CN106854151A - The production method of Triammonium citrate crystal and the Triammonium citrate crystal produced by the method - Google Patents
The production method of Triammonium citrate crystal and the Triammonium citrate crystal produced by the method Download PDFInfo
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- CN106854151A CN106854151A CN201510907486.1A CN201510907486A CN106854151A CN 106854151 A CN106854151 A CN 106854151A CN 201510907486 A CN201510907486 A CN 201510907486A CN 106854151 A CN106854151 A CN 106854151A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
The Triammonium citrate crystal produced the invention discloses a kind of production method of Triammonium citrate crystal and by the method.The production method of the Triammonium citrate crystal includes：S1, ammoniacal liquor is injected into citric acid feed liquid, when the pH value of mixed liquor is 6.3-6.8, stops the injection ammoniacal liquor, reaction obtains Triammonium citrate feed liquid；S2, heat the Triammonium citrate feed liquid and be evaporated crystallization to obtain magma, wherein in the degree of supersaturation of the process adjusting Triammonium citrate feed liquid of the evaporative crystallization controlling the speed of the evaporative crystallization.The method is by controlling ammoniacal liquor to control ph in citric acid feed liquid to judge the reaction end of ammoniacal liquor and citric acid feed liquid, be conducive to improving the Triammonium citrate content that reaction is obtained, and be conducive to improving the content of Triammonium citrate crystal in the crystal product that reaction is obtained to control the speed of the evaporative crystallization by the degree of supersaturation of the process adjusting Triammonium citrate feed liquid in the evaporative crystallization.
Description
Technical field
The present invention relates to a kind of production method of Triammonium citrate crystal, and the lemon produced by the method
Sour three ammonium crystal.
Background technology
Ammonium citrate, molecular formula (NH4)3C6H5O7, molecular weight：243.22.This product is white crystal
Or property powder, there is hygroscopy, it is soluble in water, decompose in the hot water, insoluble in ethanol, ether and acetone.
Industrial at present, using ammoniacal liquor and citric acid reactions, specific production method is：Ammoniacal liquor is passed through
Reacted in citric acid solution, then resulting solution is evaporated, after solution nature graining, crystal seed
Continue to grow up and obtain magma, magma after washing, drying, finished product Triammonium citrate crystal.
Although this method can finished product Triammonium citrate crystal, due to production process it is universal compared with
For coarse, the content that this allows for Triammonium citrate crystal in produced crystalline product is relatively low.Therefore, mesh
It is preceding to be badly in need of a kind of production method that improve Triammonium citrate crystalline content.
The content of the invention
The purpose of the present invention is to overcome technical problem of the prior art, there is provided a kind of Triammonium citrate crystal
Production method and the Triammonium citrate crystal that is produced by the method, with improving produced crystal product
The content of Triammonium citrate crystal.
Therefore, providing a kind of production method of Triammonium citrate crystal in the present invention, the method includes：
S1, ammoniacal liquor is injected into citric acid feed liquid, when the pH value of mixed liquor is 6.3-6.8, stops note
Enter the ammoniacal liquor, reaction obtains Triammonium citrate feed liquid；S2, the heating Triammonium citrate feed liquid are carried out
Evaporative crystallization is to obtain magma, wherein the mistake of the process adjusting Triammonium citrate liquid in the evaporative crystallization
Saturation degree is controlling the speed of the evaporative crystallization.
Meanwhile, a kind of Triammonium citrate crystal produced by the above method is additionally provided in the present invention.
