CN103395801B - A kind of method of urea seeding hydrolysis and device - Google Patents
A kind of method of urea seeding hydrolysis and device Download PDFInfo
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- CN103395801B CN103395801B CN201310344322.3A CN201310344322A CN103395801B CN 103395801 B CN103395801 B CN 103395801B CN 201310344322 A CN201310344322 A CN 201310344322A CN 103395801 B CN103395801 B CN 103395801B
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Abstract
The invention discloses a kind of urea seeding method for hydrolysis and device, by adding the Secondary ammonium phosphate of different ratio and primary ammonium phosphate as catalyzer in hydrolysis of urea reactor, and the urea soln of 40-50% mass concentration is delivered to hydrolysis of urea reactor, control the temperature of hydrolysis of urea reactor at 150-180 DEG C, pressure, at 0.6-0.8MPa, realizes the catalytic hydrolysis of urea.Beneficial effect of the present invention is: 1) speed of response comparatively fast can meet the requirement of denitration for ammonia; 2) add ammonia and reveal safeguard system, pressure, temperature, height of liquid level automatic control system, security is also very high; 3) working cost is low, is the half of pyrolysis.Therefore urea seeding method for hydrolysis provided by the invention and device have higher superiority.
Description
Technical field
The invention belongs to technical field of air pollution control, relate to method and the device of a kind of urea seeding hydrolysis.
Background technology
Denitrating flue gas, refer to the technology removed by objectionable impurities-NOX contained in the flue gas that (comprises coal firing boiler, oil-burning gas-fired boiler and some industrial furnaces) after high-temp combustion, comprise SCR and SNCR two kinds of major technique schools, wherein SCR is the mainstream technology of denitrating flue gas.So-called SCR technology, refers to and arrange SCR reactor between the economizer and air preheater of boiler, install catalyzer, spray into reductive agent (ammonia-containing gas), reductive agent and NO in the flue cross section before reactor in reactor
xcatalyst surface reacts and removes NO
x.
The reductive agent that SCR denitrating flue gas uses is ammonia essentially, need to arrange at the scene a set of can the device of continuous production ammonia.From raw material, ammonia preparation system can be divided into anhydrous liquid ammonia system, ammoniacal liquor system and urea system.Wherein use the system of liquefied ammonia Evaporation preparation ammonia the most conventional, reason is that its investment is the most cheap, and transport, use cost are also minimum, but there is great potential safety hazard in liquefied ammonia system, particularly its transport and storage process, the harm that A leak of liquefied ammonia brings is very large, and security incident is of common occurrence; The investment of ammoniacal liquor system, operation and transportation cost are all very high, more safe than liquefied ammonia, but still have certain potential safety hazard.
The investment of urea system and running cost height compared with liquefied ammonia system, but transportation cost is suitable, and urea system there is no potential safety hazard, is safest ammonia technology of preparing.The process for producing ammonia from urea technology of current commercial applications mainly contains hydrolysis of urea and urea pyrolysis, wherein hydrolysis of urea includes again the catalytic hydrolysis (SafeDeNOx) of common hydrolysis (AOD, U2A, domestic chemical industry hydrolysis) and U.S. Chemithon, the urea pyrolysis then mainly NOxOUTULTRA technology that provides of American Fuel company (Fueltech).
The soonest and the safest, the on-the-spot container almost not storing up ammonia, its energy consumption and working cost are very high, so comparatively early enter Chinese market, achievement is more, but in today of oil price height enterprise, though there is application, the running cost pressure of single user is very large for the speed of response of pyrolysis.Compare with pyrolysis, be hydrolyzed owing to adopting power plant compared with the steam of horn of plenty as thermal source, energy consumption is lower.But the external technology for hydrolyzing such as AOD, U2A, reaction is comparatively slow needs huge reactor and snubber assembly, its investment and energy consumption higher.
