CN101492398B - Urea production process of high-efficiency condensation, low-mounting height CO2 air stripping method and high-voltage lamp type full condensation reactor - Google Patents
Urea production process of high-efficiency condensation, low-mounting height CO2 air stripping method and high-voltage lamp type full condensation reactor Download PDFInfo
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- CN101492398B CN101492398B CN200910060466XA CN200910060466A CN101492398B CN 101492398 B CN101492398 B CN 101492398B CN 200910060466X A CN200910060466X A CN 200910060466XA CN 200910060466 A CN200910060466 A CN 200910060466A CN 101492398 B CN101492398 B CN 101492398B
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Abstract
The invention discloses a CO2-stripping process for urea with efficient condensation and low installation height and a high pressure tube condensation reactor. Problems of a traditional urea process are solved, including high civil construction framework, high device investment and hard operation, management and maintenance. With the specific high pressure tube condenser adopted, gas and liquid are separated, unreacted gas in the high pressure tube condensation reactor is directly sent to a scrubber, and simultaneously reacted liquid is sent to a synthesizing tower by a high pressure ejector. Compared with the traditional urea civil construction framework, the height of the framework of the process is lowered by 20-25m. The process has the advantages of simple modification, energy-saving property, lowered energy consumption, lowered investment, convenient operation and convenient maintenance and overhauling.
Description
Technical field
The present invention relates to a kind of industriallization urea production process and specific equipment thereof, specifically a kind of high-efficiency condensation, low-mounting height CO
2Gas formulation urea production process and high-voltage lamp type full condensation reactor.
Background technology
The industriallization urea production is with CO
2Gas and liquefied ammonia are raw material, are pressed into middle pressure or/and working procedure processing such as low pressure decomposition recovery and vacuum concentration, granulation become the solid urea product through height.
At present, the urea plant production technique mainly contains following several kinds both at home and abroad: Dutch Si Tamikabang (Stamicarbon) CO
2The ACES21 technology of gas formulation technology, Italian Si Namu (Snamprogetti) ammonia stripping process technology, Japanese TEC, the efficient synthesis technique of Switzerland card Surrey (Casale), water solution total cycling method technology etc.Wherein, carrying technology and ammonia with carbon dioxide gas, to put forward technology the most competitive.
The high pressure loop flow process of typical Si Tamikabang (Stamicarbon) CO2 gas formulation technology is, with reference to Fig. 1, with raw material CO
2Gas is sent into the high pressure gas stripper; After the gas that is decomposed out by the high pressure gas stripper gets into the falling film type high pressure condenser; Absorbed formation reaction liquid and gas with fixed attention by liquefied ammonia and the liquid cooling of first ammonium from high pressure scrubber; Gas-liquid utilizes pressure reduction to flow into urea synthesizer reaction together then, and laggard next step operation of going into is decomposed at the top that the reaction solution that urea synthesizer comes out utilizes potential difference to turn back to the high pressure gas stripper, and unreacted gas is discharged after then getting into the high pressure scrubber condensed and absorbed.
There is following problems in above-mentioned urea production process: 1, because the reaction solution that urea synthesizer comes out is to utilize potential difference to turn back to the top of high pressure gas stripper, so just require urea synthesizer bottom feed mouth to be higher than high pressure gas stripper top liquid inlet opening 10m at least; 2, because high pressure condenser adopts falling film type, first ammonium liquid and gas stripping gas (CO
2And NH
3) get into by the top; Reaction solution and gas are discharged by the bottom and are utilized pressure reduction to send into urea synthesizer; So minimum must being arranged in and the equal height of urea synthesis tower bottom in high pressure condenser bottom; Urea synthesizer (bottom) and hp ammonium carbamate condenser (bottom) must be arranged in highly on the plane about 20m as a result, thereby make its civil engineering framework up to 50-70m.Not only plant investment is high, and difficulty is all compared in operation, management and maintenance.
