CN107778186A - Catalyst Production and process of regenerating - Google Patents
Catalyst Production and process of regenerating Download PDFInfo
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- CN107778186A CN107778186A CN201610772491.0A CN201610772491A CN107778186A CN 107778186 A CN107778186 A CN 107778186A CN 201610772491 A CN201610772491 A CN 201610772491A CN 107778186 A CN107778186 A CN 107778186A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/08—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using ammonia or derivatives thereof
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is an object of the invention to provide a kind of Catalyst Production and regeneration method.The method that the present invention is produced using monoethanolamine and hydrogen-catalyst reactor in-situ regeneration is carried out simultaneously, (1) fresh liquefied ammonia use after being purified via ammonia still for producing and regenerating；(2) an ammonia still top gaseous phase part is not condensed, is directly pressurized 0.02~0.04MPa, dereaction device regenerated catalyst after heating；(3) production of monoethanolamine and the regeneration of catalyst are completed by being switched between two shell and tube reactors, realizes continuous production；(4) ammonolysis reaction regenerated catalyst is occurred using high temperature ammonia, catalyst ammonolysis regeneration product is mainly the heavy constituent such as mixed ethanolamine and small part ammonia ether；(5) liquefied ammonia is first preheated using calandria type fixed bed reactor reaction heat, reheats ammonia still charging.This method is simply efficient, saves equipment investment, energy-saving, green, in the industrial production that monoethanolamine is prepared available for liquid ammonia process for caustic soda purification.
Description
Technical field
The present invention relates to a kind of production of catalyst and process of regenerating, it particularly relates to which a kind of oxirane is urged
Change ammonification and prepare the Catalyst Production of monoethanolamine and the process of regeneration.
Background technology
Monoethanolamine is important fine chemical material, is monoethanolamine (MEA), diethanol amine (DEA), triethanolamine
(TEA) general designation, due to containing amido, hydroxyl Liang Zhong functional groups in its molecule, therefore there is the property of amine and alcohol simultaneously, it is wide
It is general for surfactant, gas absorbent, detergent, the industrial circle such as intermediate for preparing dyestuff and synthetic rubber.Due to
The demand of ethanolamine product is increasingly increased both at home and abroad, certain lack be present between especially domestic monoethanolamine production and demand
Mouthful, therefore it is extremely important to the energy-efficient new technology of original device progress capacity expansion revamping, exploitation.
Industrial production monoethanolamine is mainly using oxirane (EO) and the process route of excess ammonia reaction, using water conduct
Catalyst, monoethanolamine enterprise can be divided into according to the concentration of ammonia in the raw material used by four classes：1) SD companies in the U.S. are using low dense
The ammoniacal liquor of degree is reaction raw materials, by EO and 20~30wt% ammoniacal liquor (including fresh material and material of circulation), 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, its
Relative amount is respectively 69wt%, 21wt%, 10wt%, and excess of ammonia reclaims through being evaporated under reduced pressure in reaction system, residual ammonia with
The form repetitive cycling of ammoniacal liquor.It is high with being consumed energy in temperature-fall period in reaction heating because the water content in system is high, and product is easy
Water is dissolved in, dehydration energy is high.Therefore, although the ammoniacal liquor synthesising method reacting condition of low concentration is gentle, its energy consumption is too high, will
Gradually it is eliminated.2) Dow Chemical Company uses the ammoniacal liquor of middle and high concentration ammonia concn is 35~50wt%, is for reaction raw materials
System pressure is 3.5MPa, and reaction temperature is 115~130 DEG C.Dow Chemical Company is reclaimed using the method for high vacuum flash distillation first
Ammonia in system, product is distributed to be adjusted by the content of raw material ammonia, and the said firm is filled using the coproduction of EO and monoethanolamine in production
Put.3) BASF AG uses the ammoniacal liquor of high concentration as raw material, and ammonia concn is in more than 90wt%, system pressure 10MPa, NH3/EO
=15~25:1,3~30min of residence time, using level Four thermal insulation tubular reactor, EO is in inferior to different nodes in batches to be entered
Reactor, reacting rear material depressurize in flash column, boil off most of ammonia, and ammonia condensing returns into liquefied ammonia, and residual ammonia steams in 0.4MPa
Go out, absorbed with the water of dehydrating tower into after weak aqua ammonia, then be configured to 90% concentrated ammonia liquor with liquefied ammonia and participate in reacting.Using the ammonia of high concentration
Have become the trend of Ammonia Process technique, Ammonia Process can obtain reconciliation of inventory composition, but it is more product accessory substance to be present, separating difficulty
Height, the problems such as reaction heat can not reclaim.4) Nippon Shokubai companies are using liquefied ammonia as raw material, using the zeolite that La is modified to urge
Agent, the generation diethanol amine of high selectivity, and have been carried out industrial applications.Its process conditions is as follows：It is 100 in reaction temperature
~110 DEG C, pressure is 12~15MPa, and liquid phase air speed is 8~10h-1When, using fixed bed reactors, the one way weight of diethanol amine
Amount selectivity is 41% or so；By circulating MEA, the weight selectivities of its diethanol amine are up to 81%, and oxirane
Complete conversion can be realized, but its catalyst on-stream cycle time is short (only several days), is urgent problem.
