CN108704470A - Carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering and preparation method thereof - Google Patents
Carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering and preparation method thereof Download PDFInfo
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- CN108704470A CN108704470A CN201810461190.5A CN201810461190A CN108704470A CN 108704470 A CN108704470 A CN 108704470A CN 201810461190 A CN201810461190 A CN 201810461190A CN 108704470 A CN108704470 A CN 108704470A
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- carbide slag
- biomass
- tempering
- hardening
- stalk
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
Abstract
The present invention relates to desulfuration fields in Circulation fluidized-bed furnace, more particularly to the carbide slag composite calcium based desulphurizing agent and preparation method thereof based on biomass hardening, tempering, the desulfurizing agent is mixed using biomass with wet carbide slag, the moisture in wet carbide slag is adjusted, enters stove to solve the problems, such as wet carbide slag without heating, drying process；It is quenched to carbide slag using biomass, it realizes the chemical modification to carbide slag, contains abundant soluble potassium in biomass, the migration by potassium in quenched achievable biomass to solid waste base calcium-based desulfurizing agent carbide slag surface, to improve in sweetening process CaO in CaSO4The diffusivity of dense product layer ensures to remain to reach calcium transformation ratio when entering stove close to small particle when carbide slag enters stove with relatively large grain size；The advantages such as inventive desulfurization agent utilization ratio is high, desulfurization performance is good, preparation flow is short, production cost is low.The collaboration for not only realizing solid waste carbide slag and agricultural biomass efficiently uses, and is expected to reduce the cost of desulfurization in Circulation fluidized-bed furnace.
Description
Technical field
The present invention relates to desulfuration fields in Circulation fluidized-bed furnace, more specifically, are related to a kind of based on biomass hardening, tempering
Carbide slag composite calcium based desulphurizing agent and preparation method thereof.
Background technology
The most common desulfurizing agent of desulfurization is calcium-based desulfurizing agent lime stone in Circulation fluidized-bed furnace at present, and desulfuration efficiency is
CaCO3The resultant effect of decomposition reaction and CaO vulcanization reactions, due to sulfur product CaSO4（46cm3/mol）Molal volume it is big
In CaCO3（36.9cm3/mol）And CaO（16.9cm3/mol）, so that sulfur product CaSO4By the surfaces decomposition product CaO
Blockage of the micro orifice, hinder SO2Further with unreacted CaO reacts, and it is only 25-45% to lead to the degree of sulfation of calcium, is
Reach SO2Emission request, enterprise have to make up the low defect of calcium-based desulfurizing agent utilization rate by increasing calcium sulfur ratio, this is making
Operating cost is also increased while waste at desulfurizing agent.
Operating cost is reduced in order to improve calcium-based desulfurizing agent utilization rate, many researchs are dedicated to finding solid waste base calcium-based desulfurization
Agent, wherein Industrial Solid Waste carbide slag are a kind of solid waste base calcium-based desulfurizing agents haveing excellent performance, and main component is Ca (OH)2, have
Larger specific surface area, reactivity is higher than lime stone, and operating cost is low.Patent CN104190243A discloses a kind of combustion
Carbide slag is directly used in desulfuration in furnace by the method for coal burning boiler carbide slag desulfurization, the patent through physics drying and processing, to solve
Wet carbide slag water content after press filtration is up to 40%-50%, directly enters the problem of stove difficulty；Patent CN107213779A discloses one
The production system and production technology of kind carbide slag desulfurizing agent will be used as desulfuration in furnace agent after carbide slag drying, broken, separation,
But the carbide slag after drying, because grain diameter is thinner, there is also some defects, such as air quantity adjustment not to conform in CFB boiler utilization
Reason, can make carbide slag be blown out burner hearth before reaching maximum conversion rate, to reduce the utilization rate of desulfurizing agent.It is also right both at home and abroad
Calcium-based desulfurizing agent has carried out chemical modification processing, mainly by adding some ions, improves CaO in CaSO4Dense product layer
Diffusivity, patent CN105944552A disclose it is a kind of utilize barium ions doping vario-property calcium-based desulfurizing agent, pass through addition
BaCl2Calcium-based desulfurizing agent obtained, vacancy point defect quantity is big, and and SO2The product layer solid state ion diffusivity coefficient energy formed after reaction
Power is stronger；Patent CN103566719A discloses a kind of utilize and produces TiCl4The waste chlorination molten salt of generation passes through broken, water-soluble, mistake
The processes such as filter, substep removal of impurities obtain CaCO3Desulfurizing agent is used in combination NaCl aqueous solutions to be modified processing, and calcium base is de- in the prior art
Sulphur agent there are of high cost, industrialized difficult problem, is modified using discarded material resource modifying agent by pure chemistry agent modifier,
Operating process is related to the complicated processes such as Chemical Decomposition, and processing cost is higher.
