CN103408917B - Drag reducer applicable to desulfuration circulation system of thermal power plant and using method of same - Google Patents
Drag reducer applicable to desulfuration circulation system of thermal power plant and using method of same Download PDFInfo
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- CN103408917B CN103408917B CN201310319492.6A CN201310319492A CN103408917B CN 103408917 B CN103408917 B CN 103408917B CN 201310319492 A CN201310319492 A CN 201310319492A CN 103408917 B CN103408917 B CN 103408917B
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Abstract
The invention belongs to the field of fine chemicals, and particularly relates to a drag reducer applicable to a desulfuration circulation system of a thermal power plant and a using method of the drag reducer. The drag reducer is an aqueous solution taking PEO and PAM as main components and thiourea as an auxiliary component, wherein the total concentration range of PEO, PAM and thiourea is 600-810 mg/L, and the mass concentration ratio of PEO, PAM and thiourea is (3.0-4.0) : 1 : (2.0-2.8). According to different desulfuration circulation systems of thermal power plants and different using environments, drag reducers with different ratios are prepared, are added in a limestone slurry case, and are conveyed in a slurry pond at the bottom of a desulfurizing tower by a limestone slurry pump. The drag reducer is applicable to a desulfurized limestone slurry circulation system of a thermal power plant, has no bad influence on the desulfurizing efficiency, is remarkable in drag reducing effect, saves electricity for the thermal power plant, and brings considerable benefits. The formula has the characteristics of high drag reducing rate and strong anti-shear ability, and is guaranteed to be in long-term, efficient and stable operation.
Description
Technical field
The invention belongs to Field of Fine Chemicals, particularly a kind of flow improver and using method being applied to the heat-engine plant desulfurized recycle system.
Background technology
Thermal power plant SO
2discharge pollution on the environment occupies first place in the world for many years.Coal as main primary energy source, the SO that fire coal brings
2quantity discharged accounts for 90% of total release, and power plant desulfurization is very urgent.Most widely used general, that technology the is the most ripe doctor treatment of current thermal power plant is containing limestone serous slurry wash flue gas desulfurization process.
Flue gas desulfurization is increasingly extensive in large-size thermal power plant application, and desulphurization system running cost height is a difficult problem always, and gypsum slurries recycle pump is the power consumption rich and influential family of wet desulfurization of flue gas by limestone-gypsum method system.Through investigating consumption 602KWh of a set of 300MW unit slurry circulating pump day, if reduce by the pump resistance consumption of 10%, every day can save quite a few electric energy.Therefore, recycle pump resistance consumption is reduced most important to the cost reducing desulphurization system.Along with save energy becomes the important measures that China advocates energetically, to the research of slurries desulphurization circulating energy saving of system, there is optimistic prospect.
Overcome fluid resistance through investigation recycle pump and cause quite most power loss.In loop slurry, add flow improver with the internal structure of alter, common fluid changes viscous fluid into, and the turbulent fluctuation resistance of internal fluid declines, thus effectively reduces fluid resistance.Flow improver is widely used in the fields such as oil production, engineering in medicine, heating system, fire-fighting irrigation, Cemented filling, and it is the important means improving pipeline flow ability and reduce energy consumption.
In various water-soluble flow improver, the drag-reduction effect of polyoxyethylene (PEO), polyacrylamide (PAM) is the most noticeable.The title that PEO has " drag reduction king ", experiment finds to add the PEO of 1mg/L in water, and the fluid resistance of water also can reduce more than 20%, its in pure water drag reducing efficiency up to 63.5%.Current PEO Successful utilization in hydrant pipe, drilling mud etc.PAM is a kind of linear polymeric polymkeric substance, has excellent resistance reducing performance.The most general water-based drag reducer of current foreign applications is the polyacrylamide flow improver generated by a kind of or two kinds of different monomer copolymerizations.But PEO, PAM are under the high shear forces of turbulent fluid, its molecular weight very easily reduces because of molecule chain break, even loses anti-drag function, namely usually said permanent, irreversible shear degradation, and this is the maximum deficiency of polymer drag reducing agent.Thus in formula, anti-degraded stablizer is increased to increase the stability of flow improver, to keep the high efficiency of flow improver.
Early stage cyclic water channel flow improver applies to crude oil pipeline usually, such as US Patent No. 1352284(1974-5-8) the disclosed flow improver formula be made up of polyoxyethylene, suspension agent and tensio-active agent.The disclosed flow improver formula be made up of chlorination dodecyl dimethyl benzyl amine bactericidal algicide, lauric acid amide of ethanol corrosion inhibiting and descaling agent and hydroxy ethylene diphosphonic acid sodium of domestic patent CN101538090 is only applicable to conditioning unit or back yard industry circular water treating system.Domestic patent 02804037.6(2004-4-7) using zwitterionics together with anionic ether-containing surfactant as flow improver, apply to heat or cooling water distribution system.This patent has significant difference with this patent on flow improver formula and application.
