CN115368279B - Preparation method of granular ethanolamine sulfate crystals - Google Patents
Preparation method of granular ethanolamine sulfate crystals Download PDFInfo
- Publication number
- CN115368279B CN115368279B CN202211121399.XA CN202211121399A CN115368279B CN 115368279 B CN115368279 B CN 115368279B CN 202211121399 A CN202211121399 A CN 202211121399A CN 115368279 B CN115368279 B CN 115368279B
- Authority
- CN
- China
- Prior art keywords
- ethanolamine
- sulfuric acid
- sulfate
- crystals
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WSYUEVRAMDSJKL-UHFFFAOYSA-N ethanolamine-o-sulfate Chemical compound NCCOS(O)(=O)=O WSYUEVRAMDSJKL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000005886 esterification reaction Methods 0.000 claims abstract description 28
- -1 ethanolamine sulfuric acid ester Chemical class 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000032050 esterification Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- ROQQLNHLFCKPOQ-UHFFFAOYSA-N 2,4-dioxo-4-pyridin-4-ylbutanoic acid Chemical compound OC(=O)C(=O)CC(=O)C1=CC=NC=C1 ROQQLNHLFCKPOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 8
- 229940031098 ethanolamine Drugs 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- IQGWPPQNIZBTBM-UHFFFAOYSA-N 2-aminoethanol;sulfuric acid Chemical compound NCCO.OS(O)(=O)=O IQGWPPQNIZBTBM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229960003080 taurine Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- JZQLRTAGAUZWRH-UHFFFAOYSA-N 2-aminoethanol;hydrate Chemical compound [OH-].[NH3+]CCO JZQLRTAGAUZWRH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application belongs to the technical field of sulfate preparation, and particularly relates to a preparation method of granular ethanolamine sulfate crystals, which is characterized in that water, concentrated sulfuric acid and ethanolamine are used as raw materials, a crystallization agent is added, and the granular ethanolamine sulfate crystals are obtained through the procedures of neutralization, esterification and screening. Wherein, the neutralization reaction seeds are primed by water, and then concentrated sulfuric acid and ethanolamine are added, the mol ratio of the ethanolamine to the concentrated sulfuric acid is 1:1-1.4, the reaction temperature is 10 ℃ to 40 ℃ at normal pressure, and the ethanolamine sulfate solution with the mass fraction of 60 percent to 80 percent is obtained. In the esterification reaction, adding a crystallization modifier and an ethanolamine sulfate seed crystal slurry with the solid content of 20% -60% into the obtained ethanolamine sulfate solution, stirring, heating in vacuum at the temperature of 85-120 ℃ for 0.5-2.5 h, and centrifugally filtering the reaction mother liquor to obtain ethanolamine sulfate crystals. The preparation method can obtain more than 95% of ethanolamine sulfuric acid ester crystals with the particle size larger than 200 meshes, and has the advantages of high yield, uniform particle size of finished products and high purity.
Description
Technical Field
The application belongs to the technical field of sulfate preparation, and particularly relates to a preparation method of granular ethanolamine sulfate crystals.
Background
Ethanolamine sulfate (NH) 2 CH 2 CH 2 OSO 3 H) As an important intermediate in chemical processIs a main raw material for synthesizing taurine, ethylenimine and other compounds, and is generally prepared by esterification reaction of monoethanolamine and sulfuric acid. The reaction mechanism of ethanolamine sulfate mainly comprises:
(1) Monoethanolamine reacts with sulfuric acid as a strong base to first produce hydroxyethylammonium bisulfate: NH (NH) 2 CH 2 CH 2 OH+H 2 SO 4 →HOCH 2 CH 2 NH 3 + ·HSO 4 - ；
(2) The hydroxyethyl ammonium bisulfate is dehydrated in the molecule to generate esterification reaction, so that ethanolamine sulfate and water are generated:
the first step of reaction belongs to acid-base neutralization reaction, and the reaction is easy to control; in the second step, the intramolecular dehydration esterification reaction is a reversible reaction, water is present to make the reaction difficult to continue, and in order to make the reaction move forward, the water generated in the transfer reaction process needs to be removed in time.
