CN212915080U - Organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide - Google Patents
Organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide Download PDFInfo
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- CN212915080U CN212915080U CN202021245958.4U CN202021245958U CN212915080U CN 212915080 U CN212915080 U CN 212915080U CN 202021245958 U CN202021245958 U CN 202021245958U CN 212915080 U CN212915080 U CN 212915080U
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Abstract
The utility model discloses an organic amine desulfurizer solution purification desalination and impurity removal device for removing sulfur dioxide, which comprises a stirring type crystallizer (1), wherein an upper arc cover of the stirring type crystallizer (1) is provided with an organic amine liquid input pipe (2) with a valve and an additive pipe (5), an outlet of a crystallizer discharge pipe (11) at the bottom of the stirring type crystallizer (1) is connected with a centrifuge (12), and the centrifuge (12) is connected with a filter (13) through a pipeline with a filter pump; a refrigerating unit (6) capable of cooling the solution in the stirring crystallizer (1) to +5 ℃ to-5 ℃ is arranged on the stirring crystallizer (1), and a cooling liquid inlet and a cooling liquid outlet of the refrigerating unit (6) are respectively communicated with a cooling jacket (8) and a cooling liquid inlet and a cooling liquid outlet of a cooling coil (9) through pipelines. The device of the utility model has the advantages of large treatment capacity, small amine liquid loss, small pure water consumption, high alkali liquor utilization rate and high efficiency, and the investment is saved by more than 40%.
Description
Technical Field
The utility model relates to a flue gas organic amine method removes sulfur dioxide technical field, especially relates to organic amine liquid purification desalination edulcoration technical field, and specifically speaking is a sulfur dioxide's organic amine desulfurizer solution purification desalination edulcoration device.
Background
The flue gas discharged from various kilns or reactions often contains SO2Directly discharging to pollute the environment or cause economic loss of raw materials, and in recent years, the organic amine method is used for desulfurization due to SO2The method has the advantages of full recovery of resources, safety, environmental protection, energy conservation, high automation degree, no secondary pollution, desorption by using low-pressure saturated steam and the like, and is rapidly popularized and applied. But the SO in the flue gas is absorbed and desorbed by organic amine liquid (the mass content of the effective components is 10-30 percent, and the mass content of the sulfuric acid is 3.0-12 percent) of the desulfurizer2In the process, adsorption, absorption, side reaction and other processes can be generated to generate a large amount of sulfate, fluoride salt, acid mist, HF and HCl, and a large amount of dust and mud particles, thiosulfate, amine liquid condensation and decomposition products, elemental sulfur and the like are enriched; for example, the oxygen in the flue gas oxidizes sulfite in organic amine liquid of the desulfurizing agent to generate sulfate radicals and the like, side reaction occurs in the desorption high-temperature process to enable the sulfite or bisulfite to generate disproportionation reaction to generate sulfate radicals, thiosulfate radicals, elemental sulfur and the like, and when harmful substances in the organic amine desulfurizing agent are rapidly enriched, the consumption of desulfurization desorption steam is increased, and SO emission is caused2And (3) overproof pollution accidents even cause serious blockage in the absorption tower, serious corrosion of stainless steel metal materials and production stop of a desulfurization system in serious cases. The domestic organic amine desulphurization is in the difficulty of organic amine liquid purification, and becomes an important problem.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing an organic amine desulfurizer solution purification desalination edulcoration device of desorption sulfur dioxide to the problem that prior art exists.
The utility model aims at solving through the following technical scheme:
the utility model provides a desorption sulfur dioxide's organic amine desulfurizer solution purifies desalination edulcoration device, includes stirring formula crystallizer, its characterized in that: an organic amine liquid input pipe with a valve and an additive pipe are arranged on an arc cover at the upper part of the stirring type crystallizer, an outlet of a crystallizer discharge pipe at the bottom of the stirring type crystallizer is connected with a centrifugal machine, and the centrifugal machine is connected with a filter through a pipeline with a filter pump; the stirring crystallizer is provided with a refrigerating unit capable of cooling the solution in the stirring crystallizer to +5 ℃ to-5 ℃, and a cooling liquid inlet and a cooling liquid outlet of the refrigerating unit are respectively communicated with a cooling jacket and a cooling liquid inlet and a cooling liquid outlet of the cooling coil pipe through pipelines.
