CN105664520A - Method, amine liquid crystallizer and device for removing sodium salt in organic amine liquid - Google Patents
Method, amine liquid crystallizer and device for removing sodium salt in organic amine liquid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a method, an amine liquid crystallizer and a device for removing sodium salt in an organic amine liquid. The method comprises steps as follows: Step one, the organic amine liquid which contains sodium ions and is desorbed by a desorption column is subjected to heat exchange treatment to be cooled to 30-35 DEG C; Step two, the organic amine liquid after heat exchange treatment is cooled to 0 DEG C or below, preferably, subzero 5 DEG C to 0 DEG C, cooling, precipitation by crystallization and sedimentation are performed simultaneously, and then a dilute salt amine liquid and a concentrated salt amine liquid containing crystal particles are obtained through separation; Step three, the concentrated salt amine liquid is concentrated and aged, so that crystal particles grow. The amine liquid crystallizer (2) is provided with a crystallization sedimentation zone (2A) and a concentration zone (2B). With adoption of the method, the amine liquid crystallizer and the device, sodium hydroxide and sodium salt such as sodium sulfate, sodium sulfite and the like which are introduced during ion exchange treatment of the organic amine liquid can be removed effectively, the content of sodium ions in the organic amine liquid is lower than 10 g/L, and the risk of crystallization blockage of sodium salt in the desorption column and a reboiler is reduced.
Description
Technical field
The present invention relates to flue gas desulfurization technique field, more specifically say, relate to a kind of amine method desulfurization of removingCirculation organic amine liquid in the apparatus and method of sodium salt.
Background technology
The industrial smoke that contains a large amount of sulfur dioxide can not directly enter in atmosphere, need to pass through purification placeAfter reason, just can discharge. Conventionally, adopt organic amine absorbent to carry out purified treatment to described flue gas. It is formerReason is to form and contain inferior sulfate radical, sulfurous acid after making sulfur-containing smoke gas carry out reverse contact with organic amine absorbentThe rich solution of the anion such as hydrogen root, sulfate radical, chlorine root. In rich solution with the shape such as inferior sulfate radical, bisulfiteThe organic amine salt that formula exists can be by carrying out heating desorption in desorber, discharges containing sulfur dioxideAcid high-temperature gas mixture body, then process condensation and gas-liquid separation can be reclaimed the sulfur dioxide gas of high concentrationBody, for sulfuric acid processed or sulphur etc. The organic amine absorbent obtaining after desorb is reused with right simultaneouslySulfur-containing smoke gas carries out circular treatment.
In organic amine desulfurization operation system, inevitably there is sulfate radical, inferior sulfate radical in organic amine liquidAccumulate Deng anion. At present, the most ion-exchanges that adopt of desulfurization producer are processed sulphur in organic amine liquidHydrochlorates etc., cause sodium ion in amine liquid constantly to accumulate, and sodium ion mass fraction can reach 22g/l, sulfate radical matterAmount mark can reach 96g/l, inferior sulfate radical mass fraction can reach 40g/l.
When employing ion-exchange is removed the thermal-stable salts such as the sulfate in organic amine liquid, inevitablyIntroduce sodium ion (regenerating with diluted sodium hydroxide solution), if the content of sodium ion acquires a certain degree,Because the operation pH scope of amine liquid is 4.2～5.8, sulfate radical, inferior sulfate radical concentration are higher, at sodium ionConcentration is under the situation of reduced levels, and amine liquid intermediate ion is long-pending is also very large, easily causes sulfate, AsiaDisulfate, sulphite and thiosulfate crystallization, will cause reboiler, desorber packing andThe obstruction of pipeline.
Summary of the invention
Technical problem solved by the invention is: overcome the organic amine liquid process ion after current desulfurization is resolvedAfter exchange is processed, in organic amine liquid, sodium salt accumulation easily causes the defect of the obstruction of desulfurizing tower, reboiler,A kind of apparatus and method that remove sodium salt in circulation organic amine liquid are provided.
The present invention takes out the organic amine liquid of desorber circulating slot, makes it enter heat exchanger, adopts circulation coldBut organic amine liquid is cooled to 30～35 DEG C by water, in this temperature range, sodium sulphate (sodium sulfite)Solubility is in a big way. Then the organic amine liquid after cooling is carried out to crystallisation by cooling, make organic amineLiquid temp is down to below 0 DEG C, separates out sodium sulfate crystal, and then twice ageing makes crystal grain thing rawLong, sedimentation separation crystals of sodium salt suspension enters centrifugal separator, isolates sodium sulfate crystal, filtrate andThe supernatant of amine liquid crystallizing tank returns to desulphurization system.
The present invention adopts the bypass of the absorption tower-Analytic Tower-ion exchange resin in flue gas treating process processProcess organic amine liquid, freeze crystallization can be removed the hydrogen that ion-exchange treatment organic amine liquid is introduced effectivelySodium oxide molybdena and sodium salt (sodium sulphate, sodium sulfite etc.), guarantee in organic amine liquid that sodium ions content is lower than 10g/L，Reduce the risk of sodium salt Crystallization Plugging in desorber, reboiler.
Specifically, the present invention proposes following technical scheme.