The speed of response of catalytic hydrolysis is also very fast, and start-stop is rapid, and energy consumption is lower, but this technology is not also very ripe comparatively speaking, there is no application at home.
Summary of the invention
In order to solve the problem, the invention provides a kind of urea seeding method for hydrolysis and device, the safety and stability ammonia sources required for SCR denitration device of domestic extensive installation can not only be met, a large amount of energy can also be saved, realize harmony that is energy-conservation and environmental protection.
To achieve these goals, the present invention is by the following technical solutions:
A kind of urea seeding method for hydrolysis, comprises the following steps:
1) catalyzer Secondary ammonium phosphate and primary ammonium phosphate join in hydrolysis of urea reactor by different proportionings before starting by reaction, reach the 7-10% of reactor volume;
2) dry urea is dissolved into the urea soln of 40-50% mass concentration, is transported in hydrolysis of urea reactor by feeding pump;
3) heated by hydrolysis of urea reactor, Heating temperature: 150-180 DEG C, pressure: 0.6-0.8MPa, realizes the catalytic hydrolysis of urea.
Further, in step 1), in described catalyzer, primary ammonium phosphate proportion is 50%-80%.
Further, in step 1), hydrolysis of urea reactor lagging material uses pure aluminium silicate, insulation thickness 50mm.Above-mentioned materials is high temperature resistant, and makes hydrolysis reactor have good heat insulation effect.
Further, step 2) in dry urea powder is stored in warehouse, be transported in dissolving vessel by screw feeder, dissolve with deionized water.
Further, in step 3), hydrolysis of urea reactor is by steam-coil-heater, and Heating temperature is determined by heating steam amount, being heated evenly of such hydrolysis reactor.
Further, in step 3), hydrolysis of urea reactor also can be heated by airtight electrical tracing, and electric heating tube is arranged along hydrolysis of urea reactor even circumferential; Heating temperature is controlled by heating power Controlling System.
In the present invention, catalyzing urea hydrolysis needs through three chemical processes below:
(NH
2)
2CO(s,T1)+3H
2O(l,T1)=CO
2(g,T2)↑+2NH
4OH(aq,T2)(1)
2NH
4OH(aq,T2)+2NH
4H
2PO
4(aq,T2)=2(NH
4)
2HPO
4(aq,T2)+2H
2O(g,T2)↑(2)
2(NH
4)
2HPO
4(aq,T2)=2NH
4H
2PO
4(aq,T2)+2NH
3(g,T2)↑(3)
The starting point concentration of urea soln controls: between mass concentration 40-50%, can not be too high, otherwise side reaction can occur generates pipeline near the polymer plugging hydrolysis reactors such as water-fast biuret.Catalyzer primary ammonium phosphate and Secondary ammonium phosphate account for the 7-10% of hydrolysis reactor volume, and urea soln and catalyzer are fully mixed.
Hydrolysis reactor ideal temperature controls between 150-180 DEG C, and hydrolysis reactor is provided with back pressure valve, controls to use pressure between 0.6-0.8MPa.This is because urea at normal temperatures under normal pressure Nature comparison stablize, even if in acid, alkalescence or neutral solution, also not easily react.
The hydrolysis reaction of urea can think the reversed reaction of urea synthesis, and when temperature is below 60 DEG C, urea hardly hydrolysis reaction occurs, and along with temperature raises, hydrolysis rate is accelerated, but requires also higher to mechanical technology, simultaneously with side reaction.
A kind of urea seeding hydrolysis device, comprise: feeding pump, hydrolysis of urea reactor, described hydrolysis of urea reactor is inserted with steam coils, and outside described steam coils, top is connected with steam inlet and cooling water outlet pipeline, and below is connected with vapour outlet pipeline and entrance of cooling water pipeline.
Further, the connecting tube of described feeding pump and hydrolysis of urea reactor is provided with site pressure meter.
Further, described hydrolysis of urea reactor is also connected with wash-down water pipeline.
