CN202710535U - Equipment for quantizing urea conversion rate, and urea gasification optimization system with equipment - Google Patents
Equipment for quantizing urea conversion rate, and urea gasification optimization system with equipment Download PDFInfo
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- CN202710535U CN202710535U CN201220362804.2U CN201220362804U CN202710535U CN 202710535 U CN202710535 U CN 202710535U CN 201220362804 U CN201220362804 U CN 201220362804U CN 202710535 U CN202710535 U CN 202710535U
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- urea
- sample stream
- equipment
- ammonia
- gasification
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Abstract
The utility model discloses equipment for quantizing urea conversion rate. The equipment comprises a device which is used for introducing a urea water solution into a reactor containing hot gas, heating the urea water solution for a period of time, gasifying the urea water solution, and forming hot gasified product flow containing NH3 and HNCO, a device which is used for extracting sample flow from the hot gasified product flow, a device which is used for contacting the sample flow and a hydrolysis catalyst on the premise of sufficient water, converting the HNCO into the NH3, and forming ammonia sample flow, and a device which is used for analyzing the NH3 of the ammonia sample flow. By adoption of the equipment, gas flow which is formed by gasifying the urea water solution can be analyzed in real time and treated, so the efficiency of urea gasification is determined. The utility model also relates to a urea gasification optimization system with the equipment.
Description
Technical field
The utility model relates generally to processing and the analysis of air-flow, in order to determine the efficient of urea gasification.
Background technology
For assessing a large amount of wherein urea by the performance of the method for by the use of thermal means gasification, must determine at any time how many flow of urea chargings are suitably gasified.The as required supply of ammonia and/or isocyanic acid requires accurately conversion data.Yet, do not exist can real-time analysis the known analytical equipment of the Urea Transformation product in the air-flow after the thermal conversion reaction device.
Existing many discussion are with the reference paper of Urea Transformation ammonification.From inventor's viewpoint, these mainly are high temperature process, and such as the US patent No.7 that authorizes the people such as Sun, 090,810 has described a kind of by the use of thermal means that produces complicated product gas stream, and described product is so that control ratio is wanted is more complicated.
When the heating urea aqueous solution, determine by a large amount of chemical reactions with the control of the rate constant of temperature correlation how urea decompose:
NH
2-CO
2-NH
2→NH
3+HNCO
(urea) (ammonia) (isocyanic acid)
This reaction can be carried out under 275 ℉; Yet the impossible amount of determining ammonia or isocyanic acid is because the HNCO hydrolyzable becomes urea or forms solid by-product.HNCO can followingly transform:
(cyanuric acid)
If the formation cyanuric acid, then this cyanuric acid is approximately decomposing under 700 ℉.Urea to the fully conversion of ammonia can relate to following reaction:
HNCO+H
2O→NH
3+CO
2
(isocyanic acid) (water) (ammonia) (carbon dioxide)
HNCO+NH
2-CO
2-NH
2→ biuret
HNCO+ biuret → triuret
Triuret → cyanuric acid+NH
3
3HNCO → cyanuric acid
2NH
2-CO
2-NH
2+ H
2CO → MDU
These reactions are relevant with speed, and depend on reactant physical form, advantage temperature, the time in reactor and water and/or catalyzer existence or do not exist.Therefore, the air-flow after the thermal conversion reaction device is very complicated.This composition is not all to be desirable, and does not have the real-time quantitative measuring technique to use.
The method, apparatus and system that need at present the Urea Transformation product in the energy real-time analysis thermal conversion reaction device gas flow afterwards.
The utility model content
The utility model is provided for measuring the method, apparatus and system of product component, and described component is to provide data necessary to the effective control by the hot-working conversion of urea.
On the one hand, provide a kind of method, the method comprises: aqueous solution of urea is introduced wherein had in the reactor of hot gas, and this aqueous urea (aqueous solution of urea) is heated continue to contain NH less than 10 seconds time to guarantee the aqueous urea gasification and to form
3Hot gas product stream with HNCO; From this hot gas product stream, take out sample stream; Make sample stream in the presence of enough water, contact that HNCO is changed into NH with hydrolyst
3And formation ammonia sample stream; And the NH that analyzes the ammonia sample stream
3
In aspect preferred, urea is the aqueous solution use of 30-70 % by weight as concentration, with provide in the 2:1-20:1 scope, total mol ratio of water and urea in the system in the preferred 3:1-10:1 scope, the water in the system comprises the moisture in the hot-air in the infeed hot gas reactor.
On the other hand, a kind of equipment for quantizing conversion rate of urea is provided, and this equipment comprises: be used for the aqueous solution of urea introduced wherein to have the reactor of hot gas and make aqueous solution of urea stand temperature a period of time containing NH to guarantee the aqueous urea gasification and to form
3Device with the hot gas product stream of HNCO; Be used for taking out from this hot gas product stream the device of sample stream; Be used for making sample stream in the presence of enough water, to contact that HNCO is changed into NH with hydrolyst
3And the device of formation ammonia sample stream; And the NH that is used for analyzing the ammonia sample stream
3Device.
Described equipment for quantizing conversion rate of urea has following preferred feature:
-described the device that sample stream and hydrolyst are contacted in the presence of enough water comprises makes the mixing arrangement that this sample stream mixes with water and the hydrolyst structure that is arranged on the mixing arrangement downstream;
The size of-described hydrolyst structure is set for and is provided 1000 to 10,000hr
-1Air speed;
-described hydrolyst structure is the monolithic construction with continuous passage, and has the pitch of 1mm to 10mm;
-described the sample stream that makes also comprises the water supply line that is arranged on described mixing arrangement upstream with the device that hydrolyst contacts in the presence of enough water;
-described the device that takes out sample stream from the hot gas product stream comprises the sample stream pipeline that links to each other with the outlet of reactor and is arranged on valve in this sample stream pipeline, and comprises and pass into the purge lines in this sample stream pipeline and be arranged on valve in this purge lines;
-described NH for analyzing the ammonia sample stream
3Device comprise the ammonia analyser that receives the ammonia sample stream.
On the other hand, the utility model provides a kind of urea gasification method for optimizing that makes, and the method comprises: introduce the aqueous solution of urea in the reactor that wherein has hot gas and make aqueous urea stand temperature a period of time and contain NH to guarantee the aqueous urea gasification and to form
3Hot gas product stream with HNCO; From gasification product stream, take out sample stream; Make sample stream in the presence of enough water, contact that HNCO is changed into NH with hydrolyst
3And formation ammonia sample stream; Analyze the NH of ammonia sample stream
3Concentration; Produce NH
3The representative observation signal of concentration; Relatively this observation signal and reference value; Produce the representative control signal of comparing result; Operate described reactor in response to described control signal.
More on the one hand in, a kind of system of the gasification for optimizing urea is provided, and this system comprises aforesaid equipment for quantizing conversion rate of urea, comparer and controller, wherein, this comparer is used for quantizing the equipment reception sign NH of conversion rate of urea from this
3The observation signal of concentration, and this observation signal compared with reference value in order to produce the control signal that characterizes comparative result, this controller is in response to the operation of this control signal control reactor.
In aspect another, the utility model is used for the operation of monitoring urea gasification reactor, and this monitoring is undertaken by such method: introduce the aqueous solution of urea in the reactor that wherein has hot gas and make aqueous urea stand temperature a period of time and contain NH to guarantee aqueous urea gasification and formation
3Hot gas product stream with HNCO; From the hot gas product stream, take out sample stream; Make this sample stream in the presence of enough water, contact that HNCO is changed into NH with hydrolyst
3And formation ammonia sample stream; Analyze the NH of ammonia sample stream
3Concentration; Produce NH
3The representative observation signal of concentration; Relatively this observation signal and reference value; Produce alerting signal when time outside the limit that comparing result is presetting; Produce warning in response to described alerting signal.
Preferably, said method and equipment and computing machine and recorder combination are used, in order to can control the operation of hot Urea Transformation device.
The system that uses disclosed method and apparatus also is provided.
Other and preferred aspect of the present utility model are described below.
Description of drawings
The accompanying drawing that is incorporated in the instructions and consists of the part of instructions has been set forth at present preferred the utility model embodiment, and described accompanying drawing is explained principle of the present utility model with hereinafter provide detailed description of the preferred embodiments one is used from.In whole accompanying drawing, similarly reference number represents similar or corresponding parts.
Fig. 1 is the schematic diagram of the combustion plant of the preferred embodiment of employing method and system of the present utility model.
Fig. 2 is the schematic diagram that the more details of system of the present utility model shown in Figure 1 are shown.
Embodiment
Description of the present utility model is carried out with reference to the accompanying drawings, wherein referring to the simplification preferred embodiment that schematically shows among Fig. 1 and Fig. 2.The method of figure and their representatives is hereinafter described briefly.
Term " urea " means to comprise it, and all are purchased the urea of form, and it typically is comprised of urea substantially, contain 95 % by weight or more urea.The urea of purer form is preferred and has several advantages in method of the present utility model.Urea is approximately 30% to be used for processing to about 70% aqueous solution as concentration preferably, wherein most preferably from about 45% to approximately 60%.
As mentioned above, when making the urea gasification by thermal treatment, reactant gas not only contains ammonia and isocyanic acid (HNCO), and can contain the accessory substance from subsidiary reaction, and it depends on the temperature history of thermal decomposition product.The gasification product in this stage is not easy to be undertaken continuously, analyze accurately by available equipment.The utility model is for this problem and the low-cost solution of simple possible is provided.
The utility model is by the NH that contains of autothermal process such as people's methods such as Sun always
3Provide the data that quantize conversion rate of urea with taking out sample stream continuously in the hot gas product of HNCO, described product stream comprises mounting medium such as air or after-combustion gas, from water and some urea decomposition products of possibility of air, aqueous urea or after-combustion gas.Then make sample stream through hydrolyst so that major general HNCO changes into NH
3To form the ammonia sample stream, wherein ammonia is main nitrogen containing species.When HNCO changes into NH by this way
3The time, known urea is doomed to have for the abundant reliability of control purpose.
Fig. 1 is for utilizing the utility model so that the schematic diagram by the combustion plant of gasification flow of urea that aqueous urea hot gas is obtained to be provided.This combustion plant comprises firing chamber 10, and this firing chamber has burner, and described burner provides heat from the fuel in unshowned source and by the air that pipeline 14 provides by burning in combustion zone 12.The burning gases of heat by stove 10, come the heat of spontaneous combustion to be passed to heat interchanger 16 and 18 along the direction shown in the piece arrow, then enter in SCR (SCR) reactor 20, the NO that produces between can be with main combustion period in this reactor
xProcess with NO with the urea (comprising ammonia and HNCO) of ammonia or gasification
xChange into nitrogen and water.Perhaps, can be advantageously used in the combustion plant of independent use urea SNCR (SNCR) under higher temperature, such as the US patent No.5 of Epperly etc., 057,293 facility of instructing, and do not need reactor 20.
After SCR reactor 20, burning gases flow through air-to-air heat exchanger 22, and the extraneous air preheating that this heat interchanger is used for providing via pipeline 24 is to be delivered to combustion zone 12 via pipeline 14.The gas that leaves heat interchanger 22 was significantly cooled off entering electrostatic precipitator (ESP) by pipeline 26 in 28 o'clock, and particle is collected in this electrostatic precipitator before in through gas storehouse 30.This is the form of simplifying very much of actual industrial or practical burner and effluent disposal route, but shows feasible program.
The urea gasification system 40 that roughly illustrates in Fig. 1 comprises gas supply source 42, aqueous urea source of supply 44, contains the hot gas reactor 46 of hot gas, in this reactor aqueous urea stand gasification temperature less than time of 10 seconds guaranteeing the aqueous urea gasification and to form the hot gas product stream, this hot gas product stream is taken out via conduit 48 and is contained NH
3And HNCO, then this product stream enters in the SCR reactor 20 via annotating ammonia grid 50.
The utility model is so that can be for active NO in totally with the equipment shown in 60
xThe reduction species are expected the simplification of flowing and real-time analysis.In this equipment, sample stream is taken out from pipeline 48 via pipeline 61, such as best illustrating among Fig. 2.Shown in pipeline 61 also have purge lines 62, they are respectively by respective valve 63 and 63a control.Equipment 60 comprise mixing arrangement 64 and 64 ' and hydrolyst 65,65 ' and 65 ".Catalyzer is chosen to and can power be enough to and will transforms ammonification by the HNCO in their gas substantially fully and form thus the ammonia sample stream of carrying by the downstream part of pipeline 61, and wherein ammonia is main nitrogen containing species.Then by make this ammonia sample stream and suitable ammonia analyser 67, such as become known for this purpose such as contacting to analyze this ammonia sample stream from tunable diode lasers (TDL) the ammonia analyser that Yogokawa, Siemens, Sick, Unisearch etc. obtain.Can keep suitable air-flow by catalyzer and analyser 67 with blower fan 68.Can use suitable valve 69 in order to can close the pipeline 61 of equipment 60 ends in analyser 67 downstreams.
This urea gasification system 40 can be used for ammonia is fed than in the low capacity purposes with low temperature and low concentration separately or with HNCO, and for example with 1-30ppm only, for example the concentration of 3-10ppm feeds among the ESP.Also this System Construction can be become with higher ammonia and HNCO concentration-for example be used for SCR, so that higher concentration-for example 100-1000ppm carries feed streams.
Enter hot gas in the urea gasification system 40 urea mainly can be gasified ammonification and isocyanic acid via pipeline 42, substantially do not stay liquid or solid.Enter in the urea gasification system 40 gas preferably in the porch in the scope of 700-1200 ℉, and their time in gasification reactor be enough to make aqueous solution of urea to be gasified totally, so that the air-flow that comprises ammonia and isocyanic acid to be provided.This air-flow can be taken out from urea gasification system 40 and remains under the temperature more than 500 ℉ until arrive the introducing point of second level catalytic reactor, introduce point at this, first order air-flow enters under the temperature of 350-600 ℉ in the catalytic hydrolysis reaction device of the second level so that HNCO is transformed ammonification.
Preferably with described gas-heated to greater than 800 ℉, then should remain under the temperature more than at least 600 ℉ with them their are introduced in urea gasification system 40.Can effectively use the gas temperature that enters of 850-1200 ℉.As required, can in the chamber, supply additional heat.And preferred urea gasification system 40 insulate to help temperature to keep well.Temperature and the residence time of gas were gasified totally effectively to realizing in the past to leave urea gasification system 40.Urea gasification system 40 enter temperature and temperature keep also should be enough high with keep at least about 450 ℉ and preferably at least 500 ℉ leave temperature.
Fig. 2 schematically shows ammonia/HNCO supply system 40 in more detail.The label of Fig. 2 uses the numeral of Fig. 1, wherein applicable and continuation further feature, for example controller 70 and related sensor and valve.Enter air line 42 and can comprise air door (baffle plate) (not shown), this air door is controlled by the control pipeline of the associated exemplary shown in controller 70 and the dotted line (can be hardwire or wireless) as other air door is the same with valve.Fig. 2 also illustrates optional air-flow supply line 66, not shown source of supply.
Preferably with urea as concentration approximately 30% to the first order of about 70% aqueous solution infeed method, wherein approximately 45% to 60% being most preferred approximately.The relative molecular weight of urea, water and air is important for successfully moving.
Catalyzer 65,65 ', 65 " be preferably type used in the SCR system, it is typically has approximately 1% to those of about 4% content of vanadium.Can use other catalyzer.Catalyzer will be dimensioned to ideally and provide 1000-10,000hr
-1, for example approximately 2500 to about 7500hr
-1Air speed.Catalyst structure is preferably the integral body with continuous passage, so that very little across the pressure drop of the degree of depth of catalyzer or length, and this structure has the pitch of 1-10mm to adapt to this purpose.Based on the catalyzer of vanadium, titanium and tungsten-usually as oxide-be effective.In one embodiment, pitch is about 4mm and contain the TiO of the content of vanadium of 1-2%
2Catalyzer is effective.Catalyzer can be for discarded or with the SCR catalyzer of mistake.
The two-stage of the method all requires the control of careful temperature, and the second level requires the water of critical quantity at least and do not use the so many so that equipment must be too large and can not effectively operate and produce above required those the heat demand of effecting reaction.
It has also been found that, importantly react like this: keep the low concentration of intermediate product such as isocyanic acid, in order to the chance that for example produces the subsidiary reaction of unfavorable accessory substance in the cold spot of reactor or pipeline is minimized.
Feed catalyzer 65,65 ', 65 " in the time sample stream Air and water and urea mol ratio be the about extremely about 1000:5:1 of 500:20:1 most effectively.The mol ratio of water and urea is about 2:1 to 20:1 most effectively, preferred 3:1-10:1.For making analyser realize accurate reading to basic all ammonia, must there be the water of capacity.The amount that is used for the water of hydrolysis comprises by urea liquid, comprises the water that any dilution water and system air add, and must be enough in the second level of method the HNCO complete hydrolysis.As described, if necessary, can additional water be added as material stream via pipeline 66.
Importantly, the drop of aqueous solution of urea is fed in the urea gasification system 40 with enough little size, with short time, for example 1-10 in second the enough urea that is used for decomposition of early discharging and make the minimizing possibility of pipeline or catalyzer downstream formation accessory substance so that urea is gasified totally.Must whole one work temperature, reactant, droplet size and heat time heating time to realize the correct response power of complete urea gasification and do not produce solid by-product.In urea gasification system 40, importantly use suitable high temperature, in the chamber, realize little urea droplets size and avoid the existence of cold spot.Preferably drop size is controlled to be less than 500 μ m, typically is 20-200 μ m, as measuring by laser technology.The residence time in the chamber must be short, for example about 1-10 second, typically is 2-6 second.
The utility model is used for controlling, for example optimizes the urea gasification.In this embodiment, ammonia analyser 67 will produce and characterize NH
3The observation signal of concentration.Controller 70 or correlation computer are compared this observation signal and are produced the control signal that characterizes comparative result with reference value.Then based on this control signal, in response to described control signal control reactor 46, for example carry out temperature or the adjustment of reagent flow.
The utility model also is used for the operation of monitoring urea gasification reactor 46 and misoperation is reported to the police.In this embodiment, the operator can be warned unusually, such as low urea input concentration, low pump feed rate, charging or output stream disturbance etc.Can analyze by ammonia analyser 67 NH of ammonia sample stream
3Concentration, this analyser will produce and characterize NH
3The observation signal of concentration.Then by controller 70 or correlation computer this observation signal and reference value are contrasted, when comparing result is outside preset limit, produce alerting signal.But alarm is sounding or carry out other indication then.
Adopt the system of described method and apparatus to combine disclosed feature and as required in conjunction with the details of multiple commercial Application.
Above-mentioned explanation is used for instruction those skilled in the art and how puts into practice the utility model.No longer describe all obvious changes and modification that those skilled in the art learn through reading this instructions in detail.Yet all these classes obviously change and modification is included in the scope of the present utility model that following claim limits.Unless clearly provide opposite indication, claim is intended to contain effectively to satisfy and is intended to the claimed assembly of purpose and the step of any order.
Claims (8)
1. be used for quantizing the equipment of conversion rate of urea, comprise:
Be used for aqueous solution of urea introduced and contain the reactor of hot gas and make this aqueous solution of urea a period of time of being heated contain NH to guarantee the aqueous solution of urea gasification and to form
3Device with the hot gas product stream of HNCO;
From this hot gas product stream, take out the device of sample stream;
Make this sample stream in the presence of enough water, contact that HNCO is changed into NH with hydrolyst
3And the device of formation ammonia sample stream; And
Be used for analyzing the NH of ammonia sample stream
3Device.
2. equipment according to claim 1, it is characterized in that, the described device that sample stream and hydrolyst are contacted in the presence of enough water comprises makes the mixing arrangement that this sample stream mixes with water and the hydrolyst structure that is arranged on this mixing arrangement downstream.
3. equipment according to claim 2 is characterized in that, the size of described hydrolyst structure is set for provides 1000hr
-1To 10,000hr
-1Air speed.
4. equipment according to claim 2 is characterized in that, described hydrolyst structure is the monolithic construction with continuous passage, and has the pitch of 1mm to 10mm.
5. equipment according to claim 2 is characterized in that, the described sample stream that makes also comprises the water supply line that is arranged on described mixing arrangement upstream with the device that hydrolyst contacts in the presence of enough water.
6. equipment according to claim 1, it is characterized in that, the described device that takes out sample stream from the hot gas product stream comprises the sample stream pipeline that links to each other with the outlet of reactor and is arranged on valve in this sample stream pipeline, and comprises and pass into the purge lines in this sample stream pipeline and be arranged on valve in this purge lines.
7. equipment according to claim 1 is characterized in that, described NH for analyzing the ammonia sample stream
3Device comprise the ammonia analyser that receives this ammonia sample stream.
8. a system that is used for the gasification of optimization urea comprises according to the described equipment for quantizing conversion rate of urea of one of aforementioned claim, comparer and controller, and wherein, this comparer receives sign NH from this equipment that is used for the quantification conversion rate of urea
3The observation signal of concentration, and this observation signal compared with reference value in order to produce the control signal that characterizes comparative result, this controller is in response to the operation of this control signal control reactor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| USPCT/US2012/037201 | 2012-05-10 | ||
| PCT/US2012/037201 WO2012154901A1 (en) | 2011-05-11 | 2012-05-10 | Diagnostic tool and process for assessing thermal urea gasification performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN202710535U true CN202710535U (en) | 2013-01-30 |
Family
ID=47595121
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201220362804.2U Expired - Fee Related CN202710535U (en) | 2012-05-10 | 2012-07-20 | Equipment for quantizing urea conversion rate, and urea gasification optimization system with equipment |
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|---|---|
| CN (1) | CN202710535U (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876242A (en) * | 2015-05-11 | 2015-09-02 | 北京新叶能源科技有限公司 | Three-phase fluidization equipment and method for producing ammonia from urea by virtue of catalytic hydrolysis |
| 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 |
| CN107158902A (en) * | 2017-04-21 | 2017-09-15 | 北京国电龙源环保工程有限公司 | SO in coal-fired flue-gas3Front end removing system and its removal methods |
| CN113912083A (en) * | 2021-06-23 | 2022-01-11 | 华能巢湖发电有限责任公司 | Method for improving urea pyrolysis rate of SCR (Selective catalytic reduction) pyrolysis furnace |
-
2012
- 2012-07-20 CN CN201220362804.2U patent/CN202710535U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876242A (en) * | 2015-05-11 | 2015-09-02 | 北京新叶能源科技有限公司 | Three-phase fluidization equipment and method for producing ammonia from urea by virtue of catalytic hydrolysis |
| 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 |
| CN107158902A (en) * | 2017-04-21 | 2017-09-15 | 北京国电龙源环保工程有限公司 | SO in coal-fired flue-gas3Front end removing system and its removal methods |
| CN113912083A (en) * | 2021-06-23 | 2022-01-11 | 华能巢湖发电有限责任公司 | Method for improving urea pyrolysis rate of SCR (Selective catalytic reduction) pyrolysis furnace |
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