In addition, as traditional Si Tamikabang (Stamicarbon) CO
2The high pressure condenser of one of key equipment in the gas formulation technology, the formula structure falls in the main film that adopts of tradition, and process stream (being made up of gas, liquid) is walked to manage side by condensing surface and is from up to down moved, and steam condensate is walked shell-side.The high-pressure process material is walked tube side, because gas, liquid are descending, liquid forms film on tube wall; Gas is walked in pipe, makes that the residence time of process stream in pipe is very short, and temperature of charge is about 167 ℃; The vapor pressure of shell-side by-product is lower, is generally 0.44MP (A), is difficult to reasonable utilization.Because residence time weak point and the reactionless district of material in pipe, therefore, no urea generates in high pressure condenser.
Summary of the invention
The purpose of this invention is to provide a kind of new high-efficiency condensation, low-mounting height CO
2Gas formulation urea production process; Through high pressure loop flow process is wherein improved; When guaranteeing the effective transformation efficiency of urea, can significantly reduce the height of main high voltage circle equipment such as urea synthesizer, hp ammonium carbamate condenser, reduction equipment is established money, is installed and transform easy maintenance.
The present invention also provides a kind of high-voltage lamp type full condensation reactor that is used for production technique of the present invention.
CO of the present invention
2Gas formulation urea production process comprises the steps:
(1) with raw material CO
2Gas is sent into the high pressure gas stripper, under steam heating, makes the ammonium carbamate that comes from urea synthesizer be decomposed into NH
3And CO
2Gas is also sent into high-voltage lamp type full condensation reactor;
(2) first ammonium liquid is sent into condensed and absorbed NH in the high pressure scrubber
3And CO
2Gas, the first ammonium liquid that reaction generates utilize potential difference to flow into high-voltage lamp type full condensation reactor, and unreacted tail gas is discharged;
(3) from the first ammonium liquid of high pressure scrubber with from the NH of high pressure gas stripper
3And CO
2Gas is condensed and absorbed and reaction in high-voltage lamp type full condensation reactor, and the ammonium carbamate of generation and urea get into urea synthesizer and further reacts unreacted NH after high-pressure injector boosts
3And CO
2Gas is sent into high pressure scrubber;
(4) with raw material CO
2Gas is sent into urea synthesizer; With ammonium carbamate and urea further reaction in urea synthesizer from high-voltage lamp type full condensation reactor; After utilizing pressure reduction to flow into the high pressure gas stripper, the reaction solution that is made up of ammonium carbamate and urea that generates gets into subsequent processing, unreacted NH
3And CO
2Gas is sent into high pressure scrubber.
Said raw material CO
2From CO
2Compressor, the 15-25% of its volume total amount sends into urea synthesizer, and 75-85% sends into the high pressure gas stripper.
Said high-pressure injector is driving medium with the raw materials ammonia.
Said high pressure gas stripper is the falling film type well heater.
The urea synthesizer operating parameters is 14.0-15.0MPa (A), 183-186 ℃, NH
3/ CO
2=30-3.3, H
2O/CO
2=0.5-0.65.
Production technique of the present invention is through changing high-voltage lamp type full condensation reactor outlet unreacting gas (NH
3And CO
2) the flow direction, make it without urea synthesizer, but directly remove high pressure scrubber, make that the pressure reduction between high-voltage lamp type full condensation reactor and the high pressure scrubber reduces, first ammonium liquid potential difference capable of using flows into high-voltage lamp type full condensation reactor, and need not positive delivery; The reacted liquid that simultaneously high-voltage lamp type full condensation reactor is come out (promptly generate ammonium carbamate and urea) is through being to send into urea synthesizer after the high-pressure injector supercharging of driving medium further to react with the raw materials ammonia; The reaction solution that urea synthesizer comes out utilizes pressure reduction to flow into the high pressure gas stripper; Variation through above-mentioned production technique; Make urea synthesizer and high-voltage lamp type full condensation reactor can be arranged in ground or subaerial position, comparable traditional urea frame height reduces 20-25m.Said raw materials ammonia is also participated in reaction and is generated urea after getting into synthetic tower.
Further, in order to keep the thermal equilibrium of urea synthesizer, from CO
2The raw material CO of compressor
2In have 15-25% (percent by volume) directly to get into urea synthesizer approximately, other then sends into the high pressure gas stripper.
