CN101367025B - Calcium based composite catalysis dry desulfurizing agent for circulating fluidized bed boiler and preparation method thereof - Google Patents
Calcium based composite catalysis dry desulfurizing agent for circulating fluidized bed boiler and preparation method thereof Download PDFInfo
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- CN101367025B CN101367025B CN2008101401329A CN200810140132A CN101367025B CN 101367025 B CN101367025 B CN 101367025B CN 2008101401329 A CN2008101401329 A CN 2008101401329A CN 200810140132 A CN200810140132 A CN 200810140132A CN 101367025 B CN101367025 B CN 101367025B
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Abstract
A calcium complex catalysis dry-process desulfurizer for a circulating fluid bed boiler is capable of reducing energy source waste and exhaust emission. The desulfurizer comprises the following components according to the weight portion: 100 portions of limestone, 5-12.5 portions of hydrochloric acid, 0.65-1 portions of industrial salt, 1.5-2 portions of iron powder, and 20-28 portions of lime, wherein the content of calcium oxide in the limestone is above 44 percent, the content of sodium chloride in the industrial salt is above 90 percent, the content of ferric oxide in the iron powder is above 20 percent, and the content of calcium oxide in the lime is above 75 percent. The preparation method for the calcium complex catalysis dry-process desulfurizer for the circulating fluid bed boiler comprises the following steps of: adding the hydrochloric acid, the industrial salt and the limestone with a dosage equal to that of the industrial salt into an acid resistant reaction tank pro rata; adding the limestone, the iron powder and the lime into a mixing and stirring device together with the raw materials in the acid resistant tank pro rata; picking up and adding the raw materials intoa raw material bin before milling; feeding the raw materials into a Raymond mill from the raw material bin for milling the raw materials into desulfurizer powder less than 100 meshes; and picking up and adding into a finished product bin to obtain a finished product.
Description
Technical field
The present invention relates to a kind of calcium-based desulfurizing agent, relate in particular to a kind of CFBB calcium based composite catalysis dry desulfurizing agent and preparation method thereof.
Background technology
Now consumption maximum, most typical CFBB calcium backbone method desulfurizing agent are agstones, are 2.0 o'clock at Ca/S, and desulfurization degree has only 20%-40%, and desulfurization degree influenced by the sulfur content of coal very big, it is very difficult qualified discharge.
The enterprise that uses dry desulfurization at present adopts following several method usually, but all has defective for realizing qualified discharge:
First method is to improve Ca/S, strengthens doctor solution consumption, and this method is when being fuel with gangue or sulphur coal, not only increase cost, and can cause serious heat-energy losses, equipment heavy wears such as boiler, deduster, maintenance, operating cost increase, and cause heavy losses to enterprise.
Second method is in boiler rear portion work of water sprinkling for better material moisture, this technology will increase humidification activation tower and auxiliary device and control system, investment and floor space have not only been increased, also improved simultaneously operating cost, particularly when operation, to carry out heat again to flue gas, the energy consumption that is used for flue gas reheat is relatively very big, and this has just lost the low characteristics of in-furnace calcium spraying technology power consumption.
The third method is to use the high low-sulfur coal of price to do fuel, this method not only causes entreprise cost significantly to increase, and limitation is very big, the one, low-sulfur coal price height, quantity are few, the 2nd, near coal-mine power plant is many to be fuel, to enjoy the enterprise that national policy is supported with gangue and colm, and making is unpractical in this way.
Therefore, use present CFBB calcium backbone method desulfurizing agent desulphurization cost height, waste energy.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can reduce energy waste and can reduce CFBB calcium based composite catalysis dry desulfurizing agent of toxic emission and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is:
A kind of CFBB calcium based composite catalysis dry desulfurizing agent is characterized in that: it is made up of following each components by weight portion:
The mass content of calcium oxide is more than 44% in the described lime stone, the mass content of hydrogen chloride is 15-24% in the described hydrochloric acid, the mass content of sodium chloride is more than 90% in the described Nacl, the mass content of di-iron trioxide is more than 20% in the described iron powder, and the mass content of calcium oxide is more than 75% in the described lime.
According to described CFBB calcium based composite catalysis dry desulfurizing agent, it is characterized in that: described desulfurizing agent is made up of following each components by weight portion:
A kind of preparation method of CFBB calcium based composite catalysis dry desulfurizing agent, it is characterized in that: add the acid tolerance response pond in proportion with hydrochloric acid, Nacl with the lime stone of hydrochloric acid equivalent, react completely and mix mixing plant back the adding in proportion with lime stone, iron powder, lime, carry after stirring into former feed bin before the mill, feed Raymond mill by former feed bin and make, carry into finished bin and getting product less than 100 purpose desulfurizing agent powder.