Because the chemical property of oxirane is extremely active, self-polymeric reaction generation polyoxy is prone to when concentration is higher
The high boiling substance such as ethene or polyethers, or given birth to the material containing hydroxyl in molecule, such as water, alcohols etc., generation hydration reaction
Into high boiling substances such as polyalcohol, polyalcohol ethers.Main reaction-ammonolysis reaction that above-mentioned side reaction occurs for oxirane and ammonia
For, all it is harmful side reaction, not only reduces the yield of major product, waste EO raw materials, and had a strong impact on ethanol
The quality of amine product, especially colourity, reduce product economy, in addition, the high boiling substance of side reaction generation is covered in and urged
Agent surface, easily cause the inactivation of catalyst, it is therefore desirable to which decaying catalyst is regenerated.In order to farthest reduce
Catalyst regenerates the influence to production process, saves operating cost and time, realizes production-regeneration while just become very
It is important.
Liquid ammonia process for caustic soda purification production monoethanolamine 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 monoethanolamine technology, existing document and patent are related to consersion unit and separating technology more, without catalyst again temporarily
The report of generation method.
The content of the invention
The present invention is in liquid ammonia process for caustic soda purification production monoethanolamine technique, catalyst easy in inactivation, catalyst regenerate equipment investment height etc.
Problem, there is provided a kind of production of monoethanolamine and regeneration method, the technique are used in liquid ammonia process for caustic soda purification production monoethanolamine technique catalyst again
When raw, having does not influence production process, simple efficient, energy-saving, the advantages such as equipment investment is low.
Technical scheme is as follows：A kind of Catalyst Production and the process of regeneration, it is characterised in that this method
Follow the steps below：
(1) used after fresh liquefied ammonia purifies via ammonia still for producing and regenerating；
(2) ammonia still top gas phase, regeneration unit is direct cycled to after part supercharging, condensed another part is liquefied ammonia
Posterior circle is to reaction member；
(3) two shell and tube reactors are used in parallel, and the production of monoethanolamine and the regeneration of catalyst are completed by switching；
(4) ammonia still is delivered to after reaction product and regeneration product mixing；
(5) heat of reactor release feeds to preheat liquefied ammonia and ammonia still；
(6) it is high temperature ammonia to regenerate ammonia through two-step heating, delivers to generation ammonolysis reaction regenerated catalyst, ammonia in reactor
Solution generation monoethanolamine, diethanol amine, triethanolamine and a small amount of heavy constituent, it is recyclable to be used as product.
The easily absorption of the impurity such as water, hydro carbons in industrial liquid ammonia causes the decline of catalyst activity in catalyst surface, because
Liquefied ammonia is passed through ammonia still in advance in this present invention and carries out removing impurities purification, then delivers to reaction and regeneration unit.
Catalyst is i.e. renewable at ambient pressure, but to reduce cost, and ammonia still overhead condenser uses cooling water rather than cold
Freeze water, therefore the operating pressure of ammonia still process column overhead need to be controlled to be not less than 1.0MPaG, to make regeneration product to flow to ammonia still certainly,
The regeneration pressure of catalyst is not less than 1.0MPaG, it is preferable that the regeneration pressure of catalyst is 1.6~2.5MPaG.
The main reason for catalyst inactivation is due to acidic site caused by the covering of the impurity such as ammonia ether material, ammonia ethers thing
Matter is easily decomposed at high temperature, therefore temperature is relatively important to the regeneration of catalyst ammonolysis, and temperature is not less than 250 DEG C, when ammonolysis regenerates
Between be not less than 8h, on catalyst ammonia ether material can most of ammonolysis, and extension heavy constituent residual over time is reduced, preferably
Ground, the temperature of catalyst ammonolysis regeneration is 200~400 DEG C, and the recovery time is 4~30h.In above-mentioned technical proposal, it is highly preferred that
The temperature of catalyst ammonolysis regeneration is 250~350 DEG C.