The method of present invention production Triammonium citrate crystal, by the mixing for controlling ammoniacal liquor and citric acid feed liquid
The pH value of feed liquid is conducive to improving what reaction was obtained to judge the reaction end of ammoniacal liquor and citric acid feed liquid
The content of Triammonium citrate in Triammonium citrate solution, and by the process adjusting lemon in the evaporative crystallization
The degree of supersaturation of lemon three ammonium feed liquids of acid is conducive to improving reaction and obtains controlling the speed of the evaporative crystallization
Crystalline product in Triammonium citrate crystal content.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Following specific embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 shows the Triammonium citrate crystal produced by embodiment 1 at Olympus (OLYMPUS)
Amplify 40 times of photos under-BX41 light microscopes；
Fig. 2 shows the Triammonium citrate crystal produced by comparative example 1 at Olympus (OLYMPUS)
Amplify 40 times of photos under-BX41 light microscopes.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The production method of existing Triammonium citrate crystal is generally relatively rough, and condition is random very high, enters
And hardly result in Triammonium citrate content crystal product higher.And in existing evaporation and crystal process,
Crystal seed is typically nature nucleation, and quantity is larger, and crystallization rate is not controlled in crystallization process, causes in crystallization
During, crystal grain is sticky serious, and it is more to sandwich mother liquor, and then cause that product content is low, product not
Uniformly.
The present inventor chances under study for action, by the mixing for controlling ammoniacal liquor and citric acid feed liquid
The pH value of feed liquid is conducive to improving what reaction was obtained to judge the reaction end of ammoniacal liquor and citric acid feed liquid
Triammonium citrate content in Triammonium citrate solution, and by the process adjusting lemon in the evaporative crystallization
The degree of supersaturation of sour three ammonium feed liquids is conducive to improving what reaction was obtained to control the speed of the evaporative crystallization
The content of Triammonium citrate crystal in crystalline product.
Therefore, providing a kind of production method of Triammonium citrate crystal in the present invention, the method includes：
S1, ammoniacal liquor is injected into citric acid feed liquid, when the pH value of mixed liquor is 6.3-6.8, stops note
Enter the ammoniacal liquor, reaction obtains Triammonium citrate feed liquid；S2, the heating Triammonium citrate feed liquid are carried out
Evaporative crystallization to obtain magma, wherein in the process adjusting Triammonium citrate feed liquid of the evaporative crystallization
Degree of supersaturation is controlling the speed of the evaporative crystallization.Can be determined by on-line pH value meter in the present invention
PH value realizes precise real-time detection pH value, so as to accurately judge reaction end.
In S1 according to method of the present invention, as long as obtaining the mistake of Triammonium citrate feed liquid in reaction
Cheng Zhong, ammoniacal liquor is injected into citric acid feed liquid, when the pH value of mixed liquor is 6.3-6.8, is stopped
Inject the ammoniacal liquor, you can improve the content of Triammonium citrate crystal in final obtained crystal product.Its
In for the content of citric acid in citric acid feed liquid and the concentration of ammoniacal liquor without particular/special requirement.
In S1 according to method of the present invention, the content of citric acid is referred in citric acid feed liquid
The content of citric acid is 30-50 weight % in customary amount, such as citric acid feed liquid.The citric acid feed liquid
The content of middle citric acid refers to the content of citric acid in initial citric acid feed liquid, i.e., also unimplanted ammoniacal liquor
When citric acid feed liquid in citric acid content.
In S1 according to method of the present invention, NH in the ammoniacal liquor3H20 content is referred to
Customary amount, for example, 20-25 weight %, herein, NH in the ammoniacal liquor3H20 content refer to
On the basis of ammoniacal liquor gross weight, NH3H20 weight content.
In S1 according to method of the present invention, during reaction obtains Triammonium citrate feed liquid,
Do not have particular/special requirement for reaction condition, its popular response condition for being referred to this area, herein not
Repeat again.
It is equal in order to further improve Triammonium citrate crystalline content and product in produced crystal product
Evenness, preferably the step of the S2 heating Triammonium citrate feed liquids of the above method are evaporated crystallization
The degree of supersaturation of middle whole-process control solution is 1.02-1.16, preferably 1.05-1.13.It is excellent in one kind of the invention
Select in implementation method, the Triammonium citrate feed liquid is heated in the S2 of the above method and is evaporated crystallization
Step includes：The Triammonium citrate feed liquid is heated, in the Triammonium citrate feed liquid degree of supersaturation first
When reaching 1.02-1.16, preferably 1.05-1.13, to being added in Triammonium citrate feed liquid, Triammonium citrate is brilliant
Kind, stop heating, 0.5-1 hours is incubated, then reheating evaporative crystallization obtains that (solid content is
30-50wt%'s) magma.