Further, described steam inlet and cooling water outlet pipeline are connected, and described vapour outlet pipeline and entrance of cooling water pipeline are connected.
Further, described steam inlet is provided with under meter, temperature control valve (TCV) and site pressure meter.
Further, described vapour outlet pipeline is provided with trap.Vapor condensation can be made to release heat of condensation absorbed by urea soln, steam saving to greatest extent.
Further, described entrance of cooling water pipeline is provided with under meter and thermometer, in order to indicate temperature and the flow of water coolant.
Further, described hydrolysis of urea reactor also offers ammonia outlet.
Compared with prior art, beneficial effect of the present invention is: 1) speed of response comparatively fast can meet the requirement of denitration for ammonia; 2) add ammonia and reveal safeguard system, pressure, temperature, height of liquid level automatic control system, security is also very high; 3) working cost is low, is the half of pyrolysis.Therefore urea seeding method for hydrolysis provided by the invention and device have higher superiority.
Accompanying drawing explanation
Fig. 1 is urea seeding hydrolysis device figure of the present invention.
Fig. 2 is the embodiment of the present invention 1 and do not add catalyzer hydrolysis of urea and react and generate ammonia concentration curve comparison figure.
Wherein: 1-feeding pump; 2-hydrolysis of urea reactor; 3-steam coils; 4-ammonia outlet; 5-trap; 6,7-under meter; 8-temperature control valve (TCV); 9,10-site pressure meter; 11-thermometer.
Embodiment
Embodiment 1
Urea seeding hydrolysis device of the present invention, as shown in Figure 1, comprise: feeding pump 1, hydrolysis of urea reactor 2, feeding pump 1 with the connecting tube of hydrolysis of urea reactor 2 are provided with site pressure meter 10, steam coils 3 is inserted with in hydrolysis of urea reactor 2, steam inlet is connected with cooling water outlet pipeline, is connected with the top outside steam coils 3, and steam inlet is provided with under meter 7, temperature control valve (TCV) 8 and site pressure meter 9; Vapour outlet pipeline and entrance of cooling water pipeline are connected, be connected with the below outside steam coils 3, vapour outlet pipeline is provided with trap 5, vapor condensation can be made to release heat of condensation absorbed by urea soln, steam saving to greatest extent, entrance of cooling water pipeline is provided with under meter 6 and thermometer 11, in order to indicate temperature and the flow of water coolant.
Above hydrolysis of urea reactor 2, be also connected with wash-down water pipeline, can wash hydrolysis of urea reactor.
Above hydrolysis of urea reactor 2, also offer ammonia outlet 4, discharge the product ammonia that hydrolysis of urea reaction produces thus.
Urea seeding method for hydrolysis of the present invention, comprises the following steps:
1) dry urea powder is stored in warehouse, is transported to (not shown) in dissolving vessel by screw feeder, with deionized water, dry urea is dissolved into the urea soln of 40% mass concentration, is transported to hydrolysis of urea reactor 2 li by feeding pump 1;
2) catalyzer Secondary ammonium phosphate and primary ammonium phosphate are joined hydrolysis of urea reactor 2 li by different proportionings before starting by experiment, reach 7% of reactor 2 volume; Make urea soln and catalyst mix even
3) adopt steam heating mode, hydrolysis of urea reactor 2 is heated, Heating temperature: 150 DEG C, pressure: 0.6MPa, realize the catalytic hydrolysis of urea.
In step 3), steam is passed into by steam inlet, utilize steam coils 3, to hydrolysis of urea reactor 2 homogeneous heating, in the process, passing into of steam is controlled by under meter 7, temperature control valve (TCV) 8 and site pressure meter 9, simultaneously, be connected with entrance of cooling water pipeline at the outer side-lower of steam coils 3, can pass into water coolant thus and cool the steam from hydrolysis of urea reactor 2, water coolant is flowed out by cooling water outlet pipeline.