Because gas, liquid that high-voltage lamp type full condensation reactor is come out separate; Change has taken place in the gas flow of outlet; This also requires ammonia and carbonic acid gas condensed and absorbed in high-voltage lamp type full condensation reactor as far as possible, and formula high pressure condenser one side gas falls in traditional film, liquid from up to down moves, and the gas-liquid of outlet is difficult to separate fully; The formula high pressure condenser falls in traditional film does not simultaneously have reaction zone, NH
3And CO
2Gas condensed and absorbed rate in high pressure condenser is not high, therefore need ammonia of design and carbonic acid gas as far as possible in high-voltage lamp type full condensation reactor condensed and absorbed, can generate the specific equipment that the ammonium carbamate while can be translated into urea again.
The technical scheme of high-voltage lamp type full condensation reactor of the present invention is: comprise the condensing surface that heat transfer tube is housed; Said condenser is provided with gas feed, the liquid import of first ammonium and steam condensate import; Top is provided with the steam condensate outlet; Said gas feed and the import of first ammonium liquid communicate with the pipe side of condensing surface, and steam condensate import and steam condensate outlet communicate with the condensing surface shell-side; Said upper end of condenser also is provided with the reactor drum that communicates with the condenser tube side, and said reactor head is provided with pneumatic outlet, and the reaction solution outlet is connected with the interior downtake pipe lower end of reactor drum.
Also be provided with at least one floor height in the said reactor drum under the liquid layer and imitate tower tray.
Said gas, liquid-inlet also communicate with the condenser tube side through gas and liquid distributor.
The present invention is a vertical equipment, and reactor drum is communicated with the heat transfer tube of condensing surface, and process stream walks to manage side (being heat transfer tube) from the bottom to top in condensing surface; Steam condensate is walked shell-side, since action of gravity, full of liquid in the heat transfer tube; In the reactor drum also major part liquid is housed, gas is up by condensing surface bottom, bubbling in heat transfer tube and reactor drum; Increased the residence time of process stream greatly, and also can react when going upward to reactor drum with the abundant condensed and absorbed of liquid at heat transfer tube.At last, gas is discharged by the pneumatic outlet of reactor head and is got into high pressure scrubber, and urea that reaction generates and the downtake pipe of ammonium carbamate in reactor drum are discharged by the reaction solution outlet and got into subsequent processing.For gas-liquid is fully contacted, in reactor drum, be provided with high-efficient tower plate, said high-efficient tower plate can adopt the tower tray of porous plate, hump plate or other form; Above condenser gas, liquid-inlet, also be provided with gas and liquid distributor so that gas and liquid uniform distribution get into hot replace tubes.
Production technique of the present invention has the following advantages:
1, through improvement to existing urea production process; When guaranteeing the effective transformation efficiency of urea; Make urea synthesizer and high-voltage lamp type full condensation reactor can be arranged in ground, the civil engineering framework overall height of urea is about 40m, reduces 20-25m than traditional urea civil engineering frame height; Technological transformation is simple, reduce investment outlay, handled easily, is convenient to safeguard and maintenance.
Specific equipment high-voltage lamp type full condensation reactor of the present invention has the following advantages:
1, to compare with traditional falling film type high pressure condenser, pipe side material of the present invention moves from bottom to top; In condensing surface the residence time grow, temperature is high, about 180 ℃, therefore; It has bigger heat transfer temperature difference, thereby makes the heat interchanging area of design can reduce more than 50%, reduces investment greatly;
2; Through setting up reactor drum, prolonging the residence time of material in equipment; Make process stream in the present invention fully condensed and absorbed and the reaction; Generate carboxylamine and certain amount of urea, can shunt the load of urea synthesizer, the problem of former urea synthetic tower scarce capacity in the time of effectively solving capacity expansion revamping; Also can solve the problem that the Large Scale Urea Plant urea synthesizer is restricted at aspects such as diameter, height because of reasons such as manufacturing, transportations;
3, this structure design can improve the pressure of byproduct steam, and the pressure of steam can reach 0.5MPa (a), because the steam grade improves, helps the reasonable utilization of steam.In addition, steam condensate side (being shell-side) is a natural circulation, does not need recycle pump, reduces investment outlay, and has also reduced power consumption;
4; The volume of reactor drum can design according to different requirement among the present invention; Be specially adapted to when carrying out the capacity expansion revamping need the increase of the synthetic tower in urea technique equipment volume; Only needn't synthetic tower be transformed, reduced difficulty of construction, further practiced thrift improvement cost with the volume that increases reactor drum of the present invention.Present device not only can be used for CO
2Gas formulation urea technique also can solve other process units (mentioning improvement total recycle process technology like water solution total cycling method, ammonia) when carrying out the high pressure loop transformation, the problem that original urea synthesizer can not utilize or be difficult to arrange;
5, the condenser tube side of high-voltage lamp type full condensation reactor bottom is a high pressure, and pressure is generally 13-17MPa (A); Shell-side is a low pressure, and pressure is generally 0.4-0.9MPa (A), so device structure is simple; Need not use special internal bore welding technology, manufacturing technology requires lower, and technical risk is little; Low cost of manufacture, domestic technique can be produced fully.
