Ammonia alkane ratio is to 8：1～12：1 (mol ratio), reduces the concentration of oxirane, reduces the probability of oxirane autohemagglutination；Pass through
Circulating hot water continuously withdraws reaction heat, and control reactor temperature rise in rational scope waits measure, can improve product yield, suppression
By-product processed is generated, and product quality is high, energy consumption is low, non-wastewater discharge, safety and environmental protection.
The capacity expansion revamping of ethanolamine technique is produced for Ammonia Process, Ammonia Process and liquid ammonia process for caustic soda purification are combined, ammonia can be suitably reduced
Water law production scale, using the original ammonia still process dehydration device of Ammonia Process and product purification device, reduces equipment investment.
The content of the invention
The present invention is directed in liquid ammonia process for caustic soda purification and Ammonia Process joint production process, is to save recovery ammonia and the investment of ethanolamine product separation equipment,
During Ammonia Process and the mixing of liquid ammonia process for caustic soda purification product are focused on, a small amount of liquid phase water of aminoacid stripping tower top clip band is recycled into
A kind of liquid ammonia process for caustic soda purification reaction member, the problems such as cause catalyst activity to reduce, there is provided the recovery ammonia in new ethanolamine joint production process
Method, it is during the recovery ammonia that the method is used in ethanolamine joint production process, low with equipment investment, the advantages of catalyst activity is high.
To solve above-mentioned technical problem, technical scheme is as follows：A kind of ammonia recovery method in ethanolamine joint production process,
Characterized in that, the method is followed the steps below：
(1) recovery ammonia tower will be delivered to after liquid ammonia process for caustic soda purification and the mixing of Ammonia Process product, tower top feeds fresh liquefied ammonia as backflow
Liquid, top gaseous phase are reclaimed after the vapor condensation after high efficient gas and liquid separator separation and are recycled to reactor；
(2) ammonia flash tank, ammonia flash distillation tank deck are delivered to after recovery ammonia tower bottoms droplets mixing detached with high efficient gas and liquid separator
Ammonia Process reaction member is delivered to after portion's vapor condensation as reaction raw materials, ammonia flash tank bottom liquid phase delivers to dehydrating tower dehydration；
(3) dehydrating tower kettle liquid delivers to ethanolamine product refined unit, is dehydrated a top liquid part of the tower top containing a small amount of ammonia and delivers to ammonia
Water law reaction member goes wastewater treatment as catalyst, a part.
Tower top feeds fresh liquefied ammonia as backflow, and recovery ammonia tower adopts rectifying column, compares with stripper, and top gaseous phase water contains
Amount is reduced to 50～200ppm by 2000～5000ppm, and in liquid ammonia recovery, water content is reduced, and can extend the liquid ammonia process for caustic soda purification catalyst longevity
Life.
As liquid ammonia process for caustic soda purification product form depends primarily on NH in charging3With the ratio (NH of EO3/ EO mol ratios, ammonia alkane ratio),
The present invention considers that from product slates ratio and energy-saving angle ammonia alkane ratio is 4 in liquid ammonia process for caustic soda purification technique：1～16：1 (mol ratio),
Preferably 6：1～10：1, the concentration of oxirane can be reduced, the probability of oxirane autohemagglutination is reduced, is obtained suitable one
Ethanolamine, diethanolamine, triethanolamine product proportion.Adjustment can be reached by adjusting ammonia alkane ratio according to the market demand simultaneously
The purpose of product proportion.
In above-mentioned technical proposal, it is preferable that count ammonia content as 60～85% with mass fraction in liquid ammonia process for caustic soda purification product, also contain
There are monoethanolamine, diethanolamine, triethanolamine and heavy constituent.
Result of calculation shows that the ammonia concn in Ammonia Process technique in ethanolamine production has a significant impact to energy consumption, ammonia concn
Higher, separating energy consumption is lower.
In above-mentioned technical proposal, it is preferable that in the present invention, in Ammonia Process product, in terms of mass fraction, ammonia content is
50～75%, water content is 1～10%, also contains monoethanolamine, diethanolamine, triethanolamine and heavy constituent.Simultaneously because second
Hydramine is heat-sensitive substance, and it is key factor to be considered that during ammonia is reclaimed, operation temperature is limited.Ammonia is controlled in the present invention
180 DEG C of recovery tower bottom temperature, flash tank operation temperature and dehydrating tower bottom temperature ＜.
During aminoacid stripping tower reclaims ammonia, to avoid recovery ammonia tower bottom temperature more than 180 DEG C, tower reactor meeting remnant ammonia,
But compared with independent Ammonia Process, ammonia amount reduces by more than 50, this part recovery ammonia is extremely difficult, and processing method is will be remaining
Ammonia flash distillation or other methods are separated, then with after compressor compresses with cooling water condensation reclaim or using low temperature Jie
Matter such as propylene, freon directly condense recovery, but will increase equipment investment and operating cost.
