CN105463208A - Method and apparatus for reducing oxygen-containing copper liquid by adopting natural gas/nitrogen - Google Patents
Method and apparatus for reducing oxygen-containing copper liquid by adopting natural gas/nitrogen Download PDFInfo
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- CN105463208A CN105463208A CN201410412540.0A CN201410412540A CN105463208A CN 105463208 A CN105463208 A CN 105463208A CN 201410412540 A CN201410412540 A CN 201410412540A CN 105463208 A CN105463208 A CN 105463208A
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Abstract
The invention provides a method for reducing an oxygen-containing copper liquid by adopting natural gas/nitrogen. The method is characterized in that the natural gas and nitrogen are introduced to the copper-containing copper liquid in a non-premix mode in order to carry out reduction, and the flow amounts of the natural gas and nitrogen and a weight ratio of the flow amount of the natural gas to the flow amount of nitrogen are adjusted through monitored parameters. The invention also provides an apparatus for reducing the oxygen-containing copper liquid by adopting the natural gas/nitrogen.
Description
Technical field
The application belongs to copper weld pool field, in particular to a kind of method and the device that adopt Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Background technology
Reclaimed copper fusion process comprises fusing, is oxidized, skims and reduction phase.For improving the purity of copper, carry out removing impurities by oxidation with being blown into pressurized air, then reduce deoxidation with reductive agent.In conventional regeneration copper weld pool reduction process, people usually adopt poling.But because timber resources is valuable, be protection of the environment, reduction process gradually adopts substitute gas poling.
At present, use Sweet natural gas to carry out reduction and there is following drawback: the utilization ratio of (1) Sweet natural gas is low, and the recovery time is long; (2) Sweet natural gas and copper liquid react not exclusively, produce a large amount of black smoke and cause environmental pollution; (3) the Sweet natural gas hydrogen that cracking produces in copper liquid is easily absorbed by copper liquid, makes copper occur some micropores, affects quality product; (4) due in reduction process gas discharge do not make appropriate and adjustment in time, cause some time period Sweet natural gas of reduction process excessive, make copper liquid temperature too high.The more high easier oxygen intake of copper liquid temperature is oxidized again.Require index for making the oxygen level of copper liquid be reduced to, corresponding reduction process will be elongated.
Summary of the invention
For solving the drawback in above-mentioned copper weld pool technique, the present invention adopts Sweet natural gas and nitrogen to pass in copper liquid in the mode of non-premix and reduces, and according to the parameter regulation of monitoring the flow of Sweet natural gas and nitrogen and their flow proportional.
Inventor also attempts delivering to reduction jet pipe as reducing gas after Sweet natural gas and nitrogen carry out premix, and according in smelting furnace or in the temperature of flue outlet and the change of CO concentration parameter or copper liquid oxygen level change adjust the blending ratio of Sweet natural gas and nitrogen in reduction process.This method can strengthen the stirring intensity of copper liquid, improves the utilization ratio of Sweet natural gas, alleviates environmental pollution, reduces the solubleness of hydrogen at copper liquid, but also copper liquid surface can be stoped to contact with air, prevents again the phenomenon of dissolved oxygen to occur.But this method is owing to sending after first to Sweet natural gas and nitrogen premix into reduction jet pipe again, thus after premix the pressure of mixed gas by the restriction of Sweet natural gas before premix and nitrogen pressure.In general, can not higher than 3 kilograms of (kg/cm at the gas pressure of reclaimed copper smelting factory
2), and the pressure of nitrogen is much larger than the pressure of Sweet natural gas, can reach 10 kilograms of (kg/cm
2).Adopt and enter after mixing tank carries out the mode of premix, the pressure of mixed gas can not higher than the pressure of Sweet natural gas.Reducing gas pressure is higher, and the penetrance in copper liquid is stronger, strong with regard to Shaoxing opera to the stirring intensity of copper liquid like this, thus improves the utilization ratio of Sweet natural gas further.
