CN117583038B - Sucrose decalcification method and system - Google Patents
Sucrose decalcification method and system Download PDFInfo
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- CN117583038B CN117583038B CN202410070515.2A CN202410070515A CN117583038B CN 117583038 B CN117583038 B CN 117583038B CN 202410070515 A CN202410070515 A CN 202410070515A CN 117583038 B CN117583038 B CN 117583038B
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- ion exchange
- exchange resin
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 title claims abstract description 109
- 229930006000 Sucrose Natural products 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 109
- 239000005720 sucrose Substances 0.000 title claims abstract description 109
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 130
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 130
- 238000011069 regeneration method Methods 0.000 claims abstract description 80
- 230000008929 regeneration Effects 0.000 claims abstract description 75
- 239000011347 resin Substances 0.000 claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 230000008569 process Effects 0.000 claims abstract description 55
- 239000002699 waste material Substances 0.000 claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 claims abstract description 51
- 239000012492 regenerant Substances 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000011001 backwashing Methods 0.000 claims abstract description 28
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 238000005201 scrubbing Methods 0.000 claims abstract description 23
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 14
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000004042 decolorization Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 27
- 239000012267 brine Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 238000001728 nano-filtration Methods 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 13
- 238000009776 industrial production Methods 0.000 abstract description 6
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 description 13
- 239000011575 calcium Substances 0.000 description 12
- 239000000049 pigment Substances 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- 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
- B01J47/02—Column or bed processes
-
- 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
- B01J47/14—Controlling or regulating
-
- 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
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
-
- 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
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/60—Cleaning or rinsing ion-exchange beds
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/14—Purification of sugar juices using ion-exchange materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B20/00—Purification of sugar juices
- C13B20/14—Purification of sugar juices using ion-exchange materials
- C13B20/148—Purification of sugar juices using ion-exchange materials for fractionating, adsorption or ion exclusion processes combined with elution or desorption of a sugar fraction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a sucrose decalcification method and a system, wherein the method adopts a continuous multi-column ion exchange method to remove calcium ions in a sucrose raw material, and an ion exchange resin column used for sucrose decalcification adopts liquid obtained by acid neutralization of regenerated waste liquid of decolorized ion exchange resin in a decolorization process in sucrose purification production as a regenerant. The system comprises a production area, a scrubbing and backwashing area, a regeneration area and a leaching area. The method and the system for decalcifying the sucrose have the advantages that the regeneration waste liquid of the decoloration procedure after the neutralization of the acid is selected as the regeneration agent of the decalcification resin, a large amount of sodium chloride is contained in the regeneration waste liquid, and the regeneration waste liquid after the neutralization of the acid is used as the regeneration agent of the decalcification resin, so that the discharge of sewage in actual mass production is reduced, and the production cost of industrial production is reduced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a sucrose decalcification method and a sucrose decalcification system.
Background
In the existing sucrose production process, most of the sucrose decolorization is studied, for example, chinese patent 200610045781.1 and 200610045680.4 disclose a preparation method of activated carbon for decolorizing sugar, and the activated carbon is used for decolorizing sugar; chinese patent 200410060780.5 discloses a process for preparing sugar juice by using membrane to clean sugarcane.
In addition, china patent 201010571078.0 discloses a regeneration method of sugar-making decolored decalcification resin and a recycling method of regenerated waste liquid, and the technology of the patent has the advantages of the method, but the method is in a laboratory stage, so that the purity of sucrose is reduced during actual industrial production, the color of evaporation concentration discharge is deepened, and researches show that the reducing sugar of the sucrose raw material after decalcification treatment is increased. In the second patent, the dosage of the decalcification resin regenerant is 4-6BV, the regeneration waste liquid generated in the decolorization process in actual production is usually lower than 4BV, and the regenerated waste liquid is also required to be added with salt water, so that the regenerated waste liquid is not suitable for actual industrial production.
Based on the above, the existing industrial production of decalcification in sucrose production still cannot be stopped, because calcium salt cannot be thoroughly removed, when the subsequent process is evaporated, the calcium salt is precipitated and deposited on a heating pipe of an evaporator, after the calcium salt is deposited to a certain extent, the consumption of raw steam required by evaporation is increased, and when the evaporation heat exchange effect is poor, special high-pressure cleaning personnel can only be required to clean the calcium salt in the evaporation heating chamber.