Along with further developing of drag reduction technology, existing case drag reduction technology being applied to central heating system abroad.Such as, flow improver finds application in a medium-sized central heating system in the Herning city of Denmark, and has run 12 years.Be applied to the electricity saved in this central heating system and be about 1400MWh/, reach 2800MWh/ because pump efficiency improves the electricity saved, total total 4200MWh/, bring huge energy saving effect, visible economic benefit is considerable.
As everyone knows, the slurry circulating pump in flue gas desulphurization system runs without interruption continuously, and energy consumption is huge, is the main source of flue gas desulphurization system power consumption.Retrieve domestic and international patent, do not have the correlative study and application example that both flow improver and the desulfurization slurry recycle system are combined at present, and power plant desulfurization aspect rarely has minimizing recycle pump resistance problem and relates to.Drag reduction technology is applied in power plant desulphurization system by the present invention innovatively, significantly can reduce the resistance of recycle pump, obtain considerable energy-saving benefit.
Summary of the invention
The object of this invention is to provide a kind of flow improver and the using method that are applied to the heat-engine plant desulfurized recycle system.
Flow improver provided by the present invention, for the aqueous solution of bulk composition polyoxyethylene (PEO), polyacrylamide (PAM) and ancillary component thiocarbamide, wherein, the total concn scope of bulk composition PEO, PAM and ancillary component thiocarbamide is 600 ~ 810mg/L, PEO, the mass concentration ratio of PAM and thiocarbamide is (3.0 ~ 4.0): 1:(2.0 ~ 2.8).
This flow improver provided by the invention is applied to the method for the heat-engine plant desulfurized recycle system, needs for the different heat-engine plant desulfurized recycle systems and environment for use, the flow improver that preparation proportioning is different, is specifically divided into following steps:
(1) under certain temperature condition, prepare the desulfurization slurry of a series of different concns PEO, join in cycle cooling plating drum, fluid resistance value is measured respectively by Coping with Experiment Data of Flow device, drag-reduction effect evaluation is carried out to the desulfurization slurry only containing PEO, namely add according to drag reducing efficiency formulae discovery the drag reducing efficiency that different concns PEO produces, the concentration corresponding to maximum drag reducing efficiency, is the best drag reduction concentration of PEO; In like manner by above-mentioned experimental implementation, analyze the best drag reduction concentration of PAM.Wherein, drag reducing efficiency formula is: DR=(λ
x-λ
0)/λ
0, the drag reducing efficiency of DR-flow improver solution, λ
xthe coefficient of friction resistance of desulfurization slurry after-interpolation flow improver, λ
0the coefficient of friction resistance of-pure desulfurization slurry;
(2) the best drag reduction concentration of the PEO obtained according to step (1), in desulfurization slurry, keep the best drag reduction concentration of PEO constant, add the PAM of different concns scope respectively, measure its fluid resistance value and determined the maximum value of drag reducing efficiency by drag reducing efficiency formulae discovery, thus obtain simultaneously containing the best drag reduction total concn of PEO, PAM and ratio range;
(3) the best drag reduction total concn of mixing superpolymer PEO, PAM of obtaining according to step (2) and proportioning, be added to PEO, PAM in desulfurization slurry, then add the thiocarbamide of different concns, form the Experimental Flowing Object of a series of different concns proportioning.Measure the fluid resistance value of slurries in different time sections, analytical calculation drag reducing efficiency DR, the speed of decaying in time according to drag reducing efficiency determines the optimum dosage of thiocarbamide.
(4) the best drag reduction total concn scope of flow improver is drawn by above-mentioned experimental study, and the concentration proportioning scope of bulk composition PEO, PAM and ancillary component thiocarbamide.
(5) according to the result that step (4) obtains, the aqueous solution of preparation flow improver, then add the desulfurization slurry that Wingdale is uniformly mixed to form flow improver; Then be added to by the desulfurization slurry obtained in the lime stone slurry case of power plant's Wet Limestone desulphurization system, by the slurry pool bottom lime stone slurry pump delivery to thionizer, the temperature range of desulfurization slurry is 30 ~ 50 DEG C, and pH scope is 5 ~ 6; Desulfurization slurry constantly flows in circulating line, reduces the resistance in flow process thus realizes energy-conservation.
