CN115043703B - Purification method of high-purity methyl iodide for LED material - Google Patents
Purification method of high-purity methyl iodide for LED material Download PDFInfo
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000000746 purification Methods 0.000 title abstract description 18
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- 239000012528 membrane Substances 0.000 claims abstract description 48
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 48
- 239000002033 PVDF binder Substances 0.000 claims abstract description 43
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- 239000003463 adsorbent Substances 0.000 claims abstract description 26
- QHQOZLBDGGWMFA-UHFFFAOYSA-N 4-methyl-7-trimethylsilyloxychromen-2-one Chemical compound C1=C(O[Si](C)(C)C)C=CC2=C1OC(=O)C=C2C QHQOZLBDGGWMFA-UHFFFAOYSA-N 0.000 claims abstract description 24
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
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- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The invention discloses a purification method of high-purity methyl iodide for an LED material, and relates to the field of methyl iodide purification. The purification method comprises the steps of washing a crude product of methyl iodide with water, drying anhydrous calcium chloride, then carrying out rectification after the crude product is modified by 4-methyl-7-trimethylsiloxy coumarin and filtered by a ZSM-12 molecular sieve adsorbent subjected to impregnation treatment, and carrying out ultrafiltration by adopting a PVDF ultrafiltration membrane or a PVDF ultrafiltration membrane modified by blending polyethylene oxide and madecassoside, wherein the obtained methyl iodide has higher purity.
Description
Technical Field
The invention belongs to the technical field of methyl iodide purification, and particularly relates to a purification method of high-purity methyl iodide for an LED material.
Background
Methyl iodide, also known as methyl iodide, is a halogenated hydrocarbon of the formula CH 3 I or MeI, is formed by replacing one hydrogen atom of methane with an iodine atom. Methyl iodide is a colorless, viscous, special-odor, volatile liquid, and can generate methyl iodide vapor to float in the air. The melting point is-66.4 ℃, the boiling point is 42.5 ℃, the density is 2.28g/mL, the molecular weight is 141.95, iodine simple substance can be decomposed under the sun and is purple, therefore, the methyl iodide is usually sealed and placed in a brown bottle, placed in the shade or silver or copper wires are placed in the bottle to ensure the stability during the storage. In industrial production, methyl iodide is an important downstream industrial product in coal chemical industry, is mainly used for manufacturing intermediates of medicines and pesticides, is also a precursor of various methylation reactions, is mainly used as a methylation group in organic synthesis, and particularly can be used for methylation reaction by using a large amount of methyl iodide in a pharmaceutical process. Methyl iodide is also an initiator with good Grignard reaction and is commonly used for Grignard reaction initiation of inactive halides such as chlorinated aromatic hydrocarbon, is a raw material for preparing vitamin U, and can also be used as a raw material of a rhodium-iodine catalyst forCatalyzing methanol carbonylation reaction. The traditional method for purifying methyl iodide is complex in operation and has great influence on the environment. The invention provides a method for purifying high-purity methyl iodide for an LED material, which adopts a ZSM-12 molecular sieve adsorbent modified by 4-methyl-7-trimethylsiloxy coumarin for filtration, and adopts a PVDF ultrafiltration membrane modified by blending polyethylene oxide and madecassoside for ultrafiltration, so that the prepared methyl iodide has higher purity.
Disclosure of Invention
The invention aims to provide a method for purifying high-purity methyl iodide for an LED material, wherein the methyl iodide prepared by the method has high purity.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method for purifying high-purity methyl iodide for LED materials comprises the following steps:
(1) Obtaining dried crude iodomethane liquid;
(2) Passing the dried crude iodomethane liquid through a modified ZSM-12 molecular sieve adsorbent;
(3) Obtaining high-purity iodomethane for the LED material;
the modified ZSM-12 molecular sieve adsorbent is prepared by depositing and modifying a ZSM-12 molecular sieve by using 4-methyl-7-trimethylsiloxy coumarin and then performing impregnation treatment.