The current technology for preparing ethanolamine sulfate mainly comprises two types:
firstly, a direct dehydration method is adopted, the salt solution obtained in the first step is placed in a reaction kettle, and the salt solution is directly heated to be anhydrous under a vacuum condition to be distilled out, so that solid ethanolamine sulfate (Wang Xuejun. Research on taurine preparation process. Technical development. 1999.6:12-13) is obtained;
and secondly, placing the salt solution obtained in the first step into a reaction kettle, adding a water carrying agent, carrying out azeotropic reflux on the water carrying agent and water in the form of an azeotropic mixture under normal pressure heating, and removing water generated by the reaction, wherein the water carrying agent comprises 36% of formaldehyde solution (a new synthesis method for preparing taurine, jilin chemical society, no. 2003.9), toluene (an improved taurine synthesis process, chemical society, no. 2015.1:171-178), n-butanol, benzene, cyclohexane and other organic substances.
Among the two dehydration methods, the former has the defects that high-temperature heating is needed, ethanolamine sulfate obtained by dehydration is easy to agglomerate and agglomerate at the bottom of the reaction kettle, is adhered to the bottom and the inner wall of the reaction kettle, is difficult to take out, and is easy to cause overload outage of a stirring motor, and extremely serious stirring damage and even production accidents. The latter has the disadvantages of difficult purchase and transportation, long dehydration time, poor recovery effect, high toxicity, difficult post treatment and the like, and is extremely difficult in practical application.
Therefore, it is a key to solve the above-mentioned drawbacks of the prior art to find a simple and efficient method for growing ethanolamine sulfate crystals, which can make the product granular.
Disclosure of Invention
Aiming at the defects existing in the prior art, a preparation method of granular ethanolamine sulfate crystals is provided. By adding a certain amount of the medium crystal agent and the crystal seed slurry, the medium crystal agent can be effectively adsorbed on the surface of the crystal, the growth rate of the crystal is changed, the controllable growth of the ethanolamine sulfate crystal is realized, agglomeration is effectively prevented, and the white ethanolamine sulfate particles with stable quality are obtained.
The application provides a preparation method of granular ethanolamine sulfuric acid ester crystals, which takes water, concentrated sulfuric acid and ethanolamine as raw materials, adds a crystallization agent, and obtains the granular ethanolamine sulfuric acid ester crystals through the procedures of neutralization, esterification and screening, and the preparation method comprises the following specific steps: step one: the neutralization reaction, namely adding water into a neutralization kettle to prime, then adding concentrated sulfuric acid and ethanolamine, and carrying out acid-base neutralization reaction under normal pressure, wherein the mol ratio of the ethanolamine to the concentrated sulfuric acid is 1:1-1.4, and the reaction temperature is 10-40 ℃ under normal pressure to obtain an ethanolamine sulfate solution with the mass fraction of 60-80%; step two: and (3) carrying out esterification reaction, namely transferring the ethanolamine sulfate solution obtained in the step (I) into an esterification kettle, adding a crystallization promoter and ethanolamine sulfate seed crystal slurry with the solid content of 20% -60%, then starting stirring, opening a vacuum system, heating at the temperature of 85-120 ℃ for 0.5-2.5 h, and centrifugally filtering the reaction mother liquor to obtain ethanolamine sulfate crystals.
In particular, the preparation method further comprises a step three: screening, namely drying the ethanolamine sulfuric acid ester crystals obtained in the step II, screening ethanolamine sulfuric acid ester with the particle size larger than 200 meshes, dissolving the ethanolamine sulfuric acid ester crystals with the particle size smaller than 200 meshes in the centrifugal mother liquor of the step II to form seed crystal slurry containing the ethanolamine sulfuric acid ester, and recycling the seed crystal slurry for esterification reaction of the step II.
In particular, the molar ratio of the ethanolamine to the concentrated sulfuric acid in the step one is 1:1-1.06.
In particular, the crystallizing agent in the second step is one or more selected from sodium sulfate, sodium hexametaphosphate, sodium tripolyphosphate, succinic acid and adipic acid.