Beneficial effect of the present invention is embodied in following several respects:
(1) this flow improver is applied in heat-engine plant desulfurized limestone slurry fluid circulation, has no adverse effects to desulfuration efficiency, and drag-reduction effect is obvious, for thermal power plant saves power consumption, brings notable benefits.
(2) formula adopts daily industrial raw material, cheap, nontoxic nonirritant, is easy to commercialization and promotes.
(3) formula has the characteristic that drag reducing efficiency is high, anti-shear ability is strong, ensure that long-term efficient, the steady running of formula.
(4) stability data of recipe ingredient and materials safety are verified in an experiment, apply basis.
Accompanying drawing explanation
Fig. 1 is the relation curve of drag reducing efficiency DR with PEO, PAM change in concentration;
Fig. 2 is that PEO concentration keeps a timing, and coefficient of friction resistance λ is with the variation relation curve of PAM concentration;
Fig. 3 is the influence curve of thiocarbamide to flow improver anti-shear ability;
Fig. 4 is the SO of flue gas analyzing apparatus record
2the relation curve of concentration C and time t.
Embodiment
The invention provides a kind of flow improver and the using method that are applied to the heat-engine plant desulfurized recycle system, below the present invention will be further described.
This flow improver is formed by finite concentration proportions by bulk composition polyoxyethylene (PEO), polyacrylamide (PAM) and the ancillary component thiocarbamide with anti-shearing function, the best drag reduction concentration range of flow improver is 600 ~ 810mg/L, and in flow improver, the mass concentration ratio of each composition PEO, PAM and thiocarbamide is (3.0 ~ 4.0): 1:(2.0 ~ 2.8).
Nucleus PEO, PAM of flow improver formula are superpolymer, and superpolymer, also can be more responsive to envrionment temperature due to its peculiar backbone, and degraded to a certain degree occurs, and temperature can affect the performance of flow improver.The flow improver of the present invention's preparation is mainly for power plant desulphurization system, and slurry environments temperature is about 30 ~ 50 DEG C, therefore needs to consider that temperature is on the impact of flow improver resistance reducing performance, and namely the optimum concn of flow improver and the optimum proportioning of each composition there will be scope fluctuation.
The concrete steps of preparation are:
(1) under certain temperature condition, prepare the desulfurization slurry of a series of different concns PEO, join in cycle cooling plating drum, fluid resistance value is measured respectively by Coping with Experiment Data of Flow device, drag-reduction effect evaluation is carried out to the desulfurization slurry only containing PEO, namely add according to drag reducing efficiency formulae discovery the drag reducing efficiency that different concns PEO produces, interpretation is the relation curve of drag reducing efficiency DR with PEO change in concentration, concentration corresponding to maximum drag reducing efficiency, be the best drag reduction concentration of PEO, in like manner determine the best drag reduction concentration of PAM according to above-mentioned experimental implementation; Wherein, drag reducing efficiency formula is: DR=(λ
x-λ
0)/λ
0, the drag reducing efficiency of DR-flow improver solution, λ
xthe coefficient of friction resistance of desulfurization slurry after-interpolation flow improver, λ
0the coefficient of friction resistance of-pure desulfurization slurry;
(2) the best drag reduction concentration of the PEO obtained according to step (1), keeping best drag reduction concentration one timing of PEO, prepares the desulfurization slurry of many parts of PEO; Prepare the desulfurization slurry of a series of different concns scope PAM, the two equal-volume Homogeneous phase mixing is mixed with superpolymer mixing solutions, be i.e. the desulfurization slurry of a series of different concns proportioning PEO/PAM.Measure its fluid resistance value with Coping with Experiment Data of Flow device, calculate and determine that the maximum value of drag reducing efficiency is to obtain PEO, PAM best concentration ratio scope;
(3) PEO, PAM are obtained best concentration ratio preparation desulfurization slurry according to step (2), add the thiocarbamide of different concns more respectively, measure the fluid resistance value of different time sections slurries, calculate its drag reducing efficiency, the speed of decaying in time according to drag reducing efficiency determines the thiocarbamide of optimum concn ratio;
(4) by the best drag reduction concentration range of above-mentioned experimental analysis determination flow improver, and the concentration ratio of bulk composition PEO, PAM and ancillary component thiocarbamide;
(5) according to the result that step (4) obtains, the aqueous solution of preparation flow improver, then add the desulfurization slurry that Wingdale is uniformly mixed to form flow improver; Then be added to by the desulfurization slurry obtained in the lime stone slurry case of power plant's Wet Limestone desulphurization system, by the slurry pool bottom lime stone slurry pump delivery to thionizer, the temperature range of desulfurization slurry is 30 ~ 50 DEG C, and pH scope is 5 ~ 6; Desulfurization slurry constantly flows in circulating line, reduces the resistance in flow process thus realizes energy-conservation.