Disclosure of Invention
The invention mainly solves the technical problem that the purity of the sucrose obtained after the sucrose decalcification resin is regenerated by adopting the decolored resin regeneration waste liquid, and provides a novel sucrose decalcification method which can improve the purity of the sucrose.
The invention provides a sucrose decalcification method, which adopts a continuous multi-column ion exchange method to remove calcium ions in a sucrose raw material, and an ion exchange resin column used for sucrose decalcification adopts liquid obtained by acid neutralization of regenerated waste liquid of decolorized ion exchange resin in a decolorization process in sucrose purification production as a regenerant.
The regenerant for the ion exchange resin column for decalcification of sucrose is derived from waste brine raw material of nanofiltration concentration procedure in sucrose purification production. One process in sucrose production is a decoloring process, alkali brine is used during decoloring resin regeneration, regenerated waste liquid comprises pigment-containing waste water generated during decoloring resin regeneration and waste water leached by regenerated resin water, and part of unused sodium chloride and sodium hydroxide are contained, if the waste water is directly discharged, the treatment difficulty of a sewage treatment station is high, the treatment cost is high, and most of factories are continuously utilized after all sodium chloride and sodium hydroxide are extracted by nanofiltration concentration, but the pH value of the regenerated waste liquid in the decoloring process is higher, so that nanofiltration membrane cores are corroded. When using nanofiltration equipment, the nanofiltration membrane is usually required to be concentrated under neutral conditions, and the cost of an alkaline nanofiltration membrane suitable for concentrating the regenerated waste liquid is extremely expensive, and the selection of a factory is to add part of hydrochloric acid to neutralize the regenerated waste liquid into neutral and then enter the nanofiltration membrane. At this time, the liquid obtained by neutralizing the regenerated waste liquid with acid is the waste brine raw material of the nanofiltration concentration process, and the decalcification resin is regenerated by using the waste brine raw material, so that the effect of improving the purity of sucrose can be achieved, the production amount of the waste brine can be greatly reduced, and the load of a sewage treatment station is indirectly reduced.
The pH value of the regenerant is 5.5-7.5.
The method for removing calcium ions in sucrose by using the continuous multi-column ion exchange method comprises the following steps:
the production process comprises the following steps: carrying out ion exchange on sucrose through a plurality of resin layers of ion exchange resin columns which are arranged in parallel to decalcifie the sucrose to obtain decalcified sucrose solution;
a scrubbing step of loosening the resin in the ion exchange resin column which is failed in the production step by clean air;
backwashing: washing out the sugar solution in the ion exchange resin column and impurities in the resin column which are invalid in the production procedure by water;
and (3) a regeneration procedure: regenerating the ion exchange resin columns which are arranged in series after the backwashing process is completed by using a regenerant;
leaching: the ion exchange resin columns arranged in series after the regeneration process are washed with water.
The feeding mode of the production process is upper feeding and lower discharging.
The air inlet mode of the scrubbing procedure is lower air inlet and upper air outlet. Loosening the resin in the ion exchange resin column by clean air; the traditional process does not have the working procedure, and the aim of the working procedure is to improve the recycling rate and the recycling effect of the resin after the resin is loosened, and avoid the phenomena of resin crushing and caking caused by long-time extrusion of the resin.
The water inlet mode of the backwashing process is lower water inlet and upper material outlet. And (3) washing out a large amount of impurities in the sugar solution and the resin column in the ion exchange resin column by using water.
The feeding mode of the regeneration process is an upper feeding and lower discharging mode.
The regeneration process adopts 3 ion exchange resin columns which are arranged in series. The regeneration process comprises the steps that a first ion exchange resin column upper feed inlet in the regeneration process is fed with a regenerant, a lower discharge outlet of the regeneration process is connected with a second ion exchange resin column upper feed inlet in series, a second ion exchange resin column lower discharge outlet of the regeneration process is connected with a third ion exchange resin column upper feed inlet in series, 3 ion exchange resin columns are discharged from the third ion exchange resin column lower inlet, the optimal serial regeneration mode is adopted, the number of the ion exchange resin columns is reduced, the regeneration is not thorough, or the regenerant consumption is large, and the investment of the prior equipment is increased by increasing the ion exchange resin columns. Resulting in an increase in the budget of the new production plant. The amount of 3 ion exchange column regenerators is also controlled to be 1-2BV.