In particular, the addition amount of the crystal modifier is 0.2 to 2.5 percent of the mass of the ethanolamine sulfate solution.
In particular, the esterification vacuum heating time of the step three is 1h to 1.5h.
In particular, the esterification vacuum heating temperature of the step three is 100-110 ℃.
Particularly, the preparation method of the ethanolamine sulfate seed crystal slurry in the step three comprises the steps of adding the ethanolamine sulfate with the particle size smaller than 200 meshes after sieving into the centrifugal mother liquor, heating to dissolve part of fine crystals, and heating to dissolve the temperature of the fine crystals to be not higher than 60 ℃.
In particular, the mass ratio of the diethanolamine sulfate seed slurry to the ethanolamine sulfate solution is 1:20-60.
In particular, the particle size of the solid seed crystals in the ethanolamine sulfuric acid ester seed slurry is 30-70 μm.
The technical scheme has the following advantages or beneficial effects: 1. in the esterification process, the catalyst and the seed crystal slurry are added, so that more than 95% of finished ethanolamine sulfate products with the particle size larger than 200 meshes can be obtained, the particle size is uniform, and the yield is high. 2. The control of the esterification temperature in the esterification process makes the growth process of the ethanolamine sulfuric acid ester more stable, and the obtained ethanolamine sulfuric acid ester particles have the advantages of uniform particle size distribution and high purity. 3. In the screening process, the centrifugal mother liquor is recycled by dissolving seed crystals, so that the discharge amount of wastewater is reduced, the industrial production is facilitated, and the method has great significance for environmental protection.
Drawings
In order to more clearly illustrate the embodiments of the present application, the drawings that are used in the description of the embodiments will be briefly described below. It will be obvious to a person skilled in the art that other figures can be obtained from the figures provided without the inventive effort.
FIG. 1 is an optical diagram of crystals of ethanolamine sulfuric acid ester prepared according to example 2.
Detailed Description
The embodiments described below in detail are exemplary and intended to explain the inventive concept by referring to the figures.
The reaction mechanism of the ethanolamine sulfuric acid ester is as follows: (1) Monoethanolamine reacts with sulfuric acid as a strong base to first produce hydroxyethylammonium bisulfate: NH (NH) 2 CH 2 CH 2 OH+H 2 SO 4 →HOCH 2 CH 2 NH 3 + ·HSO 4 - The method comprises the steps of carrying out a first treatment on the surface of the (2) The hydroxyethyl ammonium bisulfate is dehydrated in the molecule to generate esterification reaction, so that ethanolamine sulfate and water are generated:
example 1
The preparation method of the granular ethanolamine sulfuric acid ester crystal comprises the following steps:
(1) 53.00g of water was added to the flask, and 81.15g of 98% concentrated sulfuric acid and 50.00g (purity: 99%) of ethanolamine were added thereto to perform a neutralization reaction under normal pressure, and the neutralization temperature was controlled to 10℃to obtain a 70% by mass ethanolamine sulfate solution.
(2) Subsequently, 0.37g of sodium hexametaphosphate as a seeding agent and 9.2g of crystal seed slurry with a solid content of 30% were added to the ethanolamine sulfate solution obtained in (1), wherein the crystal seed slurry contains solid particle ethanolamine sulfate with a particle size of 30-70 μm. Stirring is started in the whole process after the addition, then vacuum is started and heating is carried out for 1.5 hours, the heating temperature is 110 ℃, and after the esterification reaction is finished, the ethanol amine sulfate particles are obtained through centrifugal filtration.
(3) And (3) drying the ethanolamine sulfuric acid ester particles obtained in the step (2). And (3) screening to enable the ethanolamine sulfuric acid ester with the particle size smaller than 200 meshes to be dissolved in the centrifugal mother liquor at the temperature of 40 ℃ to form seed crystal slurry with the solid content of 30%, and obtaining the ethanolamine sulfuric acid ester product with the particle size larger than 200 meshes.