The present invention has improved desulfurization degree by the improvement to present desulfurizing agent, reaches environment protection emission requirement standard.Utilize this method to produce desulfurizing agent and can reach the treatment of wastes with processes of wastes against one another, combined governance, recycling, non-secondary pollution, thereby reach the double effects of increasing economic efficiency with environmental improvement.
Fig. 1 is a process chart of the present invention;
Fig. 2 is that the sulfur content when coal is 2.6%, ignition temperature is 950 ℃, wind speed when being 1.0L/min, Different Ca/S, the desulfurization degree comparison diagram of the present invention and agstone;
Fig. 3 be when Ca/S be 2.0, when wind speed is 1.0L/min, 950 ℃ of ignition temperatures, different sulfur content, the desulfurization degree comparison diagram of the present invention and lime stone.
Below in conjunction with the drawings and specific embodiments the present invention is further described:
Embodiment 1:
A kind of CFBB calcium based composite catalysis dry desulfurizing agent, it is made up of following each components by weight portion:
The mass content of calcium oxide is more than 44% in the described lime stone, the mass content of hydrogen chloride is 15-24% in the described hydrochloric acid, hydrochloric acid used in the present invention can be abraum salt acid, the mass content of sodium chloride is more than 90% in the described Nacl, the mass content of di-iron trioxide is more than 20% in the described iron powder, and the mass content of calcium oxide is more than 75% in the described lime.
A kind of preparation method of CFBB calcium based composite catalysis dry desulfurizing agent, as shown in Figure 1, add the acid tolerance response pond in proportion with hydrochloric acid, Nacl with the lime stone of hydrochloric acid equivalent, react completely and mix mixing plant back the adding in proportion with lime stone, iron powder, lime, carry after stirring into former feed bin before the mill, feed Raymond mill by former feed bin and make, carry into finished bin and getting product less than 100 purpose desulfurizing agent powder.
The present invention is applicable to enterprises such as the power plant, heat supply of fire coal circulating fluid bed boiler in-furnace calcium spraying dry desulfurization, and particularly existing discharging abraum salt acid needs the chemical enterprise administered in the zone, and the enterprise that uses the in-furnace calcium spraying dry desulfurization is arranged again.
Main chemical reactions theoretical foundation involved in the present invention is as follows:
Traditional in-furnace calcium spraying desulfurizing agent its desulfuration efficiency when qualified discharge has only 20%-40%, its reason is the restriction that is subjected to CFB boiler objective factor, as the mixability of granularity, specific area, addition, adding mode, flue-gas temperature, flue gas and the absorbent of absorbent, haptoreaction time, temperature or the like.The method that improves desulfurization degree on the basis of in-furnace calcium spraying can be that the performance of improving desulfurizing agent improves absorbent to SO
2Absorptivity, to improve desulfurization degree.
The in-furnace calcium spraying dry flue gas desulphurization belongs to the reaction between gas and the porous solid, SO in essence
2Gas is diffused into desulfurizing agent (as CaO) particle surface and react inside, the solid product (CaSO of generation
3) cover sorbent particle and pore surface, by forming product layer in outer the reaching.After this, SO
2The gas diffusion must could continue reaction with desulfurizing agent by product layer, also has research to think that the solid reactant ion comes out and SO from the product layer internal migration
2Reaction, which kind of mode no matter, the formation of product layer has hindered proceeding of reaction.Its tangible formation before the product layer, desulfurizing agent has reached certain conversion ratio, if can improve its conversion ratio as far as possible before forming product layer, will improve desulfuration efficiency.
Thinking of the present invention is to change the desulfurizing agent component, makes the raw material that participates in desulfurization be not limited to CaCO
3, also have CaCl
2, Ca (OH)
2Stronger Deng the decomposition ability, be applied in the calcium based raw material of differential responses warm area faster, shorten the time that generates CaO simultaneously, make the CaO that participates in absorption reaction that the more reaction time be arranged, thereby improve reacting dose, complex technique is fully utilized in this thinking.