The feeding mode of the leaching process is an upper water inlet and lower discharging mode.
The discharged solution of the leaching process is added into a regenerant pipeline to be mixed with the regenerant and then enters an ion exchange resin column in the regeneration process.
The leaching process adopts 2 ion exchange resin columns which are arranged in series. The 2 ion exchange resin columns are leached in series, the first ion exchange resin column in the leaching process is fed with water, the lower discharge of the first ion exchange resin column is connected to the upper feed inlet of the second ion exchange resin column in series, the lower discharge of the second ion exchange resin column is connected to the regenerant pipeline in the regeneration process in series, and the 2 ion exchange resin columns are leached in series and connected to the regeneration process in series, so that the water consumption is saved, the number of the ion exchange resin columns is reduced, and the investment cost of the prior equipment is reduced.
The single column volume of the ion exchange resin is 1-3m 3 。
The resin in the ion exchange resin column is Na type cation exchange resin.
The invention also provides a sucrose decalcification system, which adopts continuous multi-column ion exchange resin to remove calcium ions in sucrose, and comprises:
production area: the method comprises the steps that a plurality of ion exchange resin columns are arranged in parallel, a sucrose feeding pipeline is respectively communicated with the ion exchange resin columns, and sucrose is subjected to ion exchange through resin layers of the plurality of ion exchange resin columns in parallel to decalcify the sucrose to obtain decalcified sucrose solution;
scrubbing and backwashing: the method comprises the steps of connecting a failed ion exchange resin column switched from a production area with a compressed air pipeline and a water inlet pipeline, loosening resin in the ion exchange resin column by clean air, and then washing out sugar solution and impurities in the ion exchange resin column by water;
regeneration zone: the method comprises a plurality of ion exchange resin columns which are connected in series and are switched from a scrubbing and backwashing area, wherein a waste brine raw material pipeline of a nanofiltration concentration process is communicated with the ion exchange resin columns of the area, and waste brine raw material of the nanofiltration concentration process enters the ion exchange resin columns to regenerate the resin;
leaching area: the regeneration device comprises an ion exchange resin column switched from a regeneration zone, wherein a water inlet pipeline is communicated with the ion exchange resin column in the zone, water enters the ion exchange resin column, and residual regenerant in the column is washed out;
the ion exchange resin columns of the production area, the scrubbing and backwashing area, the regeneration area and the leaching area are sequentially switched, one ion exchange resin column is switched each time, and the number of the ion exchange resin columns of each working area is always kept unchanged.
Further, the sucrose decalcification system comprises:
the upper port of the ion exchange resin column of the production area is communicated with a sucrose feeding pipeline, and the lower port is communicated with a decalcification discharging tank;
the lower port of the ion exchange resin column for scrubbing the backwashing zone is communicated with a water inlet pipeline and a compressed air pipeline, the water inlet pipeline and the compressed air pipeline are respectively provided with a switch valve, and the upper port is communicated with a sweet water tank and a backwashing discharge buffer tank through pipelines;
the upper port of the first ion exchange resin column of the regeneration zone is connected with the neutralized waste brine tank, and the lower port of the last ion exchange resin column is communicated with the calcium liquid buffer tank;
the upper opening of the ion exchange resin column of the leaching zone is communicated with a water inlet pipeline, and the lower opening is communicated with a regenerant inlet pipeline of the regeneration zone. The leacheate is used in the regeneration zone, so that the leacheate can be fully utilized.
The continuous multi-column ion exchange system adopts high-efficiency intelligent automatic control of the opening and closing of valves on all pipelines so as to meet the production precondition of continuous, balanced and stable sucrose production process.
