Background technology
As everyone knows, at present the method for industrial production urea be ammonia and carbonic acid gas convenient pressure for example 125-350 normal atmosphere and high temperature for example 170-250 ℃ at first generate ammonium carbamate (hereinafter referred first ammonium) by following reaction:
The ammonium carbamate of Sheng Chenging is pressed the column balancing reaction formula then, generates urea by dehydration.
According to balanced reaction, generate the urea transformation rate, a lot of influence factors are arranged, for example temperature of reaction and pressure, employing excess of ammonia etc.Reaction products resulting is a kind of solution that mainly contains urea, water, ammonium carbamate and free ammonia.Ammonium carbamate and ammonia must be removed from this solution, in most of the cases, also ammonium carbamate and the ammonia of removing be returned synthetic district.
Typical industrial process is being called of Dutch Stamicarbon B.V. " Si Tamikaben carbonic acid gas stripping technological process " for example, is the method for preparing urea of widespread use.In this technological process, will be under high pressure and high temperature, urea synthesis solution in synthetic tower formation, under synthesis pressure, carrying out stripping handles, formed urea synthesis solution is carried out counter current contact with carbon dioxide gas providing under the situation of heat, thereby make the part ammonium carbamate that in this solution, exists be decomposed into ammonia and carbonic acid gas.These degradation productions are displaced from solution and with it with a spot of water vapor be used for carrying out steam stripped carbonic acid gas and emit.With the gaseous mixture that obtains in the stripping process, under synthesis pressure, send into hp ammonium carbamate condenser, carry out condensation reaction with ammonia, and then further handle the solution that contains urea with rectification method, the condensation reaction heat that is discharged is used for producing water vapor or is used for the fluid of heating process process.
For the optimum N H that obtains reacting
3/ CO
2Ratio also feeds the condensation reaction district with the needed most or whole initiate ammonia of this technological process.With the formed ammonium carbamate aqueous solution and the gaseous mixture of condensation not, add synthetic district from the condensation district, be used for forming urea.At this moment, the further condensation of gaseous mixture provides ammonium carbamate is converted into the required heat of urea.
Then stripped urea synthesis solution is decompressed to a low pressure, and makes a kind of urea soln or molten mass that can further be processed into solid urea.But urea purity does not satisfy the requirement of low-poison urea-formaldehyde resin adhesive.
In above-mentioned technological process, synthetic district except that containing liquid phase, also contain than relatively large ammonia, carbonic acid gas and in the past in reactive component partly with the impurity form exist as H
2S gas has the heavy corrosion effect.
The someone advises (United States Patent (USP) the 4th, 208, No. 347), can use high NH in a kind of second-stage reaction district
3/ CO
2Mol ratio prepares urea, and wherein first section is higher than second section, and first section material of emitting fed second section bottom.The top of urea synthesis solution from second section is emitted, and in two placed in-line stripping zones, handle, to decompose ammonium carbamate, the gas phase that first stripping zone is obtained directly feeds first section of reaction zone, and the gas phase that second stripping zone is obtained, in a condensation district after the condensation, also feed first section of reaction zone with the form of ammonium carbamate solution.At first section needed heat of this reaction zone, be to provide by condensation from the gaseous mixture of first stripping zone.In second section, the formation of urea is by adding the liquid NH of additional quantity
3Next promoted, thus hold onto and make balance to move right in water.According to this kind technical qualification, these measures have been avoided taking very big space and have used usually reactor being arranged on the high framework that is higher than the needed trouble of equipment of handling building-up reactions district effluent.But this kind embodiment will and need many equipment with a lot of labours.In addition, therefore the complex structure of reactor is very expensive.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, through contriver's industrial practice for many years, on original industrial production urea plant, improve, provide a kind of economy, simple to operation, cost is low, product purity is high, improve the method for industrial production urea plant efficiently.