In above-mentioned technical proposal, it is highly preferred that the catalyst recovery time is 6~20h.
In above-mentioned technical proposal, most preferably, the catalyst recovery time is 8~16h.
In above-mentioned technical proposal, it is preferable that the mass space velocity for regenerating ammonia is 0.1~5h-1。
In above-mentioned technical proposal, it is highly preferred that the mass space velocity of regeneration ammonia is 0.3~1h-1。
Because ethylene oxide ammoniation is strong exothermal reaction, to avoid catalyst hot-spot, cause target product selectivity
Reduce, in above-mentioned technical proposal, preferably have and remove hot good, reaction condition is adjustable advantage shell and tube reactor, manage outer use
Hot water removes heat, can 100% recovery reaction heat to preheat reaction raw materials liquefied ammonia and ammonia still charging.To ensure that oxirane is complete
Full conversion, and reactor apparatus investment is reduced, in above-mentioned technical proposal, it is preferable that heat-insulating of being connected after shell and tube reactor is consolidated
Fixed bed reactor.
Because heat-insulating fixed bed reactors only react in calandria type fixed bed reactor last stage reaction, therefore it is again
The raw cycle is more than calandria type fixed bed reactor, and the latter stage that can not be reacted in shell and tube reactor is regenerated, above-mentioned technology
In scheme, it is preferable that heat-insulating fixed bed reactors are regenerated at the initial stage that calandria type fixed bed reactor reacts.
Because liquid ammonia process for caustic soda purification product form depends primarily on NH in charging3With EO ratio (NH3/ EO mol 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 proportion and energy-saving angle：1~16：1 (mol ratio),
Preferably 6：1~12：1, the concentration of oxirane can be reduced, the probability of oxirane autohemagglutination is reduced, obtains a suitable ethanol
Amine, diethanol amine, triethanolamine product proportion.Adjustment product ratio can be reached by adjusting ammonia alkane ratio according to the market demand simultaneously
The purpose of example.
In above-mentioned technical proposal, it is preferable that reaction temperature is 70~90 DEG C, and reaction pressure is 6.0~8.0MPaG.
In above-mentioned technical proposal, it is preferable that regenerated catalyst produces for monoethanolamine, and oxirane conversion ratio approaches
100%, the selectivity of monoethanolamine and diethanol amine is more than 90%, and the content of ammonia ether accessory substance is less than 0.5wt% in product.
Therefore, technique of the invention can be saved significantly in equipment investment and production process energy resource consumption, operation
Expense, production cost is reduced, using the liquefied ammonia after purification, catalyst regeneration cycle extends to 3~6 months, and service life is more than 1
Year, achieve good technique effect.
Brief description of the drawings
Fig. 1 is present invention process schematic flow sheet.
In Fig. 1, R101 and R102 are shell and tube reactor, and R103 is heat-insulating fixed bed reactors, and T101 is ammonia still,
E101 is liquefied ammonia preheater, and E102 is one-level ammonia preheater, and E103 is secondary amine air preheater, and E104 is that ammonia still process column overhead is cold
Condenser, E105 are ammonia still feed preheater, and V1 and V2 are regeneration pipeline valve, and V3 and V4 are reaction pipeline valve, V5 and V6
For R102 product line valves, V7 and V8 are R101 product line valves.1 is fresh liquefied ammonia, and 2 be oxirane, and 3 be ammonia still
Top gaseous phase, 4 be liquid ammonia recovery, and 5 be reaction liquefied ammonia, and 6 be regeneration ammonia, and 7 be low temperature ammonia, and 8 be high temperature ammonia, and 9 be reaction
Or regeneration product, 10 be regeneration or reaction product, and 11 be reaction or regeneration product, and 12 be that ammonia still is fed, and 13 be ammonia still process tower reactor
Product, 14 be reactor outlet hot water, and 15 be E101 outlet hot waters, and 16 be reactor inlet hot water, and 17 be monoethanolamine, and 18 are
Diethanol amine, 19 be triethanolamine, and 20 be heavy constituent.