Liquid ammonia process for caustic soda purification and Ammonia Process coproduction can change this unfavorable situation, and during separation water, remaining liquefied ammonia is de-
Water tower top and water are separated together.
The isolated water part of dehydration tower top returns Ammonia Process unit as catalyst, and a part dumps wastewater treatment,
Main purpose is that hydro carbons, boiling point in system are less than the row such as light component impurity such as ethylene oxide polymer of ethanolamine mixtures
Abandon, reduce which and side reaction, raising product colourity and triethanolamine product top grade product occur with product in subsequent separation process
Yield.
One section of wire packing is set above recovery ammonia tower upper return mouth, the liquid carried secretly water is particularly into most of de- in gas phase
Remove.
In above-mentioned technical proposal, it is preferable that in liquid ammonia process for caustic soda purification technique, catalyst is adhesiveless ZSM-5 zeolite molecular sieve.
As in liquid ammonia process for caustic soda purification technique, catalyst is adhesiveless ZSM-5 zeolite molecular sieve, molecular sieve has strict demand to water,
In requiring liquefied ammonia, water content is no more than 100ppm.Therefore, ammonia recovering process adopts rectifying column, and feeds in tower top fresh
Liquefied ammonia, to increase substantially the separation efficiency of water, while high efficient gas and liquid separator is set in the outlet of recovery ammonia top gaseous phase, will
The liquid carried secretly in gas phase further removes as little as 50ppm (mainly water).In above-mentioned technical proposal, it is preferable that ammonia is returned
It is 10～30 to receive tower theoretical cam curve, and tower top operating pressure is 1.0～3.0MPaG, and tower top operation temperature is 30～80 DEG C.
The outlet of recovery ammonia top gaseous phase arranges high efficient gas and liquid separator, the preferred high-efficiency blade separator of high efficient gas and liquid separator.It is high
Effect blade separator adsorbs the principle of coalescence and gravitational settling simultaneously using kinetic collision, drop, to realize higher gas-liquid point
From efficiency, lower pressure drop and broader elastic operation scope.The gas of entrained drip once enters high efficiency separation blade
Passage, will be immediately split into multiple regions by blade.Gas during by regional will be forced to carry out repeatedly by blade
Quickly flow direction transformation.Gas is carrying out repeatedly quickly flowing in transition process, and under the influence of centrifugal force, drop will be with
Blade carries out kinetic collision.Blade surface is attached to by adsorbing coalescence effect between drop.It is attached to blade surface to be agglomerated into
The liquid of film enters the interlayer of blade under the synergy of self gravitation, surface tension of liquid and gas kinetic energy, and in interlayer
In conflux into stock, be flowed in the hydrops groove below blade and be collected, finally give the gas through purified treatment.
In above-mentioned technical proposal, it is preferable that ammonia flash tank operating pressure is 0.3～1.0MPaG, and operation temperature is 130～170
℃。
In above-mentioned technical proposal, it is preferable that dehydration column overhead operating pressure is -0.1～0.3MPaG, and tower top operation temperature is
60～120 DEG C.
Therefore, technique of the invention significantly can be saved in equipment investment and production process energy resource consumption, operating cost,
Production cost is reduced, technical process environmental protection achieves preferable technique effect.
Description of the drawings
Fig. 1 is present invention process schematic flow sheet.
In Fig. 1, C101 is recovery ammonia tower, and S101 is high efficient gas and liquid separator, and V101 is ammonia flash tank, and C102 is de-
Water tower, E101 are recovery ammonia tower condenser, and E102 is secondary condenser.1 is liquid ammonia process for caustic soda purification product, and 2 is that Ammonia Process is anti-
Answer product, 3 is recovery ammonia tower overhead gas, 4 is ammonia, 5 is liquefied ammonia, 6 is fresh liquefied ammonia, 7 is recovery ammonia tower bottoms, 8
For the drop of ammonia entrainment, 9 is secondary recovery liquid, and 10 is fixed gas, and 11 is flash tank bottom liquid, and 12 are dehydration liquid of top of the tower
(circulation is used as catalyst), 13 are dehydration liquid of top of the tower (going wastewater treatment), and 14 is dehydrating tower kettle liquid.