The CFBB calcium based composite catalysis dry desulfurizing agent has used above two principles just, in the calcium injection and desulfurization process, introduces catalysis technique and complex technique, has following four kinds of effects:
1, in calcium-based desulfurizing agent, adds the voidage that auxiliary agent NaCl improves CaO, make it become bulk, help SO
2Be diffused into CaO inside;
2, in calcium-based desulfurizing agent, add trace catalyst Fe
2O
3, desulphurization reaction is played certain catalytic action;
3, CaSO
4Surface coverage one deck compound salt as thin as a wafer, the sodium ion among the NaCl can stop CaSO
4Decomposition, to improve sulfur-fixing rate;
4, CaCO
3, CaCl
2, Ca (OH)
2Be distributed to the differential responses warm area, the efficient that transforms CaO significantly improves, and reduces the time that generates CaO, and then improves the time that CaO participates in desulfurization reaction in the stove.
The main chemical reactions formula that relates among the present invention is as follows:
CaCO
3+2HCl
2＝CaCl
2+H
2O+CO
2
CaCO
3＝CaO+CO
2
CaO+SO
2＝CaSO
3
CaSO
3+1/2O
2＝CaSO
4
By conventional desulfurizing agent agstone and the present invention are under equal conditions compared experiment, the main experimental data of CFBB calcium based composite catalysis dry desulfurizing agent is as follows:
One, when the sulfur content of coal is 2.6%, ignition temperature is 950 ℃, when wind speed is 1.0L/min, the contrast of the desulfurization degree of Different Ca/S, referring to Fig. 2:
| Ca/S | 1.5 | 2.0 | 3.0 | 4.0 | 5.0 | 7.5 |
| Composite desulfurizing agent | 54.2 | 61.2 | 70.2 | 79.2 | 84 | 90.8 |
| Agstone | 40 | 40.7 | 43.9 | 51.5 | 60 | 67.2 |
Two, when Ca/S is 2.0, wind speed is 1.0L/min, during 950 ℃ of ignition temperatures, the desulfurization degree contrast during different sulfur content, referring to Fig. 3:
| Sulfur content | 1.43 | 2.6 | 3.69 |
| Agstone | 28.6 | 40.7 | 41.8 |
| Composite desulfurizing agent | 60.2 | 61.2 | 62.7 |
Main feature of the present invention is as follows:
One, when equal quality, improves desulfurization degree more than 20%.
Two, when equal cost, not only can improve desulfurization degree 10%, and consumption has reduced by 46%.Reduce by 46% consumption, all reduced by 46% for the wearing and tearing of operating cost, heat-energy losses, boiler, deduster, transportation, management, maintenance etc., comprehensive benefit is very good.
Three, the sulfur content of coal height does not influence desulfurized effect, and the desulfurization degree of sulphur coal, low-sulfur coal all can improve more than 20%.
Four, improve resource utilization.Main raw material(s) in the prescription is except that Nacl, and being the lower byproduct of content, substandard products maybe needs the emission administered.Lime stone is to utilize the lower chip ballast of building stones field content.China's fat lime stone resource is not abundant, low content chip ballast in the general limestone mine product accounts for about 30% of total amount, this process not only makes full use of it, has solved the wasting of resources and problem of environmental pollution simultaneously again, and is significant to the utilization rate that improves limestone mine.Byproduct when iron oxide red is iron and steel enterprise's improvement spent acid.The particularly utilization of spent acid, promptly having administered to pollute has increased benefit again.
Five: byproduct fine coal ash composition does not have big change.Physics and chemical property do not have basic change.The main component of this product is a calcium base component, and desulfurization resultant is the calcium based component of sulfur-bearing, and the product of catalyst is the alkali metal oxide and the silicate combination product of trace, can be used for the additive of products such as cement, building materials, can not cause secondary pollution.
Use of the present invention can reduce energy waste, reduce toxic emission, meets the energy-saving and emission-reduction policy of country.
Embodiment 2:
A kind of CFBB calcium based composite catalysis dry desulfurizing agent, it is made up of following each components by weight portion:
Lime stone 100
Nacl 0.65
Iron powder 1.5
The mass content of calcium oxide is more than 44% in the described lime stone, the mass content of hydrogen chloride is 15-24% in the described hydrochloric acid, hydrochloric acid used in the present invention can be abraum salt acid, the mass content of sodium chloride is more than 90% in the described Nacl, the mass content of di-iron trioxide is more than 20% in the described iron powder, and the mass content of calcium oxide is more than 75% in the described lime.
The preparation method is with embodiment one.
