阅读说明：本技术 一种葡萄糖酸钙真空闪发连续结晶的装置及方法和应用 (Device and method for vacuum flash continuous crystallization of calcium gluconate and application of device ) 是由 赵改菊 孙荣峰 尹凤交 耿文广 员冬玲 王鲁元 于 2019-07-11 设计创作，主要内容包括：本发明涉及葡萄糖酸钙结晶技术领域,尤其涉及一种葡萄糖酸钙真空闪发连续结晶的装置及方法和应用。所述装置包括：第一溶解罐、氧化反应罐、板框压滤机、一级纳滤膜浓缩装置、第二溶解罐、加热室、单效真空降温闪发结晶装置、浆液槽、离心机、造粒机、内加热流化床干燥装置；所述方法包括如下步骤：所述方法包括如下步骤：溶解定容、酶氧化、灭酶过滤、浓缩、溶解脱色、循环过滤、成品结晶、离心洗涤、造粒干燥；本发明具有能源利用率高、占地面积小、投资费用低；劳动生产率高,可以进行自动化控制,结晶粒度均匀,且在一定范围内可以调整,不结垢、不结疤,可以长期连续性生产的优点。(the invention relates to the technical field of calcium gluconate crystallization, in particular to a device and a method for vacuum flash continuous crystallization of calcium gluconate and application of the device. The device comprises: the device comprises a first dissolving tank, an oxidation reaction tank, a plate-and-frame filter press, a primary nanofiltration membrane concentration device, a second dissolving tank, a heating chamber, a single-effect vacuum cooling flash crystallization device, a slurry tank, a centrifuge, a granulator and an internal heating fluidized bed drying device; the method comprises the following steps: the method comprises the following steps: dissolving to fix volume, carrying out enzyme oxidation, carrying out enzyme deactivation and filtration, concentrating, dissolving and decolorizing, carrying out circulating filtration, crystallizing a finished product, carrying out centrifugal washing, granulating and drying; the invention has the advantages of high energy utilization rate, small occupied area and low investment cost; high labor productivity, automatic control, uniform crystal granularity, no scaling and no scar, and can be adjusted in a certain range and continuously produced for a long time.)

1. The utility model provides a calcium gluconate vacuum flashing continuous crystallization's device which characterized in that includes: the device comprises a first dissolving tank, an oxidation reaction tank, a plate-and-frame filter press, a primary nanofiltration membrane concentration device, a second dissolving tank, a heating chamber, a single-effect vacuum cooling flash crystallization device, a slurry tank, a centrifuge, a granulator and an internal heating fluidized bed drying device; wherein:

the outlet of the first dissolving tank is connected with the inlet of the oxidation reaction tank through a thick slurry pump, the outlet of the oxidation reaction tank is connected with the inlet of the plate-and-frame filter press, the outlet of the plate-and-frame filter press is connected with a primary nanofiltration membrane concentration device through a security filter, the primary nanofiltration membrane concentration device is connected with a second dissolving tank, and the second dissolving tank is connected with the security filter; the primary nanofiltration membrane concentration device is simultaneously connected with the heating chamber;

The single-effect vacuum cooling flash crystallization device comprises: a forced circulation pump, a vacuum flash cooling crystallizer and a steam jet vacuum pump; the upper part of the vacuum flash cooling crystallizer is communicated with a steam jet vacuum pump, and the bottom of the vacuum flash cooling crystallizer is communicated with a forced circulation pump; the heating chamber is connected with the bottom of the vacuum flash cooling crystallizer, and the vacuum flash cooling crystallizer, the slurry tank, the centrifuge, the granulator and the internal heating fluidized bed drying device are sequentially connected.

2. The device for vacuum flash continuous crystallization of calcium gluconate according to claim 1, wherein the vacuum flash cooling crystallizer has a structure with an upper straight cylinder and a lower conical section, and the ratio of the straight cylinder section to the conical section is 1:1-3: 2.

3. The apparatus for vacuum flash continuous crystallization of calcium gluconate according to claim 1, wherein the nanofiltration membrane in the primary nanofiltration membrane concentration device is any one or more of a rolled nanofiltration membrane, a tubular nanofiltration membrane, a flat nanofiltration membrane and a hollow fiber nanofiltration membrane.