First aspect, the invention provides a kind of method that removes sodium salt in organic amine liquid, and the method comprises:
First step: make the organic amine liquid that contains sodium ion carry out heat exchange processing, cool to 30-35 DEG C;
Second step: heat exchange organic amine liquid after treatment is cooled to below 0 DEG C, preferably-5 DEG C to 0 DEG C,Realize crystallisation by cooling and sedimentation simultaneously, then separate, obtain rare salt amine liquid and the dense salt that contains crystal grain thingAmine liquid; And
Third step: dense salt amine liquid is concentrated and ageing, make the growth of crystal grain thing.
Preferably, wherein, in second step, crystal grain thing volume particle size distribution in described dense salt amine liquidBetween 0.1-0.4mm.
Preferably, wherein, in second step, described organic amine liquid is taking flow as 0.5-1.2m3/ h, stopsTime is 2.5-4.5h, carries out crystallisation by cooling and sedimentation simultaneously.
Preferably, wherein, in second step, the organic amine liquid that contains sodium ion with first step organicAmine liquid stereometer, described dense salt amine liquid accounts for the 10-20% of organic amine liquid total amount.
Preferably, wherein, in third step, described dense salt amine liquid carries out twice ageing.
Preferably, wherein, described dense salt amine liquid carries out ageing for the first time at-5 DEG C to 0 DEG C, and at-1 DEG CCarry out ageing for the second time to 2 DEG C.
Preferably, wherein, in amine liquid crystallizing tank 2, carry out cooling, crystallization and sedimentation, heat exchange placeOrganic amine liquid after reason enters in the central distribution cylinder 21 of amine liquid crystallizing tank 2, with 2 crystallizations of amine liquid crystallizing tankThe crystal salt of district 2A bottom is mixed at hybrid junctions crystalline region 2A-1, and mixed liquor is through central distribution cylinder 21 inwallsAnd the runner between second baffle 24 enters sedimentation separation district 2A-2, separate and obtain rare salt amine liquid and contain brilliantThe dense salt amine liquid of body particle.
Preferably, wherein, described dense salt amine liquid carries out gravitational settling at amine liquid crystallizing tank 2 enrichment region 2BAnd ageing for the first time.
Preferably, wherein, said method also comprises the 4th step, by the dense salt amine liquid after ageing through fromThe heart separates centrifugal dehydration treatment, removes remaining organic amine liquid in crystal salt.
Second aspect, the invention provides a kind of for removing the amine liquid crystallizing tank 2 of organic amine liquid sodium salt,This amine liquid crystallizing tank 2 is provided with crystallization decanting zone 2A and enrichment region 2B, and described enrichment region 2B is located at crystallizationDecanting zone 2A below;
Described crystallization decanting zone 2A is provided with central distribution cylinder 21; Described crystallization decanting zone 2A is divided into and is located atHybrid junctions crystalline region 2A-1 in central distribution cylinder 21 and be located at the sedimentation crystal region outside central distribution cylinder 212A-2。
Preferably, wherein, in described central distribution cylinder 21, be provided with crystallization mixer 22.
Preferably, wherein, described central distribution cylinder 21 inwalls are having at nearly central distribution cylinder 21 along circumferenceMachine amine liquid porch is provided with the first baffle plate 23, and its one end is fixed on central distribution cylinder 21 inwalls, anotherEnd is with raised section upwards.
Preferably, wherein, described central distribution cylinder 21 is interior is provided with second baffle 24 along circumference, and describedTwo baffle plate 24 its cross sections are L-type, and remain with space with central distribution cylinder 21 inwalls.
The third aspect, the invention provides a kind ofly for removing the device of organic amine liquid sodium salt, is provided with and complies withThe heat exchanger 1 of inferior connection and the amine liquid crystallizing tank 2 as described in above-mentioned any one.
Preferably, wherein, described device is also provided with successively salt storagetank 3 Hes after amine liquid crystallizing tank 2Centrifuge 4.
Adopt technical scheme of the present invention at least to there is following beneficial effect: the present invention processes desorber and carriesOrganic amine liquid in groove, before processing, the density of organic amine liquid is 1020～1050kg/m3, sodium ions content is15～25g/l, after crystallization of the present invention and desalting processing, having obtained main content is saltcake (Na2SO4·10H2O) salt. The sodium ions content of the rare salt amine of gained of the present invention liquid is below 10g/L.
Brief description of the drawings
Fig. 1 the present invention removes the device structure schematic diagram of sodium salt in organic amine liquid.
The structural representation of Fig. 2 amine liquid of the present invention crystallizing tank.
Detailed description of the invention
Content for a better understanding of the present invention, below in conjunction with specifically having implemented technical side of the present inventionCase is described further, but concrete embodiment is not the restriction that the present invention is done.