For the limitation of mixture pressure after premix, the application proposes a kind ofly Sweet natural gas and nitrogen are sprayed into copper liquid in a kind of mode of non-premix to reduce, thus improves the utilization ratio of Sweet natural gas further and shorten the recovery time.
Particularly, the present invention adopts the patten's design of pipe-in-pipe to reduce jet pipe Sweet natural gas and nitrogen are sprayed into copper liquid respectively to reduce.What interior pipe was carried is the Sweet natural gas that pressure is lower, and what outer tube inputted is the nitrogen that pressure is higher.Like this, the nitrogen gas stream that pressure is higher is around the lower natural gas flow of pressure.In copper liquid, the natural gas flow that the nitrogen gas stream that pressure is higher can help pressure lower improves range, thus the touch opportunity adding Red copper oxide in Sweet natural gas and copper liquid is to improve the utilization ratio of Sweet natural gas.
Therefore, on the one hand, the invention provides a kind of method adopting Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid, comprise the following steps: described Sweet natural gas and nitrogen passed in oxygen-bearing copper liquid in the mode of non-premix and reduce, the flow of wherein said Sweet natural gas and nitrogen and their flow proportional are regulated by the parameter of monitoring.
According to one preferred embodiment, described in aforesaid method, parameter is selected from:
(1) change of CO concentration in the furnace temperature change of the smelting furnace of oxygen-bearing copper liquid described in splendid attire and stove; Or
(2) the flue outlet place smoke temperature change of the smelting furnace of oxygen-bearing copper liquid described in splendid attire and the change of CO concentration in flue gas; Or
(3) change of oxygen level in described oxygen-bearing copper liquid.
During reduction, reduction jet pipe is imbedded in copper liquid and is reduced.Reduction jet pipe inserts in smelting furnace by charging opening, also can be arranged on smelting furnace top, and the jet pipe that will reduce during reduction inserts in copper liquid.When not needing, reduction jet pipe shifts out smelting furnace.
According to one preferred embodiment, the flow proportional of wherein said Sweet natural gas and nitrogen is greater than the reduction later stage at the reduction initial stage.At the reduction initial stage, because in copper liquid, the content of Red copper oxide is relatively high, at this moment need to send into more Sweet natural gas and reduce.Along with the carrying out of reduction, in copper liquid, the content of Red copper oxide reduces gradually, at this moment needs reduce amount of natural gas and increase nitrogen amount.The ratio of Sweet natural gas and nitrogen, when the initial stage of reduction, can be all Sweet natural gas, then progressively increase the content of nitrogen, makes the ratio of the two be 30: 1,15: 1,10: 1,5: 1,3: 1,2: 1,1: 1.Then along with reduction process progressively reduces, the content of Sweet natural gas reduces gradually, reaches 1: 2, and 1: 3,1: 5,1: 10,1: 15,1: 30, until can be all nitrogen.According to the above-mentioned parameter monitored, can every 1,2,3,4,5,10,15,20, or the flow proportional of 30 minutes adjustment Sweet natural gases and nitrogen.In reduction process, effectively control to send into the Sweet natural gas of reduction jet pipe and nitrogen flow and ratio thereof, can further improve the utilization ratio of Sweet natural gas, reduce black smoke and generate, reduce the dissolving of hydrogen in copper liquid and avoid copper liquid temperature too high.
The application controls to send in reduction process the reduction Sweet natural gas of jet pipe and nitrogen flow and ratio thereof in the following way:
(1) mode one: the change of CO concentration in the furnace temperature change of monitoring smelting furnace and furnace gas
Judge that whether the input of Sweet natural gas is too much by the change (dCO/dt) monitoring CO concentration in fire box temperature change (dT/dt) and furnace gas.Temperature variation calculates temperature change value dT/dt by the thermoelectricity temperature value that occasionally infrared measurement of temperature equitemperature survey sensor is measured.The changing value dCO/dt of CO is that the CO densitometer measured by CO survey sensor is calculated.Temperature and CO survey sensor are placed in burner hearth.When the temperature change value dT/dt monitored and CO change in concentration value dCO/dt is higher than set(ting)value given in advance, this just shows that the input of Sweet natural gas is too much, and nitrogen flow needs to increase.The variable signal of furnace temperature and CO can feed back to natural gas flow control valve group and nitrogen flow control valve group, is adjusted the Sweet natural gas and nitrogen flow that enter reduction jet pipe respectively, thus reach required Sweet natural gas and the throughput ratio of nitrogen by flowrate control valve group.