The scheme of the invention at least comprises the following beneficial effects:
the method for regenerating the decalcification resin by using the decoloration resin regeneration waste liquid in the prior art has the problems of reduced purity of the sucrose, increased chromaticity and the like in industrial production, so that the method is developed in 2010, but cannot be truly applied to large-scale production, and the main reason for the reduced purity of the sucrose is found through repeated experiments, namely the increased pH of the sucrose is generated when the decalcification resin is cut into the decalcification production again after regeneration. After the pH value is raised, the reducing sugar in the sucrose raw material is increased, the color of the discharged material is deepened when the subsequent working procedure is evaporated and concentrated, and the purity of the sucrose is reduced. This problem is solved by lowering the pH of the decolorized resin regeneration waste liquid. It is further found that hydrochloric acid is needed to neutralize the common decolored resin regeneration waste liquid before nanofiltration concentration, and the pH value range of the regenerated waste liquid after neutralization meets the requirement of decalcification resin regenerant, so that the nanofiltration concentrated waste brine raw material is directly used for decalcification resin regeneration, and the problem of pH increase of decalcification resin in saline-alkali water regeneration is really solved.
The sucrose decalcification method and the sucrose decalcification system provided by the invention obtain decalcification sucrose solution, namely clean sucrose solution, and after entering the subsequent procedures of an evaporator and the like, the scaling phenomenon of equipment such as the evaporator, crystallization and sugar boiling and the like is greatly reduced, the production is not stopped because the equipment such as the evaporator and the like is required to be descaled, the continuous production of sucrose is realized, and the labor cost is saved. And simultaneously, the service lives of the evaporator and the crystallization sugar boiling equipment are prolonged.
The sucrose decalcification method and system of the invention have better decalcification effect, the calcium ion content after decalcification is reduced from 300-500ppm before decalcification to below 0-20ppm after decalcification, the treatment capacity is 100-200BV, and the decalcification rate is as high as above 95%.
The regenerating agent for decalcification resin is prepared from the liquid obtained by neutralizing the waste liquid in the decoloring step with acid, and contains a large amount of sodium chloride, and preliminary researches prove that NaCl and pigment in the waste liquid for decoloring resin regeneration have an effect on the regeneration of decalcification resin, and the pH value of the regenerated waste liquid is reduced by neutralizing with hydrochloric acid, but the regenerating effect of NaCl and pigment is not influenced.
The discharge of the leaching area is connected with the feed of the regeneration area in series, so that the regeneration waste liquid of the decoloring process is ensured to be sufficiently used for the regeneration of decalcified resin, and the decalcified resin regenerant does not need to be prepared in a supplementing way.
The design of the invention can fully utilize the resin, bring the utilization rate of the resin into play to the maximum, and can save the resin consumption during actual mass production.
Drawings
FIG. 1 is a schematic diagram of the sucrose decalcification system of the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The method for decalcifying sucrose of the invention adopts a continuous multi-column ion exchange method to remove calcium ions in sucrose, and an ion exchange resin column used for decalcifying sucrose adopts liquid obtained by neutralizing regenerated waste liquid of decolorized ion exchange resin in a decolorization process in sucrose production as a regenerant.
Further, the regenerant for the ion exchange resin column used for decalcification of sucrose is derived from the spent brine raw material of nanofiltration concentration process in sucrose production.
The pH value of the regenerant is 5.5-7.5.
The concrete method for decalcification of sucrose comprises the following steps of;
the production process comprises the following steps: carrying out ion exchange on sucrose through a plurality of resin layers of ion exchange resin columns which are arranged in parallel to decalcifie the sucrose to obtain decalcified sucrose solution;
scrubbing: loosening the resin in the ion exchange resin column which is invalid in the production process by clean air;
backwashing: washing out the sugar solution in the ion exchange resin column and impurities in the resin column which are invalid in the production procedure by water;
and (3) a regeneration procedure: regenerating the ion exchange resin columns which are arranged in series after the backwashing process is completed by using a regenerant;
leaching: the ion exchange resin columns arranged in series after the regeneration process are washed with water.