Sulfur-containing oxide (SO2And SO3) flue gas or other industrial waste gases need to be after purified treatmentJust can discharge. In prior art, adopt organic amine liquid to carry out purified treatment to described flue gas, concreteSulfur-containing smoke gas carries out reverse contact in absorption tower with organic amine liquid, form and contain inferior sulfate radical, sulfurous acidThe rich solution of the anion such as hydrogen root, sulfate radical, chlorine root, flue gas after treatment discharges greatly after other post processingsGas. Rich solution is heated in Analytic Tower to parsing, in rich solution, deposit with the form such as inferior sulfate radical, bisulfiteOrganic amine salt can, by heating desorption in desorber, discharge containing sulfur dioxide sour gasHigh-temperature gas mixture body, then passes through condensation and gas-liquid separation, can reclaim the sulfur dioxide gas of high concentration,Be used for sulfuric acid processed or sulphur etc. Meanwhile, adopt ion-exchange to process in organic amine liquid sulfate etc., makeBecome sodium ion in amine liquid constantly to accumulate. Ion exchange resin column is strong basic type anion-exchange resin post, excellentSelect the strong basic type anion-exchange resin of polystyrene, for example D201 macroreticular resin, 201*4 strong basicity the moonIon exchange resin, 201*7 strongly basic anionic resin. After desorb ion exchange resin treatment, obtainOrganic amine liquid reuse that described flue gas is carried out to circular treatment.
Usually, the reboiler of the desorber of amine method desulphurization system adopts Natural Circulation thermal siphon mode, thenThe device bottom temp that boils is the highest, can reach 115 DEG C. Now, the solubility of sodium sulphate, sodium sulfite is in phaseTo lower level, easily cause crystalline particle to separate out. And flow velocity is lower in reboiler, cause crystallizationGrain accumulation. Therefore, often cause reboiler to stop up. The dissolving in the aqueous solution of sodium sulphate and sodium sulfiteDegree is respectively in table 1,2.
Table 1 sodium sulphate solubility in the aqueous solution
Table 2 sodium sulfite solubility in the aqueous solution
| Temperature/DEG C | 0.0 | 10.0 | 20.0 | 30.0 | 40.0 | 60.0 | 90.0 | 100.0 |
| Solubility/g100g-1 | 14.4 | 19.5 | 26.3 | 35.5 | 37.2 | 32.6 | 29.4 | 27.9 |
| Na+Concentration/g100g-1 | 5.3 | 7.1 | 9.6 | 13 | 13.6 | 11.9 | 10.7 | 10.2 |
The concentration that adopts GB GB/T11904-89 test potassium ion and sodium ion, solution is 15 DEG C of conditionsUnder, when organic amine liquid concentration is 15wt%, 20wt%, the saturated content of sodium ion in liquor is respectively 9.7gl-1、6.5g·l-1; Solution under 40 DEG C of conditions, when organic amine liquid concentration is 15wt%, 20wt%, 25wt%,The saturated content of sodium ion in liquor is respectively 68.0gl-1、48.6g·l-1、43.7g·l-1. As can be seen here, operationThe saturated content of sodium salt in organic amine liquid will be far below the aqueous solution under uniform temp condition, therefore, and sodium saltAccumulation easily cause the obstruction of desulfurizing tower, device. Sal glauberi is 0 as can be seen from Table 1 and Table 2DEG C solubility is very low, and sodium sulfite solubility is slightly high, and the amine liquid ion concentration of inferior sulfate radical of desorb significantlyReduce, separate out sal glauberi so the rich amine liquid of poor amine liquor ratio is more suitable for crystallisation by cooling.
The present invention is on the above basis of finding, controlling organic amine liquid degree of supercooling is 1-3 DEG C, makes salt placeJie's Yu stable state, guarantees that the particle of salt crystallization is closely knit, and the volume particle size distribution of crystalline particle is mainBetween 0.1-0.4mm, can realize effective sedimentation, obtain sodium ions content and be rare below 10g/LSalt amine liquid. Then, the dense salt amine liquid that the present invention obtains sedimentation, carrying out twice ageing, makes crystal grainThing growth, has effectively removed the salt in organic amine liquid, and salt rejection rate reaches 30%～60%.
" sulfur-containing smoke gas " of the present invention refers to sulfur-containing oxide (SO2And SO3) flue gas or other worksIndustry waste gas. " desulfurization " of the present invention refers to from flue gas or other industrial waste gases and removes oxysulfide(SO2). " organic amine " of the present invention refers to that routine can be applied to the organic of organic amine wet desulphurizationMaterial, includes but not limited to monoethanolamine, diethanol amine, methyl diethanolamine etc. Of the present invention " haveMachine amine salt " refer to the sodium salt of the organic amine existing with inferior sulfate radical, bisulfite, sulfate radical form." degree of supercooling " of the present invention refers to the theoretical crystallization temperature of sodium sulphate and the difference of actual crystallization temperature,Be that actual crystallization temperature will be lower than theoretical crystallization temperature, both differences become degree of supercooling.
Below in conjunction with equipment, describe sodium salt in removal amine method desulphurization circulating organic amine liquid of the present invention in detailMethod. The method comprises the steps:
First step: make the organic amine liquid after desorber dissection process carry out heat exchange processing, cool to30-35 DEG C. Organic amine liquid temp after described desorber dissection process is 70-90 DEG C, sodium in organic amine liquidIon concentration is 15-25g/L. This step adopts aqueous medium in heat exchanger, to carry out heat exchange processing.