The Main Function of catalyzer is by changing response path, thus greatly accelerates speed of reaction, reduces the time of response.
The ammonia that urea seeding hydrolysis produces, is discharged by the ammonia outlet on hydrolysis of urea reactor, as shown in Figure 1.
The catalyzer of fixed amount is housed in hydrolysis of urea reactor, and catalyzer can be recycled in reactor, changes when each overhaul.Under reactor operating conditions, catalyzer is molten, and control reactor and run under constant temperature, constant voltage, the reaction conditions of constant temperature and pressure can make the gaseous fraction of reaction product constant.
Meanwhile, when other reaction conditionss are identical, do not add catalyzer and carry out hydrolysis of urea reaction, namely only carry out the step 1) and 3 in embodiment 1).
Collect the ammonia of hydrolysis of urea reactor outlet at one time, and measure its concentration, as shown in Figure 2.
The present embodiment shows that the speed of response of catalytic hydrolysis is very fast, and start-stop is rapid, and performance is close to pyrolysis, and the application of vapour cooling system makes security of system very high, and energy consumption is lower, and investment is suitable with pyrolysis, and after optimizing, its expense can reduce further.
Embodiment 2
1) dry urea powder is stored in warehouse, is transported in dissolving vessel by screw feeder, with deionized water, dry urea is dissolved into the urea soln of 45% mass concentration, is transported in hydrolysis of urea reactor by feeding pump;
2) catalyzer Secondary ammonium phosphate and primary ammonium phosphate are transported in hydrolysis of urea reactor by feeding pump by different proportionings, reach 8% of reactor volume; Make urea soln and catalyst mix even.
3) adopt airtight electrical tracing mode, heated by hydrolysis of urea reactor, Heating temperature: 160 DEG C, pressure: 0.7MPa, realizes the catalytic hydrolysis of urea.
Embodiment 3
1) dry urea powder is stored in warehouse, is transported in dissolving vessel by screw feeder, with deionized water, dry urea is dissolved into the urea soln of 50% mass concentration, is transported in hydrolysis of urea reactor by feeding pump;
2) catalyzer Secondary ammonium phosphate and primary ammonium phosphate are transported in hydrolysis of urea reactor by feeding pump by different proportionings, reach 10% of reactor volume; Make urea soln and catalyst mix even.
3) adopt steam heating mode, heated by hydrolysis of urea reactor, Heating temperature: 180 DEG C, pressure: 0.8MPa, realizes the catalytic hydrolysis of urea.
Claims (3)
1. a urea seeding method for hydrolysis, comprises the following steps:
1) catalyzer Secondary ammonium phosphate and primary ammonium phosphate join in hydrolysis of urea reactor by different proportionings before starting by reaction, reach the 7-10% of reactor volume; Described hydrolysis of urea reactor is inserted with steam coils, outside described steam coils, top is connected with steam inlet and cooling water outlet pipeline, below is connected with vapour outlet pipeline and entrance of cooling water pipeline, described vapour outlet pipeline is provided with trap, and in described catalyzer, primary ammonium phosphate proportion is 50%-80%;
2) dry urea powder is stored in warehouse, is transported in dissolving vessel by screw feeder, with deionized water, dry urea is dissolved into the urea soln of 40-50% mass concentration, be transported in hydrolysis of urea reactor by feeding pump;
3) heated by hydrolysis of urea reactor, Heating temperature: 150-180 DEG C, pressure: 0.6-0.8MPa, realizes the catalytic hydrolysis of urea.
2. urea seeding method for hydrolysis as claimed in claim 1, is characterized in that, step 3) in, hydrolysis of urea reactor passes through steam-coil-heater.
3. urea seeding method for hydrolysis as claimed in claim 1, is characterized in that, step 3) in, described hydrolysis of urea reactor is heated by airtight electrical tracing, and electric heating tube is arranged along hydrolysis of urea reactor even circumferential.