Example 1
The sucrose decalcification method is described in connection with the sucrose decalcification system as follows:
as shown in fig. 1:
the sucrose decalcification system comprises multiple Na-type cation exchange resin columns, wherein the volume of each column is 1-3m 3 The plurality of ion exchange resin columns are divided into a production zone, a scrubbing backwash zone, a regeneration zone and a leaching zone, and the production process, the scrubbing process, the backwash process, the regeneration process and the leaching process are respectively executed, wherein:
production zone 101: the method comprises a plurality of ion exchange resin columns which are arranged in parallel, wherein the sucrose raw material is subjected to ion exchange through resin layers of the plurality of ion exchange resin columns which are connected in parallel to decalcify the sucrose raw material to obtain clean sucrose, and the upper opening of the ion exchange resin columns is communicated with a feed pipe 4, a decalcification feed pump I2 and a decalcification feed pump II 3, and the two pumps are used in one. The decalcification feed pump conveys the materials in the decalcification feed tank 1 to an ion exchange resin column, and the lower port of the ion exchange resin column is connected and communicated with a discharge pipe 5 and a decalcification discharge tank 6. A reflux pipeline 7 is arranged between the discharging pipe 5 and the decalcification feeding tank 1, the reason for designing the pipeline is that the pipeline is used for refluxing materials when the discharging is unqualified, and the other reason is that the materials temporarily reflux to the decalcification feeding tank when the liquid level of the decalcification discharging tank 6 is higher and the liquid level of the decalcification feeding tank 1 is lower, so that the pressure of the decalcification discharging tank 6 is relieved. The decalcification discharge tank 6 is conveyed to the evaporation section by a decalcification discharge pump I8 and a decalcification discharge pump II 9. The production area 101 of this embodiment is provided with 8 ion exchange resin columns (No. N1-N8 ion exchange resin columns), but 8 ion exchange resin columns are not fixed, and the number of ion exchange resin columns can be increased or decreased according to the yield in actual industrial production.
Scrubbing backwash zone 102: comprises a failed ion exchange resin column switched from a production area, in the embodiment, a scrubbing and backwashing area 102 is provided with 1 ion exchange resin column (No. N14 ion exchange resin column), the lower opening of the ion exchange resin column is connected and communicated with a compressed air pipeline 10 and a water inlet pipeline 12, the upper opening of the ion exchange resin column is connected and communicated with a sweet water tank 11 and a backwashing discharge buffer tank 13 in a process workshop, and automatic switch valves are arranged on the corresponding pipelines. The scrubbing process and the backwashing process are sequentially performed.
Firstly, an automatic switching valve on the compressed air pipeline 10 (the automatic switching valve on the water inlet pipeline 12 is closed) is opened, clean air is introduced to loosen the resin in the ion exchange resin column, and at the moment, the automatic switching valve on the pipeline between the upper port and the sweet water tank 11 is opened. The spent ion exchange resin column is a resin column that has been saturated with calcium ion adsorption, the resin having substantially no exchange capacity. The method of the traditional process does not have the area, and the sucrose in the ion exchange column is cleaned to have no brix by pure water after production, so that a large amount of clean water can be wasted in the process, and the backwashing efficiency of the resin is improved after the resin is loosened by arranging a scrubbing procedure, so that the regeneration utilization rate and the regeneration effect are indirectly improved, and the phenomena of resin crushing and caking caused by long-time extrusion of the resin are avoided.
After the scrubbing process is finished, the automatic switching valve on the compressed air pipeline 10 is closed, the automatic switching valve on the pipeline between the upper port and the sweet water tank 11 is closed, the automatic switching valve on the water inlet pipeline 12 is opened, and the automatic switching valve on the pipeline with the upper port connected with the backwashing discharge buffer tank 13 is opened to perform the backwashing process. The back washing process is to wash the sucrose in the ion exchange column with pure water to no hammer degree, the back washing process is to feed pure water into the lower port of the ion exchange column and discharge the material from the upper port, and the water feeding washing method can play the roles of loosening the resin and thoroughly washing the residual impurities in the sucrose material. Meanwhile, the water consumption in the area is greatly reduced, and the water consumption can be thoroughly cleaned within 1-1.5 BV.