In Fig. 1, fresh liquefied ammonia 1 purifies via ammonia still T101, and T101 top gaseous phases 3 divide for two parts, and a part is through steaming
Ammonia column overhead condenser E104 is condensed into liquid ammonia recovery 4, is recycled to reaction member recycling；Another part is directly pressurized 0.02
~0.04MPa is regeneration ammonia 6, is recycled to regeneration unit.Liquid ammonia recovery 4 is with reactor R101 or R102 outlet hot water 14 in liquid
Heat exchange is reaction liquefied ammonia 5 in ammonia preheater E101, and reactor R101 or R102 are delivered to after being mixed with oxirane 2 and is reacted；
Regeneration ammonia 6 is heated to be low temperature ammonia 7 through steam in one-level ammonia preheater E102, then is preheated by electric heater two level ammonia
Device E103 is heated to be high temperature ammonia 8, into reactor R101 or R102 reaction regeneration catalyst.Valve V1 and V3 are opened simultaneously
When, valve V2 and V4 are simultaneously closed off, and now reactor R101 is reacted, reactor R102 progress catalyst regeneration, in R103
During no catalyst inactivation, valve V5 and V8 are opened simultaneously, and valve V6 and V7 are simultaneously closed off, and reaction product 9 enters reactor R103,
R103 reaction product 11 mixes with regeneration product 10 laggard delivers to ammonia still feed preheater E105；Catalyst is carried out in R103
During regeneration, valve V5 and V8 are simultaneously closed off, and valve V6 and V7 are opened simultaneously, and now regeneration product 10 enters reactor R103,
R103 regeneration product 11 delivers to ammonia still feed preheater E105 after being mixed with reaction product 9.Valve V1 and V3 are simultaneously closed off
When, valve V2 and V4 are opened simultaneously, and now reactor R101 carries out catalyst regeneration, and reactor R102 is reacted, in R103
During no catalyst inactivation, valve V6 and V7 are opened simultaneously, and valve V5 and V8 are simultaneously closed off, and reaction product 10 enters reactor
R103, R103 reaction product 11 deliver to ammonia still feed preheater E105 after being mixed with regeneration product 9；Catalyst enters in R103
During row regeneration, valve V5 and V8 are opened simultaneously, and valve V6 and V7 are simultaneously closed off, and regeneration product 9 enters R103, R103 reproduction
Thing 11 delivers to ammonia still feed preheater E105 after being mixed with reaction product 10.The mixture of reaction product and regeneration product passes through
E101 outlet hot waters 15 preheat in ammonia still feed preheater E105 feeds 12 for ammonia still, delivers to T101 afterwards, exchanges heat it
Reactor inlet hot water 16 afterwards is back to R101 or R102, T101 tower reactor obtain product 13.
Below by embodiment, the invention will be further elaborated, but these embodiments are not anyway to this hair
Bright scope is construed as limiting.
Embodiment
【Embodiment 1】
In Fig. 1, fresh liquefied ammonia 1 purifies via ammonia still T101, and T101 top gaseous phases 3 divide for two parts, and a part is through steaming
Ammonia column overhead condenser E104 is condensed into liquid ammonia recovery 4, is recycled to reaction member recycling；Another part is directly pressurized 0.02
~0.04MPa is regeneration ammonia 6, is recycled to regeneration unit.Liquid ammonia recovery 4 is with reactor R101 or R102 outlet hot water 14 in liquid
Heat exchange is reaction liquefied ammonia 5 in ammonia preheater E101, and reactor R101 or R102 are delivered to after being mixed with oxirane 2 and is reacted；
Regeneration ammonia 6 is heated to be low temperature ammonia 7 through steam in one-level ammonia preheater E102, then is preheated by electric heater two level ammonia
Device E103 is heated to be high temperature ammonia 8, into reactor R101 or R102 reaction regeneration catalyst.Valve V1 and V3 are opened simultaneously,
Valve V2 and V4 are simultaneously closed off, and reactor R101 is reacted, and reactor R102 carries out catalyst regeneration, and valve V5 and V8 are simultaneously
Close, valve V6 and V7 are opened simultaneously, and regeneration product 10 enters reactor R103, R103 regeneration product 11 and reaction product 9
Ammonia still feed preheater E105 is delivered to after mixing.The mixture of reaction product and regeneration product is steaming through E101 outlet hot waters 15
Preheating is ammonia still charging 12 in ammonia tower feed preheater E105, delivers to T101 afterwards, the reactor inlet hot water after exchanging heat
16 are back to R101 or R102, T101 tower reactor obtain product 13.