The cooling liquid outlet of the refrigerating unit is respectively communicated with the cooling jacket and the cooling liquid inlet of the cooling coil through a pipeline with a refrigerant circulating pump, and the cooling liquid inlet of the refrigerating unit is respectively communicated with the cooling jacket and the cooling liquid outlet of the cooling coil through pipelines.
The cooling liquid of the refrigerating unit adopts 25-35% glycol, 1-15% ethanol or pure water solution as secondary refrigerant.
The crystallizer discharge pipe is provided with two valves, and the crystallizer discharge pipe between the two valves is connected with the organic amine liquid input pipe through an amine liquid circulating pipe with a valve and an amine liquid circulating pump.
And the amine liquid circulating pipe is provided with a branch pipe capable of supplementing demineralized water.
The stirring speed of the stirring mechanism in the stirring crystallizer is 15-60 rpm.
The centrifugal machine is a four-foot damping vertical stainless steel belt cover type centrifugal machine or a pushing type horizontal stainless steel self-discharging centrifugal machine.
The filter is selected from a coconut shell type columnar granular activated carbon filter and a foaming type or fiber type filter with the precision not lower than 1.0 mu m.
The temperature of the organic amine liquid to be purified input by the organic amine liquid input pipe is 25-55 ℃.
Compared with the prior art, the utility model has the following advantages:
the utility model discloses an organic amine desulfurizer solution purifies desalination edulcoration device can detach harmful substance and impurity in the organic amine desulfurizer fast- -sulfate, fluoride salt, enrichment a large amount of dirt mud particulate matters, thiosulfate, amine liquid condensationAnd decomposer, simple substance sulfur and the like, has simple operation process, but quick and effective desalination and impurity removal, the cycle of impurity removal and salt removal is only 60-120 minutes, the treatment capacity is large, and the effective volume of the stirring crystallizer is 1.5m3、2.0m3、3.0m3、5.0m3、8.0m3(ii) a Compared with the traditional anion resin and cation resin exchange method and electrodialysis method, the loss of amine liquid is small, the consumption of pure water is small, the utilization rate of alkali liquor is high, and the investment is saved by more than 40%, so the method is suitable for popularization and application.
The utility model discloses a device is through waiting to purify organic amine liquid and sending into stirring cooling in the stirring formula crystallizer, add pure caustic soda and refined limestone powder, refined barium carbonate powder, diatomaceous earth, one kind or multiple combination in the active carbon, make through reducing organic amine solution temperature and take place space crystallization and absorption, with the sulfate, the fluoride salt goes out, with solid-state dust particulate matter, amine liquid condensation and decomposition thing, parcel such as simple substance sulphur adsorbs, the mixed solution that contains crystal thing and adsorbs the dust particulate matter is put into and is attached to spin-dry in the centrifuge of putting the filter bag, solid impurity and crystalline salt are separated out, the organic amine liquid that purifies the desalination edulcoration passes through filter precision filtration again and returns desulfurization system to clear water, thereby realize organic amine liquid purification activation, resume organic amine absorbs sulfur dioxide and desorption sulfur dioxide's activity.
Drawings
FIG. 1 is a schematic structural diagram of the organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide.
Wherein: 1-stirring type crystallizer; 2-organic amine liquid input pipe; 3-amine liquid recycle tube; 4-amine liquid circulating pump; 5-an additive pipe; 6-a refrigerating unit; 7-refrigerant circulating pump; 8-cooling jacket; 9-cooling coil pipe; 10-a stirring mechanism; 11-crystallizer discharge pipe; 12-a centrifuge; 13-Filter.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples.