The invention provides a purification method of high-purity methyl iodide for an LED material, which comprises the steps of washing a crude product of methyl iodide with water, drying the crude product of methyl iodide with anhydrous calcium chloride, filtering the crude product of methyl iodide by using a modified ZSM-12 molecular sieve adsorbent obtained by modifying and impregnating 4-methyl-7-trimethylsiloxy coumarin, rectifying the filtered product of methyl iodide, and ultrafiltering the rectified product by using a PVDF ultrafiltration membrane or a modified PVDF ultrafiltration membrane to obtain the high-purity methyl iodide for the LED material with higher purity; probably because the ZSM-12 molecular sieve is modified, the adsorption activity is enhanced, and the purity of the methyl iodide is further improved. The methyl iodide product obtained by purification of the invention has stable quality, simple, convenient and safe purification process, high speed and high efficiency, meets the requirements of green chemical industry and environmental protection, and has the prospect of industrial production.
Specifically, the method for purifying the high-purity methyl iodide for the LED material comprises the following steps:
(1) Washing the crude product of methyl iodide, standing for layering, taking the lower layer liquid, and drying for 10-12h by using anhydrous calcium chloride;
(2) Passing the dried crude iodomethane liquid through a modified ZSM-12 molecular sieve adsorbent at a filtration pressure of 0.3-0.5MPa and a temperature of 23-25 ℃;
(3) And (3) putting the filtrate into a rectifying tower, refluxing for 1.5-2h at the temperature of 41-43 ℃, and then performing ultrafiltration by using an ultrafiltration membrane to obtain the high-purity iodomethane for the LED material.
In a specific embodiment of the present invention, the mass-to-volume ratio of the crude methyl iodide to water is: 1g to 2.5mL; the mass ratio of the crude iodomethane to the anhydrous calcium chloride is as follows: 1:0.1-0.3.
The invention also discloses a preparation method of the modified ZSM-12 molecular sieve adsorbent, which comprises the following steps: and (3) placing the modified ZSM-12 molecular sieve into the impregnation liquid, impregnating for 15-20h, taking out, and drying at 25-30 ℃ for 4-6h to obtain the modified ZSM-12 molecular sieve adsorbent.
In one embodiment of the present invention, the immersion liquid is prepared by mixing 2,4-dihydroxybenzophenone, salicylaldehyde, acetylacetone, and ethanol.
In an embodiment of the present invention, the mass ratio of 2,4-dihydroxybenzophenone to salicylaldehyde is: 1:0.1-0.3.
In an embodiment of the present invention, the weight ratio of 2,4-dihydroxybenzophenone to acetylacetone is: 1:5-8.
In one embodiment of the present invention, the mass ratio of 2,4-dihydroxybenzophenone to ethanol is: 1:2.5-3.
The invention also discloses a preparation method of the modified ZSM-12 molecular sieve, which comprises the following steps:
adding a ZSM-12 molecular sieve into a cyclohexane solvent, adding tetraethoxysilane and 4-methyl-7-trimethylsiloxy coumarin, stirring at room temperature for 2-3h, drying after the solvent is evaporated, heating to 520-570 ℃ at the heating rate of 2-3 ℃/min, and roasting for 5-7h to obtain the modified ZSM-12 molecular sieve.
In one embodiment of the present invention, the mass ratio of the 4-methyl-7-trimethylsiloxy coumarin to the ZSM-12 molecular sieve is: 25-30 of; the mass-volume ratio of the ZSM-12 molecular sieve to the cyclohexane is as follows: 1g, 10-15mL; the mass ratio of the ethyl orthosilicate to the 4-methyl-7-trimethylsiloxy coumarin is as follows: 1:1-1.3.
In one embodiment of the present invention, the ultrafiltration is performed using a PVDF ultrafiltration membrane or a modified PVDF ultrafiltration membrane.