In Fig. 1, after liquid ammonia process for caustic soda purification product 1 and the mixing of Ammonia Process product 2, recovery ammonia tower C101, fresh liquid are delivered to
6 feed ammonia of ammonia reclaims column overhead as backflow, and recovery ammonia tower overhead gas 3 is separated through high efficient gas and liquid separator S101 and carried secretly
Drop 8 after, ammonia 4 through recovery ammonia tower condenser E101 condensation after liquefied ammonia 5 be recycled to liquid ammonia process for caustic soda purification and Ammonia Process reaction
Used as reaction raw materials, drop 8 delivers to ammonia flash tank V101 to unit after mixing with recovery ammonia tower bottoms 7, after vacuum flashing,
After secondary condenser E102 partial condensations, the liquefied ammonia 9 containing a small amount of water delivers to Ammonia Process unit as reaction raw materials to gas phase,
Fixed gas 10 is delivered to after ammonia absorber absorbs and delivers to dehydrating tower C102 as Ammonia Process unit catalyst, flash tank bottom liquid 11,
Liquid of top of the tower is divided into two parts, and liquid of top of the tower 12 delivers to Ammonia Process unit as catalyst, and liquid of top of the tower 13 goes wastewater treatment, dehydration
Tower bottoms 14 is mixed ethanol amine product, including monoethanolamine, diethanolamine, triethanolamine and heavy constituent.
Below by embodiment, the invention will be further elaborated, but these embodiments are not anyway to the present invention's
Scope is construed as limiting.
Specific embodiment
【Embodiment 1】
As shown in figure 1, liquid ammonia process for caustic soda purification product 1 and Ammonia Process product 2 deliver to recovery ammonia tower C101, tower after mixing
The fresh liquefied ammonia 6 of top material inlet separates the drop 8 of entrainment as backflow, recovery ammonia tower overhead gas 3 through high efficient gas and liquid separator S101
Afterwards, the liquefied ammonia 5 after recovery ammonia tower condenser E101 condensations of ammonia 4 is recycled to liquid ammonia process for caustic soda purification and Ammonia Process reaction member conduct
Reaction raw materials, drop 8 deliver to ammonia flash tank V101 after mixing with recovery ammonia tower bottoms 7, after vacuum flashing, gas phase is passed through
After secondary condenser E102 partial condensations, the liquefied ammonia 9 containing a small amount of water delivers to Ammonia Process unit as reaction raw materials, fixed gas
10 deliver to ammonia absorber absorb after deliver to dehydrating tower C102, liquid of top of the tower as Ammonia Process unit catalyst, flash tank bottom liquid 11
It is divided into two parts, liquid of top of the tower 12 delivers to Ammonia Process unit as catalyst, and liquid of top of the tower 13 goes wastewater treatment, dehydrating tower kettle liquid
14 are mixed ethanol amine product, including monoethanolamine, diethanolamine, triethanolamine and heavy constituent.
Liquid ammonia process for caustic soda purification product 1, in terms of mass fraction, ammonia content is 70%, also contains monoethanolamine, diethanolamine, three
Ethanolamine and heavy constituent.
Ammonia Process product 2, in terms of mass fraction, ammonia content is 65%, and water content is 3%, also containing an ethanol
Amine, diethanolamine, triethanolamine and heavy constituent.
Recovery ammonia tower theoretical cam curve is 10, and operating pressure is 1.4MPaG, 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 60 DEG C.
Mixed ethanol amine product 13, in terms of mass fraction, ammonia≤1ppm, water≤50ppm, monoethanolamine=49%, diethyl
Hydramine=40%, triethanolamine=11%.
In liquid ammonia recovery 5 water content be 3ppm, ammonia recovery >=99.9%.
In the present embodiment, 180 DEG C of the equal ＜ of recovery ammonia tower bottom temperature, flash tank operation temperature and dehydrating tower bottom temperature.
【Embodiment 2】
Liquid ammonia process for caustic soda purification product 1, in terms of mass fraction, ammonia content is 73%, also contains monoethanolamine, diethanolamine, three
Ethanolamine and heavy constituent.
Ammonia Process product 2, in terms of mass fraction, ammonia content is 70%, and water content is 5%, also containing an ethanol
Amine, diethanolamine, triethanolamine and heavy constituent.
Recovery ammonia tower theoretical cam curve is 20, and operating pressure is 1.6MPaG, and operation temperature is 44 DEG C.
Ammonia flash tank operating pressure is 0.45MPaG, and operation temperature is 157 DEG C.
Dehydrating tower operating pressure is -0.05MPaG, and operation temperature is 78 DEG C.
Mixed ethanol amine product 13, in terms of mass fraction, ammonia≤1ppm, water≤50ppm, monoethanolamine=59%, diethyl
Hydramine=34%, triethanolamine=7%.
In liquid ammonia recovery 5 water content be 4ppm, ammonia recovery >=99.9%.
In the present embodiment, 180 DEG C of the equal ＜ of recovery ammonia tower bottom temperature, flash tank operation temperature and dehydrating tower bottom temperature.
【Embodiment 3】
Liquid ammonia process for caustic soda purification product 1, in terms of mass fraction, ammonia content is 75%, also contains monoethanolamine, diethanolamine, three
Ethanolamine and heavy constituent.