Concrete, the present invention get desorber delivery chute the about internal circulating load of organic amine liquid (volume) 5%～10% (approximately 15～25m3/ h, preferred about 15m3/ h), make organic amine liquid enter plate from hot amine liquid entrance 11Formula heat exchanger 1, after heat exchange is processed, leaves plate type heat exchanger 1 from cold amine liquid outlet 12, through plateFormula heat exchanger 1 is processed, and organic amine liquid is cooled to 30～35 DEG C. Cooling water enters from cooling water inlet 13Plate type heat exchanger 1, after organic amine liquid sufficient heat exchange, leaves plate-type heat-exchange from coolant outlet 14Device 1. Cooling water temperature rises to 28～32 DEG C by 25～28 DEG C, and the circulating cooling water yield is 150～180m3/h。It should be noted that and the invention is not restricted to use plate type heat exchanger, other can complete heat exchange processHeat exchanger all can be applied to the present invention. The present invention's plate type heat exchanger used is commercial conventional equipment.
Second step: heat exchange organic amine liquid after treatment is cooled to below 0 DEG C, preferably-5 DEG C to 0 DEG C,Realize crystallisation by cooling and sedimentation simultaneously, then separate, obtain rare salt amine liquid and the dense salt that contains crystal grain thingAmine liquid. In crystallisation by cooling and infall process, the sodium sulphate in organic amine liquid or sodium sulfite are in supersaturationState, makes sodium salt in organic amine liquid (being mainly sal glauberi) crystallization. Salt is steady in being situated betweenDetermine state, guarantee that the particle of salt crystallization is closely knit, the volume particle size distribution of crystalline particle 0.1～Between 0.4mm, can realize sedimentation effectively. The setting temperature of anhydrous sodium sulfate is about-1 DEG C, solutionWhen temperature is-5 DEG C, roughly degree of supercooling is 3 DEG C. Amine liquid is mainly that mixture and salinity kind are more, hasMachine amine has the trend that increases degree of supercooling. In addition, for crystallization, be generally divided into stable region, metastable fixedDistrict and range of instability, can realize spontaneous crystallization in range of instability; Sub-stable region needs crystal seed introducing just canCrystallization; Can not realize crystallization in stable region.
Concrete, as depicted in figs. 1 and 2, amine liquid crystallizing tank 2 has two functional areas: crystallization decanting zone2A and enrichment region 2B, enrichment region 2B is positioned at crystallization decanting zone 2A below. Described crystallization decanting zone 2ABe provided with central distribution cylinder 21; Described crystallization decanting zone 2A is divided into the hybrid junctions of being located in central distribution cylinder 21Crystalline region 2A-1 and be located at the sedimentation crystal region 2A-2 outside central distribution cylinder 21.
First step heat exchange organic amine Ye Cong after treatment center distributing barrel 21 enters amine liquid crystallizing tank 2Crystallization decanting zone 2A. The media such as refrigerant such as liquefied ammonia, liquid nitrogen or propane enter chuck from refrigerant entrance 27Cooling amine liquid crystallizing tank 2 leaves amine liquid crystallizing tank 2 from refrigerant exit 28 after heat exchange. Organic amine liquidFlow at the crystallization decanting zone of amine liquid crystallizing tank 2 2A is 0.5～1.2m3/ h, the time of staying is 2.5～4.5h, and be cooled to-5 DEG C to 0 DEG C, realizes separating of rare salt amine liquid and dense salt amine liquid. More specifically,Central distribution cylinder 21 bottoms, along the direction away from center line, expand outwardly gradually, make central distribution cylinder21 bottoms are bell mouth shape. In central distribution cylinder 21, be provided with crystallization mixer 22. Central distribution cylinder 21Interiorly be provided with the first baffle plate 23 and second baffle 24 along circumference. The setting position of the first baffle plate 23 approaches centerThe organic amine liquid entrance of distributing barrel 21, and one end is fixed on central distribution cylinder 21 inwalls, other end bandHave raised section upwards, the organic amine liquid that makes to join central distribution cylinder 21 is to central distribution cylinder 21Zone line flows. Second baffle 24 its cross sections are L-type, and retain with central distribution cylinder 21 inwallsHave living space, flow for organic amine liquid. Heat exchange organic amine Ye Cong after treatment center distributing barrel 21 enters amineLiquid crystallizing tank 2, enters hybrid junctions crystalline region 2A-1 through the first baffle plate 23, under mechanical agitation,The partially crystallizable salt of amine liquid crystallizing tank 2 hybrid junctions crystalline region 2A-1 bottoms enters central distribution cylinder 21 and newly entersOrganic amine liquid mixes, and mixed liquor, by the passage between central distribution cylinder 21 inwalls and second baffle 24, entersSedimentation separation district 2A-2. Because 2A-2 area in sedimentation separation district expands tens times rapidly, rare salt amine liquid is from rareAmine liquid crystallizing tank 2 is discharged in salt amine liquid outlet 25.
Rare salt amine liquid is collected by underground amine liquid feeder, turns back to the poor amine tank of desulfurization, flows out the crystallization of amine liquidRare salt amine liquid of tank 2 is-2 DEG C～0 DEG C amine liquid that salt is saturated, and sodium ions content is below 10g/L. ContainThe dense salt amine liquid sedimentation of crystal grain thing enters the enrichment region 2B of amine liquid crystallizing tank 2 bottoms. With first stepOrganic amine liquid stereometer after desorber dissection process, described dense salt amine liquid accounts for organic amine liquid total amount10-20％。
Third step: dense salt amine liquid is concentrated and ageing, make the growth of crystal grain thing.