As shown in fig. 1: a device for removing sulfur dioxide and salts and impurities from organic amine desulfurizer solution comprises a stirrer made of S31603 materialThe stirring type crystallizer 1 is characterized in that the stirring type crystallizer 1 comprises an inner container, a cooling jacket 8, a cooling coil pipe 9, a stirring mechanism 10, an integral arc cover, an observation manhole, a liquid level measurement device, a temperature measurement device, a pH value measurement device, a heat preservation device and the like; the effective volume of the stirred crystallizer is generally 1.5m3、2.0m3、3.0m3、5.0m3、8.0m3The stirring speed of the stirring mechanism 10 is 15rpm to 60 rpm. An organic amine liquid input pipe 2 with a valve and an additive pipe 5 are arranged on an arc cover at the upper part of the stirring crystallizer 1 so as to respectively input organic amine liquid to be purified and an additive for desalting and impurity removing; an outlet of a crystallizer discharge pipe 11 with a valve at the bottom of the stirring type crystallizer 1 is connected with a centrifuge 12, a centrifugal mother liquid outlet of the centrifuge 12 is connected with a filter 13 through a pipeline with a filter pump, and desalted organic amine liquid discharged from a liquid outlet of the filter 13 is sent to an amine desulphurization system; a refrigerating unit 6 capable of cooling the solution in the stirring crystallizer 1 to +5 ℃ to-5 ℃ is arranged on the stirring crystallizer 1, a cooling liquid outlet of the refrigerating unit 6 is respectively communicated with cooling liquid inlets of a cooling jacket 8 and a cooling coil 9 through a pipeline with a refrigerant circulating pump 7, and a cooling liquid inlet of the refrigerating unit 6 is respectively communicated with the cooling liquid outlets of the cooling jacket 8 and the cooling coil 9 through a pipeline. In addition, an amine liquid circulating pipe 3 with a valve and an amine liquid circulating pump 4 is connected between two valves on the crystallizer discharging pipe 11 and the organic amine liquid input pipe 2 to enable the solution in the stirring type crystallizer 1 to be circularly treated, and a branch pipe is added on the amine liquid circulating pipe 3 to supplement desalted water.
The utility model discloses an organic amine desulfurizing agent solution of desorption sulfur dioxide purifies the organic amine desulfurization solvent that acts on among the desalination edulcoration device is two amino dibasic hydroxyl class, molecular weight between 150 ~ 220, the active ingredient mass content is 10% ~ 30%, and sulphuric acid mass content is 3.0% ~ 12%'s organic matter class strong acid alkalescent substance.
The utility model discloses an organic amine desulfurizer solution of desorption sulfur dioxide purifies desalination edulcoration device use does:
A. inputting the organic amine liquid to be purified with the temperature of 25-55 ℃ into a stirring type crystallizer 1, and starting a stirring mechanism 10 with the rotating speed of 15-60 rpm;
B. the stirring mechanism 10 continuously stirs, and one or more of pure caustic soda and refined limestone powder, refined barium carbonate powder, diatomite and active carbon are added into the stirring crystallizer 1 as additives; the content of chloride ions in the added sodium carbonate is less than 50PPM, the sodium carbonate is added into the stirring type crystallizer 1 in a solution with the concentration of 30-50%, and the sodium carbonate is used for controlling the final pH value of the organic amine liquid in the stirring type crystallizer 1 to be 9-11 so as to remove iron ions, chromium ions, copper ions and the like in the solution through precipitation; the added refined limestone powder is used for removing fluorine ions by precipitation, and is used for controlling the fluorine ion content of the organic amine liquid in the stirring crystallizer 1 to be less than 30-100 mg/L, and the calcium carbonate content in the added refined limestone powder is more than 99 percent, and the particle fineness is less than 300 meshes and accounts for more than 70 percent; the added diatomite is used as a filter aid to improve the filtration efficiency of solid particles in the solution, the content of diatom in the adopted diatomite is more than 70 percent, the content of water insoluble substances is less than 0.5 percent, and the addition amount of the diatomite is 0.5-5.0 Kg/m3(ii) a The added active carbon is used for adsorbing macromolecular impurities condensed by amine molecules and colloidal substances of a solution system, the adopted active carbon is 20-50 meshes of coconut shell type active carbon powder, the adsorption capacity with developed pores is large, the active carbon can be repeatedly desorbed and used, and the addition amount of the active carbon is 0.5-3.0 Kg/m3(ii) a The added refined barium carbonate powder is used for precipitating and removing redundant sulfuric acid, so that the pH value of the solution reaches 8-9;