The method of improvement industrial production urea plant provided by the invention, be included in the urea synthesizer, under the urea synthesis temperature and pressure, make ammonia and carbon dioxide reaction, allow and contain urea, unreacted ammonia, the urea soln of the generation of unreacted carbonic acid gas and water, in stripping tower, heating under the urea synthesis pressure no better than, contact with at least a portion carbonic acid gas material, to separate as ammonia, the unreacted ammonia of the mixed gas of carbonic acid gas and water and unreacted carbonic acid gas, further processing contains the urea synthesis solution of unsegregated unreacted ammonia and unreacted carbonic acid gas to obtain urea, it is characterized in that improving comprising:
---the synthetic gas system that to change original employing coke be raw material is the gas-making process with grace fine coal producer in the synthesis system of material synthesis gas, this technology is in grace fine coal producer (claiming the grace vapourizing furnace), granularity is the following fine coal of 10mm, carry out fluidized-bed gasification with oxygen-rich air and superheated vapour, gasification temperature 800-1050 ℃, reduce the gas making cost greatly, make the urea cost reduce 15-20%, its characteristics are:
(1) throughput is big
Maximum single stove gas production rate can reach 40000NM
3More than/the H.
(2) stable and reliable operation, the repair and maintenance workload is little
Owing to cancelled fire grate, avoided furnace bottom slagging scorification problem, vapourizing furnace only is made up of body of heater and dismountable cloth wind nozzle of inner lining refractory, does not have transport unit and consumable accessory, so do not need too many maintenance capacity can obtain higher continuous operation rate, generally can reach more than 90%.
(3) turndown ratio is big, and the start-stop stove is convenient
Vapourizing furnace production load can be regulated in the 40-100% of design loading scope.
(4) can use 0-10mm brown coal, long-flame coal, non-caking coal or weakly caking coal, raw material sources are abundant, and cost is lower, make urea or cost reduce 15-20%.
---unstripped gas CO
2Compressor is by electric motor driving, and ammonia pump and first ammonium pump change the frequency conversion revolution into and regulate, and system pressure is easy to control steadily, and the load adjustment can be coordinated to adjust with steam system and not produce contradiction, fully reduces power consumption.
---CO
2Two sections on compressor and three is intersegmentally set up smart desulfurizer, is in order to remove CO
2Sulfide in the gas prevents downstream dehydrogenation catalyst poisoning, avoids high-tension apparatus to produce sulphur or sulfide corrosion.This essence desulfurizer is made up of placed in-line two smart desulfurizers, and iron oxide fine desulfurizer (as the T-703 type), Al are housed respectively
2O
3Three beds of type normal tempreture organic sulphur hydrolysis catalyst (as the T-504 type) and refined active carbon desulfurizer (as the T-103 type).From CO
2CO behind two sections on the compressor
2Press CO in the gas warp
2In succession by two smart desulfurizers, come out through middle pressure CO after the heater heats to 60 ℃ by the second smart desulfurizer bottom
2Return CO after the water cooler cooling
2Three sections on compressor is through the CO of this processing
2H in the gas
2S is from 25mg/NM
3Be removed to lmg/NM
3It and moderate temperature desulphurization technology relatively, it is big to have a Sulfur capacity, energy consumption is low, catalyzer shatter strength advantages of higher is especially avoided CO under the high temperature
2H in the gas
2The easy oxidation of S generates HSO
3 -, SO
4 2-And cause three, four sections cylinders of compressor to corrode.At CO
2Set up dehydrogenation reactor behind the compressor, adopt Production by Catalytic Combustion Process to remove unstripped gas CO
2In flammable component, in palladium catalyst is housed (as DH-2 type commercially available prod, loadings 0.5m
3, look the production equipment ability and decide).Assurance enters the CO of system
2Middle hydrogen content is less than 50ppm; Simultaneously, make high pressure exhaust gas can not form explosive mixture, fundamentally solved high pressure scrubber emptying end gas combustion explosion problem, CO
2Gas is from CO
2Four sections on compressor is through high pressure CO
2Heater heats is sent into dehydrogenation reactor after 185-200 ℃, dehydrogenation catalyst is a palladium catalyst, and loadings is 0.5m
3, 200-230 ℃ of dehydrogenation reaction temperature, reaction pressure are 14.5-15Mpa, the beds resistance is reduced to 0.02Mpa.CO
2In deoxidation reactor, remove combustibleconstituents, make hydrogen richness, again through high pressure CO less than 50ppm
2Water cooler is cooled to 120 ℃ and sends into synthesis system, guarantees the security of technological process.
