CN104548892A - Composite sulfur-fixing agent and application thereof - Google Patents

Composite sulfur-fixing agent and application thereof Download PDF

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Publication number
CN104548892A
CN104548892A CN201410787984.2A CN201410787984A CN104548892A CN 104548892 A CN104548892 A CN 104548892A CN 201410787984 A CN201410787984 A CN 201410787984A CN 104548892 A CN104548892 A CN 104548892A
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China
Prior art keywords
fixing agent
sulfur
sulphur
calcium
percent
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CN201410787984.2A
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Chinese (zh)
Inventor
李瑛�
颜小禹
张恒
赖立践
陈捷
李范范
董委
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention discloses a composite sulfur-fixing agent which comprises the following components in percentage by mass: 5-45 percent of copper slag and 55-95 percent of calcium base. The composite sulfur-fixing agent is mainly applied to flue gas desulfurization in the industries such as coal-fired power plants and metallurgy. When the calcium-based/copper slag composite sulfur-fixing agent is at the temperature of 800-1000 DEG C, the specific surface area of the agent is increased, so that the contact area between SO2 in flue gas and the calcium-based/copper slag composite sulfur-fixing agent is increased. According to the determining of the efficiency of the calcium-based/copper slag composite sulfur-fixing agent on an experimental platform, the result shows that the sulfur-fixing rate ranges of the calcium-based/copper slag composite sulfur-fixing agent are that the sulfur-fixing rate is between 85.98 percent and 96.69 percent when a wet process is adopted, the sulfur-fixing rate is between 57.28 percent and 83.84 percent when a semidry method is adopted, and the sulfur-fixing rate is between 45.00 percent and 63.99 percent when a dry method is adopted. Because the copper slag is added into the sulfur-fixing agent, desulfurization reaction is carried out in advance, the desulfurization reaction time is prolonged, SO2 is removed, the energy consumption is reduced, the cost of the sulfur-fixing agent is reduced, and the economic benefits are obvious. The invention aims at providing a method for reutilizing the copper slag discarded after copper smelting.