C. the stirring mechanism 10 continuously stirs, the refrigerating unit 6 is started to cool the solution in the stirring crystallizer 1 to +5 ℃ to-5 ℃, and the temperature is kept for 30min to 80min, so that the sodium sulfate in the solution is changed into Na2SO4·H2The O crystal is separated out without freezing, so that the effect of removing sulfate in the organic amine solution is achieved; calcium fluoride is separated out by precipitation and crystallization; organic matters in the solution are condensed, and micro-particles and the like are adsorbed and separated out by the active carbon;
D. opening an angle valve of the stirring type crystallizer 1, putting the solution into a centrifuge 12, and centrifugally drying;
E. and (3) collecting and pumping the centrifuged mother liquor into a filter 13 for filtering to obtain purified organic amine liquid, sending the purified organic amine liquid into an amine desulphurization system, and recovering the activity of absorbing sulfur dioxide and desorbing the sulfur dioxide by the purified organic amine liquid.
The pure caustic soda, the refined limestone powder, the diatomite, the active carbon and the refined barium carbonate powder are selected and matched according to the content of harmful substances contained in the organic amine liquid, wherein the pure caustic soda must be added, and one, two, three or all four of the refined limestone powder, the refined barium carbonate powder, the diatomite and the active carbon are selected and matched. When the pure caustic soda, the refined limestone powder, the refined barium carbonate powder, the diatomite and the active carbon are all added, the adding sequence is as follows: firstly, adding refined lime powder and refined barium carbonate powder in sequence, and adjusting the pH value of the solution to 8-9; adding sodium hydroxide to adjust the pH value of the solution to 9-11; finally, diatomite and active carbon are added in sequence.
The cooling liquid of the refrigerating unit 6 adopts 25-35% glycol, 1-15% ethanol or pure water solution as the secondary refrigerant. The adopted centrifugal machine 12 is a four-foot shock-absorption vertical stainless steel belt cover type centrifugal machine or a material-pushing horizontal stainless steel self-discharging type centrifugal machine, the centrifugal machine 13 adopts a corrosion-resistant and wear-resistant filter bag with high permeability and high permeability precision, and diatomite in the solution is unevenly dispersed and evenly attached to the surface of the filter bag of the centrifugal machine 13 in a filter aid mode so as to improve the filter precision of the filter bag. The filter 13 is selected from a coconut shell type columnar granular activated carbon filter, a foaming type or fiber type filter with the precision of 1.0 mu m or more, so as to filter out fine particles in the organic amine liquid, and when the solution passing resistance of the filter 13 exceeds 150KPa, the activated carbon or the filter element in the filter is replaced.
Example one
After a flue gas desulfurization process of a zinc slag rotary kiln of a certain company runs for one year by adopting an organic amine method, analyzing organic amine liquid (quality): 23% of organic amine main component, 3.0 pH value, 0.5g/L of particulate matter, 1.5 g/L of iron ion and 1.2 g/L of fluorine ion, the solution is black in sauce, the organic amine liquid can not be used as an absorbent any more, and the total amount is 40m3. Adopt the utility model provides an organic amine desulfurizer solution of desorption sulfur dioxide purifies desalination edulcoration device, and used stirring formula crystallizer 1's volume does2.0m3The liquid inlet temperature is 45 +/-5 ℃, and the advanced liquid is 1.6m3Turning on the stirring mechanism 10 (at a speed of 30 rpm); sequentially adding lime powder and refined barium carbonate powder to adjust the pH value to 8-9, adding pure caustic soda to adjust the pH value to 10.5, adding diatomite and activated carbon powder while adding, observing, sampling and analyzing, and finishing adding within 40 minutes; and (3) starting a refrigerating unit 6 to enable cooling liquid to circularly cool the solution in the crystallization tank of the stirring type crystallizer 1 to-3 ℃, keeping the temperature for 60min, then opening an angle valve to discharge the solution, allowing the solution to enter a centrifugal machine 12 for spin-drying, spraying a small amount of pure water to rinse crystals and solid substances, removing mixed crystals, collecting centrifugal mother liquor, pumping the collected centrifugal mother liquor into an activated carbon filter 13 for filtering to obtain purified organic amine liquid, sending the purified organic amine liquid into an amine desulfurization system, and recovering the activity of absorbing sulfur dioxide and desorbing sulfur dioxide.