4. The apparatus for vacuum flash continuous crystallization of calcium gluconate according to claim 1, wherein the internal heating fluidized bed dryer is internally provided with a built-in heat exchanger, the built-in heat exchanger comprises a plurality of steam headers, each steam header is connected end to end, the whole tube pass is S-shaped, the steam headers at the ends are respectively provided with a steam inlet and a condensate outlet, a plurality of heat exchange tubes are arranged in each adjacent steam header, and tube plates are arranged at two ends of each heat exchange tube in the vertical direction.

5. The device for vacuum flash continuous crystallization of calcium gluconate according to any one of claims 1 to 4, wherein the vacuum flash cooling crystallizer is provided with a crystallization chamber, an internal circulation draft tube and a forced circulation pump, the crystallization chamber is internally provided with the internal circulation draft tube, a support tube is arranged between the internal circulation draft tube and the crystallization chamber, the lower conical section of the crystallization chamber is provided with a feed liquid inlet and a plurality of slurry outlets, and the bottom of the crystallization chamber is provided with an evacuation port.

6. The apparatus for vacuum flash continuous crystallization of calcium gluconate according to claim 5, wherein said slurry outlet has a length of 20-70 μm and a diameter of 50-100 μm.

7. The method for vacuum flash continuous crystallization of calcium gluconate using the apparatus of any one of claims 1 to 6, comprising the steps of:

S1, dissolving to fix the volume: adding purified water into a first dissolving tank, opening a stirrer, adding glucose, calcium carbonate and a defoaming agent, and adding water to a constant volume to enable a glucose solution to reach a set concentration;

S2, enzyme oxidation: conveying the materials in the first dissolving tank to an oxidation reaction tank through a thick slurry pump, introducing air into the oxidation reaction tank, adding an enzyme preparation, stirring, starting cooling water when the reaction temperature is increased to a set value, and stopping reaction when the residual sugar content is reduced to be below 0.5%;

S3, enzyme deactivation and filtration: heating to inactivate enzyme after the reaction is stopped, performing filter pressing and filtering by a plate-and-frame filter press after the enzyme is inactivated, and performing next treatment on the obtained clear reaction liquid;

s4, concentration: introducing the clear reaction liquid obtained in the step S3 into a cartridge filter for filtering, then introducing into a primary nanofiltration membrane concentration device for concentration and filtration, controlling the concentration specific gravity of the feed liquid within a set range, and obtaining a concentrated solution for next treatment;

S5, dissolving, decoloring and circulating filtration: introducing the concentrated solution obtained in the step S4 into a second dissolving tank, measuring the specific gravity of the solution, stirring, adding a dilute reaction solution to adjust the specific gravity of the solution in the dissolving tank to a set value, adding activated carbon, stirring, precipitating, standing, sucking supernatant after the completion, introducing the supernatant into a security filter again, filtering, concentrating the filtrate in a primary nanofiltration membrane concentration device again, and controlling the concentration specific gravity of the solution within a set range to obtain a secondary concentrated solution;

S6, crystallizing finished products, and centrifugally washing: introducing the secondary concentrated solution obtained in the step S5 into a heating chamber, introducing steam for heating, then introducing into a single-effect vacuum flash cooling crystallizer for crystallization, then introducing into a centrifuge for centrifugation and dehydration, washing the materials with purified water after the centrifugation and dehydration are finished, and cleaning impurities to obtain a wet product;

s7, granulating and drying: and (5) checking the wet product obtained in the step (S6) to be qualified, then introducing the wet product into a granulator for granulation, then introducing the wet product into an internal heating fluidized bed drying device for drying, discharging, sieving and carrying out full inspection to obtain the finished product.

8. the method according to claim 7, wherein in step S1, the concentration of the glucose solution is 13-15%;

Preferably, in step S2, when the reaction temperature rises to 35 ℃, starting cooling water, keeping the reaction temperature at 38 +/-1 ℃, introducing sterile air, controlling the ventilation amount to be 1:1v/v/min, keeping the pressure of the dissolving tank at 0.2MPa, controlling the reaction period to be 10-15h, stopping the reaction when the residual sugar content is reduced to be below 0.5%, and controlling the pH value to be 6-7; wherein, the sugar content in the reaction liquid is detected according to the test of national standard GB15571-2010, and the pH detection method comprises the following steps: the reaction solution was filtered and directly measured with a pH meter.