The invention also discloses a preparation method of the modified PVDF ultrafiltration membrane, which comprises the following steps: the modified PVDF ultrafiltration membrane is prepared by blending and modifying the PVDF ultrafiltration membrane by polyethylene oxide and madecassoside.
The invention also provides a preparation method of the modified PVDF ultrafiltration membrane, which is characterized in that the PVDF ultrafiltration membrane is modified by blending polyethylene oxide and madecassoside, and the surface roughness of the modified PVDF ultrafiltration membrane is increased after blending modification, so that the effective filtration area of the membrane is increased, and the purity of high-purity methyl iodide for LED materials is further enhanced.
Specifically, the preparation method of the modified PVDF ultrafiltration membrane comprises the following steps:
PVDF is added into N-methyl pyrrolidone to dissolve in concentration of 15-20wt%, polyethylene oxide and madecassoside are then added to react at 75-80 deg.c for 20-24 hr, and through static defoaming at room temperature and soaking precipitation phase conversion process, modified PVDF ultrafiltering membrane is prepared.
In one embodiment of the present invention, the modified PVDF ultrafiltration membrane has a thickness of: 160-180 μm.
In one embodiment of the present invention, the mass ratio of the polyethylene oxide to the madecassoside is: 1, 0.1-0.3; the mass ratio of the PVDF to the madecassoside is as follows: 1:0.4-0.6.
The invention also discloses application of the modified PVDF ultrafiltration membrane obtained by the preparation method in purifying methyl iodide.
The beneficial effects of the invention include:
the invention obtains a method for purifying high-purity methyl iodide for an LED material, which comprises the steps of washing and drying a crude methyl iodide product, filtering the crude methyl iodide product by adopting a ZSM-12 molecular sieve adsorbent modified by 4-methyl-7-trimethylsiloxy coumarin and subjected to impregnation treatment, and then rectifying and ultrafiltering the crude methyl iodide product to obtain the methyl iodide with higher purity; the invention also adopts polyethylene oxide and madecassoside to carry out blending modification on the PVDF ultrafiltration membrane in the purification process, and the methyl iodide purified by the modified PVDF ultrafiltration membrane has higher purity.
Therefore, the invention provides a method for purifying high-purity methyl iodide for an LED material, and the methyl iodide prepared by the method has higher purity.
Drawings
FIG. 1 is an infrared spectrum of a modified ZSM-12 molecular sieve prepared in example 1 and example 4;
FIG. 2 is an infrared spectrum of a modified PVDF ultrafiltration membrane prepared in example 1 and example 5.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a method for purifying high-purity methyl iodide for an LED material comprises the following steps:
(1) Washing the crude product of the iodomethane, standing for layering, taking the lower layer liquid, and drying for 10 hours by using anhydrous calcium chloride;
(2) Passing the dried crude iodomethane liquid through a modified ZSM-12 molecular sieve adsorbent, wherein the filtration pressure is 0.3MPa and the temperature is 23 ℃;
(3) Placing the filtrate in a rectifying tower, refluxing for 1.5h at the temperature of 41 ℃, and then performing ultrafiltration by using an ultrafiltration membrane to obtain high-purity methyl iodide for the LED material;
wherein the mass volume ratio of the crude methyl iodide to water is as follows: 1g, 1mL; the mass ratio of the crude methyl iodide to the anhydrous calcium chloride is as follows: 1:0.1.
The preparation method of the modified ZSM-12 molecular sieve comprises the following steps:
adding a ZSM-12 molecular sieve into a cyclohexane solvent, adding tetraethoxysilane and 4-methyl-7-trimethylsiloxy coumarin, stirring for 2 hours at room temperature, drying for 1 hour at 105 ℃ after the solvent is evaporated, heating to 520 ℃ at the heating rate of 2 ℃/min, and roasting for 5 hours to obtain the modified ZSM-12 molecular sieve; wherein the mass ratio of the 4-methyl-7-trimethylsiloxy coumarin to the ZSM-12 molecular sieve is as follows: 1; the mass-volume ratio of the ZSM-12 molecular sieve to the cyclohexane is as follows: 1g, 10mL; the mass ratio of the ethyl orthosilicate to the 4-methyl-7-trimethylsiloxy coumarin is as follows: 1:1.