In this way, 40m3When the organic amine liquid to be purified is completely purified, the main amine component in the purified organic amine liquid is about 26 percent, the pH value is 10.5, the content of particles is 30mg/L, the content of iron ions is 25mg/L, and the content of fluorine ions is 15mg/L, and the solution is light yellow and transparent, so that the activity of the product is recovered.
This embodiment has fully explained the utility model provides an organic amine desulfurizer solution of desorption sulfur dioxide purifies desalination edulcoration device's validity, has solved organic amine liquid and has purified the predicament.
The above embodiments are only for explaining the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea provided by the present invention all fall within the protection scope of the present invention; the technology not related to the utility model can be realized by the prior art.
Claims (8)
1. The utility model provides a desorption sulfur dioxide's organic amine desulfurizer solution purifies desalination edulcoration device, includes stirring formula crystallizer (1), its characterized in that: an upper arc cover of the stirring crystallizer (1) is provided with an organic amine liquid input pipe (2) with a valve and an additive pipe (5), an outlet of a crystallizer discharge pipe (11) at the bottom of the stirring crystallizer (1) is connected with a centrifuge (12), and the centrifuge (12) is connected with a filter (13) through a pipeline with a filter pump; the stirring crystallizer (1) is provided with a refrigerating unit (6) capable of cooling the solution in the stirring crystallizer (1) to +5 ℃ to-5 ℃, and a cooling liquid inlet and a cooling liquid outlet of the refrigerating unit (6) are respectively communicated with a cooling jacket (8) and a cooling liquid inlet and a cooling liquid outlet of a cooling coil (9) through pipelines.
2. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 1, characterized in that: and a cooling liquid outlet of the refrigerating unit (6) is respectively communicated with cooling liquid inlets of the cooling jacket (8) and the cooling coil (9) through a pipeline with a refrigerant circulating pump (7), and a cooling liquid inlet of the refrigerating unit (6) is respectively communicated with cooling liquid outlets of the cooling jacket (8) and the cooling coil (9) through pipelines.
3. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 1, characterized in that: the crystallizer discharge pipe (11) is provided with two valves, and the crystallizer discharge pipe (11) between the two valves is connected with the organic amine liquid input pipe (2) through an amine liquid circulating pipe (3) with the valves and an amine liquid circulating pump (4).
4. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 3, characterized in that: and a branch pipe capable of supplementing demineralized water is arranged on the amine liquid circulating pipe (3).
5. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 1, characterized in that: the stirring speed of the stirring mechanism (10) in the stirring crystallizer (1) is 15-60 rpm.
6. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 1, characterized in that: the centrifugal machine (12) is a four-foot shock-absorbing vertical stainless steel belt cover type centrifugal machine or a pushing horizontal stainless steel self-discharging type centrifugal machine.
7. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 1, characterized in that: the filter (13) is a coconut shell type columnar granular activated carbon filter or a foam type or fiber type filter with the precision not lower than 1.0 mu m.
8. The organic amine desulfurizer solution purification, desalination and impurity removal device for removing sulfur dioxide as claimed in claim 1, characterized in that: the temperature of the organic amine liquid to be purified, which is input by the organic amine liquid input pipe (2), is 25-55 ℃.
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