Ammonolysis regeneration pressure is 1.6MPaG, and temperature is 300 DEG C, recovery time 8h, and the mass space velocity for regenerating ammonia is
0.3h-1。
Reaction temperature is 70 DEG C, pressure 6.0MPaG, NH3/ EO mol ratios are 8.0.
The conversion ratio of oxirane is 99.5%, and the selectivity of monoethanolamine and diethanol amine is 93.9%, ammonia ether by-product
The content of thing is 0.34wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
636kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Embodiment 2】
Ammonolysis regeneration pressure is 2.0MPaG, and temperature is 320 DEG C, recovery time 12h, and the mass space velocity for regenerating ammonia is
0.6h-1。
Reaction temperature is 80 DEG C, pressure 7.0MPaG, NH3/ EO mol ratios are 10.0.
The conversion ratio of oxirane is 99.9%, and the selectivity of monoethanolamine and diethanol amine is 95.6%, ammonia ether by-product
The content of thing is 0.22wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
622kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Embodiment 3】
Ammonolysis regeneration pressure is 2.5MPaG, and temperature is 350 DEG C, recovery time 16h, and the mass space velocity for regenerating ammonia is
1h-1。
Reaction temperature is 90 DEG C, pressure 8.0MPaG, NH3/ EO mol ratios are 12.0.
The conversion ratio of oxirane is 100%, and the selectivity of monoethanolamine and diethanol amine is 97.5%, ammonia ether accessory substance
Content be 0.15wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
640kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Embodiment 4】
Ammonolysis regeneration pressure is 4MPaG, and temperature is 250 DEG C, recovery time 4h, and the mass space velocity for regenerating ammonia is
0.5h-1。
Reaction temperature is 70 DEG C, pressure 6.0MPaG, NH3/ EO mol ratios are 8.0.
The conversion ratio of oxirane is 96.3%, and the selectivity of monoethanolamine and diethanol amine is 85.1%, ammonia ether by-product
The content of thing is 1.05wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
586kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Embodiment 5】
Ammonolysis regeneration pressure is 3MPaG, and temperature is 400 DEG C, recovery time 20h, and the mass space velocity for regenerating ammonia is
1.5h-1。
Reaction temperature is 70 DEG C, pressure 8.0MPaG, NH3/ EO mol ratios are 10.0.
The conversion ratio of oxirane is 100%, and the selectivity of monoethanolamine and diethanol amine is 98.1%, ammonia ether accessory substance
Content be 0.12wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
620kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Embodiment 6】
Ammonolysis regeneration pressure is 2.5MPaG, and temperature is 350 DEG C, recovery time 2h, and the mass space velocity for regenerating ammonia is
1h-1。
Reaction temperature is 90 DEG C, pressure 8.0MPaG, NH3/ EO mol ratios are 12.0.
The conversion ratio of oxirane is 83.8%, and the selectivity of monoethanolamine and diethanol amine is 71.3%, ammonia ether by-product
The content of thing is 4.77wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
521kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Embodiment 7】
Ammonolysis regeneration pressure is 3MPaG, and temperature is 200 DEG C, recovery time 20h, and the mass space velocity for regenerating ammonia is
1.5h-1。
Reaction temperature is 70 DEG C, pressure 8.0MPaG, NH3/ EO mol ratios are 10.0.
The conversion ratio of oxirane is 95.8%, and the selectivity of monoethanolamine and diethanol amine is 83.7%, ammonia ether by-product
The content of thing is 1.49wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
565kW。
By above scheme, monoethanolamine device continuous production can be achieved.
【Comparative example 1】
Compared with Example 1, fresh liquefied ammonia 1 purifies not via ammonia still T101, and T101 top gaseous phases 3 divide for two parts,
A part is condensed into liquid ammonia recovery 4 through ammonia still overhead condenser E104, is recycled to reaction member recycling；Another part is straight
0.02~0.04MPa of supercharging is met as regeneration ammonia 6, is recycled to regeneration unit.Liquid ammonia recovery 4 exports with reactor R101 or R102
Hot water 14 is exchanged heat in liquefied ammonia preheater E101 to react liquefied ammonia 5, and reactor R101 or R102 are delivered to after being mixed with oxirane 2
React；Regeneration ammonia 6 is heated to be low temperature ammonia 7 through steam in one-level ammonia preheater E102, then by electric heater two
Level ammonia preheater E103 is heated to be high temperature ammonia 8, into reactor R101 or R102 reaction regeneration catalyst.Valve V1 and V3
Open simultaneously, valve V2 and V4 are simultaneously closed off, and reactor R101 is reacted, and reactor R102 carries out catalyst regeneration, valve
V5 and V8 are simultaneously closed off, and valve V6 and V7 are opened simultaneously, regeneration product 10 enter reactor R103, R103 regeneration product 11 with
Reaction product 9 delivers to ammonia still feed preheater E105 after mixing.The mixture of reaction product and regeneration product exports through E101
Hot water 15 preheats in ammonia still feed preheater E105 feeds 12 for ammonia still, delivers to T101 afterwards, the reaction after exchanging heat
Device entrance hot water 16 is back to R101 or R102, T101 tower reactor obtain product 13.
