CN1558793A - Method for producing granulated sorbents and installation for carrying out the method - Google Patents
Method for producing granulated sorbents and installation for carrying out the method Download PDFInfo
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- CN1558793A CN1558793A CNA018237401A CN01823740A CN1558793A CN 1558793 A CN1558793 A CN 1558793A CN A018237401 A CNA018237401 A CN A018237401A CN 01823740 A CN01823740 A CN 01823740A CN 1558793 A CN1558793 A CN 1558793A
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- sorbent
- methyl chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/018—Granulation; Incorporation of ion-exchangers in a matrix; Mixing with inert materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/104—Alumina
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- Oil, Petroleum & Natural Gas (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for producing granulated sorbents, and to an installation for carrying out the method. The aim of the invention is to obtain the chloride form of the double hydroxide of aluminium and lithium as LiCL2AI/OH)3 nH2O (DHAL-CL) in a waste-free solid phase of aluminium hydroxide and lithium salts in a mixer, with subsequent continuous activation of crystalline DHAL-CI in a centrifugal mill activator in order to obtain a defectuous material structure. The product obtained is mixed with chlorinated polyvinyl chloride as a binding agent and with liquid methylene chloride. The granulation is carried out by extruding the paste produced and refining the same in the granulator. The methylene chloride produced is collected by an organic liquid absorbent having a high boiling point. The methylene chloride steam is guided out of the material flow in the carrier gas flow in the manner of an ideal displacement in the counter-current of the contact phases. The methylene chloride recuperation is carried out in two steps according to the thermal method, during the heating of the absorbent used. The inventive method is characterised by essentially reduced environmental impact in relation to prior art, due to the closed material circuits used. The granulated sorbent is especially suitable for the selective extraction of lithium from chloride salt lye of any mineralisation, with an extraction degree of 95 %.
Description
Technical field
The present invention relates to the inorganic sorbent field and relate to the method for making the particle sorbent, especially make the sorbent that comprises acquisition lithium the natural saline solution from the saline solution that contains lithium.The invention still further relates to the equipment that is used to implement this method.
Background technology
Lithium with and compound be widely used at various industrial circles, for example make aluminium, glass manufacturing and Chemical Manufacture.
The solid material source that obtains lithium now is exhausted to a large extent.Yet the problem that lithium is in short supply can solve by utilizing the lithium raw material sources that substitute.What belong to such source has: the waste water of the association saline solution in saline solution, oil, diamond and other mineral deposit of various saline solutions, natural salt pond colloidal sol, seawater class and mill solution and some chemical enterprises and Biochemie Gesellschaft m.b.H. (AU) A-6250 Kundl, Austria.By means of can satisfying lithium optionally, and guarantee that the sorbent of high lithium pick-up rate can obtain lithium from these solution (saline solution).
Known a kind of method in the United States Patent (USP) 4291001 is used for making a kind of controlled micro crystallization compound two hydroxyl chlorine aluminium lithium LiCl2Al (OH) of the micropore that is ion-exchanger
3NH
2O.This method proposes the ion-exchanger of following steps and handles: aluminium chloride, ammonia, hydroxyl lithium and hydrochloric acid or lithium chloride are eliminated the chemicals of excessive input with middle washing ion-exchanger.
The sorbent of the sorption/desorb that can repeatedly circulate of obtaining like this can be used for obtaining lithium from saline solution.Yet this method is but very complicated and inefficent in it is used, because the content of target product is very low in the micropore of ion-exchanger, 35 quality % to 50 quality % only have an appointment.Higher lithium pick-up rate only just can reach under higher temperature (40 ℃ to 50 ℃) under the situation of using this compound.Provide necessary heating must cause technical difficulty if be related to a large amount of saline solutions, so another significant disadvantages of this method just displays.Above-mentioned in addition method must multistep be implemented suddenly.
The 11Ausg.50 of PCT (WO) 94/19513 and Izobretenijia Mira, the further known method of making the particle sorbent on the basis of the two chlorine compounds of alkalescence in No. 1995 describedly relates to molecular formula LiCl2Al (OH) at the two chlorine compounds of alkalescence
3NH
2O (hereinafter being called DHAL-Cl).Obtain following powder size by means of anodic decomposition aluminium in 0.5 to 3.0M lithium chloride solution.Making the cream that squeezes out at this with the organic polymer that contains fluorine or chlorine in organic solution sticks with paste as bond.From also containing NaCl, MgCl
2, CaCl
2Carry out by means of water with the preparation of the sorbent of sorption lithium in other muriatic saline solution; Part at this LiCl translates into the fluid phase.The result produces the sorbent that lacks lithium in its composition, and described sorbent guarantees the carrying capacity of per 1 gram dry 5.0mg to 8.0mg lithium.Selected carrying capacity scope is desirable, has guaranteed the high selectivity of sorbent to lithium because make the sorbent composition of defective (shortage is arranged).
The copolymer of the polymer of the copolymer of bond employing vinylidene fluoride and tetrafluoroethene, hexafluoropropene or vinyl chloride, polyvinyl chloride, vinylidene chloride, perchloroethylene resin and vinylidene chloride-vinyl chloride, vinyl chloride-vinyl acetate.In conjunction with dosage amount to into dry must for 8 mass percents to 10 mass percents, this guarantees the graininess (98% to 100%) of height.
The shortcoming of this method is that it implements higher energy consumption, is must use a large amount of lithium chloride solutions under the condition of constantly proofreading and correct its concentration and be to require deposit to filter and dry its particle.This external known method does not have to propose the recovery (regeneration) at the organic solvent (acetone, methyl chloride or the like) of making cream paste, particle and emitting when concentrated in atmosphere, this causes the obvious consumption of solvent and has finally improved the cost of sorbent.
This method realizes that with a kind of equipment described equipment has an electrolysis unit and is used to separate [DHAL-Cl] sediment with one, purifies and removes its remaining LiCl solution and be used for feeding back the filter of washings to utilize again to electrolysis unit.Then sorbent is heated with hot water in drier, described hot water temperature is no more than 70 ℃.The granulation of material is then pushed described cream and is stuck with paste by [DHAL-Cl], bond and solvent are arrived cream pasty state attitude.One of shortcoming of this equipment is the possibility that does not have solvent vapors when making and pushing the cream paste.
Carbon absorption process and equipment (Harbert Kohler, Kornwestheim und Iohan Halbartshlayer, the Stuttgart of also known a kind of (recovery) methyl chloride that is used for regenerating, Staub Reinhaltung der Luft rolls up 46, the No. 2, (1986), 50-55 page or leaf).
Described equipment has the methyl chloride vapour source, is used for absorbing from the washing air-flow device, the condenser of condensation from using with isolated methyl chloride the sorbent of crossing of the sucker form of methyl chloride steam, and wherein condenser is connected with the collection container of sucker and liquid methyl chloride.The desorb of the solvent of intercepting is carried out by means of directly evaporating.The shortcoming of this equipment has: the rate of recovery of methyl chloride is low, because it pollutes because of the hydrolysate in the evaporation desorption process, needs to purify the liquid methyl chloride that obtains, owing to use a large amount of activated carbon to absorb the danger of combustion that methyl chloride steam has height.
Summary of the invention
Task of the present invention is, the environmentally friendly method of having improved that obtains with simple technology that the DHAL-Cl powder makes the particle sorbent is provided, and described method is particularly suited for obtaining effectively lithium from saline solution.Task of the present invention also has, and the equipment of this method of enforcement is provided.
Method according to the feature of task of the present invention by having claim 1 is finished.The favourable expansion of this method is provided by claim 2 to 8.
Provide the task of equipment of the present invention to finish by the equipment of the feature that has claim 9.Favourable implementation according to equipment of the present invention is described by the feature of claim 10.
The advantage of the method according to this invention and described equipment is especially by interacting in a kind of mixing arrangement at aluminium hydroxide and lithium chloride, then the DHAL-Cl compound that activation obtains in continuous centrifugal grinder-activator reaches, and described continuous centrifugal grindings-activator for example is that ZMA-02, ZMA-06 type (initiating numbers 925386 according to SU) or other have the grinder of similar operation principle.
Activate like this, granular size is no more than the material of 0.16mm, has the crystal structure of band defective, can make particle easily, and can guarantee definite sorptive power after its water treatment, and this is by lacking the lithium decision in its composition.
For quickening to obtain the compound of DHAL-Cl, initial product is suitable for extracting the monohydrate of lithium chloride.Yet also can use anhydrous LiCl, if for initial amount Al (OH)
3+ LiCl is with 0.05 to 0.30 liquid and solid-state ratio mutually (liquid: solid=0.05-0.30) add water, to obtain the material of homogeneous.If to initial amount in addition than guaranteeing liquid: the desired water that lacks in solid=0.05 just causes that the LiCl conjugation descends among the DHAL-Cl.If liquid: solid is than greater than 0.30 cream that just causes constituting the congee sample, and the cream of described congee sample must continue drying, and course of work cost is strengthened.The device that mixing arrangement can adopt high efficiency vibration to mix, for example high-revolving paddle mixer, mixing arrangement, propeller mixer or the disk mixer of the rotary-piston (fluidization that has material) of fast turn-around are arranged, have the centrifugal mixer of rotary-piston or have the centrifugal propeller mixer of rotary-piston.
The interactional course of work realizes in accurate layer liquid in paddle mixer (Fig. 1).DHAL-Cl can be from finely divided Al (OH) in the case
3In in 7 to 15 minutes synthetic about 85% income (Fig. 2).At the Al (OH that uses crystal shape
3)
3The time, after about 30 minutes, reach combination to the equivalent composition of DHAL-Cl.Can also use the blender that combines with grinder for this reason.
The DHAL-Cl powder of Zhi Zaoing is mixed into cream with known bond and sticks with paste existing under the condition of methyl chloride in spiral agitator like this; described bond directly joins in the spiral agitator together with for example chlorated methyl chloride; by press-through die described cream being stuck with paste extruding then becomes straw shape, then to manufacture the particle that granularity is 2mm to 4mm thus in comminutor.