Dense salt amine liquid, at enrichment region 2B, stops 0.5～1.5h at-5 DEG C to 0 DEG C temperature, at enrichment region 2BCrystal salt is further compressed, and squeezes the Free water of crystal salt, salt is fully concentrated, saltPart cycles of concentration is 5～10 times. Concentrated dense salt amine liquid leaves amine liquid crystallizing tank from dense salt amine liquid outlet 262。
Carried by pump through amine liquid crystallizing tank 2 concentrated dense salt amine liquid, enter salt from dense salt amine liquid entrance 31Part storagetank 3, enters chuck by media such as refrigerant such as liquefied ammonia, liquid nitrogen or propane from refrigerant entrance 32 coldBut salt storagetank 3 leaves salt storagetank 3 from refrigerant exit 33 after heat exchange. Salt storagetankIn 3, maintaining dense salt amine liquid temp is-1 DEG C～2 DEG C, and the time of staying 1～2h impels crystalline particle thing to enter oneStep ageing and growth. Then adopt high-pressure delivery pump (the about 7MPa of for example lift) by dense salt amine liquid from amineCentrifuge 4 is sent in liquid outlet 34, carries out the de-liquid of salt, and the main component of discharge centrifuge salt is saltcake,Free moisture approximately 5%. Filtrate turns back to the poor amine tank of desulfurization after collecting. Carry out centrifugal at centrifuge 4Before processing, preferably adopt water to carry out carrying out washing treatment.
The refrigerant that amine liquid crystallizing tank 2 and salt storagetank 3 are discharged for example in ammonia equipment 5 through gas-liquid separation,Compression, after condensation process, then return to amine liquid crystallizing tank 2 and salt storagetank 3 carries out cooling processing.Gas-liquid separation, compression, condensing steps gas-liquid separator used, compressor, condenser, and storage tankBe conventional commercially available equipment.
Another preferred embodiment in, can adopt the mode of freezer to replace the use of refrigerant,Put into freezer by amine liquid crystallizing tank 2 entirety.
Table 3
In the following Examples and Comparative Examples, the organic amine liquid that contains sodium ion is that following method makes.Sulfur-containing smoke gas consists of: SO2：6000～10000mg/Nm3，SO3：190～260mg/Nm3；O2：18％～19％wt；H2O：90～120g/Nm3；NxO：150～250mg/Nm3, all the other are nitrogen.
Sulfur-containing smoke gas desulfurization: adopt organic amine liquid to process sulfur-containing smoke gas. By organic amine liquid from absorbTower top end spray, sulfur-containing smoke gas passes into from bottom, absorption tower, and control liquid-gas ratio is 6.75～7.71kg/m3，Fume desulfurizing agent contacts with sulfur-containing smoke gas is reverse, and the gas being cleaned enters atmosphere through tower top, has absorbedSO2Organic amine liquid be called rich solution, by entering rich solution groove at the bottom of tower.
Desorb: by the rich solution obtaining from the rich solution groove on absorption tower with 230～290m3The flow of/h is by changingHot device preheating, then from desorber top spray, rich solution partial solution in desorber is inhaled. At the bottom of desorberThere is reboiler, in reboiler, be heated to 115 DEG C of left and right desorb again, the liquid stream after desorbEnter desorption apparatus bottom, the desorption gas of high temperature and steam are discharged from the top of desorber, then enterCondenser and vapour liquid separator, be cooled in stripping gas and return to desorber with the condensed water of separating,The purer high temperature SO arriving2Gas, sends into next procedure. After rich solution desorb, be called poor amine liquid, large portionDivide poor amine liquid again to get back to absorption tower, the poor amine liquid of fraction enters poor amine tank, the organic amine liquid warp of poor amine tankCross after strong base resin anion (R.A.) (D201 macroreticular resin) removes thermal-stable salt and enter absorption tower.
After above-mentioned sulfur-containing smoke gas desulfurization and parsing step cycle 3 times, get the organic amine in desorber delivery chuteLiquid is as the raw material of following embodiment and comparative example, and in this organic amine liquid, the concentration of organic amine is18wt%～20wt%, the density of organic amine liquid is 1020～1050kg/m3, approximately 80 DEG C of organic amine liquid temps,Na ion concentration is 15-25g/L.
Embodiment 1
Get the organic amine liquid in desorber delivery chute, flow is 15m3/ h, the density of organic amine liquid is1020kg/m3, approximately 80 DEG C of organic amine liquid temps, sodium ions content is 15g/L. Adopt as shown in Figure 1Device processes organic amine liquid.