Regeneration zone 103: comprises an ion exchange resin column switched from a scrubbing and backwashing zone, wherein the resin in the ion exchange resin column is regenerated by using the liquid neutralized by the acid from the decoloration resin regeneration waste liquid. The regeneration zone 103 is provided with 3 ion exchange columns for serial regeneration (No. N11-N13 ion exchange resin columns), the upper port of the first ion exchange resin column is connected and communicated with the neutralized waste brine tank in the nanofiltration concentration process through a waste brine pipeline 16, the lower port of the first ion exchange resin column is connected to the upper port of the second ion exchange resin column in series through a pipeline, the lower port of the second ion exchange resin column is connected to the upper port of the third ion exchange resin column in series through a pipeline, the lower port of the third ion exchange resin column is discharged, the lower port of the third ion exchange resin column is connected with a calcium solution buffer tank 14, at the moment, the material in the calcium solution buffer tank 14 is a solution rich in calcium elements, and the solution can be conveyed to a saturated front tank in the sucrose production process by a calcium solution discharge pump 15 for continuous recycling. The series regeneration is an optimal series regeneration mode by multiple experiments and calculation of 3 ion exchange columns, the quantity of the ion exchange resin columns is reduced to cause incomplete regeneration, or the quantity of the regenerant is large, the addition of the ion exchange resin columns increases the investment of earlier equipment to cause the increase of the budget of a new production workshop, the quantity of the regenerant of the 3 ion exchange columns is also stably controlled to be 1-2BV which is less than 4-6BV in the prior art, and the regeneration waste liquid of the decoloring procedure in mass production is lower than 4BV.
Leaching zone 104: comprises an ion exchange resin column switched from a regeneration zone, and pure water is used for leaching the resin in the ion exchange resin column. The cleaning at this time is mainly to clean the regenerant. The leaching zone 104 is provided with 2 ion exchange resin columns (ion exchange resin columns N9-N10) which are connected in series, wherein the upper port of the first ion exchange resin column is connected and communicated with the water inlet pipeline 12, the lower port of the first ion exchange resin column is connected in series to the upper port of the second ion exchange resin column through a pipeline, and the lower port of the second ion exchange resin column is connected in series to a waste brine pipeline connected with the upper port of the first ion exchange resin column of the regeneration zone 104 through a pipeline. Because the regeneration agent which is not thoroughly utilized is also arranged in the column, the outlet pipeline of the leaching zone is connected with the inlet pipeline of the regeneration zone, and the leaching solution is used in the regeneration zone, so that the leaching solution can be fully utilized, the consumption of water and the regeneration agent is saved, the number of ion exchange resin columns is reduced, and the investment cost of the prior equipment is reduced.
The leaching area 104 is connected in series with the regeneration area 103 in this embodiment for further resource saving, but the leaching area 104 may not be connected in series with the regeneration area 103, and the effluent of the leaching area has a small influence on the pH value of the regenerant, so that the pH value of the regenerant cannot exceed 5.5-7.5.
The sucrose decalcification system is continuously produced, ion exchange resin columns in the production area are switched out after being saturated, enter the scrubbing and backwashing area, are switched into the regeneration area and the leaching area after being cleaned, and the ion exchange resin columns in each working area are always kept unchanged in quantity through sequential switching, so that the sucrose decalcification can be continuously carried out.
Example 2
Comparative test
(1) The sucrose decalcification system of example 1 was used to perform the sucrose decalcification treatment, the on-off valve on the waste brine pipe 16 was opened, the regenerant was a waste brine raw material (a liquid obtained by neutralizing the decolored resin regeneration waste liquid) in the nanofiltration concentration process, and the pH of the regenerant was 5.5 to 7.5, and the material index parameters were as follows:
| ca feed 2+ Content (ppm) | Discharging Ca 2+ Content (ppm) | Discharge pH | Discharged reducing sugar content (%) | Post-evaporation color value (IU) |
| 270-430 | 0 | 7.5-7.8 | 0.01-0.05 | 5-10 |
The regenerant is the decolored regenerated waste liquid after neutralization, the discharge indexes are all in a normal range, and the color value of the finished sucrose obtained after the discharge is subjected to the evaporation process is lower.