(2) mode two: the change of smelting furnace flue outlet place's smoke temperature change and CO concentration in flue gas
Identical with mode one, judge that whether the input of Sweet natural gas is too much by the change (dCO/dt) of the smoke temperature change (dT/dt) that monitors and CO concentration in flue gas.Temperature and the CO concentration that temperature and CO survey sensor are placed on that smelting furnace smoke outlet place monitors flue gas with the difference of mode one.When the temperature change value dT/dt monitored and CO change in concentration value dCO/dt is higher than set(ting)value given in advance, this just shows that the input of Sweet natural gas is too much, and nitrogen flow needs to increase.The variable signal of flue-gas temperature and CO can feed back to natural gas flow control valve group and nitrogen flow control valve group, is changed the Sweet natural gas and nitrogen flow that enter reduction jet pipe, thus reach required Sweet natural gas and the throughput ratio of nitrogen by flowrate control valve group.
(3) mode three: the change of oxygen amount in copper liquid
The oxygen level of copper liquid is by mass spectrograph or other oxygen determination content apparatus measures.When the copper liquid oxygen level of monitoring exceeds the highest set(ting)value given in advance, Sweet natural gas and nitrogen flow control valve group increase gas discharge respectively and reduce nitrogen flow, and the throughput ratio making to enter the Sweet natural gas of reduction jet pipe and nitrogen is higher.When the copper liquid oxygen level of monitoring is lower than minimum set(ting)value given in advance, flowrate control valve group can reduce gas discharge and increase nitrogen flow, and the throughput ratio of Sweet natural gas and nitrogen is reduced until the oxygen level of copper liquid is reduced to require index.。
According to a particularly preferred embodiment of the present, the respective flow of described Sweet natural gas and nitrogen and flow proportional are 10: 1 at the reduction initial stage, and the reduction later stage is 1: 10.Gas discharge can by the 300 ~ 500Nm at reduction initial stage
3/ hr reduces to the 30 ~ 50Nm in reduction later stage
3/ hr, nitrogen flow can by the 30 ~ 50Nm at reduction initial stage
3/ hr is increased to the 300 ~ 500Nm in reduction later stage
3/ hr.
On the other hand, the invention provides a kind of device adopting Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid, it is characterized in that, comprising:
Natural gas supply device (1), it is connected with reduction jet pipe (5) by natural gas flow control valve group (3), for providing Sweet natural gas to reduction jet pipe (5);
Nitrogen supply (NS) device (2), it is connected with reduction jet pipe (5) by nitrogen flow control valve group (4), for providing nitrogen to reduction jet pipe (5);
Reduction jet pipe (5), comprises inner and outer tubes, for providing Sweet natural gas and nitrogen to copper liquid (6);
Smelting furnace (7), for splendid attire oxygen-bearing copper liquid to be restored;
PLC control module (10), its one end is connected with natural gas flow control valve group (3) and nitrogen flow control valve group (4), the other end is connected with the Monitoring equipment being placed in smelting furnace (7), for controlling to enter the flow of Sweet natural gas in reduction jet pipe (5) and nitrogen.
According to one preferred embodiment, described interior pipe transport gas, and described outer tube supplying nitrogen.
According to another preferred embodiment, the Monitoring equipment being placed in smelting furnace (7) described in is selected from the Monitoring equipment (13) of the oxygen level change of the copper liquid (6) in the Monitoring equipment (9) of flue outlet (8) place's smoke temperature change of described smelting furnace (7) and the change of CO concentration in flue gas, the furnace temperature change of described smelting furnace (7) and the Monitoring equipment (12) of furnace gas CO change in concentration or described smelting furnace (7).