In summary, it is necessary to which the deficiency in the presence of the prior art is improved.
Invention content
In the presence of overcoming the shortcomings of the prior art, it is multiple that the present invention provides a kind of carbide slag based on biomass hardening, tempering
Calcium-based desulfurizing agent and preparation method thereof is closed, using the humic acid with certain viscosity formed during biomass hardening, tempering, is realized
The reunion of fine grained carbide slag alleviates particulate carbide slag elutriation in CFB boiler to complete the redistribution to carbide slag grain size
The problem of loss.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
Carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, is composed of the following raw materials by weight：60-70 parts of carbide slag,
30-40 parts of biomass.
The biomass is stalk.
The stalk length is less than 3cm.
The preparation method of carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, includes the following steps：
S1, stalk is broken for be less than 3cm stalk sections, takes 30-40 parts of stalk sections to be mixed with 60-70 parts of wet carbide slags, quickly stirs
It mixes；
S2, that stalk in S1-carbide slag mixture is placed to progress in 5-6 days is quenched；
S3, stalk-carbide slag solid is made in stalk quenched in S2-carbide slag mixture natural air drying；
S4, it carries out the stalk air-dried in S3-carbide slag solid to be granulated obtained composite calcium based desulphurizing agent.
Mixture mixing time is at least 30min in the S1.
The S2 refining temperatures are 20-25oC.
Moisture is 5-10% after mixture air-dries in the S3.
Mixture pelleting grain size is 1-2cm in the S4.
It is 8-12MPa that pressure is granulated in the S4.
Compared with prior art, the advantageous effect of present invention is that：
The present invention provides a kind of carbide slag composite calcium based desulphurizing agent and preparation method thereof based on biomass hardening, tempering, utilizes biology
Matter is mixed with wet carbide slag, adjusts the moisture in wet carbide slag, to solve wet electricity without heating, drying process
Rock ballast enters stove problem；It is quenched to carbide slag using biomass, the chemical modification to carbide slag is realized, is contained in agricultural biomass
There is abundant soluble potassium, by quenched process, it can be achieved that potassium is to solid waste base calcium-based desulfurizing agent carbide slag surface in biomass
Migration, to improve in sweetening process CaO in CaSO4The diffusivity of dense product layer ensures carbide slag with relatively large grain size
It remains to reach calcium transformation ratio when entering stove close to small particle when entering stove；Inventive desulfurization agent utilization ratio is high, desulfurization performance is good, system
The standby advantages such as flow is short, production cost is low.The collaboration for not only realizing solid waste carbide slag and agricultural biomass efficiently uses, also
Hoping reduces the cost of desulfurization in Circulation fluidized-bed furnace.
Description of the drawings
Fig. 1 is a kind of carbide slag composite calcium based desulphurizing agent preparation flow figure based on biomass hardening, tempering provided by the invention；
Fig. 2 is a certain recirculating fluidized bed power plant cycle ash grain size distribution；
Fig. 3 is a certain recirculating fluidized bed flying ash in electric power plant grain size distribution.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
Carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, is composed of the following raw materials by weight：Carbide slag 60-70
Part, 30-40 parts of biomass.
In the present embodiment, biomass is the stalk that length is less than 3cm.
Fig. 1 is composite desulfurizing agent preparation flow.
Embodiment 1：
Composite desulfurizing agent matches：Carbide slag 70g, wheat stalk 30g.
