CN104815546A - Oil refinery oil burner smoke denitration reducing agent production method and application of oil refinery oil burner smoke denitration reducing agent - Google Patents
Oil refinery oil burner smoke denitration reducing agent production method and application of oil refinery oil burner smoke denitration reducing agent Download PDFInfo
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Abstract
The invention relates to a reducing agent capable of increasing the NOX conversion rate in an oil refinery oil burner smoke denitration process. According to the key point of a technology, the concentration of urea is optimized, a 20wt% to 55wt% urea aqueous solution is adopted, and a preferential scheme of a denitration reducing agent urea aqueous solution is a urea aqueous solution with the content of urea of 31.8wt% to 33.2wt%. The urea and water are purified, main quality indexes of the urea are as follows: the content (mass fraction) of formaldehyde is not more than 15mg/kg, the content (mass fraction) of biuret is not more than 0.9wt%, and the content of total nitrogen is not less than 46.4wt%; main quality indexes of soft water are as follows: conductivity is not more than 0.5ms/m, and concentration of potassium ions is not more than 0.5mg/kg. The oil refinery oil burner smoke denitration reducing agent has advantages that the crystallizing point is low, the convenience in transportation and storage can be realized, the stability is good, the NOX conversion rate is high, and the like.
Description
Technical field
The invention belongs to cleaning atmospheric pollution correlative technology field, specifically relate to a kind of oil plant oil burner denitrating flue gas reducing agent production method and application thereof, a kind of SCR technology (SCR technology is the abbreviation of the English SelectiveCatalytic Reduction) application of reducing agent in oil plant oil burner denitrating flue gas field.
Background technology
NO
xexcept flue dust and SO
2outside one of main atmosphere pollution, the harm of generation is very huge.One is the formation that can promote acid rain; Two is increase near-earth ozone concentration, produces photochemical fog, affects visibility; Three is have strong impulse effect to human body, causes breathing problem.In recent years, China became NO
xthe severely afflicated area of discharge, therefore, China also progressively strengthens the dynamics of energy-saving and emission-reduction, requires that power plant must synchronized construction denitrification apparatus.At present, in the denitration technology of boiler main flow, the denitration engineering of external more than 90% adopts SCR technology (SCR technology), and in China, use also widely, successful case is very many, and denitration efficiency is up to 90%.
Selective catalytic reduction (SCR) denitration technology refers under the effect of catalyst, reducing agent (NH
3) with flue gas in NO
xreaction generates harmless N
2and water, thus remove the NOx in flue gas; Selectively refer to reducing agent NH
3reduction reaction is there is with the NOx in flue gas.
Its basic chemical principle is:
Hydrolysis of urea: (NH
2)
2cO+H
2o → CO
2+ 2NH
3
NO
xreduction: NO+NO
2+ 2NH
3→ 2N
2+ 3H
2o
NH
3oxidation: 4NH
3+ 3O
2→ 2N
2+ 6H
2o
Canned truck transport used by reducing agent (ammonia), is stored in ammonia tank with liquid form; Liquid ammonia gasified via evaporator evaporation before injection SCR system flue gas; The ammonia of gasification and diluent air mixing, spray in the flue gas of SCR reactor upstream by ammonia-spraying grid; Abundant mixed reducing agent and flue gas react under the effect of SCR catalyst reactor, remove NO
x.When adopting ammoniacal liquor to prepare reducing agent, generally select the ammoniacal liquor of 20 ~ 30% concentration
In CN 101816886 A, disclose the method for a kind of coal-fired flue-gas desulphurization and denitration, decarburization simultaneously, the method is first by mixed flue gas dedusting, then through being equipped with the molecular sieve adsorption SO of alkali metal, alkaline-earth metal, transition metal or rare earth metal
2, NO
x, CO
2to saturated, then flue gas is discharged; By the molecular sieve desorption after absorption, after desorption, gas passes into ammoniacal liquor and processes, and the ammonium sulfate of generation, ammonium nitrate, ammonium carbonate are recycled, but when adsorb saturated bad control.