9. The method for vacuum flash continuous crystallization of calcium gluconate according to claim 7, wherein in step S2, said enzyme deactivation temperature is 85-100 ℃;

Preferably, in step S4, the primary nanofiltration membrane concentration device filters with a nanofiltration membrane having a filtration precision of 0.2 to 200 μm;

Preferably, in step S4, the filtering precision of the cartridge filter is 1-10 μm;

preferably, in the step S5, the stirring speed is 10-35 r/min;

Preferably, in step S7, the drying heat source is superheated steam or saturated steam with a pressure of 0.3-0.6MPa, and 60% -80% of the heat required for drying the wet material is provided by the superheated steam or saturated steam.

10. Use of the apparatus for vacuum flash continuous crystallization of calcium gluconate according to any one of claims 1 to 6 and/or the method according to any one of claims 7 to 9 in the chemical field.

Technical Field

the invention relates to the technical field of calcium gluconate crystallization, in particular to a device and a method for vacuum flash continuous crystallization of calcium gluconate and application of the device.

Background

The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

the calcium gluconate is white crystalline or granular powder, has melting point of 201 deg.C (decomposition), no odor, no taste, easy solubility in boiling water (20g/100ml), slightly solubility in cold water (3g/100ml, 20 deg.C), and insolubility in organic solvent such as ethanol or diethyl ether. The aqueous solution was neutral (pH about 6-7). The calcium gluconate is mainly used as calcium enhancer, nutrient, buffering agent, solidifying agent and chelating agent of food. At present, the production process of calcium gluconate mainly comprises steps of oxidizing glucose into gluconic acid, neutralizing the gluconic acid and calcium into calcium gluconate, and finally refining 3 parts. More than 95% of crystallization working sections in the refining process adopt standing crystallization, the links of evaporation concentration and crystallization directly relate to the production cost and the product quality of products, standing crystallization has the problems of high labor intensity, low discharging efficiency, high energy consumption, large occupied area, low automation degree and the like, and more importantly, the problems of uneven crystal grain size, difficult dehydration and serious influence on the product quality.

Patent document 201910294514.5 discloses a system and a process for continuous crystallization of calcium gluconate, which includes an MVR evaporator, a three-stage vacuum flash crystallizer, a steam jet vacuum pump, a mixing condenser, a heat exchanger, a slurry tank, a centrifuge, a granulator, and a dryer. The system and the process completely overcome the defect of intermittent crystallization, realize the continuous crystallization in the production of calcium gluconate, have compact equipment structure and small occupied area, greatly reduce the energy consumption and the production cost, improve the working efficiency, save the energy by 40 to 50 percent, and have uniform crystallization particle strength, smooth surface and stable product quality.

disclosure of Invention

Aiming at the problems, the invention aims to provide a device, a method and application for vacuum flash continuous crystallization of calcium gluconate. The device has the advantages of high energy utilization rate, small occupied area and low investment cost; high labor productivity, automatic control, uniform crystal granularity, no scaling and no scar, and can be adjusted in a certain range and continuously produced for a long time.

the first object of the present invention: provides a device for vacuum flash continuous crystallization of calcium gluconate.

the second object of the present invention: provides a method for vacuum flash continuous crystallization of calcium gluconate.

The third object of the present invention: provides the device and the method for vacuum flash continuous crystallization of calcium gluconate.

In order to realize the purpose, the invention discloses the following technical scheme:

Firstly, the invention discloses a calcium gluconate vacuum flash continuous crystallization device, which comprises: the device comprises a first dissolving tank, an oxidation reaction tank, a plate-and-frame filter press, a primary nanofiltration membrane concentration device, a second dissolving tank, a heating chamber, a single-effect vacuum cooling flash crystallization device, a slurry tank, a centrifuge, a granulator and an internal heating fluidized bed drying device; wherein:

The outlet of the first dissolving tank is connected with the inlet of the oxidation reaction tank through a thick slurry pump, the outlet of the oxidation reaction tank is connected with the inlet of the plate-and-frame filter press, the outlet of the plate-and-frame filter press is connected with a primary nanofiltration membrane concentration device through a security filter, the primary nanofiltration membrane concentration device is connected with a second dissolving tank, and the second dissolving tank is connected with the security filter; the first-stage nanofiltration membrane concentration device is connected with the heating chamber at the same time.