Example 2
Example 2 was essentially identical to example 1 except that: in the step (1), the neutralization reaction temperature was controlled to 40 ℃, and in the step (2), 0.37g of sodium sulfate as a seeding agent and 9.2g of a seed slurry having a solid content of 30% were added. Stirring, heating in vacuum for 1h at the temperature of 100 ℃, and centrifugally filtering after esterification to obtain ethanolamine sulfate particles.
Example 3
Example 3 was essentially identical to example 1 except that: in the step (1), the addition amount of 98% concentrated sulfuric acid is 83.58g, and in the step (2), 0.37g of sodium sulfate as a seeding agent and 9.2g of seed crystal slurry with the solid content of 30% are added. Stirring, heating in vacuum for 1h at the temperature of 100 ℃, and centrifugally filtering after esterification to obtain ethanolamine sulfate particles.
Example 4
Example 4 was essentially identical to example 3 except that: in the step (1), the neutralization reaction temperature was controlled to 40 ℃, and in the step (2), 0.37g of sodium sulfate as a seeding agent and 9.2g of a seed slurry having a solid content of 30% were added. Stirring, heating in vacuum for 1h at the temperature of 100 ℃, and centrifugally filtering after esterification to obtain ethanolamine sulfate particles.
Example 5
Example 5 was essentially identical to example 1 except that: in the step (1), the addition amount of 98% concentrated sulfuric acid is 86.02g, and in the step (2), 1.84g of sodium sulfate as a seeding agent and 9.2g of seed crystal slurry with the solid content of 40% are added. Stirring, heating in vacuum for 1h at the temperature of 100 ℃, and centrifugally filtering after esterification to obtain ethanolamine sulfate particles.
Example 6
Example 6 was essentially identical to example 1 except that: in step (2) a seed slurry having a solids content of 20% dissolved at 20 ℃ was added. Stirring, heating in vacuum for 1h at the heating temperature of 100 ℃, and centrifugally filtering after esterification to obtain ethanolamine sulfate particles.
Example 7
Example 7 was essentially identical to example 1 except that the procedure was followed: in step (2) a seed slurry having a solids content of 40% dissolved at 60 ℃ was added. Stirring, heating in vacuum for 1h at the heating temperature of 100 ℃, and centrifugally filtering after esterification to obtain ethanolamine sulfate particles.
Comparative example 1
53g of water was added to the flask, 81.15g of 98% concentrated sulfuric acid and 50g of ethanolamine were added thereto, and neutralization reaction was carried out under normal pressure to obtain an ethanolamine sulfate solution. Stirring the ethanolamine sulfate solution, heating and dehydrating for 2 hours at 120 ℃, and obtaining ethanolamine sulfate solid after esterification.
The ethanolamine sulfuric acid ester prepared in each example is dried, screened and subjected to particle size test with the product prepared in the comparative example of the prior art.
Wherein, the yield calculation method comprises the following steps:
m actual ethanolamine sulfuric acid ester : detecting the total sulfur content by a fluorescence spectrum, obtaining the sulfate radical residual quantity in the product by ion chromatography, and obtaining the yield of the ethanolamine sulfate by subtracting the sulfur content in the sulfate radical from the total sulfur content by conservation of the sulfur element;
m theoretical ethanolamine sulfate : the ethanolamine added is completely converted into ethanolamine sulfate as the theoretical ethanolamine sulfate yield.
The test results were as follows:
| sample of | Average particle diameter/. Mu.m | Yield/% |
| Example 1 | 450.2 | 97.8 |
| Example 2 | 480.6 | 97.5 |
| Example 3 | 490.8 | 97.8 |
| Example 4 | 460.2 | 97.5 |
| Example 5 | 455.7 | 95.2 |
| Example 6 | 458.6 | 93.8 |
| Example 7 | 468.2 | 94.5 |
| Comparative example 1 | 110.3 | 85.6 |
While embodiments of the present application have been illustrated and described above, it will be appreciated that the above-described embodiments are exemplary and should not be construed as limiting the present application. Various changes and modifications may be made to the present application without departing from the spirit and scope of the application, and such changes and modifications fall within the scope of the application as hereinafter claimed.