The air that is used as traction gas sent all devices in the process procedure along material stream rightabout.Stick with paste and make that material producing bears methyl chloride steam in the process of particle making cream, taken out of the absorption of the methyl chloride steam of process procedure by traction gas and carrying out in the convection current of contact phase with under the condition that is contacting under the desirable diafiltration state by means of the higher boiling organic material, described contact phase and contact conditions guarantee that maximum isolating methyl chloride and guarantee simultaneously uses methyl chloride saturated for the sorbent that regeneration is drawn fully from the sorption air-flow.Discharging methyl chloride from saturated sorbent is undertaken by the heating sorbent.If it flows in that the face upper edge of heating is, with the saturated methyl chloride steam that cooling is subsequently condensed and drawn, the condition of cooling is fully to separate from sorbent under the condition of its steam that will guarantee aspect it to condense at the same time the biglyyest.And the sorbent of having deviate from methyl chloride warmed-up at this is with being to discharge methyl chloride and mobile sorbent stream cooling and feed back and be used for sorption.Sorbent adopts freon oil, for example oil of XF22c-16 type.The methyl chloride concentration that is used for the traction gas stream of sorption remains on 700g/m
3To 1200g/m
3Level.In obturator in the sorption district height of sorbent floor at 1.70m to 1.95m.The sprinkler discharge density of the every cubic metre of gas phase sorbent that will purify is 3.7dm
3To 4.2dm
3, the linear velocity of described gas phase remains on the level of 0.04m/s to 0.06m/s in the sorption district.Heating at this saturated sorbent was carried out with two stages: at first it as thin layer stream along being heated to 105 ℃ to 110 ℃ plane with 25m
3/ m
2To 30m
3/ m
2Sprinkler discharge density flow through and on this heating surface, stayed 36 seconds to 40 seconds; Then along being heated to 115 ℃ to 120 ℃ fillers with 8m with capacity of heat transmission
3/ m
2To 9m
3/ m
2The h sprinkler discharge density flows through, and be 12 seconds to 15 seconds time of contact.Deriving methyl chloride steam from its release scope under the sorbent regeneration condition of heat realizes by means of the thermal diffusion that causes owing to the pressure differential corresponding to its methyl chloride from corresponding methyl chloride steam in the zone that saturated sorbent discharges and condensing zone.Described pressure differential is to condense owing to the methyl chloride steam undercooling of heating with in the appearance of boiling temperature.Keep constant chloromethyl condense from coagulation region draw and then cooling got rid of to condense at this and contacted up to ambient temperature with the direct of outside air.
This method realizes with a kind of equipment; described equipment has the high revolution blender (per minute 450 goes to 600 to be changeed) that is used for discrete material; described blender connects the activator grinder, and described activation grinder has ribbon mixer, extruder and the comminutor that is used to make the cream paste.The part of this external equipment also has: ventilation blower and the compressor that is used to draw the gas stream that will purify; Device is used for sorption methyl chloride steam, be implemented as arrange before and after two and mutually with a gas passage directly or the coolable sorption filler post that is connected with pipeline process pump; Device, be used for separating saturated methyl chloride steam from the sorbent of using, be connected with the vapours source, be connected with the coagulation collecting tank and be connected with the intertubular space of condenser, the latter is used to cool off methyl chloride steam and it is changed into the liquid phase, and described liquid is introduced in the collection container of liquid methyl chlorine by a cooler; Heat regenerator (hot regenerator) connects the sorbent filler post that first bunchiness is arranged, and described sorbent filler post is used to derive the sorbent of using, and also is connected with the second sorbent post through pump and cooler, is used to introduce the sorbent of regeneration.Be used herein to from being adiabatic fully with the device that separates methyl chloride the sorbent of crossing and implementing with the side pipe section with the form of tube bundle exchanger, the upside pipeline section is used for introducing intertubular space adding steam, and lower tube section, be used for deriving the coagulating agent of vapours from intertubular space, tube bundle exchanger is managed thereon by the circular cone diffuser at the end and is connected with the dropping liquid separator, and described circular cone diffuser is used for the sorbent used in the introducing of pipe space through a side pipe section that is connected with knockout.Described dropping liquid separator is a cylinder that has loam cake, wherein installs one and goes up grid and a following grid, and they constitute a space, and described space is filled with granular materials or fibrous material.The oblique acceleration shower nozzle of described dropping liquid separator by being installed in grid top is connected with the side pipe section of the methyl chloride steam that is used to draw heating and is connected its pipe end down through circular cone diffuser down, and described circular cone diffuser down is the housing that has the wedged bottom and the downside pipeline section of the sorbent that is used to draw regeneration at the installation calandria.Plate vertical in heater is radially being arranged above the downside pipeline section and is being fixed on the cylindrical shell uper side surface.Fill filler in the free space between plate, for example the ring of the coarse cloth manufactured of metal with high thermal conductivity.Last tube head in the tube bundle exchanger is in pipe end top and constitutes the batching dish of having filled the sorbent of use therewith, and wherein each is managed and all has a core and be used for tube wall is transmitted sorbent equably; Core described herein is fixed on the tube wall and is arranged on its outer surface and manages the end and contact.
Thereby the method and apparatus of being applied for compared with prior art important different as follows on it is realized:
1. to use blender and produce independently DHAL-Cl compound mutually in order to measure to homogenize by means of solid shape.
2. the DHAL-Cl of activation crystallization shape improves absorption characteristic with the activator grinder.
3. adopt a kind of ribbon mixer to make cream and stick with paste, this cream is stuck with paste pushed and granulation then.
4. adopt the device of a kind of recovery (regeneration) methyl chloride, described device causes methyl chloride steam in the traction gas and then methyl chloride is combined with high boiling organic sorbent, this organic sorbent is freon oil for example, is preferably the freon oil of XF22c-16 type.
5. adopt a kind of device that is used under the condition of the saturated sorbent of heat treatment, separating chloromethyl steam, realize the latter's regeneration thus from the sorbent of using (XF22c-16 type oil).
Description of drawings
Explain the operation of equipment of the present invention and the method according to this invention below by means of accompanying drawing.In the accompanying drawings:
Fig. 1 is the profile that is used to mix the blade mixer of bulk cargo;
Fig. 2 is that the conjugation of the LiCl among the DHAL-Cl is comply with in the figure line of the mixing duration in blade mixer, and that use in the curve 1 is Al (OH) after grinding
3And that use in the curve 2 is the Al (OH) of crystallization
3
Fig. 3-1 and Fig. 3 the-the 2nd, and the device of the sorbent that is used to make particle schematically is shown, and the significant components that is associated with it.
Fig. 4 a is the profile that separates the device of saturated methyl chloride from the sorbent of using.
Fig. 4 b is the vertical view of the device shown in Fig. 4 a.
Fig. 4 c is the sectional view of the device shown in Fig. 4 a along A-A.
Fig. 4 d is the profile of the part I of Fig. 4 a.
Fig. 5 is the time dependent dynamic diagram of methyl chloride vapour concentration from the output gas phase of hothouse.
Fig. 6 is the thermoisopleth figure line that absorbs methyl chloride by means of the higher boiling organic material from steam-air mixture.
Fig. 7 is methyl chloride (C in protective effect duration (τ p) and the steam-air mixture of sorbent
H) initial concentration correlation figure line.
Fig. 8 is the protective effect duration (τ p) and the correlation figure line of steam-air mixture by the linear velocity of sorbent (W) of sorbent.
Fig. 9 is the initial concentration correlation figure line of the methyl chloride in the steam-air mixture under the preceding battle array speed of the oily sorption linear velocity different with steam-air mixture in the sorbent.
Figure 10 be the different linear velocity of steam-air mixture and under the condition of filler fixed bed sorbent the time of the degree of absorption of methyl chloride (E) go up the dynamic diagram that changes.
Figure 11 is by means of C
H=700g/m
3Oil absorption rate, under the different sorption layer heights on filler, desirable diafiltration and relative current state under the different conditions such as sprinkler discharge density, from steam-air mixture, absorb the dynamic diagram of time change of the degree of methyl chloride.
Figure 12 is by means of C
H=1200g/m
3Oil absorption rate, under the different sorption layer height on filler, desirable diafiltration and relative current state under the different conditions such as sprinkler discharge density, from steam-air mixture, absorb the dynamic diagram of time change of the degree of methyl chloride.
Figure 13 be according to thermal diffusion method from out-of-date as thin layer at this surface current of face upper edge that is heated to 100 ℃ with the sorbent of crossing, the regeneration level of the sorbent of using (η, %) and sprinkler discharge density (q, m
3/ m
2H) correlation figure line.
Figure 14 is out-of-date at this surface current of face upper edge that is heated to 100 ℃ as thin layer with the sorbent of crossing, and reclaims degree (R, %) and sprinkler discharge density (q, the m of (regeneration) methyl chloride from the sorbent of using according to thermal diffusion method
3/ m
2H) correlation figure line.
Figure 15 is that sorbent is 27.5m at sprinkler discharge density
3/ m
2St. down out-of-date at this surface current of face upper edge as thin layer, according to thermal diffusion method with the regeneration level (η, %) of the sorbent of mistake dependence figure line to the temperature of crossing this face under length (l) condition in various flows (t, ℃).
Figure 16 is that sorbent is 27.5m at sprinkler discharge density
3/ m
2St. down out-of-date at this surface current of face upper edge as thin layer, according to thermal diffusion method from the degree (R, %) of sorbent recovery (regeneration) methyl chloride of crossing dependence to the temperature of crossing this face under length (l) condition in various flows (t, ℃).