Term " degree of supersaturation " refers to the weight of the solute actually dissolved in solvent at a certain temperature in the present invention
Measure the ratio with the weight of the solute of theoretical dissolution in solvent when solution reaches saturation at this temperature.
It is 1.02-1.16 by degree of supersaturation in the above method of the present invention, preferably 1.05-1.13's
Triammonium citrate crystal seed is added in Triammonium citrate feed liquid, and it is 0.5-1 hours, energy to control soaking time
Enough control produces the amount of nucleus first, is then evaporated crystallization by reheating, and maintain supersaturation
It is 1.02-1.16 to spend, preferably 1.05-1.13, can control the speed of growth of nucleus, and then reduce crystal
Glomerocryst, pseudo- brilliant generation, reduce crystal and mother liquor are sandwiched in growth course, so as to significantly improve crystal
The quality of product, improves the content and the uniformity of crystal product.
The container of evaporative crystallization can be the conventional crystallizer for crystallization in the present invention, the crystallizer
Application method can be once or to be continuously injected into crystallizer initial Triammonium citrate feed liquid, preferably
Ground, the step of heating the Triammonium citrate feed liquid and be evaporated crystallization, first to injecting lemon in crystallizer
Sour three ammonium feed liquids to crystallizer effective volume V.The effective volume of wherein crystallizer refers in running
The volume of liquid can be accommodated in the crystallizing tank of middle crystallizer, heater and circulation pipe.
According to method of the present invention, preferably heating the Triammonium citrate feed liquid in above-mentioned S2 is carried out
In the step of evaporative crystallization, 1.02-1.16 is reached first in the Triammonium citrate feed liquid degree of supersaturation, it is excellent
When electing 1.05-1.13 as, the granularity to the Triammonium citrate crystal seed added in Triammonium citrate feed liquid is
200-400 mesh.
According to method of the present invention, wherein, the content of Triammonium citrate can in Triammonium citrate feed liquid
With the content by configuring citric acid in raw material citric acid feed liquid, and NH in raw material ammonia water3H20 contains
Amount regulation.It can be the conventional content for crystallizing production Triammonium citrate crystal in this area, for example
Can be 34-45 weight %.The content of Triammonium citrate refers to initial lemon in the Triammonium citrate feed liquid
Effective volume V in lemon three ammonium feed liquids of acid in the content or injection crystallizer of Triammonium citrate to crystallizer
Triammonium citrate feed liquid in Triammonium citrate content, i.e., do not carry out also heating evaporation crystallization or to
The content of Triammonium citrate in the Triammonium citrate feed liquid supplemented in crystallizer.
According to method of the present invention, wherein, it is ultra-fine in obtained crystal product in order to further improve
The content of mesh Triammonium citrate crystal, it is preferable that relative to 1m3Triammonium citrate feed liquid, citric acid
The addition of three ammonium crystal seeds is 190-210g.Herein " relative to 1m3Triammonium citrate feed liquid " in
" Triammonium citrate feed liquid " refer to inject crystallizer in crystallizer effective volume V citric acid three
Ammonium feed liquid.
According to method of the present invention, wherein, heat the Triammonium citrate feed liquid in S2 and steamed
In the step of hair crystallization, the temperature of preferably heating evaporation crystallization is 55-65 DEG C, the temperature of the evaporative crystallization
Can be realized by the vacuum inside control device.
According to method of the present invention, also including the magma is carried out into separation of solid and liquid and drying successively
The step of.Separation of solid and liquid and furnace drying method can be the conventional mode in this area in the present invention, for example can be with
Separation of solid and liquid is carried out by centrifugation, is dried using dryer.It is preferred that the condition of the drying includes：
Temperature is 50-60 DEG C, and the time is 15-40 minutes.
On the other hand, present invention also offers a kind of Triammonium citrate crystal produced by above-mentioned method.