Description

A kind of compound sulphur-fixing agent and application thereof
Technical field
This invention relates to a kind of compound sulphur-fixing agent being applicable to process in industrial production sulfur-containing smoke gas, is particularly useful for the fume treatment that sulfur-containing oxide is higher.
Background technology
The domestic and international sulphur-fixing agent for the solid sulphur of flue gas is mainly based on calcium base at present, this solid sulphur temperature range based on the flue gas sulphur-fixing agent of simple calcium base is narrow, sulphur-fixing agent utilization rate is low, cost relatively high, and simultaneously calcium based sulphur-fixation reagent only has desulfurized effect and do not possess catalytic action.Along with the development of science and technology, researcher constantly gropes to sum up in process of production, develop that many both to have had captured sulfur result good, there is again the compound sulphur-fixing agent of catalytic action, and the oxide that calcium base and two or more are just had catalytic action by these compound sulphur-fixing agents mixes and obtains, often formed sulphur-fixing agent cost is higher.Make solid sulphur not science economically.The present invention inspires by the advantage of the outer compound sulphur-fixing agent of Present Domestic, the obtained calcium base/copper ashes compound sulphur-fixing agent of waste residue (copper ashes) that copper metallurgy produces is added in conventional calcium base, analyzed by related experiment, show that compound sulphur-fixing agent has desulfurization and catalysis double effects, and widened the solid sulphur temperature range of sulphur-fixing agent, significant to the recycling reducing solid sulphur cost and industrial residue.
Summary of the invention
A desulfurization catalyst effect and conventional composite desulfurizing agent cost is excessive waits deficiency is not had in order to overcome the simple calcium base of tradition, copper ashes is added the composite desulfurizing agent formed in calcium base by the present invention effectively can meet current desulfurizing agent Problems existing, compound sulphur-fixing agent constituent of the present invention and mass percent are: copper ashes 5% ~ 45%, calcium base 55% ~ 95%.Described calcium base is one or more mixture in calcium carbonate, calcium oxide, calcium hydroxide, and copper ashes is the industrial residue that Yunnan Tong Ye company copper mine Isa furnace melting slag cleaning furnace is separated.
Another object of the present invention is applied in the flue gas desulfurization of the industry such as power plant, metallurgy by compound sulphur-fixing agent, and carry out under 800 ~ 1000 DEG C of conditions, and this compound sulphur-fixing agent is used for the solid sulphur of wet method, the solid sulphur of semidry method or dry fixed sulfation.
Compound sulphur-fixing agent provided by the invention can have desulfurization and catalytic action to the full extent simultaneously, makes full use of industrial residue, thus reaches recycling of copper ashes, improves the object of desulfuration efficiency and reduction desulphurization cost.
The present invention by adding copper ashes in calcium based sulphur-fixation reagent calcium carbonate, calcium oxide or calcium hydroxide, utilizes active ingredient in copper ashes (as fayalite (Fe 2siO 4), dolomite (MgCa(CO 3) 2), magnetic iron ore (Fe 3o 4) etc.) at high temperature pyrolysis generation active principle catalytically fixed sulphur (Fe 2o 3, CaO, MgO etc.), when in this compound sulphur-fixing agent, copper ashes addition scope is 5%-45%, compound sulphur-fixing agent just can start have much solid sulfur material matter to occur at a lower temperature, illustrate that copper ashes adds to be conducive to reducing desulfurization reaction temperature, expand desulfurization reaction temperature interval, add the desulphurization reaction time, thus enable sulphur-fixing agent at comparatively large-temperature range, in the longer reaction time, desulfurization carried out to flue gas.
800 DEG C to 1000 DEG C time, compound sulphur-fixing agent specific area increases the most obvious, and compared with analyzing separately the specific area of pure calcium carbonate, calcium oxide, calcium hydroxide, its amplification is 50% to 85%, which increases SO 2with effective contact area of sulphur-fixing agent, be conducive to removing of sulfureous in flue gas, and use cost is lower, economic benefit is obvious.
Invention key is that will reach better captured sulfur result needs to make compound sulphur-fixing agent modification under 800 DEG C ~ 1000 DEG C hot conditions, makes its pyrolysis discharge relevant catalytic specie and solid sulfur material matter.
In sum, advantage of the present invention is: can utilize copper metallurgy gained waste residue to greatest extent, compound sulphur-fixing agent cost used is reduced, reaches the double effects of solid sulphur and catalysis; Industry based on fire coal as thermoelectricity, steel smelting, after its fuel combustion, discharge is containing having severe contamination oxysulfide to atmospheric environment in a large number, adopts compound sulphur-fixing agent of the present invention can reach good captured sulfur result.
Shown by the desulfurization efficiency experimental result on experiment porch, the sulfur-fixing rate scope of compound sulphur-fixing agent is: the solid sulphur of wet method is between 85.98% ~ 96.69%, and the solid sulphur of semidry method is between 57.28% ~ 83.84%, and dry fixed sulfation is between 45.00% ~ 63.99%.
Accompanying drawing explanation
Fig. 1 is compound sulphur-fixing agent of the present invention (copper ashes is 10%) XRD testing result at different temperatures, and wherein a is CaCO 3; B is CaMg (CO 3) 2; C is Fe 2siO 4; D is MgO; E is CaO; F is Fe 3o 4; G is Fe 2o 3; H is SiO 2;
Fig. 2 is when adding copper ashes ratio difference, CaCO 3/ TZ compound sulphur-fixing agent quality is with the variation relation figure of temperature T and heat time t, and wherein A is that compound sulphur-fixing agent quality is with temperature T variation relation figure; B is the variation relation figure of compound sulphur-fixing agent quality with heat time t;
Fig. 3 is CaCO 3and CaCO 3/ TZ compound sulphur-fixing agent recepts the caloric temperature variant relation;
Fig. 4 is calcium carbonate/copper ashes compound sulphur-fixing agent BET specific surface area result at different temperatures;
Fig. 5 is the SEM figure after native copper slag amplifies 3.00kx, 6.00kx, 10.00kx;
Fig. 6 is the SEM figure after calcium carbonate/copper ashes compound sulphur-fixing agent different temperatures calcining, and wherein a is normal temperature (24 DEG C), and b is 800 DEG C, c is 900 DEG C, d is 1000 DEG C.
Detailed description of the invention
Below by concrete enforcement, the invention will be further described, but scope is not limited to described content.
Embodiment 1: this compound sulphur-fixing agent constituent and mass percent are: copper ashes (TZ) 5%, calcium carbonate 95%; Copper ashes 10%, calcium carbonate 90%; Copper ashes 20%, calcium carbonate 80%.Wherein copper ashes is the industrial residue that Yunnan Tong Ye company copper mine Isa furnace melting slag cleaning furnace is separated, and the chemical composition of the present embodiment copper ashes and the content of copper ashes essential mineral are as shown in Table 1 and Table 2.
Table 1: the chemical composition of copper ashes
Table 2: the content of copper ashes essential mineral
(1) property analysis of calcium carbonate/copper ashes compound sulphur-fixing agent is as follows:
By known to calcium carbonate/copper ashes compound sulphur-fixing agent carries out XRD analysis, as shown in Figure 1, compound sulphur-fixing agent pyrolysis can discharge the material being conducive to catalytically fixed sulphur.