The specific embodiment
Be used for making the equipment of sorbent of particle and the schematic configuration of the significant components that is associated with it and be illustrated in Fig. 3-1 and 3-2:
-oar blade type blender 2 has container 2a that aluminium hydroxide is housed that is connected with the container of centrifugal grinder 1 by means of pipeline and the container 2b that a hydration lithium chloride is housed, and powder outputs to the ribbon mixer 4 from described centrifugal grinder;
-methyl chloride vapour source is made up of blender 4, and described blender 4 is connected with finished container 7 with comminutor 6 by extruder 5;
-jar the 4a that the jar 3 of regeneration liquid methyl chloride is housed and bond is housed is connected with the pipe fitting of sending into liquid methyl chlorine and bond in helical mixer 4 with pipeline by means of magnetic valve respectively;
-adjustable guiding valve 8, described adjustable guiding valve 8 is connected and is connected with extraneous air with the pipe fitting of drawing traction gas by means of gas passage;
-adjustable guiding valve 9, described adjustable guiding valve 9 is connected with the traction gas that is full of methyl chloride steam that discharges from blender 4 and the air inlet of ventilation blower 10 by means of gas passage;
-expansion tube 11;
-compressor 12 has guiding valve 13;
-receiving vessel 14 has guiding valve 15;
-be used for collecting the assembly of methyl chloride steam from drawing air-flow, filling stock column 16 and 17 by two coolable sorptions of successively erectting forms, described sorption is filled stock column 16 and directly is connected by gas passage mutually with 17, also is connected with magnetic valve 19 through pump 18 by pipeline;
-cooling unit, sorbent 20 is used to regenerate;
-pump 22 has magnetic valve 21 and is used for the sorbent of the regeneration of cooling off at heat exchanger 23 is transported to the cooling that cooling unit 20 adds;
-pump 25 has magnetic valve 24 and is used for regenerating sending heat exchanger 23 to the sorbent of crossing;
-be used for from the device 26 of the sorbent separation methyl chloride of using, include: be used to carry heat carrier pipe fitting 35, be used to draw the coagulative pipe fitting 36 of vapours, be used for carrying the pipe fitting of the sorbent of use to tube space 39, be used to draw regeneration sorbent pipe fitting 52 and draw the pipe fitting 47 of overheated methyl chloride steam;
-vapours source 60;
The condenser 28 of-methyl chloride steam;
The coagulation collecting tank 27 of-vapours;
The cooling unit 29 of-liquid phase methyl chloride;
The collection container 30 of-liquid methyl chlorine, described collection container is connected with the intertubular space of guiding valve 32 with the condenser 28 of methyl chloride steam through gas passage, and be connected with the cooling device 29 of liquid methyl chlorine through magnetic valve 31 by means of pipeline, and be connected with the jar 3 of liquid methyl chlorine with pump 65 through magnetic valve 33;
-jar 61 of the sorbent that is used for sorption methyl chloride steam is housed, be connected with the pipe fitting that sorbent is delivered into sorption column 17 through magnetic valve 64 by means of pipeline.
The device 26 that separates methyl chloride from the sorbent of using belongs to the device of recovery (regeneration) methyl chloride, is shown in greater detail among Fig. 4.Described device contains:
-have the pipe end 37 and down the pipe end 48 tube bundle exchanger 34, be used for vapours being delivered into the upper side pipe fitting 35 of intertubular space and being used for from drawing coagulative downside pipe fitting 36 between pipe;
-last circular cone diffuser 38;
-side pipe fitting 39 is used for being delivered into the tube space that has ventilation blower 40 with the sorbent of crossing;
-columniform drippage interceptor 41 has loam cake 42, and grid 43 and last grid 44 wherein are installed down, and described grid 43 down and last grid 44 constitute the space 45 of filler particles material or fibrous material;
The inclination that install-side is quickened shower nozzle 46 and is had a side pipe fitting 47 that is used to draw overheated methyl chloride steam;
-following conic type diffuser 62;
-heater is mounted in the circular cylindrical shell 50 in the calandria 49, has the end 51 of inclination and the sorbent that the downside pipe fitting is used to draw regeneration;
The supporting grating 53 of-level;
-be fixed on the plate radially 54 on the circular cylindrical shell 50;
-have a packing material 55 of high-termal conductivity;
The pipe 56 of-tube bundle exchanger has inside groove 63;
-core 57, it be can with the sorbent pipe into the net that interweaves;
-ring spring 58 and hot protective material 59.
Explain the working method of the equipment of the sorbent of making particle below.
The aluminium hydroxide and a hydration lithium chloride of the crystal shape of sending from container 2a and 2b are fed to the blade mixer 2, carry out the synthetic of DHAL-Cl in blade mixer 2.The DHAL-Cl powder feeds is advanced in centrifugal mill-activator (ZMA) 1, therein the DHAL-Cl powder is activated and refine to granularity≤0.16mm; Then this material is presented in the ribbon mixer 4, in ribbon mixer 4 from the container 4a that separates present bond and from container 3 methyl chloride of feed liquid, bond is a chliorinated polyvinyl chloride in this example.The cream of making in ribbon mixer 4 is stuck with paste and is sent to the extruder 5 that is connected with comminutor 6.Produce the particle of granularity 2mm to 4mm at this.Then particle is presented in the container 7; Be attended by the strong evaporation of methyl chloride in the process of this mixing and granulation.For fear of lose methyl chloride in workflow, each device connects hermetically mutually and is under the very little low pressure, and described low pressure is produced by ventilation blower 10 and regulates by means of adjustable guiding valve 8 and 9.In order to guarantee that maximum fully draws methyl chloride steam, draft and in device, carry traction gas (air), described traction gas is transmitted to the methyl chloride source from air through guiding valve 8 by means of gas passage.With respect to the convection current of material stream the workflow of drawing methyl chloride steam is given the driving force of maximum by traction gas.In the ending traction gas of workflow, also reach the highest methyl chloride concentration in the case.The traction gas of saturated methyl chloride steam is transferred to the suction openings of compressor and further is directed to the inlet tube of sorption filler post 16 through receiving vessel 14 through expansion tube 11 with ventilation blower 10.The effect of expansion tube 11 and receiving vessel 14 is to guarantee that stabilizing gas consumes mutually and gas transmission uniformly.In order to coordinate the capacity of ventilation blower 10 and compressor 12, the outlet of compressor 12 is connected with its inlet.The gas consumption mutually that guiding valve 13 and 15 assurances will purify.In the first sorption filler post 16, hold back the major part of methyl chloride; The second sorption filler post 17 is used to purify the traction gas of methyl chloride steam basically.The sorption of the methyl chloride steam in filler is carried out under the desirable diafiltration situation in the convection current of contact phase.Sorbent flows to pipe fitting from consumption jar 61 sorbents of outflow process voluntarily conveyings and carries out sorption the post 17 for this purpose.Consumptive use the magnetic valve 64 predetermined and adjustings of sorbent.In filler, contact with the traction gaseous exchange of guiding extraneous air from post 17 into, and sorption after the remaining methyl chloride, the sorbent of saturated methyl chloride partly is collected in the bottom of post 17 and flows into through sorbents and be sent in the sorption column 16 with pipe fitting with pump 18; In these consumptive use magnetic valve 19 controls.In filler, contact again with the convection current of the traction gas of saturated methyl chloride steam stream and the major part of sorption methyl chloride after the sorbent of maximum saturated methyl chlorides (reach 20 mass percents or more than) is collected in the bottom of post 16 and heat under by the continuous control of magnetic valve 24 and in recover 23 with pump 25 after through input with pipe fitting 39 transmission of sorbent advance in the device 26 of acquisition methyl chloride from the sorbent of using.
For the sorption degree sorption column that improves methyl chloride is provided with cooling dome, described cooling dome guarantees the operation of cooling agent in the direction of upper edge, post surface sorbent reverse movement.
In device 26, remove methyl chloride and comprise two stages.On warmed-up surface, heat when it is mobile with the sorbent of crossing, at first it having as thin layer the pipe end 37 and down tube bundle exchanger 34 upper edges at the pipe end 48 be heated on 100 ℃ to 105 ℃ the pipe 56 and flow through, be heated to 115 ℃ to 125 ℃ have in the capacity of heat transmission filler 55 and flowing dripping shape as line then.The heating of pipe is carried out by means of the vapours of sending in the vapours source 60 in tube bundle exchanger 34, and the upper side pipe fitting 35 of described vapours by the heat carrier import is delivered in the intertubular space and by the downside pipe fitting 36 that the vapours coagulation flows out and draws the vapours coagulation to the coagulative collection basin 27 of vapours from intertubular space.Heating has the circular cylindrical shell 50 of filler in being installed in calandria 49 of high-termal conductivity to realize that described circular cylindrical shell 50 has plate 54 radially, the supporting grating 53 of level and the end 51 that tilts.For the sorbent that guarantees on the pipe of tube bundle exchanger 34, to distribute and used equably, take following measure: at first present with the sorbent of crossing and be evenly distributed on the cross section of device by distributor 40, secondly go up tube head 56 and be in pipe at the end 37, and constitute the distribution locations of constantly filling the sorbent of using therewith, wherein each pipe is filled distribution locations, wherein each pipe useful can with well the interweave core 57 of blown tubular of material into the net of sorbent, the part of described flexible pipe is packed into and is managed in 56, and is pressed on its inner surface that is provided with cannelure 63 by means of ring spring 58.Utilize the capillary distribution principle of core to guarantee the height ingredients uniformity of sorbent in pipe.In this regard from install the methyl chloride steam of drawing 26 in filler 55 to rising; Described methyl chloride steam warp diffuser 62 down enters in the pipe 56 of tube bundle exchanger 34, and rises highly more, and it is concentrated more, reaches maximum concentration up to it in upper diffuser 38 and in drip interceptor 41.The driving force of methyl chloride steam motion is thermal diffusion, described thermal diffusion is that described condenser 28 is connected with the oblique accelerating jet 46 of inclination that installs 26 by means of pipe fitting 47 because the bigger pressure differential between the intertubular space of device 26 top and condenser 28 occurs; Result that to be the overheated methyl chloride steam of cooling and its condense at 40 ℃ boiling point that pressure differential produces.Drop interceptor 41 is the cylinders with loam cake 42, time grating 43 and last grating 44 wherein have been installed, their constitute the space 45 of filling with granular materials or fibrous material and draft and be used for separating the sorbent drop from methyl chloride steam, wherein transfer out sorbent from the thermal treatment zone.Condensing of the methyl chloride that occurs in the intertubular space of condenser 28 constantly is sent in the collection basin 30 of liquid methyl chlorine through refrigerator 29 mutually, and described refrigerator 29 is connected with adjusting magnetic valve 31 by means of pipeline.