According to one preferred embodiment, described reduction jet pipe (5) is inserted in smelting furnace (7) by charging opening (11).
According to another preferred embodiment, described reduction jet pipe (5) is inserted in smelting furnace (7) by smelting furnace furnace roof (14), and the jet pipe (5) that namely reduces especially is evenly distributed on furnace roof (14) along the length direction of smelting furnace (7).
According to one preferred embodiment, the side of described smelting furnace (8) is provided with burns rifle (16), and for melting and oxidation stage, and copper liquid heats up again.
Employing Sweet natural gas provided by the present invention and nitrogen with non-premix mode reduce the method and apparatus of oxygen-bearing copper liquid can effectively improve Sweet natural gas utilization ratio about 35%, improve copper liquid quality and shorten recovery time 25-45%.
Accompanying drawing explanation
Fig. 1 shows reduction jet pipe (5-1), and it inserts from smelting furnace charging opening.
Fig. 2 shows reduction jet pipe (5-2), and it enters from smelting furnace tip cutting.
Fig. 3 is the schematic diagram of a kind of embodiment adopting apparatus of the present invention Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Fig. 4 is the schematic diagram of a kind of embodiment adopting apparatus of the present invention Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Fig. 5 is the schematic diagram of a kind of embodiment adopting apparatus of the present invention Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Fig. 6 is the schematic diagram of a kind of embodiment adopting apparatus of the present invention Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Fig. 7 is the schematic diagram of a kind of embodiment adopting apparatus of the present invention Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Fig. 8 is the schematic diagram of a kind of embodiment adopting apparatus of the present invention Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid.
Embodiment
Further illustrate the present invention below by way of embodiment, but described embodiment should not be considered as limitation of the scope of the invention by any way.
Fig. 1 shows reduction jet pipe (5-1), and it inserts from smelting furnace charging opening.
Fig. 2 shows reduction jet pipe (5-2), and it enters from smelting furnace tip cutting.
As shown in Figure 3, Sweet natural gas (1), nitrogen (2) enter reduction jet pipe (5-1) respectively through natural gas flow control valve group (3) and nitrogen flow control valve group (4).In flue outlet (8) laying temperature and the CO Monitoring equipment (9) of smelting furnace (7), the change of monitoring flue-gas temperature and flue gas CO concentration.The signal feedback of flue-gas temperature and flue gas CO concentration calculates temperature change value and CO change in concentration value to PLC control module (10).When the temperature change value calculated and CO change in concentration value higher than set(ting)value given in advance, natural gas flow control valve group (3) and nitrogen flow control valve group (4) just start Sweet natural gas and the nitrogen flow that adjustment enters reduction jet pipe (5-1), gas discharge are reduced and nitrogen flow increase.Reduction jet pipe (5-1) is inserted in copper water (6) by the charging opening (11) on smelting furnace (7) reduces.
As shown in Figure 4, Sweet natural gas (1), nitrogen (2) enter reduction jet pipe (5-1) respectively through natural gas flow control valve group (3) and nitrogen flow control valve group (4).(7) laying temperature and CO Monitoring equipment (12) in smelting furnace, monitor the change of CO concentration in fire box temperature and furnace gas.The signal feedback of fire box temperature and furnace gas CO concentration calculates temperature change value and CO change in concentration value to PLC control module (10).When the temperature change value calculated and CO change in concentration value higher than set(ting)value given in advance, natural gas flow control valve group (3) and nitrogen flow control valve group (4) just start Sweet natural gas and the nitrogen flow that adjustment enters reduction jet pipe (5-1), gas discharge are reduced and nitrogen flow increase.Reduction jet pipe (5-1) is inserted in copper water (6) by the charging opening (11) on smelting furnace (7) reduces.