Claims (5)
1. The preparation method of the granular ethanolamine sulfuric acid ester crystal is characterized by taking water, concentrated sulfuric acid and ethanolamine as raw materials, adding a crystallization agent, and carrying out neutralization, esterification and screening procedures to obtain the granular ethanolamine sulfuric acid ester crystal, wherein the preparation method comprises the following specific steps of:
step one: the neutralization reaction, namely adding water into a neutralization kettle to prime, then adding concentrated sulfuric acid and ethanolamine, and carrying out acid-base neutralization reaction under normal pressure, wherein the mol ratio of the ethanolamine to the concentrated sulfuric acid is 1:1-1.4, and the reaction temperature is 10-40 ℃ under normal pressure to obtain an ethanolamine sulfate solution with the mass fraction of 60-80%;
step two: transferring the ethanolamine sulfate solution obtained in the first step into an esterification kettle, adding a crystallization modifier and ethanolamine sulfate seed crystal slurry with the solid content of 20% -60%, then starting stirring, opening a vacuum system, heating at the temperature of 85-120 ℃ for 0.5-2.5 h, and centrifugally filtering the reaction mother liquor to obtain ethanolamine sulfate crystals;
step three: screening, namely drying ethanolamine sulfate crystals obtained in the step II, screening ethanolamine sulfate with the particle size of more than 200 meshes, dissolving ethanolamine sulfate crystals with the particle size of less than 200 meshes in the centrifugal mother liquor of the step II to form seed crystal slurry containing ethanolamine sulfate, and recycling the seed crystal slurry for esterification reaction of the step II;
the crystallizing agent in the second step is one or more selected from sodium sulfate and sodium hexametaphosphate;
the addition amount of the crystal modifier is 0.2% -2.5% of the mass of the ethanolamine sulfate solution;
the mass ratio of the diethanolamine sulfate seed slurry to the ethanolamine sulfate solution is 1:20-60;
the particle size of the solid seed crystals in the ethanolamine sulfuric acid ester seed crystal slurry is 30-70 mu m.
2. The method for producing a particulate ethanolamine sulfuric acid ester crystal according to claim 1, characterized by: the mol ratio of the ethanolamine to the concentrated sulfuric acid in the first step is 1:1-1.06.
3. The method for producing a particulate ethanolamine sulfuric acid ester crystal according to claim 1, characterized by: and the esterification vacuum heating time in the third step is 1h-1.5h.
4. The method for producing a particulate ethanolamine sulfuric acid ester crystal according to claim 1, characterized by: the esterification vacuum heating temperature of the third step is 100-110 ℃.
5. The method for producing a particulate ethanolamine sulfuric acid ester crystal according to claim 1, characterized by: the preparation method of the ethanolamine sulfate seed crystal slurry in the step III comprises the steps of adding the ethanolamine sulfate with the particle size smaller than 200 meshes after screening into centrifugal mother liquor, heating to dissolve part of fine crystals, and heating to dissolve the temperature of the fine crystals to be not higher than 60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211121399.XA CN115368279B (en) | 2022-09-15 | 2022-09-15 | Preparation method of granular ethanolamine sulfate crystals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211121399.XA CN115368279B (en) | 2022-09-15 | 2022-09-15 | Preparation method of granular ethanolamine sulfate crystals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115368279A CN115368279A (en) | 2022-11-22 |
| CN115368279B true CN115368279B (en) | 2024-03-01 |
Family
ID=84071092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211121399.XA Active CN115368279B (en) | 2022-09-15 | 2022-09-15 | Preparation method of granular ethanolamine sulfate crystals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115368279B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1045718A (en) * | 1963-11-04 | 1966-10-19 | Interchem Corp | Method of preparing amino alkyl sulfates |