In CN103100293 A, disclose the technology that a kind of bioanalysis is out of stock, this technology is by flue gas and O
3the O that generator produces
3mixing, is oxidized to NO by NO
2, then the flue gas after oxidation is passed in the bioreactor containing denitrification thalline, carries out anti-nitration reaction, NO
xgas generates N
2after-purification is discharged, but suitable thalline is difficult to control.
In CN200810101151.0, disclose a kind of method of denitration of functional filter felt, the while that this technology being to flue gas ash removal, removed the SO in flue gas by catalytic reaction
xand NO
x, principle is the dust filtered by fibrous material in flue gas, utilizes the catalytic reaction of functional catalyst to remove SO in flue gas
xand/or NO
x.
In CN200910087773.7, disclose a kind of Synthesis and applications of low-vanadium denitration catalyst, the method is at V
2o
5-WO
3/ TiO
2on formula basis, greatly reduce V
2o
5and WO
3consumption, add CeO simultaneously
2prepare as the second auxiliary agent that a kind of toxicity is little, cost is low and NO
xthe novel low-vanadium denitration catalyst that removal capacity is excellent, i.e. V
2o
5-WO
3-CeO
2/ TiO
2catalyst.
The denitration of oil plant oil burner (Furnace) or blank, but along with China more and more stricter to the requirement of environmental protection, oil plant oil burner denitrating flue gas is also imperative.
Summary of the invention
The object of this invention is to provide a kind of oil plant oil burner denitrating flue gas reducing agent production method and application thereof.The raw material of this denitrification reducing agent, due to through refining, eliminate impurity, not only can make NO in flue gas
xclearance is the highest, and effectively prevents due to too high NH
3/ NOx is than the ammonia leakage caused, and the secondary pollution caused, also effectively prevent the poisoning of denitrating catalyst simultaneously.
The object of the present invention is achieved like this: a kind of oil plant oil burner denitrating flue gas reducing agent, it is characterized in that: this denitrification reducing agent refers to that urea quality mark is the aqueous solution of urea of 20 ~ 55%, the quality index of preparation aqueous solution of urea water: electrical conductivity refers to and is less than or equal to 0.5ms/m; Potassium concentration is less than or equal to 0.5mg/kg.
The present invention is for preparing the urea quality index of denitrification reducing agent: content of formaldehyde is less than or equal to 15mg/kg; Biuret Content is less than or equal to 0.9%; Total nitrogen content is more than or equal to 46.4%.
A kind of production method of oil plant oil burner denitrating flue gas reducing agent, the method is: first get commercially available urea in temperature 70-75 DEG C, urea is hydrolyzed in aqueous, after its all hydrolysis, cool the temperature to 30 DEG C, urea is crystallized out again from the aqueous solution, at least repeats a hydrolysis crystallization process, to improve urea purity; Get light water, after sandstone filtration, activated carbon filtration, the softening filtration of ion, membrane filtration, become qualified soft water successively; Carry out calculating proportioning as required, by appropriate soft water and the urea after purifying in a reservoir through abundant mixed dissolution, then carry out fillingly being denitrification reducing agent finished product; This denitrification reducing agent refers to that urea quality mark is the aqueous solution of urea of 20 ~ 55%, the quality index of preparation aqueous solution of urea: electrical conductivity refers to and is less than or equal to 0.5ms/m; Potassium concentration is less than or equal to 0.5mg/kg.
Above-mentioned membrane filtration comprises: micro-filtration, nanofiltration, ultrafiltration, dialysis, counter-infiltration or electrodialysis.
1) urea of the present invention and purification:
Urea index sees the following form:
| Project | Quality index (GB2440) agricultural is excellent |
| Biuret (mass fraction)/% | Be less than or equal to 0.90 |
| Formaldehyde (mass fraction) mg/kg | Be less than or equal to 15 |
| Total nitrogen (N) (mass fraction)/% | Be more than or equal to 46.40 |
Biuret is urea production accessory substance, and it and formaldehyde affect the hydrolysis of urea, and then affect the conversion ratio of NOX, strictly control.
If commercially available urea is not up to standard, the urea as denitrification reducing agent needs to purify, and its cardinal principle is:
Often be hydrolyzed crystallization once, its purity can be largely increased, and once, just can reach the requirement of denitrification reducing agent, its yield ratio is 1.5:1 to the crystallization of general industry one-level hydrolysis of urea.
2) water treatment of the present invention:
Because ordinary tap water contains other trace elements such as inorganic salts, chloride, therefore can not directly be used for configuring denitrification reducing agent solution, have to pass through the preparation processing and reach requirement and could be used for denitrification reducing agent solution, show that conductivity indices is: be not more than 0.5ms/m; Potassium concentration is not more than 0.5mg/kg.
3) configuration denitrification reducing agent solution of the present invention:
Carry out calculating proportioning as required, by the qualified urea after appropriate soft water and purification in a reservoir through abundant mixed dissolution, then carry out filling.
The denitrification reducing agent solution that the present invention utilizes said method to configure reaches following technical indicator:
| Project | Quality index |
| Urea content, wt% | 20～55 |
| Density, (20 DEG C) kg/m 3 | 1087.0-1093.0 |
| Index of refraction, (20 DEG C) | 1.3814-1.3843 |
| Biuret, wt% | ≤0.3 |
| Insoluble matter, mg/kg | ≤20 |
| Phosphate, mg/kg | ≤0.5 |
| Aluminium, mg/kg | ≤0.5 |
| Calcium, mg/kg | ≤0.5 |
| Iron, mg/kg | ≤0.5 |
| Potassium, mg/kg | ≤0.5 |
| Magnesium, mg/kg | ≤0.5 |
| Sodium, mg/kg | ≤0.5 |
| Chromium, mg/kg | ≤0.2 |
| Nickel, mg/kg | ≤0.2 |
| Zinc, mg/kg | ≤0.2 |
| Copper, mg/kg | ≤0.2 |
| Formaldehyde, mg/kg | ≤5 |
| Basicity is (with NH 3Meter), % | ≤0.2 |
Denitrification reducing agent urea liquid preferred version of the present invention is: urea content 31.8 ~ 33.2wt%.
This is because one is: urea content directly affects the transformation efficiency of NOx and the crystalline temperature of urea liquid.In SCR restoring system, the concentration of urea liquid is one of key factor, and too high or too low concentration not only can not improve the transformation efficiency of NOx, and the sliding of ammonia can be caused on the contrary to lose (due to too high NH
3/ NO
xammonia leakage than causing), form secondary pollution ammonia.Use urea concentration be the aqueous solution of urea of 32.5% as reducing agent, because the urea liquid crystalline temperature of concentration is for this reason minimum.
As shown in Figure 1: have expressed the relation between urea content and urea liquid crystalline temperature.
Two are: metal ion (calcium, iron, copper, zinc, chromium, nickel, magnesium, sodium, potassium, aluminium) can make the V of SCR system
2o
5/ WO
3– TiO
2catalyst poisoning inactivation, reduces the conversion ratio of NOx.Figure below is the deactivation of various element to catalyst, can find out, the impact of potassium element is the most outstanding, and its existence makes catalysqt deactivation, causes DeNOx (nitrogen oxide abatement rate) to drop to less than 10%.Think protection SCR system catalyst, improve NO
xconversion ratio, should strictly control above metal element content.
As shown in Figure 2: have expressed the relation between Determination of multiple metal elements and nitrogen oxide abatement rate.
The application mode of production method of the present invention is that it comprises by boiler, economizer, SCR denitration reactor, air preheater, electric precipitation, desulfurization, chimney, pressure fan, NO
xthe coal furnace device of monitor and boiler load signal composition; Coal furnace device place is being provided with feed arrangement, this feed arrangement is connected with air compressor and aqueous solution of urea tank outlet respectively by pipeline and feed pump, feed arrangement is connected on the passage between economizer and SCR denitration reactor by discharge nozzle, is provided with preposition temperature sensor and preposition NO in the front end of SCR denitration reactor
xsensor, is provided with rearmounted temperature sensor and rearmounted NO equally in the rear end of SCR denitration reactor
xsensor.
The another kind of application mode of production method of the present invention is that it comprises by oil burner, catalyst bed, the oil burner device of the emptying chimney composition of denitration flue gas; Oil burner device place is being provided with feed arrangement, this feed arrangement is connected with air compressor and aqueous solution of urea tank outlet respectively by pipeline and feed pump, feed arrangement is connected in the front passage of catalyst bed by discharge nozzle, is provided with preposition temperature sensor and preposition NO in the front end of catalyst bed
xsensor, is provided with rearmounted temperature sensor and rearmounted NO equally in the rear end of catalyst bed
xsensor.
The present invention owing to purifying to urea and water, and optimizes the urea concentration of denitrification reducing agent, and therefore tool has the following advantages:
1, the present invention compares with liquefied ammonia, ammoniacal liquor, and urea liquid crystalline temperature is low, not volatile, nontoxic, good stability, belongs to non-dangerous article, is convenient to transport, stores.
2, NO of the present invention
xconversion ratio reach more than 95%, the emission limit of its nitrogen oxide (NOx) is all lower than 150mg/m
3; And use traditional ammoniacal liquor, liquefied ammonia, conventional urea solution NO
xconversion ratio the highlyest just can reach 90%.
3, the present invention at utmost avoids NH
3secondary pollution, namely one be that of avoiding to resemble ammoniacal liquor easily decomposite NH in production, transport, storing process
3direct contaminated environment; Two refer in SCR course of reaction, use urea liquid can more easy control NH
3and NO
xreaction ratio, makes it to reach best, avoids NH
3surplus, be discharged in environment and form secondary pollution.
4, metal ion is very easy to catalyst poisoning was lost efficacy, and the present invention purifies to urea and water, and metal ion obtains strict control, so avoid the murder by poisoning of metal ion to denitrating catalyst.
Accompanying drawing explanation
Fig. 1 is the curve synoptic diagram that have expressed relation between urea content and urea liquid crystalline temperature;
Fig. 2 is the curve synoptic diagram that have expressed relation between Determination of multiple metal elements and nitrogen oxide abatement rate;
Fig. 3 is that denitrification reducing agent of the present invention is at coal furnace SCR technological process application sketch;
The symbol description of this accompanying drawing major part: boiler 101, economizer 102, SCR denitration reactor 103, air preheater 104, electric precipitation 105, desulfurization 106, chimney 107, pressure fan 108, NO
xmonitor 109, boiler load signal 110, urea liquid basin 111, feed pump 112, feed arrangement 113, air compressor 114, preposition temperature sensor 115, preposition NO
xsensor 116, rearmounted temperature sensor 117, rearmounted NO
xsensor 118;
Fig. 4 is that denitrification reducing agent of the present invention is at oil burner SCR technological process application sketch.
The symbol description of this accompanying drawing major part: oil burner 201, urea liquid basin 202, feed pump 203, feed arrangement 204, air compressor 205, preposition temperature sensor 206, rearmounted temperature sensor 207, preposition NO
xsensor 208, rearmounted NO
xsensor 209, catalyst bed 210, the emptying chimney 211 of denitration flue gas.
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described, but following example is only the present invention's example wherein, does not represent the interest field that the present invention limits, and interest field of the present invention is as the criterion with claims.
Detailed description of the invention
Embodiment 1:
This example adopts following production method, that is: commercially available urea is first got in temperature 70-75 DEG C, urea is hydrolyzed in aqueous, after its all hydrolysis, cool the temperature to 30 DEG C, urea is crystallized out again from the aqueous solution, at least repeats a hydrolysis crystallization process, to improve urea purity; Get light water, after sandstone filtration, activated carbon filtration, the softening filtration of ion, membrane filtration, become qualified soft water successively; Carry out calculating proportioning as required, by the urea after appropriate soft water and purification in a reservoir through abundant mixed dissolution, being mixed with 28% urea liquid of the present invention successively, 32.5% urea liquid, 37% urea liquid, please following table being refer to for answering land used and effect; Prepare the quality index of aqueous solution of urea: electrical conductivity refers to and is less than or equal to 0.5ms/m; Potassium concentration is less than or equal to 0.5mg/kg.
The embody rule mode (as shown in Figure 4) of aforementioned production method is that it comprises by oil burner 201, catalyst bed 210, the oil burner device that the emptying chimney 211 of denitration flue gas forms; Oil burner device place is being provided with feed arrangement 204, this feed arrangement 204 to export with air compressor 205 and urea liquid basin 202 respectively by pipeline and feed pump 203 and is connected, feed arrangement 204 is connected in the front passage of catalyst bed 210 by discharge nozzle, and the front end of catalyst bed 210 is provided with preposition temperature sensor 206 and preposition NO
xsensor 208, is provided with rearmounted temperature sensor 207 and rearmounted NO equally in the rear end of catalyst bed 210
xsensor 209.
Workflow: the urea liquid in urea liquid basin 202 is squeezed in feed arrangement 204 by feedstock pump 203, air compressor 205 starts simultaneously, urea liquid and air mixing, evenly sprayed in the flue gas of SCR reactor catalyst bed upstream by ammonia-spraying grid, urea decomposition under high temperature, discharges NH
3, as reducing agent, reducing agent NH
3after fully mixing with flue gas, by SCR catalyst reactor bed 210, issue biochemical reaction at catalyst action, remove NO
x, the N of generation
2be discharged in air with water.
In the process, feed arrangement uninterruptedly receives preposition, rearmounted NO
xthe NO that sensor sends
xthe temperature signal that cont signal and preposition, rearmounted temperature sensor send, automatically regulates urea injecting quantity according to these Fluctuation of analytical signal situations, makes urea liquid and NO
xreach optimum response ratio.
Meet above-mentioned technical indicator denitrification reducing agent, in application, in Fushun power plant of company and oil plant boiler, result is as shown in the table:
Embodiment 2:
By 28% urea liquid of the present invention that the production method identical in example 1 is prepared, 32.5% urea liquid, 37% urea liquid, please refer to following table for answering land used and effect; Meet above-mentioned technical indicator denitrification reducing agent, in application, in the power plant boiler of Liaoning, result is as shown in the table:
The embody rule mode (as shown in Figure 3) of aforementioned production method is that it comprises by pot boiler 101, economizer 102, SCR denitration reactor 103, air preheater 104, electric precipitation 105, desulfurization 106, chimney 107, pressure fan 108, NO
xthe coal furnace device that monitor 109 and boiler load signal 110 form; Coal furnace device place is being provided with feed arrangement 113, this feed arrangement 113 to export with air compressor 114 and urea liquid basin 111 respectively by pipeline and feed pump 112 and is connected, feed arrangement 113 is connected on the passage between economizer 102 and SCR denitration reactor 103 by discharge nozzle, and the front end of SCR denitration reactor 103 is provided with preposition temperature sensor 115 and preposition NO
xsensor 116, is provided with rearmounted temperature sensor 117 and rearmounted NO equally in the rear end of SCR denitration reactor 103
xsensor 118.
Workflow: the urea liquid in urea liquid basin 111 is squeezed in feed arrangement 113 by feedstock pump 112, air compressor starts simultaneously, and urea liquid and air mixing, evenly spray in the flue gas of SCR reactor catalyst bed upstream by ammonia-spraying grid, urea decomposition under high temperature, discharges NH
3, as reducing agent, reducing agent NH
3after fully mixing with flue gas, by SCR catalyst reactor bed, issue biochemical reaction at catalyst action, remove NO
x, the N of generation
2be discharged in air with water.
In the process, feed arrangement 113 uninterruptedly receives preposition, rearmounted NO
xthe NO that compound sensor sends
xthe temperature signal that cont signal and preposition, rearmounted temperature sensor send, automatically regulates urea injecting quantity according to these Fluctuation of analytical signal situations, makes urea liquid and NO
xreach optimum response ratio.
Embodiment 3:
By 28% urea liquid of the present invention that the production method identical in example 1 is prepared, 32.5% urea liquid, 37% urea liquid, please refer to following table for answering land used and effect; Meet above-mentioned technical indicator denitrification reducing agent, in application, in Jinzhou power plant of company and oil plant boiler, result is as shown in the table:
The embody rule mode of the production method adopted, with embodiment 1 or identical with embodiment 2, therefore omits.
Embodiment 4:
By 28% urea liquid of the present invention that the production method identical in example 1 is prepared, 32.5% urea liquid, 37% urea liquid, please refer to following table for answering land used and effect; Meet above-mentioned technical indicator denitrification reducing agent, in application, in Dalian power plant of company and oil plant boiler, result is as shown in the table:
The embody rule mode of the production method adopted, with embodiment 1 or identical with embodiment 2, therefore omits.
Embodiment 5:
By 28% urea liquid of the present invention that the production method identical in example 1 is prepared, 32.5% urea liquid, 37% urea liquid, please refer to following table for answering land used and effect; Meet above-mentioned technical indicator denitrification reducing agent, in application, in the thermal power plant boiler of Fushun, result is as shown in the table:
The embody rule mode of the production method adopted, with embodiment 1 or identical with embodiment 2, therefore omits.
Claims (9)
1. an oil plant oil burner denitrating flue gas reducing agent, is characterized in that: this denitrification reducing agent refers to that urea quality mark is the aqueous solution of urea of 20 ~ 55%, the quality index of preparation aqueous solution of urea: electrical conductivity refers to and is less than or equal to 0.5ms/m; Potassium concentration is less than or equal to 0.5mg/kg.
2. denitrating flue gas reducing agent according to claim 1, is characterized in that: for preparing the urea quality index of denitrification reducing agent: content of formaldehyde is less than or equal to 15mg/kg; Biuret Content is less than or equal to 0.9%; Total nitrogen content is more than or equal to 46.4%.
3. denitrating flue gas reducing agent according to claim 1 and 2, is characterized in that: in aqueous solution of urea, urea quality mark is 31.8 ~ 33.2%.
4. the production method of an oil plant oil burner denitrating flue gas reducing agent, the method is: first get commercially available urea in temperature 70-75 DEG C, urea is hydrolyzed in aqueous, after its all hydrolysis, cool the temperature to 30 DEG C, urea is crystallized out again from the aqueous solution, at least repeats a hydrolysis crystallization process, to improve urea purity; Get light water, after sandstone filtration, activated carbon filtration, the softening filtration of ion, membrane filtration, become qualified soft water successively; Carry out calculating proportioning as required, by appropriate soft water and the urea after purifying in a reservoir through abundant mixed dissolution, then carry out fillingly being denitrification reducing agent finished product; This denitrification reducing agent refers to that urea quality mark is the aqueous solution of urea of 20 ~ 55%, the quality index of preparation aqueous solution of urea: electrical conductivity refers to and is less than or equal to 0.5ms/m; Potassium concentration is less than or equal to 0.5mg/kg.
5. production method according to claim 4, is characterized in that: described membrane filtration comprises: micro-filtration, nanofiltration, ultrafiltration, dialysis, counter-infiltration or electrodialysis.
6. production method according to claim 4, is characterized in that: for preparing the urea quality index of denitrification reducing agent: content of formaldehyde is less than or equal to 15mg/kg; Biuret Content is less than or equal to 0.9%; Total nitrogen content is more than or equal to 46.4%.
7. production method according to claim 4, is characterized in that: in aqueous solution of urea, urea quality mark is 31.8 ~ 33.2%.
8. production method according to claim 4, is characterized in that: the application mode of described production method is that it comprises by boiler, economizer, SCR denitration reactor, air preheater, electric precipitation, desulfurization, chimney, pressure fan, NO
xthe coal furnace device of monitor and boiler load signal composition; Coal furnace device place is being provided with feed arrangement, this feed arrangement is connected with air compressor and aqueous solution of urea tank outlet respectively by pipeline and feed pump, feed arrangement is connected on the passage between economizer and SCR denitration reactor by discharge nozzle, is provided with preposition temperature sensor and preposition NO in the front end of SCR denitration reactor
xsensor, is provided with rearmounted temperature sensor and rearmounted NO equally in the rear end of SCR denitration reactor
xsensor.
9. production method according to claim 4, is characterized in that: the application mode of described production method is that it comprises by oil burner, catalyst bed, the oil burner device of the emptying chimney composition of denitration flue gas; Oil burner device place is being provided with feed arrangement, this feed arrangement is connected with air compressor and aqueous solution of urea tank outlet respectively by pipeline and feed pump, feed arrangement is connected in the front passage of catalyst bed by discharge nozzle, is provided with preposition temperature sensor and preposition NO in the front end of catalyst bed
xsensor, is provided with rearmounted temperature sensor and rearmounted NO equally in the rear end of catalyst bed
xsensor.
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|---|---|---|---|
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|---|---|---|---|
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Application publication date: 20150805 |