Using in crystal product obtained in the method for the present invention, the content of Triammonium citrate crystal is high under preferable case
Up to 99.5 weight %.
Triammonium citrate crystal provided by the present invention is further described below with reference to specific embodiment
Production method, and further prove the beneficial effect of Triammonium citrate produced using the inventive method.
(1), term explanation in the following Examples and Comparative Examples
" effective volume of crystallizer " refer in the process of running the crystallizing tank of crystallizer, heater and
The volume of liquid can be accommodated in circulation pipe.
(2) preparation of the Triammonium citrate crystal seed for being used in the following Examples and Comparative Examples
The preparation of 200-400 mesh Triammonium citrate crystal seeds：By 30-60 mesh Triammonium citrate crystal in ball milling
Machine (model：KHKQ-100) inner mill 0.5h is that can obtain 200-400 mesh Triammonium citrate crystal seeds, so
Sifted out using 200-400 mesh sub-sieves afterwards and can be prepared by.
(3) assay method of Triammonium citrate crystalline content in the crystal product for being produced
Obtained using citrate detection method in Triammonium citrate sample well known to those skilled in the art
Content to citrate is X%, then the content of Triammonium citrate is the content of Y%=citrates
* 243.22/189.13=X%*1.196
(4) measuring method and monitoring method of the degree of supersaturation of Triammonium citrate feed liquid
Degree of supersaturation refer to the weight of the solute actually dissolved in solvent at a certain temperature with it is molten at this temperature
When liquid reaches saturation in solvent the weight of the solute of theoretical dissolution ratio.Generally, the lemon under uniform temperature
The density value of the supersaturated angle value correspondence Triammonium citrate solution of lemon three ammonium salt solutions of acid, in following examples and
By the density value of online Density Measuring Instrument measurement Triammonium citrate solution in comparative example, and then obtain lemon
The supersaturated angle value of sour three ammonium salt solutions.
Embodiment 1
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid is as follows：
By in the disposable injecting reactor of citric acid feed liquid that citric acid content is 40 weight %, then will
Ammoniacal liquor feed liquid (on the basis of ammoniacal liquor, NH3H20 content is 22 weight %) it is continuously injected into citric acid
Reacted in feed liquid, reaction end value is controlled by online pH meter, as the pH of the feed liquid in crystallizer
Be worth for 6.6 when, stop injection ammoniacal liquor feed liquid, reaction obtain Triammonium citrate feed liquid, resulting lemon
The content of Triammonium citrate is 38 weight % in sour three ammonium feed liquids.
(2) method for crystallising of Triammonium citrate crystal is as follows：
By 8m3The Triammonium citrate feed liquid that step (1) is obtained is continuously injected into effective volume for 8m3Knot
In brilliant device, and it is evaporated crystallization and (is set by adjustment for 55 DEG C by the temperature of computer heating control evaporative crystallization
Standby vacuum realizes evaporative crystallization at such a temperature), when the degree of supersaturation of Triammonium citrate feed liquid is 1.09
When, the Triammonium citrate crystal seed 1600g that granularity is 300 mesh is added to disposable in Triammonium citrate feed liquid,
Stop heating, and be incubated 1 hour, then reheating controls the temperature of evaporative crystallization for 55 DEG C are steamed
Hair crystallization (degree of supersaturation of whole-process control solution is 1.09 in the step of evaporative crystallization), continues to evaporate knot
Brilliant (solid content for keeping magma is 35-50wt%) continuous doing is expected.
The crystalline substance that blowing is obtained is centrifuged, and then carries out baking 20 minutes at 55 DEG C with dryer,
Triammonium citrate crystal product is obtained.As shown in figure 1, Fig. 1 be the Triammonium citrate crystal product in light
The crystallogram under microscope is learned, crystal is sticky few.Triammonium citrate crystal in the crystal product after testing
Content is 99.9 weight %, wherein, granularity accounting (uniformity) is as shown in table 1 after crystal product sieving.
Table 1.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 72.1 | 22.8 | 3.2 | 0.9 | 0.4 | 0.2 |
Embodiment 2
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid is as follows：
By in the disposable injecting reactor of citric acid feed liquid that citric acid content is 30 weight %, then will
Ammoniacal liquor feed liquid (on the basis of ammoniacal liquor, NH3H20 content is 20 weight %) it is continuously injected into citric acid
Reacted in feed liquid, reaction end value is controlled by online pH meter, as the pH of the feed liquid in crystallizer
Be worth for 6.5 when, stop injection ammoniacal liquor feed liquid, reaction obtain Triammonium citrate feed liquid, resulting lemon
The content of Triammonium citrate is 30 weight % in sour three ammonium feed liquids.
(2) method for crystallising of Triammonium citrate crystal is as follows：
By 8m3The Triammonium citrate feed liquid that step (1) is obtained is continuously injected into effective volume for 8m3Knot
In brilliant device, and it is evaporated crystallization and (is set by adjustment for 50 DEG C by the temperature of computer heating control evaporative crystallization
Standby vacuum realizes evaporative crystallization at such a temperature), when the degree of supersaturation of Triammonium citrate feed liquid is 1.05
When, the Triammonium citrate crystal seed 1520g that granularity is 200 mesh is added to disposable in Triammonium citrate feed liquid,
Stop heating, and be incubated 0.5 hour, then reheating controls the temperature of evaporative crystallization for 50 DEG C are carried out
Evaporative crystallization (degree of supersaturation of whole-process control solution is 1.05 in the step of evaporative crystallization), evaporative crystallization
(solid content for keeping magma is 35-50wt%) continuous doing is expected.
The crystalline substance that blowing is obtained is centrifuged, and then carries out drying 15 minutes at 50 DEG C with dryer,
Triammonium citrate crystal product is obtained, Triammonium citrate crystalline content is 99.9 in the crystal product after testing
Weight %, wherein, granularity accounting (uniformity) is as shown in table 2 after crystal product sieving.
Table 2.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.5 | 71.2 | 23.8 | 3.2 | 0.8 | 0.3 | 0.2 |
Embodiment 3
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid is as follows：
By in the disposable injecting reactor of citric acid feed liquid that citric acid content is 50 weight %, then will
Ammoniacal liquor feed liquid (on the basis of ammoniacal liquor, NH3H20 content is 25 weight %) it is continuously injected into citric acid
Reacted in feed liquid, reaction end value is controlled by online pH meter, as the pH of the feed liquid in crystallizer
Be worth for 6.7 when, stop injection ammoniacal liquor feed liquid, reaction obtain Triammonium citrate feed liquid, resulting lemon
The content of Triammonium citrate is 47 weight % in sour three ammonium feed liquids.
(2) method for crystallising of Triammonium citrate crystal is as follows：
By 8m3The Triammonium citrate feed liquid that step (1) is obtained is continuously injected into effective volume for 8m3Knot
In brilliant device, and it is evaporated crystallization and (is set by adjustment for 60 DEG C by the temperature of computer heating control evaporative crystallization
Standby vacuum realizes evaporative crystallization at such a temperature), when the degree of supersaturation of Triammonium citrate feed liquid is 1.13
When, the Triammonium citrate crystal seed 1680g that granularity is 400 mesh is added to disposable in Triammonium citrate feed liquid,
Stop heating, and be incubated 1 hour, then reheating controls the temperature of evaporative crystallization for 60 DEG C are steamed
Hair crystallization (degree of supersaturation of whole-process control solution is 1.13 in the step of evaporative crystallization), continues to evaporate knot
Brilliant (solid content for keeping magma is 35-50wt%) continuous doing is expected.
The crystalline substance that blowing is obtained is centrifuged, and then carries out drying 40 minutes at 60 DEG C with dryer,
Triammonium citrate crystal product is obtained, after testing Triammonium citrate crystal in the Triammonium citrate crystal product
Content is 99.9 weight %, wherein, granularity accounting (uniformity) is as shown in table 3 after crystal product sieving.
Table 3.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.5 | 71.5 | 24.5 | 2.3 | 0.7 | 0.3 | 0.2 |
Embodiment 4
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With reference to Triammonium citrate feed liquid in embodiment 1
Preparation method, difference is reaction end value to be controlled by online pH meter, when the feed liquid in crystallizer
PH value be 6.3 when, stop injection ammoniacal liquor feed liquid.
(2) method for crystallising of Triammonium citrate crystal：With the knot of Triammonium citrate crystal in embodiment 1
Crystal method.In obtained Triammonium citrate crystal product, Triammonium citrate is brilliant in the crystal product after testing
Body content is 99.6 weight %, wherein, granularity accounting (uniformity) such as the institute of table 4 after crystal product sieving
Show.
Table 4.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 68.6 | 24.4 | 5.3 | 0.7 | 0.4 | 0.2 |
Embodiment 5
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With the system of Triammonium citrate feed liquid in embodiment 1
Preparation Method.
(2) method for crystallising of Triammonium citrate crystal：With reference to Triammonium citrate crystal in embodiment 1
Method for crystallising.Difference is, when the degree of supersaturation of Triammonium citrate feed liquid is 1.16, to citric acid three
It is disposable in ammonium feed liquid to add crystal seed, obtained Triammonium citrate crystal product, the after testing crystal product
Triammonium citrate crystalline content be 99.6 amount %, wherein, product crystal sieving after granularity accounting (uniformly
Property) as shown in table 5.
Table 5.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 66.1 | 25.2 | 5.0 | 2.7 | 0.4 | 0.2 |
Embodiment 6
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With reference to Triammonium citrate feed liquid in embodiment 1
Preparation method, difference is reaction end value to be controlled by online pH meter, when the feed liquid in crystallizer
PH value be 6.8 when, stop injection ammoniacal liquor feed liquid.
(2) method for crystallising of Triammonium citrate crystal：With reference to Triammonium citrate crystal in embodiment 1
Method for crystallising.Difference is, when the degree of supersaturation of Triammonium citrate feed liquid is 1.16, to citric acid three
It is disposable in ammonium feed liquid to add crystal seed, obtained Triammonium citrate crystal product, the after testing crystal product
Middle Triammonium citrate crystalline content is 99.5 amount %, wherein, granularity accounting is (uniform after crystal product sieving
Property) as shown in table 6.
Table 6.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 65.0 | 25.0 | 6.1 | 2.9 | 0.4 | 0.2 |
Embodiment 7
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With embodiment 1.
(2) method for crystallising of Triammonium citrate crystal：With reference to Triammonium citrate crystal in embodiment 1
Method for crystallising, difference is, to the Triammonium citrate that addition granularity in Triammonium citrate feed liquid is 500 mesh,
Obtained Triammonium citrate crystal product, Triammonium citrate crystalline content is in the crystal product after testing
99.7 weight %, wherein, granularity accounting (uniformity) is as shown in table 7 after product crystal sieving.
Table 7
| Mesh number (mesh) | 10-20 | 20-30 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 5.4 | 63.0 | 21.0 | 6.2 | 2.8 | 0.4 | 0.2 |
Embodiment 8
The present embodiment is used to illustrate Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With embodiment 1.
(2) method for crystallising of Triammonium citrate crystal：With reference to Triammonium citrate crystal in embodiment 1
Method for crystallising, difference is to add Triammonium citrate crystal seed 2000g to disposable in Triammonium citrate feed liquid,
Obtained Triammonium citrate crystal product, Triammonium citrate crystalline content is in the crystal product after testing
99.7 weight %, wherein, granularity accounting (uniformity) is as shown in table 8 after product crystal sieving.
Table 8
| Mesh number (mesh) | 10-20 | 20-30 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 63.0 | 26.7 | 6.2 | 2.1 | 0.4 | 0.2 |
Comparative example 1
This comparative example is used for reference and illustrates Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With reference to Triammonium citrate feed liquid in embodiment 1
Preparation method, difference is that, when the pH value of the feed liquid in crystallizer is 6.0, stopping is injected
Ammoniacal liquor.
(2) method for crystallising of Triammonium citrate crystal：Lemon is added without during the entire process of evaporative crystallization
Lemon three ammonium crystal seeds of acid, but natural graining, and crystal growing process does not control degree of supersaturation, and lemon is obtained
Lemon three ammonium crystal of acid.As shown in Fig. 2 Fig. 2 be the Triammonium citrate crystal product under an optical microscope
Crystallogram, crystal is sticky serious.Triammonium citrate is brilliant in the Triammonium citrate crystal product after testing
Body content is 98.0 weight %, wherein, granularity accounting (uniformity) such as the institute of table 9 after product crystal sieving
Show.
Table 9.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 40.2 | 30.2 | 16.1 | 7.5 | 5.4 | 0.2 |
Comparative example 2
This comparative example is used for reference and illustrates Triammonium citrate crystal of the invention and its production method
(1) preparation method of Triammonium citrate feed liquid：With the system of Triammonium citrate feed liquid in embodiment 1
Preparation Method.
(2) method for crystallising of Triammonium citrate crystal：Lemon is added without during the entire process of evaporative crystallization
Lemon three ammonium crystal seeds of acid, but natural graining, and crystal growing process does not control degree of supersaturation, and lemon is obtained
Lemon three ammonium crystal of acid.Triammonium citrate crystalline content is 98.5 in the Triammonium citrate crystal product after testing
Weight %, wherein, granularity accounting (uniformity) is as shown in table 10 after product crystal sieving.
Table 10.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 41.2 | 29.7 | 15.3 | 7.6 | 5.6 | 0.2 |
Comparative example 3
This comparative example is used for Triammonium citrate crystal of the invention and its production method as directed
(1) preparation method of Triammonium citrate feed liquid：With reference to Triammonium citrate feed liquid in embodiment 1
Preparation method, difference is that, when the pH value of the feed liquid in crystallizer is 7.5, stopping is injected
Ammoniacal liquor.
(2) method for crystallising of Triammonium citrate crystal：With Triammonium citrate evaporative crystallization in embodiment 1
Method.In obtained Triammonium citrate crystal product, Triammonium citrate crystalline content is 98.4 after testing
Weight %, wherein, granularity accounting (uniformity) is as shown in table 11 after product crystal sieving.
Table 11.
| Mesh number (mesh) | 10-20 | 20-25 | 30-40 | 40-50 | 50-60 | 60-70 | Under 70 mesh sieves |
| Proportion (%) | 0.4 | 60.3 | 25.1 | 11.6 | 2.2 | 0.3 | 0.2 |
Embodiment 1-8 is compared with comparative example 1-3 as can be seen that crystal obtained in the method for the present invention is produced
The content of Triammonium citrate crystal is higher than the crystal product of comparative example production in product, by method of the present invention institute
The content of Triammonium citrate crystal is up to 99.5-99.9 weight % in the crystal product of production.
Embodiment 1-3 is compared with embodiment 4-6 as can be seen that ammoniacal liquor is injected into citric acid feed liquid
Reacted, control endpoint pH is in preferred scope, or the degree of supersaturation for controlling crystal growing process
In preferred scope, especially while the degree of supersaturation of control control endpoint pH and crystal growing process
In preferred scope, be conducive to improving the content of Triammonium citrate crystal in obtained crystalline product.
Embodiment 1-3 is compared with embodiment 7-8 as can be seen that the addition of control Triammonium citrate crystal seed
Amount and addition granularity, are conducive to improving the content of Triammonium citrate crystal in obtained crystalline product.
In sum, in the production method of Triammonium citrate crystal provided by the present invention, the method is led to
The pH value of mixed solution of control control ammoniacal liquor and citric acid feed liquid is crossed to judge ammoniacal liquor and citric acid feed liquid
Reaction terminal, be conducive to improving Triammonium citrate content in the Triammonium citrate solution that obtains of reaction,
And it is described to control by the degree of supersaturation of the process adjusting Triammonium citrate feed liquid in the evaporative crystallization
The speed of evaporative crystallization, is conducive to improving the content of Triammonium citrate crystal in crystalline product.
Further, in heating the step of the Triammonium citrate feed liquid is evaporated crystallization, by
Degree of supersaturation is 1.02-1.16, and Triammonium citrate crystal seed is added in the citric acid feed liquid of preferably 1.05-1.13,
And control soaking time for 0.5-1 hours, can control to produce the amount of nucleus first, then by secondary
Heating is evaporated crystallization, can control the speed of growth of nucleus, and then reduces crystal glomerocryst, pseudo- crystalline substance
Occur, reduce crystal and mother liquor is sandwiched in growth course, so as to significantly improve the quality of crystal product,
The content and the uniformity of crystal product are additionally provided simultaneously.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment,
In the case of reconcilable, can be combined by any suitable means.In order to avoid unnecessary
Repeat, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of production method of Triammonium citrate crystal, it is characterised in that the method includes：
S1, ammoniacal liquor is injected into citric acid feed liquid, when the pH value of mixed liquor is 6.3-6.8, stopped
The ammoniacal liquor is only injected, reaction obtains Triammonium citrate feed liquid；
S2, the heating Triammonium citrate feed liquid are evaporated crystallization to obtain magma, wherein described
The degree of supersaturation of the process adjusting Triammonium citrate feed liquid of evaporative crystallization is controlling the speed of the evaporative crystallization
Degree.
2. the method according to claim 1, wherein, as the pH of mixed liquor in the S1
It is worth during for 6.5-6.7, stops the injection ammoniacal liquor.
3. method according to claim 1, wherein, the Triammonium citrate is heated in the S2
In the step of feed liquid is evaporated crystallization, the degree of supersaturation of whole-process control solution is 1.02-1.16, preferably
1.05-1.13。
4. the method according to claim 1, wherein, the citric acid three is heated in the S2
The step of ammonium feed liquid is evaporated crystallization includes：The Triammonium citrate feed liquid is heated, in the citric acid
When three ammonium feed liquid degree of supersaturations reach 1.02-1.16, preferably 1.05-1.13 first, to Triammonium citrate material
Triammonium citrate crystal seed is added in liquid, stops heating, be incubated 0.5-1 hours, then reheating evaporation
Crystallization, obtains the magma.
5. method according to claim 4, wherein, the granularity of the Triammonium citrate crystal seed is
200-400 mesh.
6. method according to claim 4, wherein, relative to 1m3Triammonium citrate feed liquid,
The addition of Triammonium citrate crystal seed is 190-210g.
7. method according to claim 1, wherein, the Triammonium citrate feed liquid that the S1 is obtained
The content of middle Triammonium citrate is 30-47 weight %.
8. method according to claim 1, wherein, the temperature of evaporative crystallization is in the S2
50-60℃。
9. method according to claim 1, wherein, the method also includes：By the crystalline substance successively
The step of separation of solid and liquid and drying is carried out, the condition of preferably described baking step includes：Temperature is 50-60 DEG C,
Time is 15-40 minutes.
10. the Triammonium citrate crystal that a kind of method in claim 1 to 9 described in any one is produced.
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| CN101050173A (en) * | 2006-04-05 | 2007-10-10 | 黄石兴华生化有限公司 | Method for producing potassium citrate through continuous condensing crystallizing, and apparatus for realizing the method |
| CN103159615A (en) * | 2011-12-13 | 2013-06-19 | 李月平 | Ammonium citrate synthesizing method |
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| CN101050173A (en) * | 2006-04-05 | 2007-10-10 | 黄石兴华生化有限公司 | Method for producing potassium citrate through continuous condensing crystallizing, and apparatus for realizing the method |
| CN103159615A (en) * | 2011-12-13 | 2013-06-19 | 李月平 | Ammonium citrate synthesizing method |
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| CN112593234A (en) * | 2020-12-03 | 2021-04-02 | 南通恒兴电子材料有限公司 | Preparation method of ammonium citrate |
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