---it is liquid phase cross-flow type high capacity tray that urea synthesizer changes former common sieve plate column plate, and change former general carbonic acid gas and boost that------deactivation method is that steam is rapidly heated---deactivation method heats up, in adorn 11 blocks of column plates, because the gas by synthetic tower reduces gradually from bottom to top, thereby top tray perforate number is less than the bottom opening number, opposite two column plate liquid channels become 180 ° of installations of level, and each piece column plate, the liquid crossflow mistake, and keep certain height, enter the lastblock column plate through liquid channel, the ascending gas that is come by next piece column plate contacts upwards by sieve plate hole and liquid phase are reverse, makes gas phase can fully contact with liquid phase.This novel column plate makes the material of synthetic tower be plunger flow, has suppressed back-mixing, has guaranteed that again material has enough residence time in synthetic tower, reach about 64% thereby Synthesis conversion is improved simultaneously.The described steam deactivation method that is rapidly heated, be when utilizing original feeding intake, Installed System Memory carries out steam intensification passivation at air, passivation is added by synthetic tower downtake bottom with steam, steam enters the synthetic tower top by downtake, condensation on the tower wall, the phlegma of heat to dirty, evenly heats up the tower wall along the tower wall from the top to the bottom.Gas stripping column and hp ammonium carbamate condenser are by shell-side steam, synthetic tower and high pressure scrubber are by the passivation steam heating, the temperature rise rate of high-tension apparatus is no more than 30 ℃/h, and this method passivation time is 2.5-3.0h only, has fast, convenient and reliable operation, advantage such as effective.
The synthetic tower processing parameter is:
| Synthesis pressure (Mpa is exhausted) | Synthesis temperature (℃) | NH3/CO
2 *
| H2O/CO
2 *
| CO
2Transformation efficiency (%) *
|
Before the transformation | 13.6 | 183 | 2.85 | 0.39 | 57 |
After the transformation | 14.5 | 186-188 | 3.15 | 0.6 | 64 |
Annotate:
*All refer to the urea synthesizer liquid phase
High-pressure system adopts full low pressure to feed intake, and makes the driving program simple, easy to operate, makes CO
2Transformation efficiency improves more than 10%;
---high pressure scrubber, high pressure CO
2Water cooler, low pressure carbamate condenser all adopt system's closed cycle phlegma as refrigerant, reduce industrial colling consumption; Gas stripping column in the urea plant, rectifying tower can produce a large amount of steam condensates in process of production with equipment such as recirculation heater, general, flash evaporators, are stored in usually in the condensation liquid bath, and temperature is 55-70 ℃.Now these steam condensates are used as low pressure carbamate condenser, high pressure scrubber, high pressure CO
2The circulating cooling medium of water cooler can reduce industrial colling consumption, helps saving energy and reduce the cost.
Three device technique parameters are that low pressure carbamate condenser shell side medium is a first ammonium liquid, and inlet temperature is 110--119 ℃, exports 73--75 ℃; The tube side medium is a steam condensate, and inlet temperature is 55 ℃, exports to be 65--67 ℃.
High pressure scrubber tube side medium is a first ammonium liquid, and inlet temperature is 183--185 ℃, and outlet is 165 ℃; The shell side heat-eliminating medium is a steam condensate, and inlet temperature is 80--90 ℃, exports to be 95--105 ℃.
High pressure CO
2Water cooler tube side medium is CO
2, inlet temperature is 200--230 ℃, and outlet is 120 ℃, and the shell side medium is a steam condensate, and inlet temperature is 95--105 ℃, exports to be 100--115 ℃.
Use the circulation of self-produced steam phlegma as heat-eliminating medium, can satisfy production requirement fully, help saving energy and reduce the cost.
---reclaim urea and ammonia in the decomposition of effluent with the depth hydrolysis method, the desorption tower liquid effluent by original ammonia content be 100PPM to ammonia content below 5PPM, directly send the water-tube boiler water.
Can produce in the urea plant production process and contain ammonia and technology of urea phlegma in a large number, in order to reclaim ammonia and the urea in these processing wastewaters, reduce to produce and consume, avoid causing environmental pollution simultaneously, be provided with desorb, hydrolysis system, contain ammonia and technology of urea phlegma in the ammonia vessel are delivered to first desorption tower after the heating of desorption tower interchanger, the gas that comes with the hydrolysis tower and second desorption tower in tower puts forward the ammonia in the phlegma, go out in the solution of tower to contain urea and a spot of ammonia, with the hydrolysis tower feeding pump this solution pressurization after the hydrolysis tower interchanger is sent into hydrolysis tower.Hydrolysis of urea is under 200--205 ℃ and 1.70-1.72Mpa pressure, and the residence time that keeps certain carries out.Heat with 2.5Mpa, 224 ℃ high pressure steam in hydrolysis tower bottom, guarantee to reach in the equipment the desired temperature and pressure of hydrolysis of urea.The liquid phase of coming out in the hydrolysis tower bottom enters second desorption tower through the hydrolysis tower interchanger.Add low-pressure steam in second desorption tower bottom, make column bottom temperature be controlled at solution boiling temperature under the working pressure.The second desorption tower gas phase enters first desorption tower by riser, the second desorption tower liquid phase is reduced to 60 ℃ through desorption tower interchanger, gaseous effluent cooler temperature, and ammonia and urea content are lower than 5PPM in the solution, and the process condensate after desorb, hydrolysis treatment was delivered to and done oiler feed usefulness outside the battery limit (BL) this moment.The first desorption tower gas phase enters reflux exchanger and carries out condensation, is pumped into synthesis system through the low pressure carbamate condenser with the first ammonium.