The preparation method of the modified ZSM-12 molecular sieve adsorbent comprises the following steps: placing the modified ZSM-12 molecular sieve in an impregnation liquid prepared by mixing 2,4-dihydroxy benzophenone, salicylaldehyde, acetylacetone and ethanol, impregnating for 15 hours, then taking out, and drying for 4 hours at 25 ℃ to prepare a modified ZSM-12 molecular sieve adsorbent; wherein the mass ratio of 2,4-dihydroxy benzophenone to salicylaldehyde is as follows: 1, 0.1; 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the acetylacetone is as follows: 1:5; 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the ethanol is as follows: 1:2.5.
The preparation method of the modified PVDF ultrafiltration membrane comprises the following steps:
adding PVDF into N-methyl pyrrolidone to dissolve at a concentration of 15wt%, adding polyethylene oxide and madecassoside, reacting at 75 ℃ for 20h, standing at room temperature for defoaming for 12h, and preparing a modified PVDF ultrafiltration membrane by an immersion precipitation phase conversion method; controlling the thickness of the film at 160 mu m by using a scraper; wherein the mass ratio of the polyethylene oxide to the madecassoside is as follows: 1, 0.1; the mass ratio of PVDF to madecassoside is as follows: 1:0.4.
Example 2:
the difference between the purification method of high-purity methyl iodide for the LED material and the embodiment 1 is that: the mass volume ratio of the crude iodomethane to the water is as follows: 1g, 2.5mL; the mass ratio of the crude iodomethane to the anhydrous calcium chloride is as follows: 1:0.3.
The difference between the preparation method of the modified ZSM-12 molecular sieve and the preparation method of the modified ZSM-12 molecular sieve in example 1 is as follows: the mass ratio of the 4-methyl-7-trimethylsiloxy coumarin to the ZSM-12 molecular sieve is as follows: 1; the mass volume ratio of the ZSM-12 molecular sieve to the cyclohexane is as follows: 1g, 15ml; the mass ratio of the ethyl orthosilicate to the 4-methyl-7-trimethylsiloxy coumarin is as follows: 1:1.3.
The difference between the preparation method of the modified ZSM-12 molecular sieve adsorbent and the preparation method of the modified ZSM-12 molecular sieve adsorbent in example 1 is as follows: 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the salicylaldehyde is as follows: 1, 0.3; 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the acetylacetone is as follows: 1:8; 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the ethanol is as follows: 1:3.
The difference between the preparation method of the modified PVDF ultrafiltration membrane and the embodiment 1 is that: the mass ratio of the polyethylene oxide to the madecassoside is as follows: 1, 0.3; the mass ratio of PVDF to madecassoside is as follows: 1:0.6.
Example 3:
the difference between the purification method of high-purity methyl iodide for the LED material and the embodiment 1 is that: the mass volume ratio of the crude iodomethane to the water is as follows: 1.5mL; the mass ratio of the crude iodomethane to the anhydrous calcium chloride is as follows: 1:0.2.
The difference between the preparation method of the modified ZSM-12 molecular sieve and the preparation method of the modified ZSM-12 molecular sieve in example 1 is as follows: the mass ratio of the 4-methyl-7-trimethylsiloxy coumarin to the ZSM-12 molecular sieve is as follows: 1; the mass-volume ratio of the ZSM-12 molecular sieve to the cyclohexane is as follows: 1g, 13mL; the mass ratio of the tetraethoxysilane to the 4-methyl-7-trimethylsiloxy coumarin is as follows: 1:1.1.