As shown in Figure 5, Sweet natural gas (1), nitrogen (2) enter reduction jet pipe (5-1) respectively through natural gas flow control valve group (3) and nitrogen flow control valve group (4).The oxygen level of the copper water (6) in smelting furnace (7) is measured with instrument (13), and the oxygen content signal measured feeds back to PLC control module (10).When copper liquid (6) oxygen level of monitoring exceeds the highest set(ting)value given in advance in PLC control module (10), natural gas flow control valve group (3) and nitrogen flow control valve group (4) will enter reduces jet pipe (5-1) gas discharge and nitrogen flow and increases respectively and reduce.When the oxygen level of the copper liquid (6) of monitoring is lower than minimum set(ting)value given in advance, flowrate control valve group (3) and (4) require index by reducing gas discharge and increasing nitrogen flow until the oxygen level of copper liquid (6) is reduced to.Reduction jet pipe (5-1) is inserted in copper water (6) by the charging opening (11) on smelting furnace (7) reduces.
As shown in Figure 6, Sweet natural gas (1), nitrogen (2) enter reduction jet pipe (5-2) respectively through natural gas flow control valve group (3) and nitrogen flow control valve group (4).At flue outlet (8) laying temperature and the CO concentration monitor instrument (9) of smelting furnace (7), the change of monitoring flue-gas temperature and flue gas CO concentration.The signal feedback of flue-gas temperature and flue gas CO concentration calculates temperature change value and CO change in concentration value to PLC control module (10).When the temperature change value calculated and CO change in concentration value higher than set(ting)value given in advance, natural gas flow control valve group (3) and nitrogen flow control valve group (4) just start Sweet natural gas and the nitrogen flow that adjustment enters reduction jet pipe (5-2), gas discharge are reduced and nitrogen flow increase.Reduction jet pipe (5-2) is evenly distributed on furnace roof (14) along the length direction of smelting furnace (7).Reduction phase, reduction jet pipe (5-2) is inserted in copper water (6) reduces.The mode of this furnace roof inserted mode can allow feed door (11) close completely in reduction process, so not only can reduce heat waste, and can reduce air and enter burner hearth and be again oxidized copper water.After reduction terminates, reduction jet pipe (5-2) can extract smelting furnace (7) out.The side of smelting furnace (7) is provided with burns pipe (15) for melting, oxidation, and the temperature rise period use again of copper liquid.
As shown in Figure 7, Sweet natural gas (1), nitrogen (2) enter reduction jet pipe (5-2) respectively through natural gas flow control valve group (3) and nitrogen flow control valve group (4).(7) laying temperature and CO concentration monitor instrument (12) in smelting furnace, monitor the change of CO concentration in fire box temperature and furnace gas.The signal feedback of fire box temperature and furnace gas CO concentration calculates temperature change value and CO change in concentration value to PLC control module (10).When the temperature change value calculated and CO change in concentration value higher than set(ting)value given in advance, natural gas flow control valve group (3) and nitrogen flow control valve group (4) just start Sweet natural gas and the nitrogen flow that adjustment enters reduction jet pipe (5-2), gas discharge are reduced and nitrogen flow increase.Reduction jet pipe (5-2) is evenly distributed on furnace roof (14) along the length direction of smelting furnace (7).Reduction phase, reduction jet pipe (5-2) is inserted in copper water (6) reduces.After reduction terminates, reduction jet pipe (5-2) can extract smelting furnace (7) out.
As shown in Figure 8, Sweet natural gas (1), nitrogen (2) enter reduction jet pipe (5-2) respectively through natural gas flow control valve group (3) and nitrogen flow control valve group (4).The oxygen level of the copper water (6) in smelting furnace (7) is measured with instrument (13), and the oxygen level signal feedback measured is to PLC control module (10).When copper liquid (6) oxygen level of monitoring exceeds the highest set(ting)value given in advance in PLC control module (10), natural gas flow control valve group (3) and nitrogen flow control valve group (4) will enter reduces jet pipe (5-2) gas discharge and nitrogen flow and increases respectively and reduce.When the oxygen level of the copper liquid (6) of monitoring is lower than minimum set(ting)value given in advance, flowrate control valve group (3) and (4) require index by reducing gas discharge and increasing nitrogen flow until the oxygen level of copper liquid (6) is reduced to.Reduction jet pipe (5-2) is evenly distributed on furnace roof (14) along the length direction of smelting furnace (7).Reduction phase, reduction jet pipe (5-2) is inserted in copper water (6) reduces.After reduction terminates, reduction jet pipe (5-2) can extract smelting furnace (7) out.