Collect in the basin 30 in order to guarantee continuously the liquid of methyl chloride to be delivered into mutually through the stable pressure of collecting in the basin of liquid level, and prevent that thus methyl chloride from contacting with extraneous air, with guiding valve 32 intertubular space of collection basin 30 with condenser 28 is connected by means of gas passage.From collect basin 30 in the consumption jar 3 of the methyl chloride of liquid phase by means of a pump pumping liquid methyl chloride; In these consumptive use magnetic valve 33 controls.The sorbent that breaks away from methyl chloride (regeneration) is drawn from installing 26 by pipe fitting 52, cool off at heat exchanger 23 by means of the sorbent of using, with pump 22, regulating under the condition that consumes with magnetic valve 21, import and to advance to cool off in the unit 20, and then present into sorbent and consume in jars 61 with further cooling.
Below with concrete example explanation the present invention.
Example 1
In the blender of 10 liters of as shown in Figure 1 capacity, send into the finely divided gibbsite Al (OH) of 2.5kg
3(aluminium hydroxide) and 0.98kg one hydration lithium chloride LiClH
2O.Then blender container 4 is improved up to the stop place, enter in the charging at leisure at this agitator.When container reaches aspect, agitator is switched at full speed (about per minute 450 changes).Closed blender later at 15 minutes, the conjugation of LiCl is 85%.Charging is filled in the container of centrifugal grinding-activation equipment ZMA-06; The composition conjugation reaches 92% when moving by centrifugal grinding-activation equipment, and the molar ratio LiCl in the DHAL-Cl that produces: Al (OH)
3Be 0.46.Molar ratio LiCl: Al (OH) in the product with material for water treatment the time
3Reach and equal 0.33, take out 28% LiCl in other words, and lithium amount (mg), with respect to sorbent quality (g), tackling the sorption capacity that lithium converts mutually is 7.7mg/g.
Be listed in the table 1 below to use when having water and in the oar blade type blender, carry out the synthetic example of DHAL-Cl under a hydration lithium chloride and the anhydrous Lithium chloride condition.Example 1 to 4 is failed, because add a large amount of water (liquid phases: solid phase＞0.3) make material lose its laxity in charging.
| Example | The charging composition | Molar ratio | Exchange capacity mg/g | τ/minute | Annotate | ||||
| AL(OH) 3 | ?LiCl·H 2O | ?LiCl | ?H 2O | H in the charging 2O∶LiCl | LiCl in the product: AL (OH) 3 | ||||
| 1-1 | ????2.5 | ????0.98 | ?- | ?- | ????0.1 | ????0.46 | ??7.7 | ??15 | Bulk cargo |
| 1-2 | ????2.5 | ????- | ?0.657 | ?0.16 | ????0.05 | ????0.45 | ??7.8 | ??30 | Bulk cargo |
| 1-3 | ????2.5 | ????- | ?0.657 | ?0.95 | ????0.3 | ????0.44 | ??7.7 | ??30 | |
| The 1-4 failure | ????2.5 | ????- | ?0.657 | ?1.25 | ????0.4 | ????0.45 | ??7.8 | ??30 | The material forfeiture is dispersed |
Table 1: the DHAL-Cl in the paddle type mixer is synthetic
Example 2
Make DHAL-Cl according to example 1 described method, and molar ratio LiCl: Al (OH)
3Equal 0.46.Product becomes be grouped into make particle as solvent with different as bond and methyl chloride (MCI) by means of the polyvinyl chloride (PVC) of chlorination.The results are shown in the table 2:
| Example | The blending constituent of granulation, % at most | The composition of dried particle, % at most | Exchange capacity mg/g | Mechanical strength, % | |||
| DHAL-Cl | ????PVC | ????MCI | H in the charging 2O∶LiCl | LiCl in the product: AL (OH) 3 | |||
| ?2-1 | ??45.7 | ????3.8 | ????50.5 | ??92.3 | ????7.7 | ????7.2 | ????99.3 |
| ?2-2 | ??44.2 | ????3.7 | ????51.9 | ??91.9 | ????8.1 | ????7.0 | ????99.4 |
| ?2-3 | ??42.8 | ????4.0 | ????53.2 | ??91.5 | ????8.5 | ????7.0 | ????99.5 |
| ?2-4 | ??40.1 | ????4.2 | ????55.7 | ??90.5 | ????9.5 | ????6.9 | ????99.8 |
| ?2-5 | ??38.5 | ????4.3 | ????57.2 | ??90.0 | ????10.0 | ????6.8 | ????99.9 |
| ?2-6 | ??47.1 | ????3.7 | ????49.2 | ??92.7 | ????7.3 | ????6.9 | ????96.0 |
| ?2-7 | ??37.1 | ????4.4 | ????58.5 | ??89.3 | ????10.7 | ????6.5 | ????99.9 |
The one-tenth of table 2:DHAL-Cl granulation is grouped into
PVC is dissolved in the methyl chloride, wherein adds the DHAL-Cl powder and be stirred to constitute the cream paste in the solution of the viscous that produces.By extruder described cream paste is squeezed into the tangerine rod of 2mm size, and then narrows down to the granularity of 2mm to 4mm.Particle is dry in the open.Methyl chloride loss when making the sorbent of particle is 100%, therefore needs to receive it and regenerates and reuse in workflow.
The sorptive power of the particle of making is at room temperature measured under dynamic condition.10 grams are particles filled in the high post of 10mm diameter and 350mm.Water is with 100cm
3The velocity flow of/h is crossed this post.The lithium that absorbs is counted 6.8mg/g to 7.2mg/g with lithium.The low sorptive power of comparing with the DHAL-Cl powder can obtain from the bond that has 7.7% to 9.5% amount explaining.
The lithium sorption is carried out from the chloride solution of following constituent (g/l): LiCl-2.5; NaCl-76.0; KCl-23.0; CaCl
2-182.0; MgCl
2-52.0.Lithium recovery rate 95.5%.Fully dynamic cubical content is 7mg/g.The intensity of particle is 99.3% to 99.9% (table 2, routine 2-1**2-5) after the circulation of 10 sorption-desorbs.
Example 2-6 and 2-7 fail: be reduced in conjunction with dosage and cause reducing mechanical strength (routine 2-6) below 7.7%; Exchange capacity descends when improving in conjunction with dosage.
The method of the manufacturing particle sorbent of being developed has obtained check in the sampling of 2 tons of particle sorbents.
Example 3
By means of a special laboratory equipment, the hothouse that inlet pipe fitting and outlet pipe fitting are arranged, research is from the process by separating methyl chloride in dissolving PVC and the cream that the DHAL-Cl sorbent under agitation obtains is stuck with paste methyl chloride.It is dry to adopt the cream that carries out under air draught (traction gas) and low pressure to stick with paste as the possible method of separating methyl chloride.Low pressure in the hothouse and to wherein carrying air by means of Air fan be arranged in guaranteeing on the entrance and exit on the hothouse by the control magnetic valve.Air consumption is measured with rotameter, and low pressure U-shaped manometry.The sampling of the gas phase of drawing from hothouse is carried out with the 100ml gas syringe in the exit of hothouse.Methyl chloride separate to the sampling of the exit gas phase that impinges upon hothouse the time carry out according to gas chromatography with respect to methyl chloride with the analyzer that is attached thereto.The process of separating methyl chloride is 1g/m at it in the gas of the outlet that hothouse the sends concentration in mutually
3Even if in time, finish.In research process, change the parameter of hothouse.Make basic hothouse at this container with diameter 260mm.Another hothouse is made up of the container of the diameter 105mm that erect two front and back.Comparative studies in this container is carried out identical cream paste amount, in other words, fill its whole amounts in big hothouse, and little hothouse loads with its half amount exactly separately.Described research is carried out in 20 ℃ temperature and 40 ℃ temperature.The result who obtains is shown in Figure 5 for relational expression CXM=f (τ), methyl chloride vapour concentration (CXM, the g/m of the gas in the exit that this relational expression is sent by means of hothouse in mutually
3) indicating: 1-is the low pressure of 400Pa and t=20 ℃; 2-is the low pressure of 2000Pa and t=20 ℃; 3-flows and t=20 ℃ at the air of 1.0 l/ minutes consumption; 4-flows and t=40 ℃ at the air of 0.5 l/ minute consumption; 5-flows and t=20 ℃ at the air of 0.5 l/ minute consumption; 6-flows and t=20 ℃ at the air of 0.5 l/ minute consumption.Adopt big dry chamber in example 1 to 5, and the little hothouse of arranging before and after in example 6, adopting two.From the value that obtains, can find out significantly, in traction gas stream, from cream is stuck with paste, separate methyl chloride and carry out by force in than low pressure, especially in the end mutually of process.The rising of traction gas consumption means that methyl chloride separate to quicken (curve 3), yet descends in the concentration of this its gas in mutually.Traction gas influences the speed that methyl chloride separates with the condition of material contact with tangible degree.Can allow traction gas by hothouse (curve 5) thereby traction gas can just be separated to methyl chloride fast by the hothouse of arranging before and after two (curve 6), but in this example, guarantee at methyl chloride on the time of length at the Cmax of gas in mutually.The result who obtains obtains tangible conclusion thus: the process of separating methyl chloride from manufacturing installation is adapted to carry out in traction gas stream, because quickened on the one hand process and this guaranteed manufacturing installation exit gas mutually in the higher concentration of methyl chloride, and guarantee the stable temporal consumption of gas phase on the other hand.In material stream, be adapted under the situation of material movement; oppositely adopt along material stream (in other words from comminutor to blender) and to draw and motion traction gas stream; methyl chloride separates because only in this way just can reach completely, and can guarantee minimum traction gas consumption and the highest methyl chloride vapour concentration on the exit of manufacturing installation.