(2) The sucrose decalcification system of example 1 was used for the sucrose decalcification treatment, the switch valve on the waste brine pipe 16 was opened, but the switch valve on the hydrochloric acid pipe before the neutralization of the waste brine tank was closed, and the decolorized resin regeneration waste liquid (which was not subjected to neutralization treatment and was alkaline) was used as a resin regenerant, the pH of the regenerant was 8 to 9, and the material index parameters were as follows:
| ca feed 2+ Content (ppm) | Discharging Ca 2+ Content (ppm) | Discharge pH | Discharged reducing sugar content (%) | Post-evaporation color value (IU) |
| 270-430 | 0 | 8.5-9.0 | 0. 1-0.2 | 60-100 |
After the resin is regenerated by the alkaline waste brine in the decoloring process of the regenerant, the discharged calcium ions can be reduced to the minimum, but the pH value of the discharged material is increased beyond the normal range of 7.5-8.0, the reducing sugar in the sucrose is increased after the pH value is increased, the quality of the sucrose is reduced, the color value of the finished sucrose after the discharged material is subjected to the evaporating process is also increased, and the normal color value range is less than 10.
(3) The sucrose decalcification system of example 1 was used for the sucrose decalcification treatment, but the on-off valve on the waste brine pipe 16 was closed, and saline-alkali water added with pigment was used as the resin regenerant (the regenerant at this time was artificially prepared saline-alkali water, naCl content was 9%, naOH content was 0.25%, and the composition of the decolorized resin regeneration waste liquid of comparative experiment (2) was substantially the same), the regenerant had a pH value of 8-9, and the material index parameters were as follows:
| ca feed 2+ Content (ppm) | Discharging Ca 2+ Content (ppm) | Discharge pH | Discharged reducing sugar content (%) | Post-evaporation color value (IU) |
| 270-430 | 0 | 8.5-9.0 | 0.1-0.2 | 60-100 |
After the regenerant regenerates the resin by using the saline-alkali water added with pigment, the discharged calcium ions can be reduced to the minimum, but the pH value of the discharged material is increased to 7.5-8.0 beyond the normal range, reducing sugar in sucrose is increased after the pH value is increased, the quality of the sucrose is reduced, the color value of the finished sucrose after the discharged material is subjected to an evaporation process is also increased, and the normal color value range is less than 10.
(4) The sucrose decalcification system of example 1 was used for the sucrose decalcification treatment, but the switch valve on the waste brine pipe 16 was closed, and brine was used as a regenerant for the resin (the brine was prepared in the same manner as in comparative test (3), no pigment was added), the pH of the regenerant was 8-9, and the material index parameters were as follows:
| ca feed 2+ Content (ppm) | Discharging Ca 2+ Content (ppm) | Discharge pH | Discharged reducing sugar content (%) | Post-evaporation color value (IU) |
| 270-430 | 30-70 | 8.5-9.0 | 0.1-0.2 | 60-100 |
The regenerant adopts saline-alkali water to regenerate the saturated calcium-rich resin, after repeated feeding, reducing sugar is increased, the color value of the finished product after evaporation and concentration is increased, and meanwhile, the content of calcium ions is also increased, which indicates that the pigment is also beneficial to resin regeneration because of electrostatic attraction of anions and calcium ions in the pigment and desorption of calcium.
The comparative tests (1) and (2) show the influence of the pH change of the regenerant on the content and the color value of discharged reducing sugar, and the reduction of the pH of the regenerant can obviously improve the quality of the finished sucrose product, reduce the reducing sugar and reduce the color value. (3) And (4) shows the effect of pigment in the regenerant on the content of discharged calcium, and pigment in the regenerant can obviously reduce the content of discharged calcium.
Sucrose decalcification by using a multi-unit continuous ion exchange system, and the statistical results are as follows through resin treatment capacity and water consumption:
| throughput of production zone material (BV) | Water consumption in rinsing area (BV) | Water consumption (BV) for scrubbing and backwashing area | Regeneration zone consumes Brine (BV) | |
| Comparative test (1) | 100-200 | 1.0-1.3 | 1-1.5 | 1-1.5 |
| Comparative test (2) | 100-200 | 1.5-2.0 | 1-1.5 | 1-1.5 |
Wherein, BV: resin volume multiple. 1.5BV, i.e., 1.5 times the resin volume.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A method for decalcifying sucrose adopts a continuous multi-column ion exchange method to remove calcium ions in the sucrose raw material, and is characterized in that an ion exchange resin column used for decalcifying sucrose adopts liquid obtained by acid neutralization of regenerated waste liquid of decolorized ion exchange resin in a decolorization process in sucrose purification production as a regenerant, and the pH value of the regenerant is 5.5-7.5;
the method for removing calcium ions in sucrose by using the continuous multi-column ion exchange method comprises the following steps:
the production process comprises the following steps: carrying out ion exchange on sucrose through a plurality of resin layers of ion exchange resin columns which are arranged in parallel to decalcifie the sucrose to obtain decalcified sucrose solution;
a scrubbing step of loosening the resin in the ion exchange resin column which is failed in the production step by clean air;
backwashing: washing out the sugar solution in the ion exchange resin column and impurities in the resin column which are invalid in the production procedure by water;
and (3) a regeneration procedure: regenerating the ion exchange resin columns which are arranged in series after the backwashing process is completed by using a regenerant;
leaching: the ion exchange resin columns arranged in series after the regeneration process are washed with water.