Add copper ashes ratio different time CaCO 3/ TZ compound sulphur-fixing agent quality with temperature T variation relation as shown in Figure 2 A, add copper ashes ratio different time CaCO 3/ TZ sulphur-fixing agent quality with the heat time variation relation as shown in Figure 2 B, analyze known compound sulphur-fixing agent weightlessness start to terminate duration △ t all different.They start weightless temperature T 1, weightless end temp T 2, weightless temperature scope △ T and the temperature variant time range △ t of quality is as table 3.
Table 3: sulphur-fixing agent quality is with temperature T and time t variation relation
Can be reached a conclusion by table analysis: when adding copper ashes mass ratio and being 10%, due to CaCO 3/ TZ compound sulphur-fixing agent is heated and starts weightlessness at a lower temperature, than the pure CaCO of analysis 3weightless beginning and end temp reduce 85.9 DEG C and 105.2 DEG C respectively, illustrate that compound sulphur-fixing agent can start chemical change occurs at a lower temperature, are conducive to reducing SO 2with reactive desulfurizing agent temperature, expand desulfurization reaction temperature interval, add the desulphurization reaction time, thus enable sulphur-fixing agent at comparatively large-temperature range, in the longer reaction time, desulfurization carried out to flue gas.
CaCO 3and CaCO 3/ TZ compound sulphur-fixing agent recepts the caloric temperature variant relation as shown in Figure 3.As seen from the figure: copper ashes add DSC peak value is diminished and toward low temperature skew, this illustrate, copper ashes adds can make the heat absorption of sulphur-fixing agent reduce, plays positive modifying function, reduce energy consumption to compound sulphur-fixing agent, saving desulphurization cost.
Copper ashes BET specific surface area testing result is at different temperatures as shown in table 4, as can be seen from Table 4, carries out calcination processing can not change its specific area explanation temperature largely on the specific area impact of copper ashes not quite to copper ashes.And copper ashes content CaCO when being 10%, 20% 3after/TZ compound sulphur-fixing agent sample carries out calcination processing under normal temperature (24 DEG C), 800 DEG C, 900 DEG C, 1000 DEG C conditions, BET specific surface area test result is table 5.
Table 4: the specific area of copper ashes under different calcining heat
Table 5: BET test result after compound sulphur-fixing agent different temperatures calcination processing
Fig. 4 is drawn by calcium carbonate/copper ashes compound sulphur-fixing agent BET result at different temperatures.From map analysis: when adding copper ashes mass ratio and being 10%, 20%, at 800 DEG C of temperature, compound sulphur-fixing agent specific area is respectively 6.198 m 2/ g and 3.627 m 2/ g; 8.799 m are respectively at 900 DEG C of temperature 2/ g and 4.215 m 2/ g; 4.792 m are respectively at 1000 DEG C of temperature 2/ g and 2.721 m 2/ g.Comparative analysis is known, and when adding that copper ashes is 10%, temperature is 900 DEG C, composite solid agent specific area reaches maximum 8.799 m 2/ g, its amplification reaches 75.98%, and larger surface area is conducive to more SO in flue gas 2with sulphur-fixing agent haptoreaction, thus reach and remove SO 2object.
Native copper slag and CaCO 3as shown in Figure 5 and Figure 6, as can be seen from Figure 5, copper ashes is that compact structure, has glass surface in block to SEM after the calcining of/TZ compound sulphur-fixing agent.The specific area of copper ashes is little is and its compact structure, and tight is relevant.As seen from Figure 6, with the rising of calcining heat, CaCO contained in compound sulphur-fixing agent 3the CaO particle volume formed after decomposes, reaches maximum and very fluffy 900 DEG C time, splits and form many less dough 1000 DEG C time, and sintering appears in CaO 1000 DEG C time.This illustrate compound sulphur-fixing agent heat through 900 DEG C after the volume of particle reach maximum, can with more SO 2gas fully contacts, and the utilization rate of sulphur-fixing agent is improved, and desulphurization reaction is more quick thoroughly, is conducive to improving smoke desulfurization efficiency.
By above-mentioned data and experimental analysis, can obtain drawing a conclusion: at CaCO 3in add the composite solid desulfurizing agent pyrolysis that a certain amount of copper ashes forms and discharge a lot of material desulfurization to positive role, copper ashes adds and is conducive to making compound sulphur-fixing agent reduce desulfurization reaction temperature, expand desulfurization reaction temperature range, add the desulfurization reaction time, thus enable sulphur-fixing agent at comparatively large-temperature range, in the longer reaction time, desulfurization carried out to flue gas.Compound sulphur-fixing agent specific area increases obvious, is beneficial to SO in flue gas 2more with sulphur-fixing agent haptoreaction, there is facilitation to the solid sulphur of flue gas.
(2) wet method, semidry method, dry fixed sulfation test will be carried out after the copper ashes of aforementioned proportion and calcium carbonate Homogeneous phase mixing on experimental bench, wherein each volume components mark of simulated flue gas is nitrogen 72%, carbon dioxide 14%, oxygen 6.8%, steam 7%, sulfur dioxide 1000ppm.Laboratory simulation flue gas feed rate is 200mml/min, and the moral Figure 30 4 type flue gas analyzer adopting Germany to produce detects, and experimental result is as table 6:
Table 6: when to add copper ashes amount be 5%, 10%, 20%, desulfurization efficiency after calcium carbonate/copper ashes compound sulphur-fixing agent heat treatment
Embodiment 2: wet method, semidry method, dry fixed sulfation test will be carried out after the copper ashes of different proportion and calcium oxide Homogeneous phase mixing on experimental bench, wherein each volume components mark of simulated flue gas, laboratory simulation flue gas feed rate, detecting instrument are with embodiment 1, and experimental result is as table 7:
Table 7: when to add copper ashes amount be 15%, 25%, 30%, calcium oxide/copper ashes compound sulphur-fixing agent desulfurization efficiency
Embodiment 3: wet method, semidry method, dry fixed sulfation test will be carried out after the copper ashes of different proportion and calcium hydroxide Homogeneous phase mixing on experimental bench, wherein simulated flue gas each volume components mark, laboratory simulation flue gas feed rate, detecting instrument are the same, experimental result table 8:
Table 8: when to add copper ashes amount be 35%, 40%, 45%, calcium hydroxide/copper ashes compound sulphur-fixing agent desulfurization efficiency
Embodiment 4: calcium carbonate, calcium oxide, calcium hydroxide are made compound sulphur-fixing agent by adding copper ashes after 1:1 mixing, and on experimental bench, carry out wet method, semidry method, dry fixed sulfation test, wherein each volume components mark of simulated flue gas, laboratory simulation flue gas feed rate, detecting instrument are with embodiment 1, shown in experimental result table 9, table 10, table 11:
Table 9: when to add copper ashes ratio be 5%, 10%, 20%, compound sulphur-fixing agent wet method desulfurization efficiency
Table 10: when to add copper ashes ratio be 5%, 10%, 20%, compound sulphur-fixing agent semidry method desulfurization efficiency
Table 11: when to add copper ashes ratio be 5%, 10%, 20%, compound sulphur-fixing agent dry fixed sulfation efficiency
As can be seen from table 6 ~ 11, compound sulphur-fixing agent obtained after adding copper ashes is placed on experimental bench and carries out the experiment of flue gas desulfurization efficiency, show that solid sulphur percentage (sulfur-fixing rate) is by correlation data calculation: wet method is between 85.98% ~ 96.69%, semidry method is between 57.28% ~ 83.84%, and dry method is between 45.00% ~ 63.99%.4 embodiments illustrate above, and copper ashes joins the compound sulphur-fixing agent formed in calcium base and not only has good captured sulfur result, and can utilize copper ashes fully, and the recycling for industrial residue provides a good direction.