Example 4
Use by make by the steam-air mixture unit of the setting value of predetermined methyl chloride concentration, fill the fluoroplastics ring as the sucker of the diameter 3.25cm of filler and high 100cm, have the consumption meter of pressure regulator valve and the special experimental laboratory equipment that Air fan is formed, studied from the process of steam-air mixture sorption methyl chloride.
Transmit the oil charging at this to sucker, and allow the air that contains methyl chloride pass through along the direction of " from bottom to top " by this oil.Drawing the air that has purified carries out through the outlet pipe fitting of sucker.Draw with flowing through down outlet voluntarily from the oil that sucker flows out.
For driving, continuous convection current is provided with from the device of running stores jar continuous oil supply.Sorption is controlled, and wherein measures the airborne methyl chloride steam at the entrance and exit place of sucker.Static fully capability value calculates by following formula:
a＝q/m，????(1)
In the formula: q constitutes its initial containing in steam-air mixture behind the sorption layer
Measure the amount (mg) of the methyl chloride of identical concentration time sorption before;
M sorption quality (g).
The rejection of methyl chloride during sorption (E, %) is calculated according to following formula:
E＝C
H-C
K/C
H·100?????????????(2)
In the formula: C
HAnd C
KMethyl chloride is dense in the air-flow at the entrance and exit place of sucker
Degree, g/m
3Under the condition of the sorption under the desirable diafiltration state, use Mi Xieer
Formula is calculated the height of agent layer:
H＝H
o·T
p-T
np/T
p-(1-Φ)(T
p-T
np)，????(3)
In the formula: τ
NpMethyl chloride concentration reaches 0.05C outside the outlet of sucker
0Value
Time (minute) (breakdown time);
τ
pMethyl chloride concentration reaches 0.95C in the exit of sucker
0Value
Time (minute) (the protective effect time of sucker);
The uniformity coefficient of Φ elution curve;
H
oThe height (m) of (will study) sorbent layer does not move.
The value of uniformity coefficient is the area ratio on figure line, following drawing:
Φ＝S
a/(S
a+S
b)，?????????(4)
In the formula: S
aThe area that elution curve is above,
S
bThe area that elution curve is following.
Studied the oils that name is called XF22c-16 and BM-4 as sorbent.
Sorption isotherm by means of the methyl chloride steam of oils XF22c-16 and BM-4 illustrates as correlation in Fig. 6.
Can find out clearly that from the thermoisopleth of quoting oily XF22c-16 (curve 1) surpasses BM-4 significantly according to its capacity feature in whole concentration range.In this sorption limiting value with oily XF22c-16 is 370mg/g (322mg/cm
3), higher by 48% than the corresponding coefficient of oily BM-4.Therefore all dynamic studies all use oily XF22c-16 to carry out.
Correlation (Ck, g/m that the time of the output concentration of methyl chloride changes
3) by its different initial concentration (C
H, g/m
3) study: 1-C
H=470g/m
32-C
H=1100g/m
33-C
H=1800g/m
34-C
H=660g/m
35-C
H=910g/m
36-C
H=1200g/m
37-C
H=1410g/m
3Described research is at t=20 ℃, steam-air mixture linear velocity W=0.01m/s, the sorbent layer H by sorption column
o=1.0m and sorbent quality are that 88g carries out under the condition of desirable diafiltration state.By means of the change of the protective effect duration of the sorbent as a result of the research of carrying out correlation τ p=f (C to the initial concentration in the steam-air mixture
H) shown in Figure 7 under the W=0.01m/s condition.
Draw from this correlation, have the desirable initial concentration of the methyl chloride in the steam-air mixture in the process of oily sorption, described desirable initial concentration guarantees desirable condition for absorbing methyl chloride, reaches maximum absorbability in other words.For the ideal range of system's initial concentration of research at 700g/m
3To 1200g/m
3Between, maximum is being 900g/m corresponding to methyl chloride concentration
3The point.
Example 5
By means of the special experimental laboratory equipment described in the example 3 and with identical method, research its by sucker by the friction speed of 0.08m/s to 0.015m/s under the research of the process of oily sorption methyl chloride from steam-air mixture.
Described correlation is at t=20 ℃, sorption layer height H
o=1.0m, sorbent quality (oily XF22c-16) is 88g, desirable diafiltration state is issued to.
By means of the result of the research of being carried out, the change of the protective effect duration of sorbent to the correlation τ p=f (W) of the linear velocity of steam-air mixture by sorbent at C
H=670g/m
3Condition under shown in Figure 8.Can draw from this correlation; oily sorption protective effect duration descends in the lower and precipitate zone of linear velocity of on-line velocity; yet be to start with the linear velocity of W=0.02m/s, correlative character is same to be changed and τ p only has less decline along with the rising of W precipitously.Can also determine, when W＞0.08m/s because the transition of method of operation sorption process is the operating desirable diafiltration of bubbling.
The height value of the working lining that in result of study, reaches (H,
M) in table 3, list.
| W，M/sC H、g/m 3 | ??450 | ?670 | ??1000 |
| ????0.005 | ??- | ?0.8±0.1 | ??- |
| ????0.010 | ??0.8±0.1 | ?0.9±0.1 | ??1.0±0.1 |
| ????0.020 | ??1.3±0.1 | ?1.3±0.1 | ??1.4±0.1 |
| ????0.030 | ??1.3±0.1 | ?1.3±0.1 | ??1.4±0.1 |
| ????0.040 | ??1.4±0.1 | ?1.3±0.1 | ??1.4±0.1 |
| ????0.060 | ??1.4±0.1 | ?1.5±0.1 | ??1.5±0.1 |
Table 3: the correlation of sorbent working lining height H (m) and sorption condition.
Can find out clearly in the methyl chloride concentration range of research and be in the scope of 0.02m/s to 0.06m/s from table 3 in the linear velocity of steam-air mixture, the working lining height of sorbent is actually constant value in the filler, and 1.4 meters of average out to, excursion are 1.3 to 1.5 meters.Consider, in the transition of industrial sorption filler post, be no more than proportionality coefficient 30% (the strong transition in the chemical technology, by means of hydrodinamical model exploitation manufacturing equipment, chief editor A.M.Rosen, Moscow: The Chemicals, 1981) (grasping the inhomogeneities of equipment medium velocity field boundary), the actual height of the sorbent layer of working in the filler (for oily XF22c-16) is 1.70 to 1.95.
Relevant with the ideal rate value of steam-air mixture in sorbent is, the basis that its scope is selected must be: must reach peak power in mutually at gas on the one hand, sorption process only carries out with the method for operation of desirable diafiltration on the other hand.Consider that the desirable in this example linear velocity scope of these two factors is 0.04m/s to 0.06m/s.
Under the working method of dynamically studying desirable diafiltration with the movement velocity of battle array (U Φ, m/h) before determining sorption by the inferior formula formula of the following stated Weir in the process of the oily XF22c-16 sorption methyl chloride from steam-air mixture in the filler:
UΦ＝W·C
H/C
H+a(C
H)??????(5)
In the formula: the linear velocity of steam-air mixture in the W sorption process, m/h;
C
HMethyl chloride initial concentration in the steam-air mixture, kg/m
3
A (C
H) identical concentration C in steam-air mixture
HThe time, You Zhongjia
The concentration of base chlorine (by means of sorption isotherm, Fig. 6 calculates).
Methyl chloride initial concentration in witness whereof shown in Figure 9 and the steam-air mixture illustrates the correlation that the speed of battle array before the sorption is changed into feature explicitly :-zero-value calculated according to the inferior formula formula of Weir;--the value of measuring; 1-W=0.02m/s; 2-W=0.04m/s; 3-W=0.06m/s.
Example 6
By means of the special experimental laboratory equipment of explanation in example 3 and 4, and use identical method to carry out in the working method of desirable diafiltration, interrupting fuel feeding and contacting under the condition of relative current sprinkler discharge density to the research of the effect of the process of oily sorption methyl chloride from steam-air mixture with oily XF22c-16.
Beyond the entrance and exit of sucker, controlling concentration, the methyl chloride content in research process in the mensuration oil of the exit of sucker.Change the methyl chloride content (a, mass percent) that calculates in the sorbent in this density that is used in sorbent, pure oil and pure methyl chloride by means of known formula:
a＝(ρ
a-ρ
M)100/(ρ
XM-ρ
M)????(6)
In the formula: ρ
aSorbent density, g/cm
3
ρ
MOil density, g/cm
3(ρ
M=1.15g/cm
3);
ρ
XMMethyl chloride density, g/cm
3(ρ
XM=1.324g/cm
3).
Because change the dynamic characteristic (1-W=0.01m/s of (E, %) as shown in figure 10 and in the working method of explanation desirable diafiltration under the linear velocity of different steam-air mixtures and the fixed bed acceptance condition in filler on time of intercepting degree of methyl chloride; 2-W=0.02m/s; 3-W=0.03m/s; 4-W=0.04m/s; C
H=700g/m
3H
0=10m; Sorbent quality 88g) correlation, so Jie Qu degree descends very apace corresponding to being absorbed feature in time, and the linear velocity of steam-air mixture is high more, it is just fast more to descend.If adopt relative current (supplying with and draw sorbent continuously) in the working method of desirable diafiltration, correlation E=f (τ) changes significantly, also illustrates with figure line in Figure 11 and 12 thus.
Different sprinkler discharge densities (q, dm at different sorption layer heights, the steam-air mixture that will purify have been shown among Figure 11
3/ m
3) under the condition, W=0.04m/s; C
H=700g/m
3The time, from the dynamic characteristic of the time change of the degree of steam-air mixture intercepting methyl chloride; Sorbent uses in the working method in desirable diafiltration and in relative current: 1-H
0=1.2m (H
0＜H); 2-H
0=1.6m (H
0＞H);-zero-q=3.7dm
3/ m
3--q=3.5dm
3/ m
3-△-q=4.0dm
3/ m
3
Different sprinkler discharge densities (q, dm at different sorption layer heights, the steam-air mixture that will purify have been shown among Figure 12
3/ m
3) under the condition, W=0.04m/s; C
H=1200g/m
3The time, the behavioral characteristics that the time of the degree of intercepting methyl chloride changes from steam-air mixture; Sorbent uses in the working method in desirable diafiltration and in relative current: 1-H
0=1.2m (H
0＜H); 2-H
0=1.6m (H
0＞H);-zero-q=4.2dm
3/ m
3--q=4.0dm
3/ m
3-△-q=4.4dm
3/ m
3
Can draw clearly from the correlation shown in Figure 11 and 12, the intercepting degree of methyl chloride at first with its methyl chloride initial concentration in steam-air mixture at 700g/m
3To 1200g/m
3Scope in irrelevant, and irrespectively keep stable in time at height with the sorbent layer; (H when next height at sorbent surpasses the working lining height
0=1.6m＞H) (correlation 2) is correspondingly at C
H=700g/m
3And C
H=1200g/m
3Reach 95% and 97.1% methyl chloride intercepting respectively, this guarantees at sucker exit 35g/m
3The methyl chloride residual concentration.
At this each input concentration is existed sprinkler discharge density (q, a dm
3/ m
3), the intercepting degree maximum of one side methyl chloride and maintenance are in time stablized under this sprinkler discharge density, and reach the highest methyl chloride composition on the other hand in the sorbent of crossing and draw during the course.The result lists in table 4.
| Methyl chloride initial concentration C in the steam-air mixture H、g/m 3 | Methyl chloride content a in the sorption process, mass percent | |||||
| H=1.2m and sprinkler discharge density are | H=1.6m and sprinkler discharge density are | |||||
| ?q＝3.5 ?dm 3/m 3 | ?q＝3.7 ?dm 3/m 3 | ?q＝4.0 ?dm 3/m 3 | ?q＝34.0 ?dm 3/m 3 | ?q＝4.2 ?dm 3/m 3 | ?q＝4.4 ?dm 3/m 3 | |
| ????700 | ?17.40 | ?17.38 | ?16.08 | ?16.01 | ?15.25 | ?14.55 |
| ????1200 | ?20.07 | ?20.74 | ?20.75 | ?20.72 | ?20.75 | ?19.71 |
Table 4: draw the methyl chloride content in the sorbent in different sprinkler discharge densities and the steam-air mixture under the methyl chloride initial concentration condition during the course.
From the result that reaches as can be known, for 700g/m is arranged
3The desirable sprinkler discharge density of steam-air mixture of methyl chloride initial concentration be q=3.7dm
3/ m
3Sprinkler discharge density, and for 1200g/m is arranged
3The desirable sprinkler discharge density of steam-air mixture of methyl chloride initial concentration be q=4.2dm
3/ m
3Sprinkler discharge density.
Example 7
Equipment that use illustrates in example 3,4 and 5 and method have been carried out the research of hydromechanical working method to the effect of oily sorption methyl chloride underlying parameter from steam-air mixture.
The working method that has compared two oily sorptions for this purpose: the convection current work of desirable diafiltration in the filler and the convection current work of in froth bed, stirring ideally.
For the employing of the sorption in the work of studying desirable stirring has the glass column of microwell plate to make sucker.The residual content that in the comparative studies process, the methyl chloride content in the steam-air mixture of sucker input is kept constant and methyl chloride in sucker exit check air-flow.The interruption concentration of methyl chloride is got 35g/m
3Value.The sprinkler discharge density that contains in comparative studies: under the condition of desirable diafiltration, be 3.7dm
3/ m
3To 4.2dm
3/ m
3, in service in desirable stirring is 0.6dm
3/ m
3The content of the methyl chloride in the sorbent is checked in the sucker exit.Thus obtained the results are shown in the table 5.
| C H，g/m 3 | The operation of desirable diafiltration | Desirable operation (froth bed) of stirring | ||||||||
| ?q， ?dm 3/m 3 | ?W， ?m/s | ?H 0， ?m | τ np, minute | A, mass percent | ?q， ?dm 3/m 3 | ?W， ?m/s | Foam layer height | τ np, minute | A, mass percent | |
| ??700 | ?3.7 | ?0.06 | ?1.6 | Do not puncture | 17.38 | ?0.6 | ?1.0 | ?0.30 | 0.5 below | 1.47 |
| ??1200 | ?4.2 | ?0.06 | ?1.6 | Do not puncture | 20.75 | ?0.6 | ?1.0 | ?0.30 | 0.5 below | 2.52 |
Table 5 underlying parameter of the methyl fluorocarbon oil sorption in the steam-air mixture under the different hydrodynamics method of operation in sucker.
Can infer from the result who draws, the oily sorption of stirring the methyl chloride in service of (in froth bed) in ideal is inapplicable, although its gas that will purify mutually in better performances, because can not guarantee on the one hand degree of depth intercepting methyl chloride, and on the other hand in mistake and sorbent that will draw the content of methyl chloride be 1.5 to 2.5 mass percents.Thereby the convection current of desirable diafiltration operation is comparatively favourable, because can guarantee the methyl chloride intercepting of height in the case, and reaches methyl chloride the highest content in the sorbent of using simultaneously.
Example 8
Equipment is arranged by two front and back and interconnective sorption filler post is formed, the diameter of each sorption filler post all is 3.25cm and highly all is 175cm that the desirable oily XF22c-16 of diafiltration usefulness in service in the convection current of contact phase absorbs methyl chloride mutually from gas with described equipment research.The methyl chloride content of check in the steam-air mixture of the exit of each sorption column.The parameter that draws is listed in table 6.
| C H，g/m 3 | ?q，dm 3/m 3 | W，m/s | ??????C k，g/m 3 | A, mass percent | The research duration, hour | |
| Behind |
Behind |
|||||
| ??700 | ????3.7 | ??0.06 | ????19 | ????＜5.0 | ??17.14 | ????3 |
| ??1200 | ????4.2 | ??0.06 | ????27 | ????＜5.0 | ??20.84 | ????5 |
Table 6: in filler, carry out, move and in relative current, divide from steam-air mixture the result of study of two-stage absorption methyl chloride in desirable diafiltration with oily XF22c-16.
Can infer by the process of suitably implementing the branch two-stage from the result who obtains and can guarantee the economic criterion that reaches higher: two-stage has been guaranteed the purified steam air mixture, and the degree of depth of methyl chloride from 20g/m
3Be reduced to not enough 5g/m
3Thus total methyl chloride intercepting degree is brought up to 99.3 to 99.6%.
Example 9
On the simulator of a special form of implementation, studied by means of heating the process that the sorbent that the regeneration of softening methyl chloride steam used is drawn in thermal diffusion subsequently.Described drawing relies on the pressure differential of the methyl chloride steam between its scope that discharges from saturated and its scope of condensing to be carried out, and described condensation is because the cooling effect generation of effluent air phase.Model described herein comprises all basic components of the unit of the sorbent used of being used to regenerate, and described parts are parts of the reclaimer shown in Fig. 3 and 4 (reclaim equiment).They are: from the sorbent of using, discharge the device of methyl chloride steam, contain useful internal diameter and be the stainless steel manufacturing of 13mm pipe, have the cover that is used for heating and be used for carrying equably the inlet of the sorbent of using to described device; Dosing pump is used for being transported to thermal desorption device with the sorbent of crossing; Glass condenser is used to cool off methyl chloride steam; The cooler of methyl chloride fluid phase condenses; The container that has the sorbent of using; The collection basin of the collection container of the sorbent of regeneration and the methyl chloride that is used to regenerate.Be used for the steam that the heat carrier of sorbent heating adopts steam generation to produce, the refrigerant of condensation and cooling usefulness adopts running water.Adopt oily XF22c-16 with the sorbent of crossing, contain the methyl chloride of 13 mass percents.The monitoring amount of methyl chloride steam and the methyl chloride that condenses in the temperature of temperature, oil of the sorbent introduced, vapours and device exit that is used to regenerate in research process.Carried out studying in the process effect of sprinkler discharge density, heating-up temperature, the sorbent duration on heating surface to methyl chloride regeneration level degree in experiment, be on the one hand, the effect to from the degree of the sorbent desorb used is another aspect.
Methyl chloride desorb degree (sorbent regeneration degree, η %) draws from following relational expression:
η＝(a
H-a
K)100/a
H?????(7)
In the formula: a
HWith (a in mass of the methyl chloride content in the sorbent of crossing
H=0.13);
a
kMethyl chloride content in the sorbent of regeneration in mass;
From sorbent the recovery degree (regeneration degree) (R, %) of methyl chloride draw by following relational expression:
R＝M
R·100/M
H?????????????????(8)
In the formula: M
RIn fact from the constant sorbent of using, the methyl chloride quality that r makes;
M
HThe real constant sorbent of using, the initial methyl chloride quality among the r;
The sorbent (η) used correspondingly is shown and from the recovery degree (regeneration level) of sorbent (R) methyl chloride used sprinkler discharge density (q, m to the open cross-sections of desorption apparatus in Figure 13 and 14
3/ m
2St) correlation is that the thin layer stream of 100 ℃ of sorbents is that l=1.5m is condition (sorbent stays duration on heating surface is 18 seconds to 20 seconds) along the length in the highway section on this face on the whole with the temperature at the sorbent of exit regeneration here.As drawing from the correlation of quoting, for reach regeneration most with the sorbent of crossing guarantee again simultaneously from the sorbent of using recovery (regeneration) methyl chloride most, sprinkler discharge density is adjusted in 25m
3/ m
2H to 30m
3/ m
2Be suitable in the scope of h.As long as sprinkler discharge density depart from slightly ideal value will or because of in exit methyl chloride concentration revolution (sprinkler discharge density excessive descent) or because of sorbent thin layer flow disturbance and the transition (sprinkler discharge density excessively improves) that moves in " boiling " and " overflowing " thereof, cause so decline of ascending of methyl chloride recovery degree (regeneration degree).
In Figure 15 and 16, drawn the result of this research, the length that η and R stretch along heating surface the correlation of the temperature thin layer stream by sorbent and pass through q=27.5m
3/ m
2The sprinkler discharge density of h indicates.
From correlation shown in Figure 16 as can be seen, the regeneration degree of sorbent had both depended on that the temperature of its heating also depended on the length (curve 1 that the thin layer stream of sorbent extends along heating surface
ι=1.5m; Line 2
ι=3.0m; Curve 3
ι=4.5m; Curve 4
ι=6.0m).
Can virtually completely from sorbent, separate methyl chloride (η=99.5%) at this, but the thin layer of sorbent stream must be 6m along the length that the face that is heated to 105 ℃ to 110 ℃ stretches at least.Regeneration degree η=90% that will determine sorbent has simultaneously just reached at ι=1.5m.The value that records shows, sorbent thin layer stream when ι＞3.0m just the minimizing to desorb do not acted on.With the recovery degree (regeneration degree) relevant (Figure 16) of methyl chloride be, so just reach its maximum, do not cause obviously improving R and the length that the thin layer of sorbent stream stretches is extended to ι=3m (curve 2) to 4.5m (curve 3).It is unsuitable simultaneously the amount of ι being adjusted to less than 3.0m, is reduced to 1.5m (curve 1) recovery degree (regeneration degree) and just drops to 70% because ι measured.Determine that in the process of research the loss of methyl chloride is 6% because of its density deficiency in this simulator, and 4% methyl chloride (as the steam in the free space of equipment) in circulation.Therefore on the angle of optimizing extraction and recovery (regeneration) methyl chloride from the sorbent of use, at sprinkler discharge density at 25m
3/ m
2H to 30m
3/ m
2Guarantee under the condition of h that attached dose the thin layer stream of inhaling along being heated to 105 ℃ to 110 ℃ is suitable.The length adjustment of its stretching, extension is to 3.0m, this with 36 seconds to 40 seconds to contact duration corresponding.
Example 10
On a special test platform of making corresponding to the construction unit of in the bottom of device shown in Figure 4, installing, studied the process of sorbent regeneration in the line merchant moulding in warmed-up metal charge.For having (example 7) in the thin layer stream of methyl chloride residual content of 1.3 mass percents in its regeneration back, this sorbent is delivered in the filler desorption device (the coarse cloth ring with the stainless steel manufacturing is made filler) of the adjustable device heating of heat-insulating usefulness along from top to bottom direction.In the process of research, change temperature (in exit monitoring sorbent temperature), sprinkler discharge density, the packed height (duration that sorbent stays) of filler on warmed-up filler surface, and the remnants of methyl chloride manage in exit check sorbent.Resulting the results are shown in the table 7.
| The research number | Exit sorbent temperature, ℃ | The filler sprinkler discharge density, m 3/m 2h | The duration that sorbent contacts with filler, c | The residual content of methyl chloride, mass percent | Sorbent regeneration degree, % | Annotate |
| ??1 | ????110 | ????6.0 | ????20 | ????0.08 | ????99.4 | |
| ??2 | ????110 | ????7.0 | ????20 | ????0.08 | ????99.4 | |
| ??3 | ????110 | ????7.0 | ????20 | ????0.09 | ????99.3 | |
| ??4 | ????110 | ????9.0 | ????20 | ????0.12 | ????99.1 | |
| ??5 | ????110 | ????9.5 | ????20 | ????0.12 | ????99.1 | Filler begins to overflow |
| ??6 | ????115 | ????6.0 | ????12 | ????0.07 | ????99.5 | |
| ??7 | ????115 | ????6.0 | ????15 | ????0.07 | ????99.5 | |
| ??8 | ????115 | ????6.0 | ????20 | ????0.07 | ????99.5 | |
| ??9 | ????115 | ????8.0 | ????12 | ????0.07 | ????99.5 | |
| ??10 | ????115 | ????8.0 | ????15 | ????0.07 | ????99.5 | |
| ??11 | ????115 | ????8.0 | ????20 | ????0.07 | ????99.5 | |
| ??12 | ????115 | ????9.0 | ????12 | ????0.07 | ????99.4 | |
| ??13 | ????115 | ????9.0 | ????15 | ????0.07 | ????99.5 | |
| ??14 | ????115 | ????9.0 | ????20 | ????0.07 | ????99.5 | |
| ??15 | ????120 | ????8.0 | ????12 | ????0.07 | ????99.5 | |
| ??16 | ????120 | ????8.0 | ????15 | ????0.07 | ????99.5 | |
| ??17 | ????120 | ????9.0 | ????12 | ????0.07 | ????99.5 | |
| ??18 | ????120 | ????9.0 | ????15 | ????0,07 | ????99.5 |
Table 7: sorbent Study on Regeneration result when when its online moulding, in the metal charge of heating, moving
From the value that draws as can be seen, be suitable with two stage regeneration with the sorbent of crossing.Phase I is the thin layer stream along the face of heating, and be 36 seconds to 40 seconds time of contact.Second stage is to carry out line to drip moulding in warmed-up metal charge.Sorbent must be crossed up to methyl chloride from reducing more than 30% from fully isolating the total length that stretches for this along the surface current of heating in the case.In order when its line drips moulding, from sorbent, to separate the residual content of methyl chloride, its with filler contact 12 seconds to 15 seconds just enough.In order to reach same value when the thin layer moulding of sorbent, require double contact duration, that is to say the double spread length that drips.
The application that line drips moulding is suitable at 115 ℃ to 120 ℃ and apart from spilling density at 8.0m
3/ m
2H to 9.0m
3/ m
2Between the h.Value with respect to 115 ℃ reduce measure require a contact duration proposed 20 seconds or more than.Also be not enough to implement this operation in the temperature that surpasses 120 ℃ simultaneously, because it further quickens seldom the raising that methyl chloride separates on the one hand, secondly because will avoid the thermal cracking of methyl chloride.In this regard, sprinkler discharge density must not surpass 9m
3/ m
2H avoiding filler " overflowing ", and must not be lower than 8m
3/ m
2H is to prevent decrease in efficiency.
Example 11
Develop the mobile device that from the used oil XF22c-16 of refrigeration unit, reclaims (regeneration) methyl chloride according to the schematic diagram shown in Fig. 3 and 4.
The function of this equipment is based on the principle of thermal diffusion, the thin layer that described thermal diffusion is present in used oil adds to be pined for, the thin layer of described used oil is with the drawing of the methyl chloride steam that flows and discharge from used oil of the face upper edge of the panel heater of Steam Heating to 105 ℃, rely on corresponding in the release areas and the saturated vapour pressure difference in the coagulation region carry out.Described pressure differential occurs when overheated methyl chloride steam being cooled in its temperature below boiling point.
After equipment continuous service a period of time, obtain following end value: the ability-65dm of oil processing
3/ h; Methyl chloride-1.0 remaining in the oil is to 1.5 mass percents; The recovery degree of methyl chloride (regeneration degree)-95.5%; Loss 4.5%.
Condensing of the methyl chloride of this manufacturing corresponding to the feature chemistry principal parameter of listing in the table 8 according to the GOST9968-73 standard.
| Density during 2.20 ℃ of |
Liquid 1.324-1.329 0.04 0.0008 indicator color dropout indicator color dropout according to the water white machinery-free foreign matter of GOST9968-73 standard composition | Find out the methyl chloride 1.324 0.03 0.0006 indicator color dropout indicator color dropout of recovery (regeneration) |
Table 8: the Main physical chemical parameters that reclaims the methyl chloride of (regeneration)
The method according to this invention and the equipment of implementing usefulness thereof enable under the condition of the carrying capacity of environment of having alleviated in fact by the material circulation of sealing and by guaranteeing to make the sorbent of particle by being recovered in the methyl chloride industry that is used as solvent in the workflow under the condition that recuperation of heat cuts down the consumption of energy.
Label list
1 centrifugal grinder
2 oar blade type blenders
2a aluminium hydroxide container
The container of 2b one hydration lithium
3 methyl chloride tanks
4 ribbon mixers
5 extruders
6 comminutors
7 finished containers
8 guiding valves
9 guiding valves
10 ventilation blowers
11 expansion tubes
12 compressors
13 guiding valves
14 absorb container
15 guiding valves
16 sorption packed columns
17 sorption packed columns
18 pumps
19 magnetic valves
20 cooling units
21 magnetic valves
22 pumps
23 heat exchangers
24 magnetic valves
25 pumps
26 are used for separating from the sorbent of using the device of methyl chloride
The coagulation of 27 vapours is collected basin
The condenser of 28 methyl chloride steam
The cooling device of 29 liquid methyl chlorine
The collection basin of 30 liquid methyl chlorine
31 magnetic valves
32 guiding valves
33 magnetic valves
34 tube bundle exchanger
35 transmit the last pipe fitting of vapours
36 draw the coagulative downside pipe fitting of vapours
Manage at the end on 37
38 times pipe ends
39 are used for transmitting to the tube space that has measurer 40 the side pipe fitting of the sorbent of using
40 measurers
41 liquid drop separators
42 have the cylinder of loam cake
43 Under The Grilles
Grid on 44
Space between 45 Under The Grilles 42 and the last grid 43
46 inclination accelerating jets
47 draw the side pipe fitting of overheated methyl chloride steam
48 times pipe ends
49 calandrias
50 hydrostatic columns
51 ends that tilt
52 draw the pipe fitting of the sorbent of purification
53 carrying gratings
54 radially plates
The filler of 55 heat conduction
56 have the pipe of the tube bundle exchanger 34 of cannelure 63
57 cores
58 ring springs
59 heat-insulating materials
60 vapours sources
The jar of 61 existing sorbents
62 times circular cone diffusers
63 inside grooves
64 magnetic valves
65 pumps
66 centrifugal grinder housings
67 store housing
68 blender axis
69 mixture containers
70 mixing paddles
71 hoisting geares
72 motor
73 drivers
Claims (10)
1. make the method for particle sorbent, described particle sorbent is used for obtaining lithium from the saline solution that contains lithium, and its basis is that the manufacturing molecular formula is LiCl2Al (OH)
3NH
2Two oxyhydroxides of the aluminium of O and lithium and then with the organic polymer that contains fluorine or chlorine as bond and methyl chloride as organic solvent with and the recycling followed, it is characterized in that,
-LiCl2Al (OH)
3NH
2O is with aluminium hydroxide and lithium salts manufacturing and then be processed into powder,
-in described powder, be mixed into cream under the condition of the bond of interpolation powder weight 8% to 10% and liquid methyl chlorine then to stick with paste, and then granulation,
-derive by means of traction gas at the methyl chloride steam of making that cream is stuck with paste and discharge during granulation, wherein this traction gas flows by all devices and material continuously and oppositely is directed,
-methyl chloride steam passes through by means of high boiling point organic compound as sorbent, from the traction air-flow, spun off by sorption with under desirable diafiltration method of operation contact relative current and the condition that contacts, described contact relative current guarantees farthest to separate methyl chloride and guarantees to be the fully saturated methyl chloride of sorbent that regeneration is drawn at the same time with contact from the traction air-flow
-saturated sorbent along a heatable conveying, wherein discharge methyl chloride and then the condensation methyl chloride steam of drawing and its on the one hand sulfuric acid fully extract methyl chloride apace from sorbent, and condensation methyl chloride steam most at the same time, and
The stream cooling of the saturated sorbent of-warmed-up and sorbent that discharge from methyl by participating in discharging methyl chloride, and feed back and be used for sorption.
2. the method for claim 1 is characterized in that, LiCl2Al (OH)
3NH
2O makes in high-power mixing arrangement, and is processed into powder and proceeds to granularity≤0.16mm and use the polyvinyl chloride of chlorination to make bond by means of centrifugal grinder-activator.
3. method as claimed in claim 1 or 2 is characterized in that, with a hydration lithium chloride as lithium salts.
4. as claim 1 or 2 or described method, it is characterized in that, make lithium salts with anhydrous lithium chloride existing under the condition of water, this is in order to obtain uniform bulk cargo in 0.05 to 0.30 the liquid and solid-state interpolation of ratio mutually.
5. as each described method in the claim 1～4, it is characterized in that, use freon oil, is that the freon oil of XF22c-16 is made sorbent with model preferably.
6. as each described method in the claim 1～5, it is characterized in that the methyl chloride concentration in the traction gas stream of participation sorption remains on 700g/m
3To 1200g/m
3Scope, the floor height of sorbent is at 1.70m to 1.95m in the sorption district of obturator, the sprinkler discharge density of the every cubic metre of gas phase sorbent that will purify is adjusted in 3.7dm
3To 4.2dm
3, and the linear velocity of described gas phase remains on the level of 0.04m/s to 0.06ms in the sorption district.
7. as each described method in the claim 1～6, it is characterized in that, carry out with two stages in the heating of this saturated sorbent: at first it as thin layer stream along being heated to 105 ℃ to 110 ℃ plane with 25m
3/ m
2Sprinkler discharge density flow through and on the face of this heating, stayed 36 seconds to 40 seconds; Then along being heated to 115 ℃ to 120 ℃ fillers with 8m with capacity of heat transmission
3/ m
2H to 9m
3/ m
2The h sprinkler discharge density flows through, and be 12 seconds to 15 seconds time of contact.
8. as each described method in the claim 1～7, it is characterized in that, derive from its release scope under the sorbent regeneration condition of heat methyl chloride steam by means of its from zone that saturated sorbent discharges with constitute incessantly methyl chloride condense mutually with its condition that contacts at eliminating and outside air under be cooled to the thermal diffusion realization that the pressure differential of the methyl chloride the zone of external temperature causes.
9. be used for making equipment, contain as claim 1～8 particle sorbent of method as described in each: the methyl chloride source, draw device, the condenser of the methyl chloride that condenses and the container of liquid methyl chlorine of methyl chloride, it is characterized in that,
-high-power blender (2), being used to make molecular formula is LiCl2Al (OH)
3NH
2Two oxyhydroxides of the aluminium of O and lithium, described high-power blender is connected with centrifugal grinder-activator (1),
-ribbon mixer (4) is used to make cream and sticks with paste, and has the LiCl2Al (OH) that refine to granularity≤0.16mm
3NH
2The feedback conveyer of O, transmit as the conveyer of the organic polymer that contains fluorine or chlorine of bond with from jar (3) from jar (4a) and to transmit the conveyer of methyl chloride,
-the extruder (5) that is connected with ribbon mixer (4), described extruder is connected with comminutor (6) as the methyl chloride vapour source, and wherein comminutor (6) is connected with the container (7) of finished product;
-assembly, contain the methyl chloride steam that ventilation blower (10) and compressor (12) are used for drawing from material stream traction gas, and the gas stream that is used for will purifying to this assembly introducing is to absorb methyl chloride steam, by the direct mutually of two series connection and coolable sorption filler post (16 through connecting through pump (18) with pipeline, 17), wherein sorption filler post (17) is connected with the jar (61) that absorbs sorbent, and this jar is connected with the unit (20) of cooling sorbent and the pipeline connection of the sorbent of whole assembly through being used for feed back purifying from heat exchanger (23), has
-heatable device (26) is used for discharging saturated methyl chloride steam from the sorbent of using, be connected with the condenser (28) of methyl chloride steam, the condenser of described methyl chloride steam (28) is being connected with the collection container (30) of liquid methyl chlorine by cooler (29) aspect it, wherein draws the device (26) of purifying adsorbent and the collection container of described liquid methyl chlorine both also was connected with jar (3) of the methyl chloride that will come into operation with condenser (28) through pipe fitting (52) heat exchanger.
10. equipment as claimed in claim 9 is characterized in that,
-be used for fully using heat-insulating material (59) to isolate and implement with the form of the tube bundle heat exchanger (34) that has the side pipe fitting from the device (26) that separates methyl chloride with the sorbent of crossing, and correspondingly there is the upper side pipe fitting to be used for being used for drawing the vapours coagulation from intertubular space (36) to intertubular space introducing vapours (35) and downside pipe fitting
-upward arrange to have the circular cone diffuser (38) of the ventilation blower (40) that has side pipe fitting (39) to be used for introducing the sorbent of using at the pipe end (37) of going up of heat exchanger (34) to intertubular space,
-upward circular cone diffuser (38) has the columniform lid (42) of going up, arrange upper and lower grid (43,44) in the lid (42), fill with granular materials or fibrous material in the space of Gou Chenging betwixt, and liquid drop separator (41) is provided with the inclination accelerating jet (46) that is installed in grid (44) top, described inclination accelerating jet (46) has the side pipe fitting (47) that is used to cool off overheated methyl chloride steam
-(48) last circular cone diffuser (62) of arranging to have heatable device (49) at the bottom of the following pipe of heat exchanger (34), described circular cone diffuser (62) has the end (51) that has inclination and is used to draw the cylindrical housings (50) of following pipe fitting (52) of the sorbent of regeneration,-in cylindrical housings (50), fixing to pipe fitting (52) upper horizontal carrying grating (53) down, radially arrange to be vertically fixed on the plate (54) on housing (50) inwall on it, and fill the filler of heat conduction in the free space between plate, preferably fill the fabric loop of metal, tube bundle exchanger (34) is in the top of the pipe end (37) and constitutes the batching dish that can fill with the sorbent of using therewith, and each pipe of tube bundle exchanger (34) respectively have one can with the interweave core (57) of blown tubular into the net of sorbent, and the core of described blown tubular (57) is pressed into by means of tension link (58) by ring spring (58) in the cannelure (63) on the inner surface that is arranged on pipe (56) in the upper end of pipe (56), and another part of the core of blown tubular (57) from inside to outside through pipe (56) turnup, is led to the pipe end (37) along pipe (56).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/DE2001/004062 WO2003041857A1 (en) | 2001-10-25 | 2001-10-25 | Method for producing granulated sorbents and installation for carrying out the method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1558793A true CN1558793A (en) | 2004-12-29 |
| CN1302844C CN1302844C (en) | 2007-03-07 |
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ID=5648305
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|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN1302844C (en) |
| DE (1) | DE10197095D2 (en) |
| WO (1) | WO2003041857A1 (en) |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198000A (en) * | 1990-09-10 | 1993-03-30 | The University Of Connecticut | Method and apparatus for removing gas phase organic contaminants |
| RU2009714C1 (en) * | 1992-01-27 | 1994-03-30 | Менжерес Лариса Тимофеевна | Process of manufacturing pelletized sorbing material for lithium recovery from salt brines |
| RU2050184C1 (en) * | 1993-02-16 | 1995-12-20 | Научно-производственное акционерное общество "Экостар" | Method to produce granulated sorbent for lithium extraction from brines |
| WO1994019280A1 (en) * | 1993-02-16 | 1994-09-01 | Nauchno-Proizvodstvennoe Aktsionernoe Obschestvo 'ekostar' | Process for obtaining lithium chloride from solutions and a device for carrying out the same |
-
2001
- 2001-10-25 WO PCT/DE2001/004062 patent/WO2003041857A1/en active Application Filing
- 2001-10-25 CN CNB018237401A patent/CN1302844C/en not_active Expired - Lifetime
- 2001-10-25 DE DE10197095T patent/DE10197095D2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2003041857A1 (en) | 2003-05-22 |
| DE10197095D2 (en) | 2004-09-16 |
| CN1302844C (en) | 2007-03-07 |
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