A kind of preparation method of the carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, includes the following steps：
S1, the broken sieving of stalk is obtained into the raw material that length is about 2cm, 30g wheat stalks and the wet carbide slags of 70g is mixed, soon
Speed stirring 30min；
S2, by stalk in S1-carbide slag mixture 20oIt is quenched that C places progress in 6 days；
S3, by stalk quenched in S2-carbide slag mixture natural air drying to moisture be 8% obtained stalk-carbide slag solid；
S4, the stalk air-dried in S3-carbide slag solid is granulated under 8MPa pressure, the composite calcium that grain size is 2cm is made
Base desulfurizer.
10 composite calcium based desulphurizing agents obtained are placed in 850oIn the tube furnace of C, it is passed through simulated flue gas, CO in flue gas2、
O2、SO2Volume fraction be respectively 15%, 3%, 0.3%, with N2For Balance Air, after reacting 8min, to the grain of composite calcium based desulphurizing agent
Diameter is distributed and mineral composition is analyzed, and the average grain diameter for obtaining composite calcium based desulphurizing agent is 0.45mm, calcium-based desulfurizing agent conversion
Efficiency for calcium sulfate is 96%.
Embodiment 2：
Composite desulfurizing agent matches：Carbide slag 60g, maize straw 40g.
A kind of preparation method of the carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, includes the following steps：
S1, the broken sieving of stalk is obtained into the raw material that length is about 2cm, 40g maize straws and the wet carbide slags of 60g is mixed, soon
Speed stirring 30min；
S2, by stalk in S1-carbide slag mixture 25oIt is quenched that C places progress in 5 days；
S3, by stalk quenched in S2-carbide slag mixture natural air drying to moisture be 5% obtained stalk-carbide slag solid；
S4, the stalk air-dried in S3-carbide slag solid is granulated under 10MPa pressure, the composite calcium that grain size is 2cm is made
Base desulfurizer.
10 composite calcium based desulphurizing agents obtained are placed in 850oIn the tube furnace of C, it is passed through simulated flue gas, CO in flue gas2、
O2、SO2Volume fraction be respectively 15%, 3%, 0.3%, with N2For Balance Air, after reacting 8min, to the grain of composite calcium based desulphurizing agent
Diameter is distributed and mineral composition is analyzed, and the average grain diameter for obtaining composite calcium based desulphurizing agent is 0.58mm, calcium-based desulfurizing agent conversion
Efficiency for calcium sulfate is 98%.
Embodiment 3：
Composite desulfurizing agent matches：Carbide slag 60g, maize straw 40g.
A kind of preparation method of the carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, includes the following steps：
S1, the broken sieving of stalk is obtained into the raw material that length is about 2cm, 60g maize straws and the wet carbide slags of 40g is mixed, soon
Speed stirring 30min；
S2, by stalk in S1-carbide slag mixture 23oIt is quenched that C places progress in 6 days；
S3, by stalk quenched in S2-carbide slag mixture natural air drying to moisture be 10% obtained stalk-carbide slag solid；
S4, the stalk air-dried in S3-carbide slag solid is granulated under 10MPa pressure, the composite calcium that grain size is 2cm is made
Base desulfurizer.
10 composite calcium based desulphurizing agents obtained are placed in 850oIn the tube furnace of C, it is passed through simulated flue gas, CO in flue gas2、
O2、SO2Volume fraction be respectively 15%, 3%, 0.3%, with N2For Balance Air, after reacting 8min, to the grain of composite calcium based desulphurizing agent
Diameter is distributed and mineral composition is analyzed, and the average grain diameter for obtaining composite calcium based desulphurizing agent is 0.22mm, calcium-based desulfurizing agent conversion
Efficiency for calcium sulfate is 94%.
As Figure 2-3, it is the particle diameter distribution of a certain recirculating fluidized bed power plant cycle ash and flying dust, the average grain of circulating ash
Diameter is 0.108mm, and wherein 0.065-0.2mm particle size ranges account for 88.89%, 0.05-0.088mm particle size ranges in flying dust
The possibility that up to 87-94%, i.e. grain size are brought into back-end ductwork in 0.2mm or less is very big, when grain size is less than 0.088mm, takes off
Poplar analysis loss easily occurs for sulphur agent.Experiment shows that stalk-carbide slag mixture passes through 20-25oQuenched 5-6 days of C, may be implemented electricity
The redistribution of rock ballast grain size makes the average grain diameter of composite calcium based desulphurizing agent after stove significantly increase, poplar analysis loss be reduced to 5% with
Under.