2. The method for decalcification of sucrose according to claim 1, wherein the feeding means of the production process is upper feeding and lower discharging; the air inlet mode of the scrubbing procedure is lower air inlet and upper air outlet; the water inlet mode of the backwashing procedure is lower water inlet and upper material outlet; the feeding mode of the regeneration procedure is an upper liquid feeding and lower discharging mode; the feeding mode of the leaching process is an upper water inlet and lower discharging mode.
3. The method according to claim 2, wherein the regeneration step is carried out by using 3 ion exchange resin columns arranged in series.
4. The method of decalcification of sucrose according to claim 2, wherein the effluent solution from the rinsing step is fed to a regenerant line and mixed with regenerant into the ion exchange resin column of the regeneration step.
5. The sucrose decalcification method according to claim 1, wherein the ion exchange resin has a single column volume of 1-3m 3 。
6. A sucrose decalcification system for removing calcium ions from a sucrose material using a continuous multi-column ion exchange resin, comprising:
production area: the method comprises the steps that a plurality of ion exchange resin columns are arranged in parallel, a sucrose feeding pipeline is respectively communicated with the ion exchange resin columns, and sucrose is subjected to ion exchange through resin layers of the plurality of ion exchange resin columns in parallel to decalcify the sucrose to obtain decalcified sucrose solution;
scrubbing and backwashing: the method comprises the steps of connecting a failed ion exchange resin column switched from a production area with a compressed air pipeline and a water inlet pipeline, loosening resin in the ion exchange resin column by clean air, and then washing out sugar solution and impurities in the ion exchange resin column by water;
regeneration zone: the method comprises a plurality of ion exchange resin columns which are connected in series and are switched from a scrubbing and backwashing area, wherein a waste brine raw material pipeline of a nanofiltration concentration process is communicated with the ion exchange resin columns of the area, waste brine raw material of the nanofiltration concentration process enters the ion exchange resin columns to regenerate the resin, and a regenerant is liquid obtained by neutralizing regenerated waste liquid of decolored ion exchange resin in a decoloration process in sucrose purification production;
leaching area: the regeneration device comprises an ion exchange resin column switched from a regeneration zone, wherein a water inlet pipeline is communicated with the ion exchange resin column in the zone, water enters the ion exchange resin column, and residual regenerant in the column is washed out;
the ion exchange resin columns of the production area, the scrubbing and backwashing area, the regeneration area and the leaching area are sequentially switched, one ion exchange resin column is switched each time, and the number of the ion exchange resin columns of each working area is always kept unchanged.
7. The sucrose decalcification system according to claim 6, wherein the ion exchange resin column in the leaching zone has an upper port in communication with the water inlet conduit and a lower port in communication with the regenerant inlet conduit of the regeneration zone.
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| CN112795710A (en) * | 2020-12-08 | 2021-05-14 | 武汉美味源生物工程有限公司 | Regeneration method of ion exchange resin in sugar production process |
| CN114807456A (en) * | 2022-03-10 | 2022-07-29 | 欧尚元(天津)有限公司 | Sucrose decoloring method and system |
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| JPH0228000A (en) * | 1988-07-15 | 1990-01-30 | Itochu Seito Kk | Method for cleaning sugar liquid |
| JPH10229900A (en) * | 1997-02-17 | 1998-09-02 | Nippon Rensui Kk | Purification of beet leachate |
| JPH1170000A (en) * | 1997-08-28 | 1999-03-16 | Japan Organo Co Ltd | Apparatus for purifying sucrose syrup and regeneration of sucrose syrup purification apparatus |
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