The single-effect vacuum cooling flash crystallization device comprises: a forced circulation pump, a vacuum flash cooling crystallizer and a steam jet vacuum pump; the upper part of the vacuum flash cooling crystallizer is communicated with a steam jet vacuum pump, and the bottom of the vacuum flash cooling crystallizer is communicated with a forced circulation pump. The heating chamber is connected with the bottom of the vacuum flash cooling crystallizer, and the vacuum flash cooling crystallizer, the slurry tank, the centrifuge, the granulator and the internal heating fluidized bed drying device are sequentially connected.

As a further technical scheme, the vacuum flash cooling crystallizer is in a structure with an upper straight cylinder and a lower conical section, and the ratio of the straight cylinder section to the conical section is 1:1-3: 2.

as a further technical scheme, the nanofiltration membrane in the primary nanofiltration membrane concentration device is any one or more of a rolled nanofiltration membrane, a tubular nanofiltration membrane, a flat nanofiltration membrane and a hollow fiber nanofiltration membrane.

As a further technical scheme, a built-in heat exchanger is arranged in the internal heating fluidized bed dryer and comprises a plurality of steam headers, the steam headers are connected end to end, the whole tube pass is S-shaped, the steam headers at the end and the tail are respectively provided with a steam inlet and a condensate outlet, a plurality of heat exchange tubes are arranged in adjacent steam headers, and tube plates are arranged at the two ends of each heat exchange tube in the vertical direction.

as a further technical scheme, a crystallization chamber, an internal circulation guide cylinder and a forced circulation pump are arranged in the vacuum flash cooling crystallizer, the internal circulation guide cylinder is arranged in the crystallization chamber, a support pipe is arranged between the internal circulation guide cylinder and the crystallization chamber, a feed liquid inlet and a plurality of slurry outlets are arranged on a lower conical section of the crystallization chamber, and an evacuation port is arranged at the bottom of the crystallization chamber.

As a further technical scheme, the length of the slurry outlet is 20-70 μm, and the diameter is 50-100 μm.

Secondly, the invention discloses a method for vacuum flash continuous crystallization of calcium gluconate, which comprises the following steps:

S1, dissolving to fix the volume: adding purified water into a first dissolving tank, opening a stirrer, adding glucose, calcium carbonate and a defoaming agent, and adding water to a constant volume to enable a glucose solution to reach a set concentration;

S2, enzyme oxidation: conveying the materials in the first dissolving tank to an oxidation reaction tank through a thick slurry pump, introducing air into the oxidation reaction tank, adding an enzyme preparation, stirring, starting cooling water when the reaction temperature is increased to a set value, and stopping reaction when the residual sugar content is reduced to be below 0.5%;

S3, enzyme deactivation and filtration: heating to inactivate enzyme after the reaction is stopped, performing filter pressing and filtering by a plate-and-frame filter press after the enzyme is inactivated, and performing next treatment on the obtained clear reaction liquid;

S4, concentration: introducing the clear reaction liquid obtained in the step S3 into a cartridge filter for filtering, then introducing into a primary nanofiltration membrane concentration device for concentration and filtration, controlling the concentration specific gravity of the feed liquid within a set range, and obtaining a concentrated solution for next treatment;

s5, dissolving, decoloring and circulating filtration: introducing the concentrated solution obtained in the step S4 into a second dissolving tank, measuring the specific gravity of the solution, stirring, adding a dilute reaction solution to adjust the specific gravity of the solution in the dissolving tank to a set value, adding activated carbon, stirring, precipitating, standing, sucking supernatant after the completion, introducing the supernatant into a security filter again, filtering, concentrating the filtrate in a primary nanofiltration membrane concentration device again, and controlling the concentration specific gravity of the solution within a set range to obtain a secondary concentrated solution;

S6, crystallizing finished products, and centrifugally washing: introducing the secondary concentrated solution obtained in the step S5 into a heating chamber, introducing steam for heating, then introducing into a single-effect vacuum flash cooling crystallizer for crystallization, then introducing into a centrifuge for centrifugation and dehydration, washing the materials with purified water after the centrifugation and dehydration are finished, and cleaning impurities to obtain a wet product;

S7, granulating and drying: and (5) checking the wet product obtained in the step (S6) to be qualified, then introducing the wet product into a granulator for granulation, then introducing the wet product into an internal heating fluidized bed drying device for drying, discharging, sieving and carrying out full inspection to obtain the finished product.