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| EP3470639A1 (en) * | 2017-10-16 | 2019-04-17 | Winterthur Gas & Diesel Ltd. | Device and method for generating a reducing agent gas from a liquid or solid reducing agent |
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| CN105129818B (en) * | 2015-08-10 | 2017-05-31 | 大唐环境产业集团股份有限公司 | The urea seeding hydrolysis reactor and method of a kind of pair of air chamber heating |
| CN105129817B (en) * | 2015-08-10 | 2017-05-17 | 大唐环境产业集团股份有限公司 | Flue gas SCR denitration urea catalytic hydrolysis ammonia production system and method |
| CN105753017A (en) * | 2016-01-27 | 2016-07-13 | 北京新叶能源科技有限公司 | Urea catalytic hydrolysis method capable of replenishing catalyst on line |
| CN107321275A (en) * | 2017-08-28 | 2017-11-07 | 贾海亮 | A kind of methylquinoline complex compound hydrolysis device |
| CN110775986A (en) * | 2019-11-20 | 2020-02-11 | 北京新叶能源科技有限公司 | Urea catalytic hydrolysis ammonia production equipment and preparation method thereof |
| CN111408389A (en) * | 2020-04-22 | 2020-07-14 | 江苏中立环保科技有限公司 | Composite catalyst for urea catalytic hydrolysis reaction |
| CN113185561A (en) * | 2021-04-24 | 2021-07-30 | 无锡济煜山禾药业股份有限公司 | Method for obtaining 1-N-ethyl gentamicin C1a by pipeline reaction hydrolysis |
| CN114715915A (en) * | 2022-05-09 | 2022-07-08 | 北京新叶科技有限公司 | Novel urea catalytic hydrolysis method and device |
| CN115057454B (en) * | 2022-06-28 | 2023-06-23 | 江苏国瑞特环保工程技术有限公司 | High alkaline environment improvement type urea hydrolysis ammonia production system |
| CN115069197A (en) * | 2022-07-05 | 2022-09-20 | 安徽昊源化工集团有限公司 | Urea synthesis is with device of hydrolysising |
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| US5252308A (en) * | 1991-12-31 | 1993-10-12 | Union Oil Company Of California | Transporting urea for quantitative conversion into ammonia |
| US6436359B1 (en) * | 2000-10-25 | 2002-08-20 | Ec&C Technologies, Inc. | Method for controlling the production of ammonia from urea for NOx scrubbing |
| US6761868B2 (en) * | 2001-05-16 | 2004-07-13 | The Chemithon Corporation | Process for quantitatively converting urea to ammonia on demand |
| DE10206028A1 (en) * | 2002-02-14 | 2003-08-28 | Man Nutzfahrzeuge Ag | Process and apparatus for producing ammonia |
| US20030211024A1 (en) * | 2002-05-10 | 2003-11-13 | Wojichowski David Lee | Methods of converting urea to ammonia for SCR, SNCR and flue gas conditioning |
| US6887449B2 (en) * | 2002-11-21 | 2005-05-03 | The Chemithon Corporation | Method of quantitatively producing ammonia from urea |
| JP4646063B2 (en) * | 2005-02-15 | 2011-03-09 | バブコック日立株式会社 | Exhaust gas denitration method and apparatus using urea decomposition catalyst |
| JP2008530447A (en) * | 2005-02-16 | 2008-08-07 | アイエムアイ・ビジョン・リミテッド | Exhaust gas treatment |
| US20080267837A1 (en) * | 2007-04-27 | 2008-10-30 | Phelps Calvin E | Conversion of urea to reactants for NOx reduction |
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| EP3470639A1 (en) * | 2017-10-16 | 2019-04-17 | Winterthur Gas & Diesel Ltd. | Device and method for generating a reducing agent gas from a liquid or solid reducing agent |
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