Behind 4 crust (0.4Mpa) low pressure absorption towers, set up low-pressure washer and make and drain into that tail gas contains ammonia less than 0.06% (V) in the atmosphere.
---vapo(u)rization system adopts the vacuum-evaporation granulation, has reduced vaporization temperature, effectively reduces the formation of biuret.Simultaneously, liquid levels such as gas stripping column, rectifying tower, urine groove and flash evaporator are controlled lower bound, have reduced the residence time of material, guarantee that also inferior limit generates biuret, urine in the urine groove is delivered to one section vaporizer, and one section evaporator temperature is 128-130 ℃, and pressure is 0.033Mpa.Urine enters flash evaporator through one section vapor seperator, and the dual circulation temperature is 138-140 ℃, and pressure is 0.003Mpa.Urine is beaten to prilling tower by melt urea pump through the dual circulation separator and is carried out granulation.The gas phase of each section vapor seperator is sent into ammonia vessel after condenser condenses.By measures such as two sections vacuum-evaporation and tower liquid level control lower bound, biuret in the urea≤0.5%.
The quality product of the method by above-mentioned improved industrial production urea plant provided by the invention satisfies the requirement of system low-poison urea-formaldehyde resin adhesive fully, the basic mechanical design feature index and the consumption indicators of urea are respectively biuret :≤0.5% (weight), vitriol :≤0.01% (weight), free ammonia :≤0.015% (weight), water :≤0.3% (weight), nitrogenous 〉=46.4% (weight), iron :≤0.005% (weight), granularity 〉=1.0-2.4 millimeter.
Ammonia 567Kg, CO
2735Kg, 2.5Mpa steam 1006Kg, water coolant is less than 80 tons, electricity 110 degree, by-product 0.5Mpa steam (referring to urea product per ton), make the technico-economical comparison of urea product obviously be better than the technico-economical comparison of former method and apparatus, and do not have the steam driven of use centrifugal compressor, reduce investment in fixed assets.
The characteristics of the method for improvement industrial production urea plant provided by the invention
1, gas making changes former to be with grace fine coal producer with coke, to make the urea cost lower 15-20%, use a series of measures such as cross-flow type high capacity tray and corresponding synthesis technologic parameter instead that transformation efficiency is improved more than 10%, and the driving program is simple, and is easy to operate.
2, set up smart sweetener, reduce H
2The S quantity discharged is improved the ambient atmosphere environment greatly, has eliminated a top hidden danger of equipment corrosion; Adopt catalyticcombustion to remove CO
2Flammable component in the gas is guaranteed the security of technological process.
3, the urea in the employing depth hydrolysis method decomposition of effluent makes the liquid effluent ammonia content below 5PPM.
4, set up low-pressure washer, both reclaimed the ammonia in the tail gas, make again that ammonia content reaches below 0.06% in the tail gas.
5, adopt the vacuum-evaporation granulation, make two urine content≤0.5% (Wt) that contract in the urea product, the urea product Functionality, quality and appealing design satisfies the requirement of low-poison urea-formaldehyde resin adhesive fully, before the product technology economic target obviously is better than transforming, and reduces investment in fixed assets.
The product of the method for improvement industrial production urea plant provided by the invention can be used as outside soil and the leaf fertilizer, in industry and pharmaceutical industries application is more widely arranged all, be mainly used in the production urea-formaldehyde resin, the tackiness agent of plastics and paint, the condenses trimeric cyanamide and the coating of urea.Also can be used as medicine materials such as petroleum spirit preparation, fabric softening, explosive stablizer, the dentifrice that reaches medical aspect and urine agent.