During biomass is quenched to carbide slag, itself can also be chemically modified, solid waste base calcium-based desulfurizing agent calcium carbide
Calcium in slag can be migrated into biomass, react to form calcium humate with the humic acid formed during biomass hardening, tempering,
It realizes the redistribution of calcium in biomass-carbide slag, and constructs the compound desulfurization system coexisted by calcium humate and calcium hydroxide.
When the composite calcium based desulphurizing agent coexisted by calcium humate and calcium hydroxide is used for desulfuration in furnace, due to the thermal decomposition of calcium humate
Temperature range is 300-440 DEG C, and the heat decomposition temperature section of calcium hydroxide is 430-590 DEG C, is far below calcium carbonate 600-
900 DEG C of heat decomposition temperature, therefore had more compared with conventional limestone by the composite desulfurizing agent that calcium humate and calcium hydroxide form
Good desulfurization performance, and extended compound based on calcium humate and calcium hydroxide by thermally decomposing the difference to calcium releasability
The time range that calcium discharges in desulfurizing agent, is conducive to SO2With the lasting fractional order reaction of calcium-based desulfurizing agent.
Only presently preferred embodiments of the present invention is explained in detail above, but the present invention is not limited to above-described embodiment,
Within the knowledge of a person skilled in the art, it can also make without departing from the purpose of the present invention each
Kind variation, various change should all be included in the protection scope of the present invention.
Claims (9)
1. the carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, which is characterized in that be composed of the following raw materials by weight：Electricity
60-70 parts of rock ballast, 30-40 parts of biomass.
2. the carbide slag composite calcium based desulphurizing agent according to claim 1 based on biomass hardening, tempering, it is characterised in that：It is described
Biomass is stalk.
3. the carbide slag composite calcium based desulphurizing agent according to claim 2 based on biomass hardening, tempering, it is characterised in that：It is described
Stalk length is less than 3cm.
4. the preparation method of the carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering, which is characterized in that include the following steps：
S1, stalk is broken for be less than 3cm stalk sections, takes 30-40 parts of stalk sections to be mixed with 60-70 parts of wet carbide slags, quickly stirs
It mixes；
S2, that stalk in S1-carbide slag mixture is placed to progress in 5-6 days is quenched；
S3, stalk-carbide slag solid is made in stalk quenched in S2-carbide slag mixture natural air drying；
S4, it will carry out being granulated obtained composite calcium based desulphurizing agent under the stalk that air-dried in S3-carbide slag solid.
5. the preparation method of the carbide slag composite calcium based desulphurizing agent according to claim 4 based on biomass hardening, tempering, special
Sign is：Mixture mixing time is at least 30min in the S1.
6. the preparation method of the carbide slag composite calcium based desulphurizing agent according to claim 4 based on biomass hardening, tempering, special
Sign is：The S2 refining temperatures are 20-25oC。
7. the preparation method of the carbide slag composite calcium based desulphurizing agent according to claim 4 based on biomass hardening, tempering, special
Sign is：Moisture is 5-10% after mixture air-dries in the S3.
8. the preparation method of the carbide slag composite calcium based desulphurizing agent according to claim 4 based on biomass hardening, tempering, special
Sign is：Grain size is 1-2cm after mixture pelleting in the S4.
9. the preparation method of the carbide slag composite calcium based desulphurizing agent according to claim 4 based on biomass hardening, tempering, special
Sign is：It is 8-12MPa that the S4, which is granulated pressure,.
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| CN113368848A (en) * | 2021-06-30 | 2021-09-10 | 山西大学 | Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof |
| CN113509833A (en) * | 2021-03-25 | 2021-10-19 | 山西大学 | Synchronous desulfurization and denitrification agent in solid waste base furnace and preparation method and application thereof |
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