Embodiment 3:
A kind of CFBB calcium based composite catalysis dry desulfurizing agent, it is made up of following each components by weight portion:
Lime stone 100
Hydrochloric acid 12.5
Nacl 1
Lime 28
The mass content of calcium oxide is more than 44% in the described lime stone, the mass content of hydrogen chloride is 15-24% in the described hydrochloric acid, hydrochloric acid used in the present invention can be abraum salt acid, the mass content of sodium chloride is more than 90% in the described Nacl, the mass content of di-iron trioxide is more than 20% in the described iron powder, and the mass content of calcium oxide is more than 75% in the described lime.
The preparation method is with embodiment one.
Claims (1)
1. CFBB calcium based composite catalysis dry desulfurizing agent, it is characterized in that: it is made up of following each components by weight portion:
The mass content of calcium oxide is more than 44% in the described lime stone, the mass content of hydrogen chloride is 15-24% in the described hydrochloric acid, the mass content of sodium chloride is more than 90% in the described Nacl, the mass content of di-iron trioxide is more than 20% in the described iron powder, and the mass content of calcium oxide is more than 75% in the described lime.
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|---|---|---|---|
| CN2008101401329A CN101367025B (en) | 2008-08-13 | 2008-08-13 | Calcium based composite catalysis dry desulfurizing agent for circulating fluidized bed boiler and preparation method thereof |
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| CN101367025B true CN101367025B (en) | 2011-07-27 |
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Citations (8)
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|---|---|---|---|---|
| US5078784A (en) * | 1990-03-14 | 1992-01-07 | Elkem Metals Company | Desulfurization agent |
| CN1127776A (en) * | 1995-01-28 | 1996-07-31 | 西安正阳环保能源有限公司 | Sulfur-immobilizing coal-saving additive |
| FR2747132A1 (en) * | 1996-04-04 | 1997-10-10 | Pechiney Electrometallurgie | DESULFURANT MIXTURE BASED ON CALCIUM CARBIDE |
| CN1250080A (en) * | 1999-09-07 | 2000-04-12 | 王在仕 | High-efficiency desulfating coal-saving agent and its production process |
| EP1010765A1 (en) * | 1998-12-15 | 2000-06-21 | ALMAMET GmbH | Desulfuring agent |
| CN1386867A (en) * | 2002-04-16 | 2002-12-25 | 太原理工大学 | Composite desulfurizer of iron and steel and its preparing process |
| CN1698930A (en) * | 1999-05-17 | 2005-11-23 | 三菱重工业株式会社 | Flue gas desulphurization method and system |
| CN101074402A (en) * | 2006-05-17 | 2007-11-21 | 陈钧 | Efficient sulfur-fixing agent and its usage |
-
2008
- 2008-08-13 CN CN2008101401329A patent/CN101367025B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5078784A (en) * | 1990-03-14 | 1992-01-07 | Elkem Metals Company | Desulfurization agent |
| CN1127776A (en) * | 1995-01-28 | 1996-07-31 | 西安正阳环保能源有限公司 | Sulfur-immobilizing coal-saving additive |
| FR2747132A1 (en) * | 1996-04-04 | 1997-10-10 | Pechiney Electrometallurgie | DESULFURANT MIXTURE BASED ON CALCIUM CARBIDE |
| EP1010765A1 (en) * | 1998-12-15 | 2000-06-21 | ALMAMET GmbH | Desulfuring agent |
| CN1698930A (en) * | 1999-05-17 | 2005-11-23 | 三菱重工业株式会社 | Flue gas desulphurization method and system |
| CN1250080A (en) * | 1999-09-07 | 2000-04-12 | 王在仕 | High-efficiency desulfating coal-saving agent and its production process |
| CN1386867A (en) * | 2002-04-16 | 2002-12-25 | 太原理工大学 | Composite desulfurizer of iron and steel and its preparing process |
| CN101074402A (en) * | 2006-05-17 | 2007-11-21 | 陈钧 | Efficient sulfur-fixing agent and its usage |
Non-Patent Citations (1)
| Title |
|---|
| JP特開2002-058957A 2002.02.26 |
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Assignee: Zaozhuang embellish Environmental Protection Technology Co., Ltd. Assignor: Chen Hong Contract record no.: 2011370000397 Denomination of invention: Calcium based composite catalysis dry desulfurizing agent for circulating fluidized bed boiler and preparation method thereof Granted publication date: 20110727 License type: Exclusive License Open date: 20090218 Record date: 20110826 |
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