| CN102503862A (en) * | 2011-09-21 | 2012-06-20 | 江苏远洋药业股份有限公司 | Method for synthesizing sulfuric acid amino ethyl ester |
| CN104829585A (en) * | 2015-05-15 | 2015-08-12 | 河北科技大学 | Preparation technology for piperonal crystal |
| CN112357890A (en) * | 2020-11-24 | 2021-02-12 | 浙江金科日化原料有限公司 | Method for controlling growth of potassium hydrogen peroxymonosulfate composite salt crystal |
-
2022
- 2022-09-15 CN CN202211121399.XA patent/CN115368279B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1045718A (en) * | 1963-11-04 | 1966-10-19 | Interchem Corp | Method of preparing amino alkyl sulfates |
| CN102503862A (en) * | 2011-09-21 | 2012-06-20 | 江苏远洋药业股份有限公司 | Method for synthesizing sulfuric acid amino ethyl ester |
| CN104829585A (en) * | 2015-05-15 | 2015-08-12 | 河北科技大学 | Preparation technology for piperonal crystal |
| CN112357890A (en) * | 2020-11-24 | 2021-02-12 | 浙江金科日化原料有限公司 | Method for controlling growth of potassium hydrogen peroxymonosulfate composite salt crystal |
Non-Patent Citations (2)
| Title |
|---|
| 姚汝华 等编.《微生物工程工艺原理 第3版》.2013,347. * |
| 王静康 编.《化学工程手册 结晶》.1996,13-14. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115368279A (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3976832B2 (en) | Method for isolating 2-keto-L-gulonic acid | |
| JP5164033B2 (en) | Method for producing silica porous aggregate | |
| CN107353198B (en) | Pentanediamine adipate and crystal thereof | |
| CN115368279B (en) | Preparation method of granular ethanolamine sulfate crystals | |
| JP2019131448A (en) | Method for producing lithium hydroxide | |
| CN109265355B (en) | Pentanediamine suberate salt and crystal thereof | |
| CN112694098A (en) | Method for recovering and synthesizing molecular sieve ZSM-5X from silicon-containing sewage | |
| CN110407220B (en) | Rapid preparation method of SAPO-34 molecular sieve with large specific surface area | |
| CN1686816A (en) | Method for multipurpose use of material of acid split phosphate ore and associated production of high purified microsphere nano calcium carbonate | |
| CN116903020A (en) | Method for preparing alpha-hemihydrate gypsum stable under normal pressure | |
| CN115676788B (en) | High-purity potassium dihydrogen phosphate and preparation method thereof | |
| CN109180494B (en) | Pentanediamine succinate and crystal thereof | |
| CN110697731A (en) | Method for preparing ammonium sulfate and calcium carbonate from desulfurized gypsum | |
| CN114437005B (en) | Butanediamine furan diformate and crystal thereof | |
| CN110040740A (en) | The method that crystal seed is oriented to method synthesis total silicon SOD zeolite | |
| CN111087295B (en) | Pentanediamine succinic acid terephthalic acid eutectic salt and preparation method thereof | |
| CN110698326B (en) | Synthesis method of 1-hydroxypyrene | |
| CN115872451B (en) | Preparation method of sulfur-free spherical manganese carbonate powder | |
| CN115872435B (en) | Method for preparing high-purity gypsum by crystal phase reconstruction | |
| CN115850092B (en) | Nylon 511 salt crystal and preparation method thereof | |
| CN115286025B (en) | Mother liquor purification and recovery process of magnesium sulfate heptahydrate | |
| CN112552188B (en) | Preparation method of sertraline hydrochloride crystal form I | |
| CN115353131B (en) | Production method of magnesium sulfate monohydrate | |
| CN109535028B (en) | Method for preparing pure anilinoacetonitrile by suspension melting crystallization method | |
| JP2024001848A (en) | Cyclic preparation method for columnar taurine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Country or region after: China Address after: Hangzhou Bay Shangyu economic and Technological Development Zone, Shangyu District, Shaoxing City, Zhejiang Province Applicant after: Zhejiang Jinke Daily Chemical New Materials Co.,Ltd. Address before: 312369 Hangzhou Shangyu economic and Technological Development Zone, Shaoxing, Zhejiang Applicant before: ZHEJIANG JINKE HOUSEHOLD CHEMICAL MATERIALS Co.,Ltd. Country or region before: China |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |