CN104174181A - Separation and purification system of organic synthesis feed liquid and separation and purification method thereof - Google Patents
Separation and purification system of organic synthesis feed liquid and separation and purification method thereof Download PDFInfo
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- CN104174181A CN104174181A CN201410403559.9A CN201410403559A CN104174181A CN 104174181 A CN104174181 A CN 104174181A CN 201410403559 A CN201410403559 A CN 201410403559A CN 104174181 A CN104174181 A CN 104174181A
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Abstract
The invention aims at the field of chemical industry and relates to a separation and purification system of organic synthesis feed liquid and a separation and purification method of the organic synthesis feed liquid. The separation and purification system comprises a crystallization system and a solid-liquid separation system which are sequentially arranged from front to back, wherein the crystallization system comprises a mixed suspension-mixed product-removal (MSMPR) crystallizer and a draft-tube-baffled (DTB) crystallizer which are connected with each other in series; the separation and purification system also comprises a liquid processing system used for processing waste liquid produced by the solid-liquid separation system; the liquid processing system comprises a desalting device and a membrane concentration device which are sequentially arranged from front to back. By virtue of the separation and purification system of the organic synthesis feed liquid and the separation and purification method thereof, the organic synthesis feed liquid is separated and purified by using a continuous crystallization technology, an electrodialysis technology and a membrane separation and concentration technology; the produced waste liquid is fully recycled and used, so that the separation and purification efficiency is improved, the purity and the yield of products are improved and the discharge of the waste liquid is reduced; the separation and purification system of the organic synthesis feed liquid and the separation and purification method thereof are strong in production industrialization and low in costs, and are especially suitable for producing iminodiacetonitrile.
Description
Technical field
The present invention is directed to chemical field, relate to a kind of separation and purification system and isolation and purification method of organic synthesis feed liquid.
Background technology
Organic synthesis is a kind of major way that chemical industry obtains target product, and its reacted reaction material liquid system is mainly made up of target product, residual raw material and accessory substance.Industrial, how reaction feed liquid is carried out to separation and purification with efficient, highly purified acquisition target product, and to greatest extent waste liquid, waste residue are recycled, closely bound up with industrial efficiency and cost.And the lab scale in laboratory is compared with industrialized large-scale production, the latter's parameter control and the homogeneity control of reaction system are also more difficult.Therefore, how to design one and be enclosed within large-scale industrialization production, the system that can carry out to organic synthesis feed liquid efficient separation and purification, farthest improves product yield, purity, and waste liquid and waste residue are recycled fully, there is huge industrialization meaning.
The separation and purification of an organic synthesis feed liquid generally includes the step of crystallization and Separation of Solid and Liquid.The crystallizer adopting is generally the crystallizing tank with temperature control and agitating device, and traditional handicraft adopts primary crystal, mother liquor heating again to get brilliant mode after concentrating conventionally.Because product has higher solubility in water, cause getting brilliant rate lower; Meanwhile, because mother liquor, in heating concentration process, all kinds of chemical reactions occurs, cause its quality fast-descending, thereby cannot continue to utilize, raffinate can only be served as wastewater treatment, and mother liquor utilization rate is low, and waste water generation is large.The equipment for separating liquid from solid adopting is generally centrifuge, suction filtration machine, rejection filter machine etc., and operation relates to that filter cake rinses, the problem such as product loss in filtrate.In a word, yield and the purity of the product that the final separation and purification of these equipment obtains, more depend on reaction material liquid system itself, and complicated operation, and waste liquid, waste residue are not easy to be recycled.
Taking the organic synthesis feed liquid of iminodiacetonitrile as example, its organic synthesis principle is as follows:
Main reaction:
Side reaction:
NH
3+HOCH
2CN←→NH
2CH
2CN+H
2O
After above-mentioned reaction finishes, the organic synthesis feed liquid system of acquisition at least comprises residual ammonia and hydroxyacetonitrile, iminodiacetonitrile and accessory substance thereof.To from this reaction feed liquid, separate and obtain iminodiacetonitrile, ammonia need to be converted into inorganic salts and remove, and as much as possible mother liquor be recycled, to improve finished product yield, reduce discharging of waste liquid.China granted patent CN1331844C discloses a kind of preparation technology of iminodiacetonitrile, its final yield that obtains is more than 90%, purity is more than 98%, can find out according to embodiment, the lifting of its ultimate yield and purity depends primarily on the control of synthetic reaction condition, last separation and purification operation does not produce contribution function to yield and purity, and what reason was just its use is conventional separation and purification device and method.
The shortcoming existing based on above-mentioned prior art and needs, the present invention improves the separation and purification system of organic synthesis feed liquid.
Summary of the invention
In view of this, the present invention first provides a kind of separation and purification system of the organic synthesis feed liquid that can improve separation and purification efficiency, product yield and purity.
For achieving the above object, technical scheme of the present invention is:
A kind of separation and purification system of organic synthesis feed liquid, comprise the crystal system and the solid-liquid separation system that set gradually from front to back, described crystal system is the multistage continuous crystallizing system that more than two crystallizer is composed in series, or be the crystal system that more than two crystallizer composes in parallel, or formed by single crystallizer.
Further, described crystal system is discharged crystallizer (MSMPR pattern crystallizer) series connection guide shell crystallizer (DTB crystallizer or DP crystallizer) by mix suspending-product mix and is formed, or discharging crystallizer by guide shell crystallizer series hybrid suspension-product mix forms, or discharge crystallizer by more than two mix suspending-product mix and be composed in series, or be composed in series by more than two guide shell crystallizer.
MSMPR pattern crystallizer is the abbreviation that mix suspending-product mix is discharged (Mixed Suspension-Mixed Product Removal) crystallizer, be characterized in mixing therein cmpletely, making in crystallizer the suspension density of crystal and size distribution on any material position is all homogeneous, and suspension density and the size distribution of its magma of product of discharging from crystallizer are also identical with in device, indiscriminate to varigrained crystal in the time of discharge, and be different from classification discharge.Fig. 1 is shown in by the feature sketch of MSMPR pattern crystallizer of the present invention.DTB crystallizer is the abbreviation of guide shell crystallizer (Drabt Tube Babbled), is a kind of typical magma internal-circulation type crystallizer.In crystallization process, the degree of supersaturation of solution, the uniformity consistency of temperature of charge and speed of agitator and film-cooled heat, be the deciding factor that affects product grains size and appearance form.DTB crystallizer has adopted special paddle, and temperature, rotating speed of agitator is adjustable, easily realize system automatic control system, to adapt to the requirement of various material crystallizations, the structure that it is unique and operation principle have determined that it has the features such as heat transfer efficiency is high, configuration is simple, convenient operation and control, good operational environment.DP crystallizer is the modified of DTB type, and the outer survey of its guide shell is also provided with one group of propeller blade, and crystal particle mean size is increased, and production capacity improves.Combination by above-mentioned MSMPR pattern crystallizer, DTB crystallizer, DP crystallizer is carried out Crystallization Separation to organic synthesis feed liquid, and more than the product crystal average grain diameter that crystallization obtains can reach 0.3mm, evenly, uniformity is high for size; Meanwhile, because crystalline quality is higher, the product after centrifuge carries out solid-liquid separation, its water content can directly reach quality index, can save product drying step, thereby saves in a large number human and material resources.
Further, this separation and purification system also comprises the liquid processing system that the liquid of solid-liquid separation system extraction is processed, this liquid processing system comprises the desalter and the film condensing device that set gradually from front to back, desalter is for the liquid of solid-liquid separation system extraction is carried out to desalination, and film condensing device is for concentrating the liquid after desalter desalination.Described desalter comprises the device that the methods such as counter-infiltration (RO), electrodialysis, diffusion dialysis, forward osmosis are corresponding etc., preferably electrodialysis plant or diffusion dialysis device, particularly electrodialysis plant.Described film condensing device comprises the devices corresponding to method such as counter-infiltration, ultrafiltration, nanofiltration.Wherein, described counter-infiltration in principle water be unique by the material of film; Particularly the material of all dissolvings and suspension is trapped.This system adopts the technology such as film separation, electrodialysis separation, and in mother liquor, product recovery rate promotes, and product yield is obviously improved; Meanwhile, this system produces without the concentrated raffinate of traditional handicraft, and cost for wastewater treatment reduces greatly.
Further, described desalter is electrodialysis plant or diffusion dialysis device.
Further, described solid-liquid separation system comprises a pair of above concentrator and the centrifuge setting gradually.Described concentrator is the solid-liquid separating equipment based on gravitational settling effect, be generally by concrete, timber or metal welding fishplate bar and build up the band cylindrical shape shallow slot at the cone end as structural material, feed liquid is carried out sedimentation therein, and top is more peace and quiet clarified solution (overflow), and bottom is thick feed liquid.Described centrifuge can be one or more in suspended centrifuge, vane type filtration machine and continuous centrifugal machine.Wherein, described continuous centrifugal machine belongs to vertical centrifugal discharging filter screen flow-guiding type centrifuge.When work, material is entered in centrifuge by top, tripper is continuously inserted material in flow-guiding channel, under the effect of centrifugal force, material flows downward along flow-guiding channel, in flow process, liquid sees through filter screen and enters liquid-collecting bin, and solid material is discharged into the solid collection storehouse of bottom along flow-guiding channel.Utilize centrifugal force, continuous centrifugal machine has completed centrifugal filtration and centrifugal discharge simultaneously, and the angle of flow-guiding channel can arbitrarily be adjusted, thereby can change the length of passage, control the time of staying of material in flow-guiding channel, the moisture content of solid material is controlled to optimum state.
Further, described solid-liquid separation system comprises the one-level concentrator, suspended centrifuge, secondary concentrator and the vane type filtration machine that set gradually; The charging aperture of described one-level concentrator is connected with the discharging opening of crystal system, the thick material outlet of underflow of one-level concentrator is connected with the charging aperture of suspended centrifuge, and the top stream purified liquor outlet of one-level concentrator and the filtrate (liquid of suspended centrifuge are connected with the charging aperture of secondary concentrator; The thick material outlet of underflow of described secondary concentrator is connected with the charging aperture of crystal system, and the top stream purified liquor outlet of secondary concentrator is connected with the charging aperture of vane type filtration machine; The filtrate (liquid of described vane type filtration machine is connected with the charging aperture of desalter.This is the form that specifically arranges of " a pair of above concentrator and the centrifuge setting gradually ", dense by secondary, fully isolate the crystal in crystalline mixture, thin magma can be back to crystal system crystallization again, isolated filtrate impurity also still less, filtrate enters in follow-up desalination and concentration operation, and also less to the damage of equipment, equipment is more durable.
Further, the concentrated solution outlet of described film condensing device is connected with the charging aperture of centrifuge and/or crystal system crystallizer.That is, reclaim the washing of this concentrate for filter cake, or return of value crystallizer carries out the crystallization of product again.
Further, before described crystal system, be provided with decolouring system, for removing impurities that organic synthesis feed liquid is decoloured; Or, between described solid-liquid separation system and desalter, be provided with decolouring system, for the liquid of solid-liquid separation system extraction is decoloured.
Further, described decolouring system is made up of the ultrafiltration apparatus of connecting and nanofiltration device.Ultrafiltration (UF) is macromolecule component (HMWC), and as protein, suspended solid are trapped, and all lower molecular weight components are freely by the process of film; The negatively charged ions that exceedes monovalence is held back in nanofiltration (NF) in theory, as sulfate, phosphate (in the present invention, can hold back the inorganic salts in feed liquid), and can be by the anion of unit price.According to bulk of molecule and shape, nanofiltration also can be held back neutral, dissolved matter and positive charge ion.Decolouring system adopts the combination of ultrafiltration (UF)+nanofiltration (NF), treats that destainer first passes through hyperfiltration treatment that is:, removes the suspension part macromolecule impurity in solution; Ultrafiltration sees through liquid and enters nanofiltration separation, successively removes impurity and the part inorganic salts in solution through the NF membrane of larger membrane aperture and less membrane aperture; Nanofiltration sees through liquid and continues on in production, and trapped fluid is by atomization burning disposal after evaporation and concentration.
Further, before described desalter, be also provided with filter or filtrate collecting tank, for the liquid of solid-liquid separation system extraction being filtered to or leave standstill clarification; In the time being provided with decolouring system after solid-liquid separation system, described filter is the pre-treatment part of decolouring system, and the liquid of solid-liquid separation system extraction enters the decolouring of decolouring system after filtering again.For the latter, as, filter now consists of: strainer, ultrafilter and nanofiltration device, and the charging aperture of described strainer is connected with the filtrate (liquid of centrifuge, and the filtrate discharging opening of strainer is connected with the charging aperture of ultrafilter; The filtrate (liquid of described ultrafilter is connected with the charging aperture of nanofiltration device; The filtrate (liquid of described nanofiltration device is connected with the charging aperture of desalter.Further, the charging aperture of described strainer is also connected with the top stream purified liquor outlet of described concentrator, and the precipitation discharging opening of described strainer is connected with the charging aperture of crystallizer.The precipitation that aforementioned filter or filtrate collecting tank obtain can import crystallizer, uses as crystal seed, and product fully reclaims and also improves total yield of products.
Mentioned device systems and device in the separation and purification system of above-mentioned organic synthesis feed liquid, as long as the adjustment of reasonable increase, omission, replacement or rotine positioning that those skilled in the art can infer all should be included in design of the present invention; Equally, some auxiliary equipment and the device in this system, do not mentioned in detail, as the setting of the devices such as heating, cooling, pump, basin, every those skilled in the art can expect, also should be included in design of the present invention.As, the above-mentioned feeder of mentioning and strainer, object is collect liquid and clarify or further filter liquide for leaving standstill, it reasonably omits or by the replacement of other devices, is all included in design of the present invention.
The separation and purification system of above-mentioned organic synthesis feed liquid can be used for the separation and purification of multiple organic synthesis product feed liquid, and these feed liquids mainly refer to the mixed liquor containing organic products and a large amount of inorganic salts.Preferably, the separation and purification for the synthetic feed liquid of iminodiacetonitrile, the synthetic feed liquid of iminodiacetic acid, the synthetic feed liquid of glycine or the synthetic feed liquid of methionine by described separation and purification system.
Corresponding with above-mentioned separation and purification system, the present invention also provides a kind of isolation and purification method of the organic synthesis feed liquid that can improve separation and purification efficiency, product yield and purity.
For achieving the above object, technical scheme of the present invention is:
An isolation and purification method for organic synthesis feed liquid, comprises the following steps: described organic synthesis feed liquid adopts crystal system to carry out crystallization and obtains magma, and described magma obtains product and filtrate through Separation of Solid and Liquid; Described crystal system is the multistage continuous crystallizing system that more than two crystallizer is composed in series, or is the crystal system that more than two crystallizer composes in parallel, or is made up of single crystallizer.
Further, described crystal system is the continuous crystallizing system that mix suspending-product mix discharge crystallizer (MSMPR pattern crystallizer) series connection guide shell crystallizer (DTB crystallizer or DP crystallizer) or guide shell crystallizer series hybrid suspension-product mix are discharged crystallizer or two mix suspending of connecting above-product mix discharge crystallizers or two guide shell crystallizers of connecting above.
Further, in described organic synthesis feed liquid, contain organic products and inorganic salts.
Further, the filtrate of described Separation of Solid and Liquid gained is by electrodialysis or the desalination of diffusion dialysis technology, and the liquid after desalination concentrates by membrane separation technique again.Preferably, remove more than 90% inorganic salts through electrodialysis desalination, then extraction desalinization liquor concentrates.
Further, described organic synthesis feed liquid is carrying out before continuous crystallisation, the removing impurities of also decolouring operation; Or, the filtrate of described Separation of Solid and Liquid gained before electrodialysis desalination, the operation of also decolouring.
Further, described decolouring operation is to complete by the ultrafiltration nanofiltration of connecting.
Further, described Separation of Solid and Liquid completes by a pair of above concentrator and the centrifuge setting gradually.
Further, described Separation of Solid and Liquid completes by the one-level concentrator, suspended centrifuge, secondary concentrator and the vane type filtration machine that set gradually; The thick material of underflow of described one-level concentrator enters the centrifugal acquisition product of suspended centrifuge, and the top stream clear liquid of one-level concentrator and the centrifuge mother liquor of suspended centrifuge enter secondary concentrator; The thick material of underflow of described secondary concentrator returns to continuous crystallisation step again, and the top stream clear liquid of secondary concentrator enters vane type filtration machine and filters to get filtrate, and filtrate is carried out electrodialysis desalination again.
Further, described magma solid content is promoted to 40%-50% by described concentrator, the thicker material of extraction underflow and top stream clear liquid.
Further, clarification is also filtered or left standstill to the filtrate of described Separation of Solid and Liquid gained before electrodialysis desalination, and the precipitation of filtering or leave standstill collection is back to continuous crystallisation step and uses as crystal seed.When also decolour step before electrodialysis desalination time, decolouring now and filtration can a step complete, essence filter, ultrafiltration and the nanofiltration carried out successively as filtration is arranged to.
Further, the concentrate of the concentrated gained of described membrane separation technique is back to the crystallization again of continuous crystallisation step, and/or is back to solid-liquid separation step washing leaching cake.
Further, in described continuous crystallizing system, the temperature of rear one-level crystallizer crystallization is lower than the temperature of previous stage crystallizer crystallization.As, when mix suspending-product mix is discharged crystallizer series connection guide shell crystallizer, the temperature of the latter's crystallization is lower than the temperature of the former crystallization.
The isolation and purification method of above-mentioned organic synthesis feed liquid can be used for the processing of multiple organic synthesis product feed liquid, preferably, the separation and purification for the synthetic feed liquid of iminodiacetonitrile, the synthetic feed liquid of iminodiacetic acid, the synthetic feed liquid of glycine or the synthetic feed liquid of methionine by described isolation and purification method.
More preferably, the present invention also provides a kind of isolation and purification method of the synthetic feed liquid of iminodiacetonitrile that can improve separation and purification efficiency, product yield and purity.
For achieving the above object, technical scheme of the present invention is:
An isolation and purification method for the synthetic feed liquid of iminodiacetonitrile, described synthetic feed liquid be taking hydroxyacetonitrile and ammonia as the reactant liquor of raw material synthesizing iminodiacetic acid (salt) nitrile with inorganic acid or organic acid mixed liquor for neutralization of ammonia, comprise the following steps:
A, described synthetic feed liquid adopt crystal system to carry out crystallization and obtain magma, and described magma obtains product and filtrate through Separation of Solid and Liquid; Described crystal system is the multistage continuous crystallizing system that more than two crystallizer is composed in series, or is the crystal system that more than two crystallizer composes in parallel, or is made up of single crystallizer;
The filtrate of B, described Separation of Solid and Liquid gained is by electrodialysis or the desalination of diffusion dialysis technology, liquid after desalination concentrates by membrane separation technique again, the concentrate of concentrated gained is back to the crystallization again of continuous crystallisation step, and/or is back to solid-liquid separation step washing leaching cake.
Further, described crystal system is the continuous crystallizing system that mix suspending-product mix discharge crystallizer series connection guide shell crystallizer or guide shell crystallizer series hybrid suspension-product mix are discharged crystallizer or two mix suspending of connecting above-product mix discharge crystallizers or two guide shell crystallizers of connecting above.
Further, described organic synthesis feed liquid is carrying out before continuous crystallisation, the removing impurities of also decolouring operation; The operation of described decolouring removing impurities completes by the ultrafiltration nanofiltration of connecting.
Further, described Separation of Solid and Liquid completes by a pair of above concentrator and the centrifuge setting gradually.
Further, described magma solid content is promoted to 40%-50% by described concentrator, the thicker material of extraction underflow and top stream clear liquid.
Further, the filtrate of described Separation of Solid and Liquid gained is removed more than 90% inorganic salts through electrodialysis desalination, then extraction desalinization liquor.
Further, the temperature of discharging the crystallizer crystallization of material in described crystal system is controlled at 10～12 DEG C, and pH is controlled at 2.5～4.0.
The separation and purification system and method for above-mentioned organic synthesis feed liquid, optimization setting and condition that it is mentioned, be all applicable to the separation and purification of this part iminodiacetonitrile feed liquid.
Relevant to the separation and purification system of the organic synthesis feed liquid of foregoing invention, the present invention also provides a kind of waste water utilization fully and can improve the recycling system of the waste liquid producing in the organic synthesis feed liquid separation and purification of product yield.
For achieving the above object, technical scheme of the present invention is:
A recycling system for the waste liquid producing in the separation and purification of organic synthesis feed liquid, comprises the filter, desalter and the film condensing device that set gradually from front to back; Described desalter is connected with the liquid outlet of filter, and described film condensing device is connected with the desalinization liquor outlet of desalter; Or comprise the filtrate collecting tank, desalter and the film condensing device that set gradually from front to back; Described desalter is connected with the outlet of feeder, and described film condensing device is connected with the desalinization liquor outlet of desalter.Described feeder plays a part to collect waste liquid, can omit or be replaced by other tank body.
Further, the apparatus system that described separation and purification adopts comprises the decolouring system, crystal system and the solid-liquid separation system that set gradually from front to back; Described solid-liquid separation system is made up of the concentrator setting gradually from front to back and centrifuge; Described concentrator is provided with the thick material outlet of underflow and top stream purified liquor outlet, and the thick material outlet of described underflow is connected with centrifuge.
Further, described decolouring system is made up of the ultrafiltration apparatus of connecting and nanofiltration device.
Or, above-mentioned decolouring is located at after crystallization, as, the processing of decolouring before the filtrate desalination of centrifuge, completes this operation by filter.Particularly, described filter is made up of the strainer setting gradually from front to back, ultrafilter and nanofiltration device; The filtrate discharging opening of described strainer is connected with the charging aperture of ultrafilter; The filtrate (liquid of described ultrafilter is connected with the charging aperture of nanofiltration device; The filtrate (liquid of described nanofiltration device is connected with the charging aperture of desalter.
Further, the apparatus system that described separation and purification adopts comprises the crystal system and the solid-liquid separation system that set gradually from front to back; Described solid-liquid separation system is made up of the concentrator setting gradually from front to back and centrifuge; Described concentrator is provided with the thick material outlet of underflow and top stream purified liquor outlet, and the thick material outlet of described underflow is connected with centrifuge; The charging aperture of described strainer is connected with the filtrate (liquid of centrifuge.
Further, the charging aperture of described strainer is also connected with the top stream purified liquor outlet of described concentrator.
Further, the discharge of filter residues mouth of described strainer is connected with the charging aperture of crystal system.Described filter residue enters crystal system and uses as crystal seed.
Further, the concentrated solution outlet of described film condensing device is connected with the charging aperture of centrifuge and/or crystal system.Described concentrate is for washing leaching cake, or enters crystal system and further extract product.
Relevant to the isolation and purification method of the organic synthesis feed liquid of foregoing invention, the present invention also provides a kind of waste water utilization fully and can improve the recoverying and utilizing method of the waste liquid producing in the organic synthesis feed liquid separation and purification of product yield.
For achieving the above object, technical scheme of the present invention is:
A recoverying and utilizing method for the waste liquid producing in the separation and purification of organic synthesis feed liquid, comprises the following steps:
First the waste liquid producing in A, the separation and purification of described organic synthesis feed liquid filters with filter, obtains filtrate;
B, described filtrate, by desalter desalination, obtain desalinization liquor;
C, described desalinization liquor concentrate by film condensing device, obtain concentrate.
Further, in described organic synthesis, in the waste liquid after separation and purification, contain organic products and inorganic salts.
Further, the waste liquid producing in the separation and purification of described organic synthesis feed liquid is obtained after decolouring step, crystallisation step, solid-liquid separation step by organic synthesis feed liquid.
Or, above-mentioned decolouring step is located at after crystallisation step, as, the processing of decolouring before filtrate desalination, completes this operation by filter.Particularly, the waste liquid in described organic synthesis after separation and purification first filters by strainer, obtains thin magma and front filtrate; Described front filtrate is filtered by ultrafilter and nanofiltration device more successively, obtains filtrate.
Further, the waste liquid producing in the separation and purification of described organic synthesis feed liquid is obtained after crystallisation step, solid-liquid separation step by organic synthesis feed liquid; The thin magma that described strainer obtains is back to crystallisation step, uses as crystal seed.
Further, the concentrate that described step C obtains is back to crystallisation step crystallization again, and/or is back to the washing of solid-liquid separation step for filter cake.
Further, in described step B, described desalter is electrodialysis plant or diffusion dialysis device, and described filtrate is removed more than 90% inorganic salts through desalter, then extraction desalinization liquor.
Further, the application of the waste liquid that the recoverying and utilizing method of the waste liquid producing in organic synthesis feed liquid separation and purification described above produces in the separation and purification of recycling iminodiacetonitrile feed liquid, described iminodiacetonitrile synthesizes taking hydroxyacetonitrile and ammonia as raw material, and by inorganic acid or organic acid neutralization of ammonia.
Other setting and the system of above-mentioned waste liquid recycling system, be also applicable to the application in the recoverying and utilizing method of this part, especially for the processing of waste liquid in the separation and purification of iminodiacetonitrile feed liquid.
Useful technique effect of the present invention is:
The present invention has fully utilized CGS Continuous Grain Silicon, electrodialytic technique and membrane separation concentration technology etc. organic synthesis feed liquid has been carried out to separation and purification, and the waste liquid producing is carried out to sufficient recovery and utilization, the efficiency of separation and purification and the purity of product and yield are improved, reduced the discharge of waste liquid, manufactureization is strong, cost is low.Be embodied in following aspect:
(1), by the continuous crystallisation of MSMPR pattern crystallizer, DTB crystallizer or DP crystallizer, more than product crystal average grain diameter can reach 0.3mm, evenly, uniformity is high for size; Meanwhile, because crystalline quality is higher, the product after centrifuge carries out solid-liquid separation, its water content can directly reach quality index, can save product drying step.With regard to product water content, traditional production technology is because product crystallization crystal grain is little, distribution of sizes is wide, cause product centrifugal filter cake water content on average more than 6.0%, this technique is due to lifting (the crystal average grain diameter increase of product crystalline quality, crystal size distribution scope is narrower), taking iminodiacetonitrile as example, only can make product filter cake be less than the moisture of 0.5% (w/w%) by centrifugation, greatly be better than the quality index of Grade A moisture≤3.0% (w/w%) in GB/T23958-2009 " industrial iminodiacetonitrile ", thereby centrifugal follow-up product drying operation in omission traditional handicraft, greatly simplify production procedure, reduce artificial consumption.
(2) prior art is again got brilliant mode after adopting heating concentrated to product crystalline mother solution and is processed, because product has higher solubility in water, cause getting brilliant rate lower, simultaneously, because mother liquor, in heating concentration process, all kinds of chemical reactions occurs, cause its quality fast-descending, thereby cannot continue to utilize, raffinate can only be served as wastewater treatment.Or prior art is taken out the mode that adopts repeatedly evaporation and concentration, consume a large amount of steam.On the whole, mother liquor utilization rate is low, and waste water generation is large.The present invention adopts the technology such as electrodialysis, membrane separation concentration to carry out abundant recovery and reuse to crystalline mother solution, product yield, quality all have remarkable lifting, taking the production of iminodiacetonitrile as example, in reactant liquor, product extraction efficiency is promoted to more than 95% by 80%, the main content of product rises to 97% by 95%, production efficiency is high, and production cost is low.
(3) wastewater flow rate obviously declines, and taking the production of iminodiacetonitrile as example, product wastewater flow rate per ton is about 0.15m
3be only 1/10 of former technique, and waste water be high concentration without salting liquid, be easy to burning disposal; Compared with prior art, the inorganic salts that enter waste water are separated, realized recycling, reduced wastewater treatment difficulty simultaneously.
(4) production overall process becomes continuous operation from intermittently operated, is easy to realize whole-course automation control, and artificial quantity required obviously reduces, and labour intensity greatly reduces, and production cost reduces.
(5) said system and method are applied to the production of iminodiacetonitrile, and product quality is significantly improved, and product extraction efficiency is high, has reduced waste discharge, has reduced production cost.
Brief description of the drawings
Fig. 1 is the structural representation (in figure, a-b is charging aperture, and c-f is discharging opening, and g is cylindrical shell, and h is inner draft tube, and i is agitating device, and j is at the bottom of " W " type or at the bottom of ellipse head) of MSMPR pattern crystallizer;
Fig. 2 is the equipment flowsheet (in figure, decolouring system is located at before crystal system) of the separation and purification system of a kind of organic synthesis feed liquid of the present invention;
Fig. 3 is a kind of structural representation of Fig. 2 equipment;
Fig. 4 is the concrete equipment flowsheet of the one of solid-liquid separation system in Fig. 2;
Fig. 5 is a kind of structural representation of Fig. 4 equipment;
Fig. 6 is the equipment flowsheet (in figure, decolouring system is located at after crystal system, decolours and synchronously completes while filtration by filter) of the separation and purification system of the another kind of organic synthesis feed liquid of the present invention;
Fig. 7 is a kind of structural representation of Fig. 6 equipment;
Fig. 8 is equipment flowsheet and the flow direction of material figure (having omitted storage tank in figure) while utilizing system separation and purification iminodiacetonitrile of the present invention;
Fig. 9 is a kind of structural representation of Fig. 8 equipment and flow direction of material;
Figure 10 is the concrete equipment flowsheet of the one of solid-liquid separation system in Fig. 8 and flow direction of material figure;
Figure 11 is a kind of structural representation of Figure 10 equipment and flow direction of material.
Detailed description of the invention
As shown in Figures 2 and 3, a kind of organic synthesis feed liquid separation and purification system of the present invention and liquid waste treatment system thereof, comprise the liquid processing system 3 that the decolouring system 4, crystal system 1, solid-liquid separation system 2 and the waste liquid to solid-liquid separation system 2 extraction that set gradually are from front to back processed.Described decolouring system 4 is made up of the ultrafiltration apparatus of connecting and nanofiltration device.Described crystal system 1 is made up of MSMPR pattern crystallizer series connection DTB crystallizer.Described solid-liquid separation system 2 comprises the concentrator and the centrifuge that arrange from front to back.Described liquid processing system 3 comprises the filter 301 (this filter 301 also can be cancelled, or is replaced by a feeder 6, works to collect filtrate, clarification), desalter 302 and the film condensing device 303 that set gradually from front to back; Described filter 301 is connected with the filtrate (liquid of centrifuge, and described desalter 302 is connected with the liquid outlet of filter 301, and described film condensing device 303 is connected with the desalinization liquor outlet of desalter 302.The concentrated solution outlet of described film condensing device 303 is connected with the charging aperture of centrifuge and/or crystallizer.
The organic synthesis feed liquid separation and purification system of Fig. 2 and liquid waste treatment system thereof are in the time of work, the material flow direction is therein: first organic synthesis feed liquid enters decolouring system 4 removal of impurities of decolouring, enter successively MSMPR pattern crystallizer and the crystallization of DTB crystallizer, the material liquid mixture of crystallization enters solid-liquid separation system 2 again and carries out fractional defecation, centrifugation again; The filtrate of centrifugal acquisition filters by filter 301 successively, desalter 302 desalinations, and film condensing device 303 is concentrated, finally obtains concentrate and is back to centrifuge washing leaching cake, or be back to the crystallization again of DTB crystallizer.
Preferred as one of the present invention, as shown in Figure 4 and Figure 5, solid-liquid separation system 2 wherein comprises the one-level concentrator 201, suspended centrifuge 202, secondary concentrator 203 and the vane type filtration machine 204 that set gradually from front to back.The top flow export of described one-level concentrator 201 is connected with secondary concentrator 203 charging apertures, and underflow outlet is connected with suspended centrifuge 202 charging apertures; Described suspended centrifuge 202 filtrate (liquids are connected with secondary concentrator 203 charging apertures.Secondary concentrator 203 top flow exports are connected with vane type filtration machine 204 charging apertures, and underflow outlet is connected with decolouring system 4 or crystal system 1; The outlet of vane type filtration machine 204 is connected with the charging aperture of desalter 302.
The solid-liquid separation system 2 of Fig. 4 is in the time of work, the material flow direction is therein: sent in one-level concentrator 201 by the magma of DTB crystallizer extraction, promote solid content to target component, underflow is sent into suspended centrifuge 202 and carry out solid-liquid separation, the filter cake obtaining is packaged to be finished product by centrifuge automatic discharging, vibrations tape transport and automatic packaging machine.The top stream of one-level concentrator 201 and the filtrate that suspended centrifuge 202 obtains proceed in secondary concentrator 203, and the underflow of secondary concentrator 203 is back to decolouring system 4 or crystal system 1 extracts product again; The top stream of secondary concentrator 203 is sent into vane type filtration machine 204 and is filtered, and the clear liquid obtaining enters desalter 302 desalinations.
As shown in Figure 6 and Figure 7, a kind of organic synthesis feed liquid separation and purification system of the present invention and liquid waste treatment system thereof, comprise the liquid processing system 3 that the crystal system 1, solid-liquid separation system 2 and the waste liquid to solid-liquid separation system 2 extraction that set gradually are from front to back processed.Described crystal system 1 is made up of MSMPR pattern crystallizer series connection DTB crystallizer.Described solid-liquid separation system 2 comprises the concentrator and the centrifuge that arrange from front to back.Described liquid processing system 3 comprises the filter 301, desalter 302 and the film condensing device 303 that set gradually from front to back; Described filter 301 is connected with the filtrate (liquid of centrifuge, and described desalter 302 is connected with the liquid outlet of filter 301, and described film condensing device 303 is connected with the desalinization liquor outlet of desalter 302.Described filter 301 is made up of the strainer setting gradually from front to back, ultrafilter and nanofiltration device; The charging aperture of described strainer is connected with the filtrate (liquid of centrifuge, and the filtrate discharging opening of strainer is connected with the charging aperture of ultrafilter; The filtrate (liquid of described ultrafilter is connected with the charging aperture of nanofiltration device; The filtrate (liquid of described nanofiltration device is connected with the charging aperture of desalter 302.The concentrated solution outlet of described film condensing device 303 is connected with the charging aperture of centrifuge and/or DTB crystallizer.In addition, the charging aperture of described strainer is also connected with the top stream purified liquor outlet of described concentrator, and the discharge of filter residues mouth of described strainer is connected with the charging aperture of crystallizer.
The organic synthesis feed liquid separation and purification system of Fig. 6 and liquid waste treatment system thereof are in the time of work, the material flow direction is therein: organic synthesis feed liquid enters continuous crystallizing system, and the material liquid mixture of crystallization enters solid-liquid separation system 2 again and carries out fractional defecation, centrifugation; The filtrate of centrifugal acquisition filters by filter 301 successively, desalter 302 desalinations, and film condensing device 303 is concentrated, finally obtains concentrate and is back to centrifuge washing leaching cake, or be back to crystallizer crystallization again.In addition, the strainer of filter 301 also receives the top stream clear liquid of concentrator, by aforementioned flow process, this waste liquid is recycled; Strainer filters the filter residue (or dope) obtaining, and is also back to crystallizer and uses as crystal seed.
Embodiment 1
Be described in detail referring to Fig. 8-11 pair the preferred embodiments of the present invention.The organic synthesis feed liquid of this embodiment iminodiacetonitrile obtains according to the production method of patent CN1331844C; The following sulfuric acid adding, for the neutralization of reaction system ammonia.The operation of unreceipted actual conditions in embodiment, carries out according to routine operation condition.
By the material (material code name: FED1, wherein iminodiacetonitrile content is 300g/L, 65 DEG C of temperature, pH=7.0) of iminodiacetonitrile reactor extraction with 10.5m
3the speed of/h is sent in dosage bunker 5 continuously, and the material of sending into continuously also comprises simultaneously: product centrifugal filter cake washing lotion and secondary thickener underflow mixed liquor (material code name: FED2; Wherein iminodiacetonitrile content is 50g/L, 12 DEG C of temperature, feed rate: 2m
3/ h), the saturating washing lotion of nanofiltration (material code name: FED3; Wherein iminodiacetonitrile content is 20g/L, 35 DEG C of temperature, feed rate: 3m
3/ h), (25 DEG C of temperature, flow is about 0.22m to 93% sulfuric acid
3/ h).All materials mix in dosage bunker 5, and extraction is to film decolouring integrated system continuously, and in extraction material (code name FED4), iminodiacetonitrile content is 140g/L, 35 DEG C of temperature, and extraction speed is about 15m
3/ h.Ultrafiltration and nanofiltration processing that FED4 decolours in integrated system by film successively.Nanofiltration see through liquid (material code name FED5, iminodiacetonitrile content is 152g/L, 36 DEG C of temperature, rate of feed is 9m
3/ h) enter storage tank and (material code name FED6, iminodiacetonitrile content is 180g/L, 42 DEG C of temperature, flow 2.6m at this and film concentrate
3/ h) mix after, be pumped to and in crystal system, carry out crystallization; (material code name FED7, iminodiacetonitrile content is 2g/L to nanofiltration trapped fluid, 18 DEG C of temperature, flow 2.6m
3/ h) enter temporary storage tank, and deliver to evaporimeter 7 and concentrate, concentrate is finally sent into and is burned device 8, with burning disposal after natural gas mixed aerosol; The saturating washing lotion of nanofiltration (material code name: FED3; Wherein iminodiacetonitrile content is 20g/L, 35 DEG C of temperature) after collecting, return to dosage bunker 5.This continuous crystallizing system is made up of MSMPR pattern crystallizer series connection DTB crystallizer, crystallized stock carries out crystallization by MSMPR pattern crystallizer and DTB crystallizer successively, the temperature of charge of controlling in DTB crystallizer is stable at 9 DEG C～12 DEG C, pH value is controlled between 2.0～4.0, by regulating crystallizer feed rate, making the mean residence time of crystallized stock in crystallizer is 1 to 3 hour.
Sent in one-level concentrator by the magma of crystal system extraction, thickener underflow is the product magma of solid content 50% (V/V%), crystal average grain diameter is more than 0.3mm, send into suspended centrifuge and carry out solid-liquid separation, obtain the solid product filter cake of moisture < 1% (w/w%), be packaged to be finished product by centrifuge automatic discharging, vibrations tape transport and automatic packaging machine.Centrifuge mother liquor (material code name: FED8; Wherein iminodiacetonitrile content is 60g/L, 12 DEG C of temperature) after collecting, be pumped to secondary concentrator.Top stream (material code name: FED9 in one-level concentrator; Wherein iminodiacetonitrile content is 75g/L, 10 DEG C of temperature, flow: 10m
3/ h) enter secondary concentrator with gravity current form.The underflow of secondary concentrator enters feeder 6, and mixes with product centrifugal filter cake washing lotion at this, and mixed liquor (FED2) returns to dosage bunker 5, mixes with FED1 and FED3.Secondary concentrator top stream (material code name: FED10; Wherein iminodiacetonitrile content is 65g/L, 12 DEG C of temperature, flow: 10m
3/ h) filter clear liquid (the material code name: FED11 obtaining by vane type filtration machine; Wherein iminodiacetonitrile content is 65g/L, and ammonium sulfate content is: 20g/L, 12 DEG C of temperature, flow: 10m
3/ h) enter electrodialysis desalination integrated system.
FED11 obtains two strands of materials after treatment: one is haline water (material code name: FED12, ammonium sulfate content 80g/L), sends into evaporating, concentrating and crystallizing device, and crystallization obtains solid ammonium sulfate product; Another strand of material is that (FED13, iminodiacetonitrile content is 60g/L to desalinization liquor, ammonium sulfate content 0.15g/L, flow 10m
3/ h), send into reverse osmosis membrane (RO film) concentration systems, (material code name FED6, iminodiacetonitrile content is 180g/L, 42 DEG C of temperature, flow 2.6m to obtain after treatment material concentrate
3/ h) with fresh water (FED15, flow 7.5m
3/ h).FED6 enters crystal system after mixing with FED5.
Compared with traditional handicraft, this technique has following some main advantage:
(1) large-scale industrial production, product yield, quality all have remarkable lifting, and in reactant liquor, product extraction efficiency is promoted to more than 95% by 80%, and the main content of product rises to 97% by average 95%, and outward appearance becomes near-white from brown.
(2) wastewater flow rate obviously declines, and product wastewater flow rate per ton is about 0.15m
3, be only 1/10 of former technique, and waste water be high concentration without salting liquid, be easy to burning disposal.
(3) compared with former technique, the ammonium sulfate that enters waste water is isolated, realize recycling, reduced wastewater treatment difficulty simultaneously.
(4) traditional handicraft adopts repeatedly the mode of evaporation and concentration to take out, and consumes a large amount of steam; Adopt after film concentration technique, concentrated expense greatly reduces.
(5) production overall process becomes continuous operation from intermittently operated, is easy to realize whole-course automation control, greatly reduces artificial use.
(6) traditional production technology is because product crystallization crystal grain is little, distribution of sizes is wide, cause product centrifugal filter cake water content on average more than 6.0%, this technique is due to lifting (the crystal average grain diameter increase of product crystalline quality, crystal size distribution scope is narrower), taking iminodiacetonitrile as example, only can make product filter cake be less than the moisture of 0.5% (w/w%) by centrifugation, greatly be better than the quality index of Grade A moisture≤3.0% (w/w%) in GB/T23958-2009 " industrial iminodiacetonitrile ", thereby centrifugal follow-up product drying operation in omission traditional handicraft, greatly simplify production procedure, reduce artificial consumption.
Embodiment 2
Be described in detail referring to Fig. 8-11 pair the preferred embodiments of the present invention.The organic synthesis feed liquid of this embodiment iminodiacetonitrile obtains according to the production method of patent CN1331844C; The following sulfuric acid adding, for the neutralization of reaction system ammonia.The operation of unreceipted actual conditions in embodiment, carries out according to routine operation condition.
By the material (material code name: FED1, wherein iminodiacetonitrile content is 300g/L, 65 DEG C of temperature, pH=7.0) of iminodiacetonitrile reaction system extraction with 10.5m
3the speed of/h is sent to dosage bunker 5 continuously.The material of sending into continuously also comprises simultaneously: clear liquid (the material code name: FED2 that product centrifugal filter cake washing lotion obtains after mixing, filtering with secondary thickener underflow; Wherein iminodiacetonitrile content is 50g/L, 12 DEG C of temperature, feed rate: 7.25m
3/ h), film separates mixed liquor (the material code name: FED3 of ultrafiltration and the saturating washing lotion of nanofiltration system; Wherein iminodiacetonitrile content is 30g/L, 35 DEG C of temperature, feed rate: 8.75m
3/ h), (25 DEG C of temperature, flow is about 0.185m to 93% sulfuric acid
3/ h).Above-mentioned four kinds of materials enter preparation liquid storage tank after mixing by one group of static mixer, and extraction is to film decolouring integrated system continuously, in extraction material (code name FED4), iminodiacetonitrile content is for being 140g/L, 35 DEG C of temperature, extraction speed is about 26.5m
3/ h.FED4 is successively by ultra-filtration process and nanofiltration process processing in Integrated Films piece-rate system.Nanofiltration see through liquid (material code name FED5, iminodiacetonitrile content is 138g/L, 36 DEG C of temperature, rate of feed is 26.5m
3/ h) enter storage tank; Meanwhile, by the mixed liquor of product centrifugal filter cake washing lotion and secondary thickener underflow, (material code name FED6, iminodiacetonitrile content is 350g/L, 20 DEG C of temperature, flow 2.2m
3/ h) send into same storage tank, after mixing, be pumped to and in crystal system, carry out crystallization.
The nanofiltration system of this example is made up of two kinds of different films of pore size, the NF membrane composition one-level nanofiltration system that aperture is larger, the film composition secondary nanofiltration system that aperture is less.Solution after hyperfiltration treatment is successively by two-stage nanofiltration system.(iminodiacetonitrile content is 30g/L to one-level nanofiltration trapped fluid, 35 DEG C of temperature, flow 2m
3/ h) enter temporary storage tank, and deliver to evaporimeter 7 and concentrate, concentrate is finally sent into and is burned device 8, with burning disposal after natural gas mixed aerosol; (wherein iminodiacetonitrile content is 40g/L to secondary nanofiltration trapped fluid, ammonium sulfate content 70g/L, 35 DEG C of temperature, flow 4m
3/ h) after collecting, deliver to electrodialysis system to remove ammonium sulfate (in solution, ammonium sulfate content is 5g/L after electrodialysis process), then see through liquid with one-level nanofiltration and mix, jointly enter secondary nanofiltration system.
Crystal system and later technical process thereof are identical with example 1.Finally, sent in one-level concentrator by the magma of crystal system extraction, thickener underflow is the product magma of solid content 50% (V/V%), crystal average grain diameter is more than 0.3mm, send into suspended centrifuge and carry out solid-liquid separation, obtain the solid product filter cake of moisture < 1% (w/w%), be packaged to be finished product by centrifuge automatic discharging, vibrations tape transport and automatic packaging machine.In reactant liquor, product extraction efficiency is 96%, and the main content of product is 99%, and outward appearance is near-white.Product wastewater flow rate per ton is about 0.06m
3, be only 1/10 of former technique.
Comparative example (Traditional Method)
The organic synthesis feed liquid of this embodiment iminodiacetonitrile obtains according to the production method of patent CN1331844C; The following sulfuric acid adding, for the neutralization of reaction system ammonia.The operation of unreceipted actual conditions in embodiment, carries out according to routine operation condition.
By the material (material code name: FED1, wherein iminodiacetonitrile content is 300g/L, 65 DEG C of temperature, pH=7.0) of iminodiacetonitrile reaction system extraction with 3.5m
3the speed of/h enters (crystallization kettle is at least more than 2, when after a still splendid attire full with substance, will react feed liquid and import another crystallization kettle, and two or more crystallization kettles switch use) in stirred crystallization still.The material of sending into continuously also comprises that (25 DEG C of temperature, flow is about 0.07m to 93% sulfuric acid simultaneously
3/ h).In crystallization kettle chuck, pass into 10 DEG C of water at low temperature material is carried out to decrease temperature crystalline, in the time that temperature of charge is reduced to 20 DEG C, be considered as crystallization process terminal.The magma obtaining is sent into rotation siphon centrifuge and carry out solid-liquid separation (once centrifugal).The centrifugal solid obtaining (former liquid material) cake moisture, more than 6.0%, is sent in vibrated fluidized bed and is dried, so that solid product moisture is down to below 3.0%.Dry qualified product carries out obtaining finished product after quantitative package.Centrifuge mother liquor is sent into downward film evaporator and is carried out evaporation and concentration, 1 ton of product of every production, and the water yield that need evaporate in this step is about 3m
3.Mother liquor after concentrated is sent in crystallizer and is carried out decrease temperature crystalline, and the magma obtaining is sent into rotation siphon centrifuge and carried out solid-liquid separation (secondary centrifuging).Solid filter cake (falling liquid film material) is mixed into vibrated fluidized bed with former liquid material and is dried.(1 ton of product of every production, secondary centrifuging mother liquor amount is 0.5m to centrifuge mother liquor
3, wherein iminodiacetonitrile content is about 200g/L, and ammonium sulfate content is about 300g/L) after collecting, send into burning device, with burning disposal after natural gas mixed aerosol.
Product quality aspect, traditional handicraft, because impurity in solution in crystallization process is more, causes product crystalline quality poor, and it is unformed Powdered that major part is, and wrapped up a large amount of impurity simultaneously, and therefore outward appearance is light brown.Meanwhile, traditional handicraft has used high temperature evaporation concentration process to improve the extraction efficiency of product from solution, and in this course, high temperature can cause the thermal decomposition of product, and product quality is further reduced.So, the product that general large-scale industrial production obtains, its main content is only 95% left and right.
Yield aspect, due to iminodiacetonitrile higher solubility in the aqueous solution, traditional handicraft is used the limiting value of concentrated way increase product extraction efficiency lower, large-tonnage product is got brilliant mother liquor discharge with concentrating, and making the overall yield of post processing (process by the synthetic liquid of reactor extraction to finished product) is only 88～90%.
It should be noted that: the structure of this description institute accompanying drawing, ratio, size etc.; and the configuration of common apparatus and use; all contents in order to coordinate description to disclose only; understand and read for person skilled in the art scholar; not in order to limit scope of the invention process; the adjustment of the modification of any structure, the change of proportionate relationship or size; and the increase and decrease of common apparatus and replacement; not affecting under the function that the present invention can produce and the object of reaching, all should drop in the protection domain of disclosed technology contents.
Extraction index, the system parameter setting of above-described embodiment and add the amount of sulfuric acid should not be defined as above-mentioned value, can need to adjust according to concrete technology.The invention is not restricted to the production of iminodiacetonitrile, other feed liquid system that has similar composition also can adopt apparatus system of the present invention and method to carry out separation and purification and liquid waste processing.Above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (29)
1. the separation and purification system of an organic synthesis feed liquid, comprise the crystal system (1) and the solid-liquid separation system (2) that set gradually from front to back, it is characterized in that: described crystal system (1) is the multistage continuous crystallizing system that more than two crystallizer is composed in series, or be the crystal system that more than two crystallizer composes in parallel, or formed by single crystallizer.
2. the separation and purification system of organic synthesis feed liquid according to claim 1, it is characterized in that: described crystal system (1) is discharged crystallizer series connection guide shell crystallizer by mix suspending-product mix and formed, or discharging crystallizer by guide shell crystallizer series hybrid suspension-product mix forms, or discharge crystallizer by more than two mix suspending-product mix and be composed in series, or be composed in series by more than two guide shell crystallizer.
3. the separation and purification system of organic synthesis feed liquid according to claim 1, it is characterized in that: also comprise the liquid processing system (3) that the liquid of solid-liquid separation system (2) extraction is processed, this liquid processing system (3) comprises the desalter (302) and the film condensing device (303) that set gradually from front to back, desalter (302) is for the liquid of solid-liquid separation system (2) extraction is carried out to desalination, and film condensing device (303) is for concentrating the liquid after desalter (302) desalination.
4. the separation and purification system of organic synthesis feed liquid according to claim 3, is characterized in that: described desalter (302) is electrodialysis plant or diffusion dialysis device.
5. the separation and purification system of organic synthesis feed liquid according to claim 3, is characterized in that: described solid-liquid separation system (2) comprises a pair of above concentrator and the centrifuge setting gradually.
6. the separation and purification system of organic synthesis feed liquid according to claim 5, is characterized in that: the concentrated solution outlet of described film condensing device (303) is connected with the charging aperture of centrifuge and/or crystal system (1) crystallizer.
7. the separation and purification system of organic synthesis feed liquid according to claim 3, is characterized in that: the front decolouring system (4) that is provided with of described crystal system (1), for removing impurities that organic synthesis feed liquid is decoloured; Or, between described solid-liquid separation system (2) and desalter (302), be provided with decolouring system (4), for the liquid of solid-liquid separation system (2) extraction is decoloured.
8. the separation and purification system of organic synthesis feed liquid according to claim 7, is characterized in that: described decolouring system (4) is made up of the ultrafiltration apparatus of connecting and nanofiltration device.
9. the separation and purification system of organic synthesis feed liquid according to claim 7, it is characterized in that: front filter (301) or the filtrate collecting tank (6) of being also provided with of described desalter (302), for the liquid of solid-liquid separation system (2) extraction being filtered to or leaves standstill clarification; In the time being provided with decolouring system (4) after solid-liquid separation system (2), the pre-treatment part that described filter (301) is decolouring system (4), the liquid of solid-liquid separation system (2) extraction enters decolouring system (4) decolouring after filtering again.
10. the application of the separation and purification system of the organic synthesis feed liquid described in claim 1 to 9 any one in the synthetic feed liquid of iminodiacetonitrile, the synthetic feed liquid of iminodiacetic acid, the synthetic feed liquid of glycine or the synthetic feed liquid separation and purification of methionine.
The isolation and purification method of 11. 1 kinds of organic synthesis feed liquids, is characterized in that, comprises the following steps: described organic synthesis feed liquid adopts crystal system to carry out crystallization and obtains magma, and described magma obtains product and filtrate through Separation of Solid and Liquid; Described crystal system is the multistage continuous crystallizing system that more than two crystallizer is composed in series, or is the crystal system that more than two crystallizer composes in parallel, or is made up of single crystallizer.
The isolation and purification method of 12. organic synthesis feed liquids according to claim 11, is characterized in that: described crystal system is the continuous crystallizing system that mix suspending-product mix discharge crystallizer series connection guide shell crystallizer or guide shell crystallizer series hybrid suspension-product mix are discharged crystallizer or two mix suspending of connecting above-product mix discharge crystallizers or two guide shell crystallizers of connecting above.
The isolation and purification method of 13. organic synthesis feed liquids according to claim 11, is characterized in that: in described organic synthesis feed liquid, contain organic products and inorganic salts.
The isolation and purification method of 14. organic synthesis feed liquids according to claim 11, is characterized in that: the filtrate of described Separation of Solid and Liquid gained is by electrodialysis or the desalination of diffusion dialysis technology, and the liquid after desalination concentrates by membrane separation technique again.
The isolation and purification method of 15. organic synthesis feed liquids according to claim 14, is characterized in that: described organic synthesis feed liquid is carrying out before continuous crystallisation, the removing impurities of also decolouring operation; Or, the filtrate of described Separation of Solid and Liquid gained before electrodialysis desalination, the operation of also decolouring.
The isolation and purification method of 16. organic synthesis feed liquids according to claim 15, is characterized in that: described decolouring operation is to complete by the ultrafiltration nanofiltration of connecting.
The isolation and purification method of 17. organic synthesis feed liquids according to claim 14, is characterized in that: described Separation of Solid and Liquid completes by a pair of above concentrator and the centrifuge setting gradually.
The isolation and purification method of 18. organic synthesis feed liquids according to claim 17, is characterized in that: described Separation of Solid and Liquid completes by the one-level concentrator, suspended centrifuge, secondary concentrator and the vane type filtration machine that set gradually; The thick material of underflow of described one-level concentrator enters the centrifugal acquisition product of suspended centrifuge, and the top stream clear liquid of one-level concentrator and the centrifuge mother liquor of suspended centrifuge enter secondary concentrator; The thick material of underflow of described secondary concentrator returns to continuous crystallisation step again, and the top stream clear liquid of secondary concentrator enters vane type filtration machine and filters to get filtrate, and filtrate is carried out electrodialysis desalination again.
The isolation and purification method of 19. organic synthesis feed liquids according to claim 14, it is characterized in that: clarification is also filtered or left standstill to the filtrate of described Separation of Solid and Liquid gained before electrodialysis desalination, the precipitation of filtering or leave standstill collection is back to continuous crystallisation step and uses as crystal seed.
The isolation and purification method of 20. organic synthesis feed liquids according to claim 14, is characterized in that: the concentrate of the concentrated gained of described membrane separation technique is back to the crystallization again of continuous crystallisation step, and/or is back to solid-liquid separation step washing leaching cake.
The isolation and purification method of 21. organic synthesis feed liquids according to claim 12, is characterized in that: in described continuous crystallizing system, the temperature of rear one-level crystallizer crystallization is lower than the temperature of previous stage crystallizer crystallization.
The application of the isolation and purification method of the organic synthesis feed liquid described in 22. claim 11 to 21 any one in the synthetic feed liquid of iminodiacetonitrile, the synthetic feed liquid of iminodiacetic acid, the synthetic feed liquid of glycine or the synthetic feed liquid separation and purification of methionine.
The isolation and purification method of 23. 1 kinds of synthetic feed liquids of iminodiacetonitrile, described synthetic feed liquid be taking hydroxyacetonitrile and ammonia as the reactant liquor of raw material synthesizing iminodiacetic acid (salt) nitrile with inorganic acid or organic acid mixed liquor for neutralization of ammonia, it is characterized in that, comprise the following steps:
A, described synthetic feed liquid adopt crystal system to carry out crystallization and obtain magma, and described magma obtains product and filtrate through Separation of Solid and Liquid; Described crystal system is the multistage continuous crystallizing system that more than two crystallizer is composed in series, or is the crystal system that more than two crystallizer composes in parallel, or is made up of single crystallizer;
The filtrate of B, described Separation of Solid and Liquid gained is by electrodialysis or the desalination of diffusion dialysis technology, liquid after desalination concentrates by membrane separation technique again, the concentrate of concentrated gained is back to the crystallization again of continuous crystallisation step, and/or is back to solid-liquid separation step washing leaching cake.
24. iminodiacetonitriles according to claim 23 synthesize the isolation and purification method of feed liquid, it is characterized in that: described crystal system is the continuous crystallizing system that mix suspending-product mix discharge crystallizer series connection guide shell crystallizer or guide shell crystallizer series hybrid suspension-product mix are discharged crystallizer or two mix suspending of connecting above-product mix discharge crystallizers or two guide shell crystallizers of connecting above.
The isolation and purification method of the synthetic feed liquid of 25. iminodiacetonitriles according to claim 23, is characterized in that: described organic synthesis feed liquid is carrying out before continuous crystallisation, the removing impurities of also decolouring operation; The operation of described decolouring removing impurities completes by the ultrafiltration nanofiltration of connecting.
The isolation and purification method of the synthetic feed liquid of 26. iminodiacetonitriles according to claim 23, is characterized in that: described Separation of Solid and Liquid completes by a pair of above concentrator and the centrifuge setting gradually.
The isolation and purification method of the synthetic feed liquid of 27. iminodiacetonitriles according to claim 26, is characterized in that: described magma solid content is promoted to 40%-50% by described concentrator, the thicker material of extraction underflow and top stream clear liquid.
The isolation and purification method of the synthetic feed liquid of 28. iminodiacetonitriles according to claim 23, is characterized in that: the filtrate of described Separation of Solid and Liquid gained is removed more than 90% inorganic salts through electrodialysis desalination, then extraction desalinization liquor.
The isolation and purification method of the synthetic feed liquid of 29. iminodiacetonitriles according to claim 23, is characterized in that: the temperature of discharging the crystallizer crystallization of material in described crystal system is controlled at 10～12 DEG C, and pH is controlled at 2.5～4.0.
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| CN201420462923.4U Expired - Fee Related CN204173991U (en) | 2014-05-14 | 2014-08-15 | The recycling system of the waste liquid produced in the separation and purification of a kind of organic synthesis feed liquid |
| CN201410403632.2A Pending CN104176844A (en) | 2014-05-14 | 2014-08-15 | Recycling system and recycling method for waste liquor produced in separation and purification of organically synthesized feed liquid |
| CN201420462991.0U Expired - Fee Related CN204170452U (en) | 2014-05-14 | 2014-08-15 | A kind of separation and purification system of organic synthesis feed liquid |
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| CN104844487A (en) * | 2015-04-05 | 2015-08-19 | 杭州蓝然环境技术有限公司 | Method for decoloring methionine crystallization mother liquor by adopting membrane integration technology |
| EP3246310A4 (en) * | 2015-02-12 | 2018-01-10 | Shandong Nhu Amino Acid Co., Ltd. | Method for continuous preparation of high bulk density methionine crystal |
| CN108671578A (en) * | 2018-05-10 | 2018-10-19 | 江苏鼎烨药业有限公司 | One kind having impurity-eliminating effect and 2,4 dichloro phenol concentration and crystallization device easy to operation |
| CN108794364A (en) * | 2017-05-02 | 2018-11-13 | 宁夏紫光天化蛋氨酸有限责任公司 | A kind of isolation and purification method of methionine |
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| CN113044863A (en) * | 2021-04-25 | 2021-06-29 | 百色学院 | Method for improving decomposition rate of seed precipitation in alumina production |
| CN114669076A (en) * | 2022-03-30 | 2022-06-28 | 上海东庚化工技术有限公司 | Micro-melt crystallization and falling film crystallization combined material purification system and method |
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| CN204173991U (en) * | 2014-05-14 | 2015-02-25 | 重庆紫光化工股份有限公司 | The recycling system of the waste liquid produced in the separation and purification of a kind of organic synthesis feed liquid |
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- 2014-08-15 CN CN201420462991.0U patent/CN204170452U/en not_active Expired - Fee Related
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| CN101456822A (en) * | 2008-11-28 | 2009-06-17 | 山东恩贝生物工程有限公司 | Novel process for extracting threonine |
| CN102459138A (en) * | 2009-06-04 | 2012-05-16 | 基因组股份公司 | Process of separating components of a fermentation broth |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3246310A4 (en) * | 2015-02-12 | 2018-01-10 | Shandong Nhu Amino Acid Co., Ltd. | Method for continuous preparation of high bulk density methionine crystal |
| US10293273B2 (en) | 2015-02-12 | 2019-05-21 | Shandong Nhu Amino Acid Co. Ltd. | Method for continuous preparation of high bulk density methionine crystal |
| CN104844487A (en) * | 2015-04-05 | 2015-08-19 | 杭州蓝然环境技术有限公司 | Method for decoloring methionine crystallization mother liquor by adopting membrane integration technology |
| CN108794364A (en) * | 2017-05-02 | 2018-11-13 | 宁夏紫光天化蛋氨酸有限责任公司 | A kind of isolation and purification method of methionine |
| CN108671578A (en) * | 2018-05-10 | 2018-10-19 | 江苏鼎烨药业有限公司 | One kind having impurity-eliminating effect and 2,4 dichloro phenol concentration and crystallization device easy to operation |
| CN110812877A (en) * | 2019-10-12 | 2020-02-21 | 西安交通大学 | Glyphosate mother liquor treatment method and device |
| CN113044863A (en) * | 2021-04-25 | 2021-06-29 | 百色学院 | Method for improving decomposition rate of seed precipitation in alumina production |
| CN114669076A (en) * | 2022-03-30 | 2022-06-28 | 上海东庚化工技术有限公司 | Micro-melt crystallization and falling film crystallization combined material purification system and method |
| CN114669076B (en) * | 2022-03-30 | 2023-03-28 | 上海东庚化工技术有限公司 | Micro-melt crystallization and falling film crystallization combined material purification system and method |
| CN115159756A (en) * | 2022-06-30 | 2022-10-11 | 江苏峻尚新材料科技有限公司 | Filter-aid device and method for improving performance of ammonia-process desulfurization slurry |
| CN115159756B (en) * | 2022-06-30 | 2023-09-01 | 江苏峻尚新材料科技有限公司 | Filtering assisting device and method for improving performance of ammonia desulfurization sewage slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN204173991U (en) | 2015-02-25 |
| CN204170452U (en) | 2015-02-25 |
| CN104176844A (en) | 2014-12-03 |
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