Ammonolysis regeneration pressure is 1.6MPaG, and temperature is 300 DEG C, recovery time 8h, and the mass space velocity for regenerating ammonia is
0.3h-1。
Reaction temperature is 70 DEG C, pressure 6.0MPaG, NH3/ EO mol ratios are 8.0.
The conversion ratio of oxirane is 99.5%, and the selectivity of monoethanolamine and diethanol amine is 93.9%, ammonia ether by-product
The content of thing is 0.34wt%.
Liquefied ammonia and ammonia still charging are preheated using reaction heat, reaction heat recovery rate is 100%, and product per ton reduces energy consumption
636kW。
But catalyst inactivation is aggravated, the regeneration period shortens, and service life declines, and does not possess commercial viability.
Claims (10)
1. a kind of Catalyst Production and the process of regeneration, it is characterised in that this method follows the steps below：
(1) used after fresh liquefied ammonia purifies via ammonia still for producing and regenerating；
(2) ammonia still top gas phase, regeneration unit is direct cycled to after part supercharging, it is to follow after liquefied ammonia that another part is condensed
Ring is to reaction member；
(3) two shell and tube reactors are used in parallel, and the production of monoethanolamine and the regeneration of catalyst are completed by switching；
(4) ammonia still is delivered to after reaction product and regeneration product mixing；
(5) heat of reactor release feeds to preheat liquefied ammonia and ammonia still；
(6) it is high temperature ammonia to regenerate ammonia through two-step heating, delivers to generation ammonolysis reaction regenerated catalyst in reactor, ammonolysis life
Into monoethanolamine, diethanol amine, triethanolamine and a small amount of heavy constituent, ammonia still is gone to recycle.
2. the technological process of Catalyst Production and regeneration according to claim 1, it is characterised in that parallel reactor is tubulation
Formula fixed bed reactors, tandem reactor are heat-insulating fixed bed reactors.
3. the technological process of Catalyst Production and regeneration according to claim 1, it is characterised in that heat-insulating fixed bed reaction
The regeneration period of device is more than calandria type fixed bed reactor, and can only enter in first, the mid-term that calandria type fixed bed reactor reacts
Row regeneration, the latter stage that can not be reacted in shell and tube reactor are regenerated.
4. the technological process of Catalyst Production and regeneration according to claim 1, it is characterised in that the recovery time is 4~30h.
5. the technological process of Catalyst Production and regeneration according to claim 4, it is characterised in that the recovery time is 6~20h.
6. the technological process of Catalyst Production and regeneration according to claim 5, it is characterised in that the recovery time is 8~16h.
7. according to claim 1 Catalyst Production and regeneration technological process, it is characterised in that regeneration pressure be 0~
4MPaG, regeneration temperature are 200~400 DEG C.
8. according to claim 7 Catalyst Production and regeneration technological process, it is characterised in that regeneration temperature be 250~
350℃。
9. the technological process of Catalyst Production and regeneration according to claim 1, it is characterised in that the quality for regenerating ammonia is empty
Speed is 0.1~5h-1。
10. the technological process of Catalyst Production and regeneration according to claim 10, it is characterised in that regenerate the quality of ammonia
Air speed is 0.3~1h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610772491.0A CN107778186A (en) | 2016-08-30 | 2016-08-30 | Catalyst Production and process of regenerating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610772491.0A CN107778186A (en) | 2016-08-30 | 2016-08-30 | Catalyst Production and process of regenerating |
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ID=61450618
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Cited By (1)
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| CN112358408A (en) * | 2020-11-30 | 2021-02-12 | 江苏凯美普瑞工程技术有限公司 | Production process and device of glycine |
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