Claims (11)
1. one kind adopts the method for Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid, comprise the following steps: described Sweet natural gas and nitrogen passed in oxygen-bearing copper liquid in the mode of non-premix and reduce, the flow of wherein said Sweet natural gas and nitrogen and their flow proportional are regulated by the parameter of monitoring.
2. method according to claim 1, wherein said parameter is selected from:
(1) the flue outlet place smoke temperature change of the smelting furnace of oxygen-bearing copper liquid described in splendid attire and the change of CO concentration in flue gas; Or
(2) change of CO concentration in the furnace temperature change of the smelting furnace of oxygen-bearing copper liquid described in splendid attire and stove; Or
(3) change of oxygen level in described oxygen-bearing copper liquid.
3. method according to claim 1, the flow proportional of wherein said Sweet natural gas and nitrogen is greater than at the reduction initial stage and reduces the later stage.
4. method according to claim 1, the flow proportional of wherein said Sweet natural gas and nitrogen is 30: 1 to 1: 30, is preferably 10: 1 to 1: 10.
5. adopt a device for Sweet natural gas/nitrogen reduction oxygen-bearing copper liquid, it is characterized in that, comprising:
Natural gas supply device (1), it is connected with reduction jet pipe (5) by natural gas flow control valve group (3), for providing Sweet natural gas to reduction jet pipe (5);
Nitrogen supply (NS) device (2), it is connected with reduction jet pipe (5) by nitrogen flow control valve group (4), for providing nitrogen to reduction jet pipe (5);
Reduction jet pipe (5), comprises inner and outer tubes, for providing Sweet natural gas and nitrogen to copper liquid (6);
Smelting furnace (7), for splendid attire oxygen-bearing copper liquid to be restored;
PLC control module (10), its one end is connected with natural gas flow control valve group (3) and nitrogen flow control valve group (4), the other end is connected with the Monitoring equipment being placed in smelting furnace (7), for controlling to enter the flow of Sweet natural gas in reduction jet pipe (5) and nitrogen.
6. device according to claim 5, is characterized in that described interior pipe transport gas.
7. device according to claim 5, is characterized in that described outer tube supplying nitrogen.
8. device according to claim 5, the Monitoring equipment being placed in smelting furnace (7) described in it is characterized in that is selected from the Monitoring equipment (13) of the oxygen level change of the copper liquid (6) in the Monitoring equipment (9) of flue outlet (8) place's smoke temperature change of described smelting furnace (7) and the change of CO concentration in flue gas, the furnace temperature change of described smelting furnace (7) and the Monitoring equipment (12) of furnace gas CO change in concentration or described smelting furnace (7).
9. device according to claim 5, is characterized in that described reduction jet pipe (5) is inserted in smelting furnace (7) by charging opening (11).
10. device according to claim 5, is characterized in that described reduction jet pipe (5) is inserted in smelting furnace (7) by smelting furnace furnace roof (14).
11. devices according to claim 5, it is characterized in that the side of described smelting furnace (7) is provided with and burn pipe (15), for melting and oxidation stage, and copper liquid heats up again.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410412540.0A CN105463208A (en) | 2014-08-20 | 2014-08-20 | Method and apparatus for reducing oxygen-containing copper liquid by adopting natural gas/nitrogen |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113093820A (en) * | 2020-02-25 | 2021-07-09 | 北京首钢朗泽新能源科技有限公司 | Gas concentration stabilizing device and control method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA1326138C (en) * | 1988-08-08 | 1994-01-18 | Walter Curlook | Removal of copper converter mush |
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| CN113093820B (en) * | 2020-02-25 | 2023-09-01 | 北京首钢朗泽科技股份有限公司 | Gas concentration stabilizing device and control method thereof |
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Application publication date: 20160406 |