Organic amine liquid enters plate type heat exchanger 1 from hot amine liquid entrance 11, after heat exchange is processed, from cold aminePlate type heat exchanger 1 is left in liquid outlet 12, processes through plate type heat exchanger 1, and organic amine liquid is cooled to 30DEG C. Cooling water enters plate type heat exchanger 1 from cooling water inlet 13, after organic amine liquid sufficient heat exchange,Leave plate type heat exchanger 1 from coolant outlet 14. Cooling water temperature rises to 28～32 DEG C by 25～28 DEG C,The circulating cooling water yield is 150m3/h。
The crystallization sedimentation that heat exchange organic amine Ye Cong after treatment center distributing barrel 21 enters amine liquid crystallizing tank 2District 2A. Organic amine liquid is 0.5m/h at the flow velocity of the crystallization decanting zone of amine liquid crystallizing tank 2 2A, when stopBetween be 2.5h, and be cooled to (5) DEG C, the degree of supercooling that makes organic amine liquid is 3 DEG C, crystalline volume granularityBe distributed as between 0.1-0.4mm. Rare salt amine liquid is collected by the collecting tank of amine liquid crystallizing tank 2, turns back to de-The poor amine tank of sulphur, the rare salt amine liquid sodium ions content that flows out amine liquid crystallizing tank 2 is 7.5g/L. Containing crystalThe dense salt amine liquid sedimentation of grain thing enters the enrichment region 2B of amine liquid crystallizing tank 2 bottoms.
Dense salt amine liquid is (5) DEG C in enrichment region 2B holding temperature, and time of staying 0.5h, at enrichment region 2BCrystal salt is further compressed, and squeezes the Free water of crystal salt, salt is obtained fully concentrated and oldChange, salt cycles of concentration is 5 times. Concentrated dense salt amine liquid leaves the crystallization of amine liquid from dense salt amine liquid outlet 24Tank 2
Carried by pump through amine liquid crystallizing tank 2 concentrated dense salt amine liquid, enter salt from dense salt amine liquid entrance 31Storagetank 3, enters the cooling salt storagetank 3 of chuck by refrigerant liquefied ammonia from refrigerant entrance 32, through heat exchangeAfter leave salt storagetank 3 from ammonia outlet 33. In salt storagetank 3, maintaining dense salt amine liquid temp is(1) DEG C, time of staying 1h, impels the further ageing of crystalline particle thing and growth. Then adopt high pressure defeatedSend pump (the about 7MPa of for example lift) that dense salt amine liquid is sent into centrifuge 4, carry out the de-liquid of salt, discharge fromThe main component of scheming salt is saltcake, free moisture 4.5%. Filtrate turns back to the poor of desulfurization after collectingAmine tank. The salt rejection rate of surveying organic amine liquid by Hypo-sensitve line and barium sulfate precipitate titration is 65.91%.Hypo-sensitve line is surveyed the instrument that in amine liquid, Na ion concentration uses: 1. AA-7020 atomic absorption spectrophotometry lightDegree meter (Beijing DongXi Analytical Instrument Co., Ltd); 2. sodium hollow cathode lamp (Beijing thing analytical instrumentCo., Ltd.
Embodiment 2
Get the organic amine liquid in desorber delivery chute, flow is 15m3/ h, the density of organic amine liquid is1050kg/m3, approximately 80 DEG C of organic amine liquid temps, sodium ions content is 22g/L. Adopt as shown in Figure 1Device processes organic amine liquid.
Organic amine liquid enters plate type heat exchanger 1 from hot amine liquid entrance 11, after heat exchange is processed, from cold aminePlate type heat exchanger 1 is left in liquid outlet 12, processes through plate type heat exchanger 1, and organic amine liquid is cooled to 35DEG C. Cooling water enters plate type heat exchanger 1 from cooling water inlet 13, after organic amine liquid sufficient heat exchange,Leave plate type heat exchanger 1 from coolant outlet 14. Cooling water temperature rises to 28～32 DEG C by 25～28 DEG C,The circulating cooling water yield is 180m3/h。
Heat exchange organic amine liquid after treatment enters the crystallization decanting zone 2A of amine liquid crystallizing tank 2 from central tube 21.Organic amine liquid is 1.2m/h at the flow velocity of the crystallization decanting zone of amine liquid crystallizing tank 2 2A, and the time of staying is4.5h, and be cooled to 0 DEG C, the degree of supercooling that makes organic amine liquid is 1 DEG C, crystalline volume size distribution isBetween 0.1-0.4mm. Rare salt amine liquid is collected by the collecting tank of amine liquid crystallizing tank 2, turns back to the poor of desulfurizationAmine tank, the rare salt amine liquid sodium ions content that flows out amine liquid crystallizing tank 2 is 17g/L. Containing crystal grain thingThe sedimentation of dense salt amine liquid enters the enrichment region 2B of amine liquid crystallizing tank 2 bottoms.
Dense salt amine liquid is 0 DEG C in enrichment region 2B holding temperature, and time of staying 1.5h concentrates to abundant, saltPart cycles of concentration is 10 times. Concentrated dense salt amine liquid leaves amine liquid crystallizing tank 2 from dense salt amine liquid outlet 24
Carried by pump through amine liquid crystallizing tank 2 concentrated dense salt amine liquid, enter salt from dense salt amine liquid entrance 31Storagetank 3, enters the cooling salt storagetank 3 of chuck by refrigerant liquefied ammonia from refrigerant entrance 32, through heat exchangeAfter leave salt storagetank 3 from ammonia outlet 33. In salt storagetank 3, maintaining dense salt amine liquid temp is2 DEG C, time of staying 2h, impels the further ageing of crystalline particle thing and growth. Then adopt high-pressure deliveryPump (the about 7MPa of for example lift) is sent dense salt amine liquid into centrifuge 4, carries out the de-liquid of salt, discharges centrifugalThe main component of machine salt is saltcake, free moisture 2.3%. Filtrate turns back to the poor amine of desulfurization after collectingTank. The salt rejection rate of actual measurement amine liquid is 22.73%.
Comparative example 1
Get the organic amine liquid in desorber delivery chute, flow is 15m3/ h, the density of organic amine liquid is1050kg/m3, approximately 80 DEG C of organic amine liquid temps, sodium ions content is 22g/L. Adopt as shown in Figure 1Device processes organic amine liquid.
Organic amine liquid enters plate type heat exchanger 1 from hot amine liquid entrance 11, after heat exchange is processed, from cold aminePlate type heat exchanger 1 is left in liquid outlet 12, processes through plate type heat exchanger 1, and organic amine liquid is cooled to 35DEG C. Cooling water enters plate type heat exchanger 1 from cooling water inlet 13, after organic amine liquid sufficient heat exchange,Leave plate type heat exchanger 1 from coolant outlet 14. Cooling water temperature rises to 28～32 DEG C by 25～28 DEG C,The circulating cooling water yield is 180m3/h。
Heat exchange organic amine liquid after treatment enters the crystallization decanting zone 2A of amine liquid crystallizing tank 2 from central tube 21.Organic amine liquid is 1.3m/h at the flow velocity of the crystallization decanting zone of amine liquid crystallizing tank 2 2A, and the time of staying is 2h,And be cooled to 0 DEG C. Rare salt amine liquid is collected by the collecting tank of amine liquid crystallizing tank 2, turns back to the poor of desulfurizationAmine tank, the rare salt amine liquid sodium ions content that flows out amine liquid crystallizing tank 2 is 19g/L. Containing crystal grain thingThe sedimentation of dense salt amine liquid enters the enrichment region 2B of amine liquid crystallizing tank 2 bottoms.
Dense salt amine liquid is 0 DEG C in enrichment region 2B holding temperature, time of staying 1.5h, and salt cycles of concentration is10 times. Concentrated dense salt amine liquid leaves amine liquid crystallizing tank 2 from dense salt amine liquid outlet 24
Carried by pump through amine liquid crystallizing tank 2 concentrated dense salt amine liquid, enter salt from dense salt amine liquid entrance 31Storagetank 3, enters the cooling salt storagetank 3 of chuck by refrigerant liquefied ammonia from refrigerant entrance 32, through heat exchangeAfter leave salt storagetank 3 from ammonia outlet 33. In salt storagetank 3, maintaining dense salt amine liquid temp is2 DEG C, time of staying 2h, impels the further ageing of crystalline particle thing and growth. Then adopt high-pressure deliveryPump (the about 7MPa of for example lift) is sent dense salt amine liquid into centrifuge 4, carries out the de-liquid of salt, discharges centrifugalThe main component of machine salt is saltcake, free moisture 2.1%. Filtrate turns back to the poor amine of desulfurization after collectingTank. The salt rejection rate of actual measurement amine liquid is 13.64%.
Comparative example 2
Get the organic amine liquid in desorber delivery chute, flow is 15m3/ h, the density of organic amine liquid is1050kg/m3, approximately 80 DEG C of organic amine liquid temps, sodium ions content is 22g/L. Adopt as shown in Figure 1Device processes organic amine liquid.
Organic amine liquid enters plate type heat exchanger 1 from hot amine liquid entrance 11, after heat exchange is processed, from cold aminePlate type heat exchanger 1 is left in liquid outlet 12, processes through plate type heat exchanger 1, and organic amine liquid is cooled to 35DEG C. Cooling water enters plate type heat exchanger 1 from cooling water inlet 13, after organic amine liquid sufficient heat exchange,Leave plate type heat exchanger 1 from coolant outlet 14. Cooling water temperature rises to 28～32 DEG C by 25～28 DEG C,The circulating cooling water yield is 180m3/h。
Heat exchange organic amine liquid after treatment enters the crystallization decanting zone 2A of amine liquid crystallizing tank 2 from central tube 21.Organic amine liquid is 1.2m/h at the flow velocity of the crystallization decanting zone of amine liquid crystallizing tank 2 2A, and the time of staying is4.5h, and be cooled to 1 DEG C. Rare salt amine liquid is collected by the collecting tank of amine liquid crystallizing tank 2, turns back to desulfurizationPoor amine tank, the rare salt amine liquid sodium ions content that flows out amine liquid crystallizing tank 2 is 22g/L. Dense salt amine liquid is heavyThe enrichment region 2B that enters amine liquid crystallizing tank 2 bottoms falls.
Dense salt amine liquid is 1 DEG C in enrichment region 2B holding temperature, time of staying 1.5h. Dense salt amine liquid is from dense saltAmine liquid crystallizing tank 2 is left in amine liquid outlet 24
Carried by pump through amine liquid crystallizing tank 2 concentrated dense salt amine liquid, enter salt from dense salt amine liquid entrance 31Storagetank 3, enters the cooling salt storagetank 3 of chuck by refrigerant liquefied ammonia from refrigerant entrance 32, through heat exchangeAfter leave salt storagetank 3 from ammonia outlet 33. In salt storagetank 3, maintaining dense salt amine liquid temp is2 DEG C, time of staying 2h. Then adopt high-pressure delivery pump (the about 7MPa of for example lift) that dense salt amine liquid is sentEnter centrifuge 4, carry out the de-liquid of salt. Do not obtain centrifugal salt. Filtrate turns back to desulfurization after collectingPoor amine tank. The salt rejection rate of actual measurement organic amine liquid is 0%.
Claims (14)
1. a method that removes sodium salt in organic amine liquid, the method comprises:
First step: make the organic amine liquid that contains sodium ion carry out heat exchange processing, cool to 30-35 DEG C;
Second step: heat exchange organic amine liquid after treatment is cooled to below 0 DEG C, preferably-5 DEG C to 0 DEG C,Realize cooling, crystallization and sedimentation simultaneously, then separate, obtain rare salt amine liquid with containing crystal grain thingDense salt amine liquid; And
Third step: dense salt amine liquid is concentrated and ageing, make the growth of crystal grain thing.
2. method according to claim 1, is characterized in that, in second step, and described dense salt amineIn liquid, crystal grain thing volume particle size distribution is between 0.1-0.4mm.
3. method according to claim 1 and 2, is characterized in that, in second step, described in haveMachine amine liquid is taking flow as 0.5-1.2m3/ h, the time of staying is 2.5-4.5h, carries out crystallisation by cooling and heavy simultaneouslyFall.
4. according to the method described in claim 1-3 any one, it is characterized in that, in second step, withThe organic amine liquid stereometer that first step contains sodium ion, described dense salt amine liquid accounts for organic amine liquid total amount10-20％。
5. according to the method described in claim 1-4 any one, it is characterized in that, in third step, instituteState dense salt amine liquid and carry out twice ageing.
6. method according to claim 5, is characterized in that, described dense salt amine liquid is at-5 DEG C to 0 DEG CCarry out ageing for the first time, and carry out ageing for the second time at-1 DEG C to 2 DEG C.
7. method according to claim 1, is characterized in that, in amine liquid crystallizing tank (2), entersCooling, the crystallization of row and sedimentation, heat exchange organic amine liquid after treatment enter amine liquid crystallizing tank (2) inIn heart distributing barrel (21), mixing with the crystal salt of amine liquid crystallizing tank (2) crystal region (2A) bottomCrystal region (2A-1) mixes, mixed liquor through central distribution cylinder (21) inwall and second baffle (24) itBetween runner enter sedimentation separation district (2A-2), separate and obtain rare salt amine liquid and dense containing crystal grain thingSalt amine liquid.
8. method according to claim 7, is characterized in that, described dense salt amine liquid is in the crystallization of amine liquidTank (2) enrichment region (2B) carries out gravitational settling and ageing for the first time.
9. one kind for removing the amine liquid crystallizing tank (2) of organic amine liquid sodium salt, it is characterized in that,This amine liquid crystallizing tank (2) is provided with crystallization decanting zone (2A) and enrichment region (2B), described concentratedDistrict (2B) is located at below, crystallization decanting zone (2A);
Described crystallization decanting zone (2A) is provided with central distribution cylinder (21); Described crystallization decanting zone (2A)Be divided into and be located at the hybrid junctions crystalline region (2A-1) in central distribution cylinder (21) and be located at central distribution cylinder(21) outer sedimentation crystal region (2A-2).
10. amine liquid crystallizing tank according to claim 9 (2), is characterized in that, described inIn heart distributing barrel (21), be provided with crystallization mixer (22).
11. according to the amine liquid crystallizing tank (2) described in claim 9 or 10, it is characterized in that, described inCentral distribution cylinder (21) inwall is provided with in the organic amine liquid porch of nearly central distribution cylinder (21) along circumferenceThe first baffle plate (23), its one end is fixed on central distribution cylinder (21) inwall, and the other end is with upwardsRaised section.
12. amine liquid crystallizing tanks according to claim 11 (2), is characterized in that described centerIn distributing barrel (21), be provided with second baffle (24) along circumference, its cross section of described second baffle (24) is LType, and remain with space with central distribution cylinder (21) inwall.
13. 1 kinds for removing the device of organic amine liquid sodium salt, it is characterized in that, is provided with successively and connectsHeat exchanger (1) and the amine liquid crystallizing tank (2) as described in claim 9-12 any one.
14. devices according to claim 13, is characterized in that, described device is at amine liquid crystallizing tank(2) after, be also provided with successively salt storagetank (3) and centrifuge (4).
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| CN111760456A (en) * | 2020-06-30 | 2020-10-13 | 双盾环境科技有限公司 | Organic amine desulfurizer solution purification, desalination and impurity removal process for removing sulfur dioxide |
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Effective date of registration: 20190429 Address after: 244001 Yangtze River West Road, Tongling City, Anhui Province Co-patentee after: Hefei University of Technology Patentee after: Tongling Nonferrous Metals Group Co., Ltd. Address before: 244401 Tongling coloured circular economy industrial park, Cui Hu six road, Tongling, Anhui Co-patentee before: Hefei University of Technology Patentee before: TONGGUAN SMELTING BRANCH OF TONGLING NONFERROUS METALS GROUP CO., LTD. |