Description of drawings
Fig. 1 is traditional CO
2The process flow sheet of gas formulation urea production process;
Fig. 2 is high-efficiency condensation of the present invention, low-mounting height CO
2The process flow sheet of gas formulation urea production process;
The structural representation of Fig. 3 high-voltage lamp type full condensation reactor of the present invention.
Wherein, 1-high-voltage lamp type full condensation reactor, 2-urea synthesizer, 3-high pressure gas stripper, 4-high pressure scrubber, 5-high-pressure injector, 6-gas and liquid distributor, 7-heat transfer tube, 8-high-efficient tower plate, 9-downtake pipe, 10-gas feed, the import of 11-first ammonium liquid, the import of 12-steam condensate, the outlet of 13-steam condensate, the outlet of 14-reaction solution, 15-pneumatic outlet, 16-condensing surface, 17-reactor drum, 18-high pressure condenser.
Embodiment
Below in conjunction with accompanying drawing the present invention is further explained:
With reference to Fig. 2, in the high pressure loop flow process, will be by CO
214.5MPa after the compressor compresses (A), 120 ℃ CO
2Gas divides two portions to get into high-pressure system, the CO of 75-85%
2The pipe side that gas gets into high pressure gas stripper 3 by the bottom, the CO of 15-25%
2Gas gets into urea synthesizer 2 by the bottom, to keep its thermal equilibrium; High pressure gas stripper 3 is the falling film type well heater, and shell-side decomposes needed heat with 2.2MPa (A) steam heating so that the ammonium carbamate from urea synthesizer 2 to be provided, and the gas stripping gas that reaction generates (is NH
3And CO
2Gas) get into high-voltage lamp type full condensation reactor 1 lower tube side by the 3 pipe side roof part outlets of high pressure gas stripper; On the other hand, first ammonium liquid gets into high pressure scrubber 4, with the NH from high-voltage lamp type full condensation reactor 1 and urea synthesizer 2
3And CO
2The gas condensation by contact absorbs; Said high pressure scrubber 4 tops are packing section; The bottom is provided with heat exchanging segment, adopts the hot water cooling, and hot water is taken first ammonium liquid in the high pressure scrubber 4 away in closed circulation system generation H/C coagulates heat; Uncooled gas gets into the top packing section, and the first ammonium liquid of being sent here from circulating process carries out washing and recycling NH
3And CO
2, the first ammonium liquid that is generated gets into high-voltage lamp type full condensation reactor 1 lower tube side from high pressure scrubber 4 overflows.The gas of high pressure scrubber 4 outlets contains a spot of ammonia and carbonic acid gas, is admitted to the low pressure absorption tower, and after absorbing with process condensate and steam condensate, the tail gas after the absorption enters in the atmosphere.