Embodiment
(1) under the constant temperature of 30 DEG C, the commercially available polyoxyethylene (molecular weight 3,000,000) taking a series of different mass is respectively dissolved in 4.5L water, the aqueous solution of preparation PEO, take commercially available Wingdale 500g again, stirring and dissolving makes the lime stone slurry that massfraction is 10%, mechanical stirring, after 30 minutes, namely prepares the desulfurization slurry of superpolymer PEO.Measuring is carried out, record piping flow and pressure reduction, then Fluid Computation Resistance Value with Coping with Experiment Data of Flow device.The coefficient of friction resistance of different concns PEO desulfurization slurry is calculated, then by drag reducing efficiency formulae discovery drag reducing efficiency, the best drag reduction concentration of the concentration that the maximum value of drag reducing efficiency DR is corresponding and PEO through data analysis.In like manner, according to above-mentioned experimental implementation, prepare the PAM desulfurization slurry of a series of concentration range, measure its fluid resistance value to determine the best drag reduction concentration of PAM.Interpretation becomes the relation curve of drag reducing efficiency DR and concentration C, and as shown in Figure 1, under 30 DEG C of conditions, the best drag reduction concentration of PEO, PAM is respectively 600mg/L, 200mg/L.
(2) under the constant temperature of 30 DEG C, first, prepare the PEO desulfurization slurry of many parts of 600mg/L according to the best drag reduction concentration of PEO, namely take commercially available polyoxyethylene 3g and be first dissolved in the water of 4.5L, then add commercially available Wingdale 500g and be uniformly mixed to form PEO desulfurization slurry.In like manner, the PAM solution of a series of mass concentration is prepared by above-mentioned experimentation.Then, by the PEO aqueous solution of a 600mg/L and another part, the aqueous solution equal-volume only containing PAM mixes, and mechanical stirring 30 minutes, is uniformly mixed to form the superpolymer mixing solutions of a series of different concns proportioning.Finally, adopt Coping with Experiment Data of Flow device to measure the maximum value of its fluid resistance and analytical calculation drag reducing efficiency DR, determine the best drag reduction total concn of PEO, PAM and proportioning thereof.Experimental result as shown in Figure 2, reflect the relation of mixing solutions drag reducing efficiency DR and PAM concentration C, research shows that the best drag reduction total concn of PEO, PAM is 400mg/L under 30 DEG C of conditions, optimum proportioning is 3:1, namely commercially available polyoxyethylene 1.5g is taken, polyacrylamide 0.5g is dissolved in the water of 4.5L, and being added to massfraction after forming flow improver solution is in the lime stone slurry of 10%.Circulate in the duct and just can reach best drag-reduction effect.
(3) under the isoperibol of 30 DEG C, according to above-mentioned experimental result, first take polyoxyethylene 1.5g, polyacrylamide 0.5g is dissolved in 4.5L water, get commercially available Wingdale 500g again, and add the thiocarbamide of different mass, mechanical stirring 30 minutes, uniform dissolution forms series of experiments solution.The solution of preparation is added in tubing system and circulates, survey its Resistance Value with Coping with Experiment Data of Flow device.Measure the impact of thiocarbamide on mixing flow improver anti-shear ability, and calculate its drag reducing efficiency.The anti-shear ability impact of thiocarbamide on flow improver shows the speed that drag reducing efficiency is decayed in time, therefore with the initial drag reducing efficiency DR of solution
0drag reducing efficiency DR ratio (DR/DR in time after degraded
0) the concentration corresponding to maximum value, namely add the optimum concn of thiocarbamide.Thus determine the best drag reduction concentration of flow improver and the optimum proportioning of each component.Experimental result as shown in Figure 3, under the temperature condition of 30 DEG C, strengthen degree the best when adding 1g thiocarbamide to the anti-shear ability of superpolymer, the best drag reduction total concn of flow improver is 600mg/L, and the mass concentration proportioning of each component PEO of flow improver, PAM, thiocarbamide is 3:1:2.
(4) single change temperature condition, repeats above-mentioned experimentation.Meeting under slurries operating temperature environment, the best drag reduction total concn of flow improver changes in interval 600 ~ 810mg/L, and each composition best concentration ratio scope is (3.0 ~ 4.0): 1:(2.0 ~ 2.8).
(5) desulfurization slurry preparing a series of different concns flow improver is placed in bubbling thionizer, under 30 DEG C of conditions, carries out desulfurization.Through flue gas analyzing apparatus record SO
2change in concentration, experimental result is converted into SO
2the relation curve (as shown in Figure 4) of concentration C-time h.Change the concentration revision test of flow improver, experimental result shows flow improver formula to desulfuration efficiency without impact.
Claims (2)
1. one kind is applied to the flow improver of the heat-engine plant desulfurized recycle system, it is characterized in that: this flow improver is the aqueous solution of bulk composition PEO, PAM and ancillary component thiocarbamide, wherein, the total concn scope of bulk composition PEO, PAM and ancillary component thiocarbamide is 600 ~ 810mg/L, PEO, the mass concentration ratio of PAM and thiocarbamide is (3.0 ~ 4.0): 1:(2.0 ~ 2.8).
2. flow improver described in claim 1 is applied to a method for the heat-engine plant desulfurized recycle system, it is characterized in that, for the different heat-engine plant desulfurized recycle systems and environment for use, the flow improver that preparation proportioning is different, is specifically divided into following steps:
(1) under the constant temperature of 30 DEG C, prepare the desulfurization slurry of a series of different concns PEO, join in cycle cooling plating drum, fluid resistance value is measured respectively by Coping with Experiment Data of Flow device, drag-reduction effect evaluation is carried out to the desulfurization slurry only containing PEO, namely add according to drag reducing efficiency formulae discovery the drag reducing efficiency that different concns PEO produces, the concentration corresponding to maximum drag reducing efficiency, is the best drag reduction concentration of PEO; In like manner by above-mentioned experimental implementation, analyze the best drag reduction concentration of PAM; Wherein, drag reducing efficiency formula is: DR=(λ
x-λ
0)/λ
0, the drag reducing efficiency of DR-flow improver solution, λ
xthe coefficient of friction resistance of desulfurization slurry after-interpolation flow improver, λ
0the coefficient of friction resistance of-pure desulfurization slurry;
(2) the best drag reduction concentration of the PEO obtained according to step (1), in desulfurization slurry, keep the best drag reduction concentration of PEO constant, add the PAM of different concns scope respectively, measure its fluid resistance value and determined the maximum value of drag reducing efficiency by drag reducing efficiency formulae discovery, thus obtain the best drag reduction total concn simultaneously containing PEO, PAM and ratio range;
(3) the best drag reduction total concn of mixing superpolymer PEO, PAM of obtaining according to step (2) and proportioning, PEO, PAM are added in desulfurization slurry, add the thiocarbamide of different concns again, form the Experimental Flowing Object of a series of different concns proportioning: the fluid resistance value measuring slurries in different time sections, analytical calculation drag reducing efficiency DR, the speed of decaying in time according to drag reducing efficiency determines the optimum dosage of thiocarbamide;
(4) the best drag reduction total concn scope of flow improver is drawn by above-mentioned experimental study, and the concentration proportioning scope of bulk composition PEO, PAM and ancillary component thiocarbamide;
(5) according to the result that step (4) obtains, the aqueous solution of preparation flow improver, then add the desulfurization slurry that Wingdale is uniformly mixed to form flow improver; Then be added in lime stone slurry case by the desulfurization slurry obtained, by the slurry pool bottom lime stone slurry pump delivery to thionizer, the temperature range of desulfurization slurry is 30 ~ 50 DEG C, and pH scope is 5 ~ 6.
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| CN111220501B (en) * | 2019-12-04 | 2022-04-29 | 西南石油大学 | On-line evaluation method for drag reducer drag reduction effect in oil pipeline |
| CN111921370A (en) * | 2020-07-16 | 2020-11-13 | 杭州斯曼特建材科技有限公司 | High-molecular environment-friendly desulfurizer and preparation method thereof |
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| US4771799A (en) * | 1987-10-29 | 1988-09-20 | Conoco Inc. | Method for improving the performance of highly viscous concentrates of high molecular weight drag reducing polymers |
| US20010049402A1 (en) * | 2000-05-03 | 2001-12-06 | Foster Cy E. | Polyisobutylene injection slurry for pipeline use |
| CN101528889A (en) * | 2006-08-17 | 2009-09-09 | 普拉德研究及开发股份有限公司 | Friction reduction fluids |
| CN100460448C (en) * | 2007-04-09 | 2009-02-11 | 中国石油化工集团公司 | Preparation method of multifunctional resistance-reducing polymer suspension |
| CN101851493B (en) * | 2009-11-13 | 2013-03-13 | 新疆德蓝股份有限公司 | Preparation of water-soluble salt-resistant dispersing drag reducer for heavy oil exploitation |
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