Ammonia Process product 2, in terms of mass fraction, ammonia content is 71%, and water content is 8%, also containing an ethanol
Amine, diethanolamine, triethanolamine and heavy constituent.
Recovery ammonia tower theoretical cam curve is 20, and operating pressure is 1.85MPaG, and operation temperature is 49 DEG C.
Ammonia flash tank operating pressure is 0.65MPaG, and operation temperature is 144 DEG C.
Dehydrating tower operating pressure is -0.01MPaG, and operation temperature is 86 DEG C.
Mixed ethanol amine product 13, in terms of mass fraction, ammonia≤1ppm, water≤50ppm, monoethanolamine=65%, diethyl
Hydramine=29%, triethanolamine=6%.
In liquid ammonia recovery 5 water content be 4ppm, ammonia recovery >=99.9%.
In the present embodiment, 180 DEG C of the equal ＜ of recovery ammonia tower bottom temperature, flash tank operation temperature and dehydrating tower bottom temperature.
【Comparative example 1】
Embodiment is identical with embodiment 1～3, is except for the difference that not provided with high-efficiency gas reservoir in the outlet of recovery ammonia top gaseous phase
Device, the life-span of catalyst shorten at least 1/3rd than embodiment 1～3.
【Comparative example 2】
Coproduction mode is not adopted to liquid ammonia process for caustic soda purification and Ammonia Process technique in comparative example 2, a set of ammonia recovery unit, liquefied ammonia is respectively adopted
Method technique needs low-grade cryogen such as propylene, and freon is as liquefied ammonia cooling medium or needs to increase compressor, needs
Increase by a recovery ammonia tower, a flash tank increases equipment investment expense.
【Comparative example 3】
Embodiment is identical with embodiment 1～3, is except for the difference that dehydrated overhead product all as catalyst Returning reactor, second
Alcohol amine product colourity increases by 5～20, and triethanolamine Grade A yield reduces >=1%.
Claims (9)
1. the ammonia recovery method in a kind of ethanolamine joint production process, it is characterised in that the method is followed the steps below：
(1) recovery ammonia tower will be delivered to after liquid ammonia process for caustic soda purification and the mixing of Ammonia Process product, tower top feeds fresh liquefied ammonia as backflow
Liquid, top gaseous phase are reclaimed after the vapor condensation after high efficient gas and liquid separator separation and are recycled to reactor；
(2) ammonia flash tank, ammonia flash distillation tank deck are delivered to after recovery ammonia tower bottoms droplets mixing detached with high efficient gas and liquid separator
Ammonia Process reaction member is delivered to after portion's vapor condensation as reaction raw materials, ammonia flash tank bottom liquid phase delivers to dehydrating tower dehydration；
(3) dehydrating tower kettle liquid delivers to ethanolamine product refined unit, is dehydrated a top liquid part of the tower top containing a small amount of ammonia and delivers to ammonia
Water law reaction member goes wastewater treatment as catalyst, a part.
2. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that liquid ammonia process for caustic soda purification reaction is produced
In terms of mass fraction, ammonia content is 60～85% to thing, also contains monoethanolamine, diethanolamine, triethanolamine and heavy constituent.
3. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that Ammonia Process product
Ammonia content is counted as 50～75% with mass fraction, water content is 1～10%, also contains monoethanolamine, diethanolamine, triethanolamine
And heavy constituent.
4. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that recovery ammonia tower top sets
It is equipped with wire packing.
5. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that in recovery ammonia tower overhead gas
Mutually outlet arranges high efficient gas and liquid separator.
6. the ammonia recovery method in the ethanolamine joint production process according to claim 1 or 5, it is characterised in that recovery ammonia tower
Top gas Vapor Entrainment liquid water content after high efficient gas and liquid separator process is less than 100ppm.
7. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that recovery ammonia tower is theoretical
The number of plates is 10～30, and tower top operating pressure is 1.0～3.0MPaG, and tower top operation temperature is 30～80 DEG C.
8. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that ammonia flash tank is operated
Pressure is 0.3～1.0MPaG, and operation temperature is 130～170 DEG C.
9. ammonia recovery method according to claim 1 in ethanolamine joint production process, it is characterised in that dehydration column overhead is grasped
It is -0.1～0.3MPaG to make pressure, and tower top operation temperature is 60～120 DEG C.
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| CN108334118A (en) * | 2018-03-15 | 2018-07-27 | 中石化宁波工程有限公司 | A kind of ethanol amine device mesohigh absorption tower outlet ammonia concn control system and control method |
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| CN108334118B (en) * | 2018-03-15 | 2023-08-18 | 中石化宁波工程有限公司 | Ammonia water concentration control system and method at outlet of high-pressure absorption tower in ethanolamine device |
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