From the gas stripping gas of high pressure gas stripper 3 and together, get into high-voltage lamp type full condensation reactor 1 by the bottom, at this CO from high pressure scrubber 4 first ammonium liquid
2, NH
3The absorption that is condensed generates ammonium carbamate and urea, is the high-pressure injector 5 of the driving medium back entering urea synthesizer 2 that boosts through raw materials ammonia again, unreacted CO
2, NH
3Gas is sent into high pressure scrubber 4 by the top.Said raw materials ammonia is as the actuating fluid of high-pressure injector 5, sends into the 2-urea synthesizer after ammonium carbamate that high-voltage lamp type full condensation reactor 1 is come out and the urea soln supercharging, with CO
2The CO that compressor comes
2Gas further condensed and absorbed reaction in urea synthesizer 2 generates the reaction solution that is made up of ammonium carbamate and urea; Reaction solution utilizes pressure reduction from flowing into high pressure gas stripper 3 pipe sides, gets into the low pressure decomposing system then through high pressure gas stripper 3 bottoms and carries out next step operation.Urea synthesizer 2 unreacted CO
2And NH
3Gas is sent into high pressure scrubber 4 from the top.Be provided with the polylith high-efficient tower plate in said urea synthesizer 2 towers, guarantee the thorough mixing and the contact of vapour, liquid material in the tower, prevent the process stream back-mixing, improve transformation efficiency.The reaction conditions of urea synthesizer 2 is: 14.0-15.0MPa (A), 183-186 ℃, NH
3/ CO
2=30-3.3, H
2O/CO
2=0.5-0.65, CO
2The about 60-63% of transformation efficiency.
Urea synthesizer 2 is arranged on the ground; The bottom of the bottom of high-voltage lamp type full condensation reactor 1 and high pressure gas stripper 3 is arranged in subaerial height (in the vertical height 2m of ground); The vertical height at high pressure scrubber 3 distance from bottom high-voltage lamp type full condensation reactors 1 top is at least 4m, and civil engineering framework overall height is about 40-42m.
Said high-voltage lamp type full condensation reactor 1 is a vertical equipment; Comprise the condensing surface 16 that many heat transfer tubes 7 are housed and the reactor drum 17 of upper end thereof; Said condensing surface 16 bottoms are provided with gas feed 10, the first ammonium liquid import 11 that is communicated with heat transfer tube 7 (promptly managing side); And the steam condensate import 12 that is communicated with shell-side, said gas feed 10, the import 11 of first ammonium liquid are communicated with heat transfer tube 7 through gas and liquid distributor 6.Condensing surface 16 tops are provided with the steam condensate outlet 13 that is communicated with shell-side; Said reactor drum 17 is communicated with the pipe side of condensing surface 16, is provided with multi-layer efficient tower tray 10 and downtake pipe 9 in the reactor drum 17, and pneumatic outlet 12 is established at its top, the reaction solution outlet 11 on the downtake pipe 9 lower end ligation devices 17.
The principle of work of high-voltage lamp type full condensation reactor 1:
With CO
2Gas formulation urea technique is an example, the gas stripping gas (CO that is come out by the high pressure gas stripper
2, NH
3Gas) and the first ammonium liquid that comes out of high pressure scrubber get into condensing surfaces 16 by the gas feed 10 of bottom with first ammonium liquid import 11 respectively, get into reactor drum 17 and continue up along pipe side bubbling through gas and liquid distributor 6 backs through the high-efficient tower plate 8 in the reactor drum 17.Gas stripping gas (CO
2, NH
3Gas) and first ammonium liquid abundant absorbing contacting in pipe; And further condensed and absorbed generates ammonium carbamate and urea in reactor drum 17; Reacted gas is discharged by the pneumatic outlet 12 at reactor drum 17 tops, and ammonium carbamate and urea are then discharged by reaction solution outlet 11 through downtake pipe 9.Steam condensate gets into the circulation of condensing surface 16 shell-sides by steam condensate import 12, and is discharged by steam condensate outlet 13, to absorb the reaction heat (about 180 ℃ of temperature) of material in the heat transfer tube 7, by-product 0.45-0.5MPa (A) steam.Said pipe side is a high pressure, and pressure is 13-17MPa (A), and shell-side is a low pressure, and pressure is 0.4-0.9MPa (A).