As a further technical scheme, in the step S1, the concentration of the glucose solution is 13-15%.

as a further technical scheme, in the step S2, when the reaction temperature rises to 35 ℃, cooling water is started, the reaction temperature is kept at 38 +/-1 ℃, sterile air is introduced, the ventilation rate is controlled to be 1:1v/v/min, the pressure of a dissolving tank is kept at 0.2MPa, the reaction period is 10-15h, the reaction is stopped when the residual sugar content is reduced to be below 0.5%, and the pH value is controlled to be 6-7. Wherein, the sugar content in the reaction liquid is detected according to the test of national standard GB15571-2010, and the pH detection method comprises the following steps: the reaction solution was filtered and directly measured with a pH meter.

As a further technical scheme, in the step S2, the enzyme deactivation temperature is 85-100 ℃.

As a further technical scheme, in step S4, the primary nanofiltration membrane concentration device filters by using a nanofiltration membrane with a filtration precision of 0.2-200 μm.

As a further technical solution, in step S4, the cartridge filter has a filtering precision of 1-10 μm.

As a further technical scheme, in the step S5, the stirring speed is 10-35 r/min.

As a further technical solution, in step S6, the detection of impurities (sulfate, chloride (refer to the second part of 2010 edition in the chinese pharmacopoeia), oxalate (refer to the national standard GB/T9730-2007)) in the wet product should meet the regulations.

As a further technical scheme, in the step S7, the drying heat source is superheated steam or saturated steam with the pressure of 0.3-0.6MPa, and 60% -80% of heat required by the drying of the wet material is provided by the superheated steam or the saturated steam.

As a further technical scheme, in step S7, the obtained finished product meets the quality standard of calcium gluconate of the second pharmacopoeia 2010 edition.

finally, the invention discloses an application of the calcium gluconate vacuum flash continuous crystallization device and method in the field of chemical engineering.

Compared with the prior art, the invention has the following beneficial effects:

(1) The present invention is also improved over the device in patent document 201910294514.5 in terms of the crystallization mode: MVR evaporation concentration is replaced by membrane concentration, and a triple-effect vacuum flash crystallizer is replaced by a single-effect vacuum cooling flash crystallization device, so that the energy consumption is lower, the crystallization process of the calcium gluconate is simpler, and the energy consumption is saved.

(1) The continuous crystallization device has low comprehensive energy consumption, less accessory equipment, no need of a refrigeration system, only need of steam and cooling circulating water, small occupied area, investment saving and greatly improved labor efficiency and labor productivity.

(2) The continuous crystallization device has uniform crystallization granularity, avoids the problem that the salt-containing feed liquid is easy to crystallize and block in a heat exchanger in the conventional process by forced internal circulation vacuum flash evaporation and cooling continuous crystallization, does not scale or scar, and can realize long-term continuous production.

(3) The calcium gluconate product prepared by the continuous crystallization device has high solubility, high calcium content and good absorption effect.

drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.

Fig. 1 is a schematic structural diagram of a device for vacuum flash continuous crystallization of calcium gluconate in embodiment 1 of the present invention.

FIG. 2 is a flow chart of vacuum flash continuous crystallization of calcium gluconate in examples 3 to 6 according to the present invention.

The designations in the above figures represent respectively: 1-a first dissolving tank, 2-an oxidation reaction tank, 3-a plate-and-frame filter press, 4-a primary nanofiltration membrane concentration device, 5-a second dissolving tank, 6-a heating chamber, 7-a forced circulation pump, 8-a vacuum flash-evaporation cooling crystallizer, 9-a steam jet vacuum pump, 10-a slurry tank, 11-a centrifuge, 12-a granulator and 13-an internal heating fluidized bed drying device.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms also are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should be further understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.

As mentioned above, the existing standing crystallization of calcium gluconate has the problems of high labor intensity, low discharging efficiency, high energy consumption, large occupied area, low automation degree and the like, and more importantly, the crystal size is not uniform, the dehydration is difficult, and the product quality is seriously affected. Therefore, the invention provides a device and a method for vacuum flash continuous crystallization of calcium gluconate; the invention will now be further described with reference to the accompanying drawings and detailed description.