Claims (4)

1. a compound sulphur-fixing agent, is characterized in that constituent and mass percent are: copper ashes 5% ~ 45%, calcium base 55% ~ 95%.
2. compound sulphur-fixing agent according to claim 1, is characterized in that: calcium base is one or more mixture in calcium carbonate, calcium oxide, calcium hydroxide.
3. the application of compound sulphur-fixing agent described in claim 1 in the solid sulphur of flue gas, is characterized in that: compound sulphur-fixing agent needs carry out modification to it under 800 DEG C ~ 1000 DEG C conditions.
4. the application of compound sulphur-fixing agent according to claim 3 in flue gas desulfurization, is characterized in that: compound sulphur-fixing agent is used for the solid sulphur of wet method, the solid sulphur of semidry method or dry fixed sulfation.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105733737A (en) * 2016-02-24 2016-07-06 太原理工大学 Copper slag composite additive for reducing ignition temperature of civilian coke, preparation method and application
CN108238735A (en) * 2018-01-19 2018-07-03 辽宁鑫隆科技有限公司 A kind of cement burning desulfurization, sulphur-fixing agent

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CN1229128A (en) * 1998-03-13 1999-09-22 河北省环境保护研究所 Coal-fired sulfur fixing agent containing steel slag additive

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Publication number Priority date Publication date Assignee Title
CN1229128A (en) * 1998-03-13 1999-09-22 河北省环境保护研究所 Coal-fired sulfur fixing agent containing steel slag additive

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105733737A (en) * 2016-02-24 2016-07-06 太原理工大学 Copper slag composite additive for reducing ignition temperature of civilian coke, preparation method and application
CN105733737B (en) * 2016-02-24 2018-12-21 太原理工大学 The copper ashes compound additive and preparation method of reduction domestic coke ignition temperature and application
CN108238735A (en) * 2018-01-19 2018-07-03 辽宁鑫隆科技有限公司 A kind of cement burning desulfurization, sulphur-fixing agent

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Application publication date: 20150429