Claims (5)
1. a high-efficiency condensation, low-mounting height CO
2Gas formulation urea production process is characterized in that, comprises the steps:
(1) with raw material CO
2Gas is sent into the high pressure gas stripper, under steam heating, makes the ammonium carbamate that comes from urea synthesizer be decomposed into NH
3And CO
2Gas is also sent into high-voltage lamp type full condensation reactor;
(2) first ammonium liquid is sent into condensed and absorbed NH in the high pressure scrubber
3And CO
2Gas, the first ammonium liquid that reaction generates utilize potential difference to flow into high-voltage lamp type full condensation reactor, and unreacted tail gas is discharged;
(3) from the first ammonium liquid of high pressure scrubber with from the NH of high pressure gas stripper
3And CO
2Gas is condensed and absorbed and reaction in high-voltage lamp type full condensation reactor, and the ammonium carbamate of generation and urea get into urea synthesizer and further reacts unreacted NH after high-pressure injector boosts
3And CO
2Gas is sent into high pressure scrubber;
(4) with raw material CO
2Gas is sent into urea synthesizer; With ammonium carbamate and urea further reaction in urea synthesizer from high-voltage lamp type full condensation reactor; After utilizing pressure reduction to flow into the high pressure gas stripper, the reaction solution that is made up of ammonium carbamate and urea that generates gets into subsequent processing, unreacted NH
3And CO
2Gas is sent into high pressure scrubber;
Said raw material CO
2From CO
2Compressor, the 15-25% of its volume total amount sends into urea synthesizer, and 75-85% sends into the high pressure gas stripper; Said high-voltage lamp type full condensation reactor comprises the condensing surface that heat transfer tube is housed; Said condenser is provided with gas feed, the liquid import of first ammonium and steam condensate import; Top is provided with the steam condensate outlet; Said gas feed and the import of first ammonium liquid communicate with the pipe side of condensing surface, and steam condensate import and steam condensate outlet communicate with the condensing surface shell-side; Said upper end of condenser also is provided with the reactor drum that communicates with the condenser tube side, and said reactor head is provided with pneumatic outlet, and the reaction solution outlet is connected with the interior downtake pipe lower end of reactor drum.
2. high-efficiency condensation as claimed in claim 1, low-mounting height CO
2Gas formulation urea production process is characterized in that, said high-pressure injector is driving medium with the raw materials ammonia.
3. high-efficiency condensation as claimed in claim 1, low-mounting height CO
2Gas formulation urea production process is characterized in that, said high pressure gas stripper is the falling film type well heater.
4. high-voltage lamp type full condensation reactor; Comprise the condensing surface that heat transfer tube is housed; It is characterized in that said condenser is provided with gas feed, the liquid import of first ammonium and steam condensate import, top is provided with the steam condensate outlet; Said gas feed and the import of first ammonium liquid communicate with the pipe side of condensing surface, and steam condensate import and steam condensate outlet communicate with the condensing surface shell-side; Said upper end of condenser also is provided with the reactor drum that communicates with the condenser tube side, and said reactor head is provided with pneumatic outlet, and the reaction solution outlet is connected with the interior downtake pipe lower end of reactor drum.
5. high-voltage lamp type full condensation reactor as claimed in claim 4 is characterized in that: also be provided with at least one floor height in the said reactor drum under the liquid layer and imitate tower tray.
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| EP2505581A1 (en) * | 2011-03-31 | 2012-10-03 | Stamicarbon B.V. | Zero emission urea process and plant |
| CN102635536A (en) * | 2012-05-03 | 2012-08-15 | 内蒙古乌拉山化肥有限责任公司 | Method for preventing CO2 from being liquefied in five-section type CO2 compressor |
| CN110817900B (en) * | 2019-11-15 | 2021-03-16 | 山西中科惠安化工有限公司 | Device and method for separating ammonia gas containing carbon dioxide and organic matters |
| CN112295389B (en) * | 2020-08-31 | 2022-06-17 | 中石化南京化工研究院有限公司 | Method and device for removing hydrogen sulfide in acid water stripping ammonia gas |
| CN112028089B (en) * | 2020-09-30 | 2024-02-06 | 四川金象赛瑞化工股份有限公司 | Production device and method of ammonium nitrate |
| CN114669264B (en) * | 2022-04-08 | 2023-09-05 | 长沙鑫本药业有限公司 | Device and method for producing ammonium formate by adopting external circulation ammonification |
| CN115466200A (en) * | 2022-10-24 | 2022-12-13 | 上海超希实业有限公司 | High-quality synthetic urea processed by sectional control reaction and processing method |
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| CN201350404Y (en) * | 2009-01-09 | 2009-11-25 | 中国五环工程有限公司 | High pressure tubular full-condensation reactor |
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