The difference between the preparation method of the modified ZSM-12 molecular sieve adsorbent and the preparation method of the modified ZSM-12 molecular sieve adsorbent in example 1 is as follows: the mass ratio of 2,4-dihydroxy benzophenone to salicylaldehyde is as follows: 1, 0.25; 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the acetylacetone is as follows: 1:7; 5363 and the mass ratio of the 2,4-dihydroxy benzophenone to the ethanol is as follows: 1:2.8.
The difference between the preparation method of the modified PVDF ultrafiltration membrane and the embodiment 1 is that: the mass ratio of the polyethylene oxide to the madecassoside is as follows: 1, 0.2; the mass ratio of PVDF to madecassoside is as follows: 1:0.5.
Example 4:
the difference between the purification method of high-purity methyl iodide for the LED material and the embodiment 1 is that: the modified ZSM-12 molecular sieve adsorbent was prepared in this example.
The preparation of the modified ZSM-12 molecular sieve differs from example 1: 4-methyl-7-trimethylsiloxy coumarin is not added in the preparation process of the modified ZSM-12 molecular sieve.
The difference between the preparation method of the modified ZSM-12 molecular sieve adsorbent and the preparation method of the modified ZSM-12 molecular sieve adsorbent in example 1 is as follows: the modified ZSM-12 molecular sieve was prepared in this example.
The modified PVDF ultrafiltration membrane was prepared in the same manner as in example 1.
Example 5:
the difference between the purification method of high-purity methyl iodide for the LED material and the embodiment 1 is that: a modified PVDF ultrafiltration membrane was prepared in this example.
Preparation of modified PVDF ultrafiltration membrane differs from example 1: the madecassoside is not added in the preparation process of the modified PVDF ultrafiltration membrane.
The preparation method of the modified ZSM-12 molecular sieve adsorbent is the same as that of the example 1.
The modified ZSM-12 molecular sieve was prepared in the same manner as in example 1.
Example 6:
the difference between the purification method of high-purity methyl iodide for the LED material and the embodiment 5 is as follows: the modified ZSM-12 molecular sieve adsorbent was prepared in this example.
The difference between the preparation of the modified ZSM-12 molecular sieve and the preparation of the molecular sieve in example 5 is that: 4-methyl-7-trimethylsiloxy coumarin is not added in the preparation process of the modified ZSM-12 molecular sieve.
The difference of the preparation method of the modified ZSM-12 molecular sieve adsorbent and the preparation method of the modified ZSM-12 molecular sieve adsorbent in example 5 is as follows: the modified ZSM-12 molecular sieve was prepared in this example.
The modified PVDF ultrafiltration membrane was prepared in the same manner as in example 5.
Test example 1:
infrared Spectrum testing
Infrared spectroscopy was performed on the samples using a tesser 27 type fourier transform infrared spectrometer.
The modified ZSM-12 molecular sieves prepared in example 1 and example 4 were subjected to the above tests, and the results are shown in fig. 1. As can be seen from FIG. 1, the length of the groove is 400-1400cm -1 The characteristic peak appearing in the range is the framework vibration peak of the molecular sieve, and the position change of the peak before and after modification is small; the deposition modification of 4-methyl-7-trimethylsiloxy coumarin has little influence on the structure of the ZSM-12 molecular sieve, but the modified ZSM-12 molecular sieve prepared in example 1 has 1226cm -1 The peak is obviously widened, which indicates that the 4-methyl-7-trimethylsiloxy coumarin is deposited and changedThe crystallinity has an effect on the crystallinity of the ZSM-12 molecular sieve.
The modified PVDF ultrafiltration membranes prepared in examples 1 and 5 were subjected to the above-described test, and the results are shown in fig. 2. As can be seen from FIG. 2, the modified PVDF ultrafiltration membrane prepared in example 1 was 1633cm in length, as compared with example 5 -1 Characteristic absorption peak at which C = C bond is present; at 1732cm -1 The characteristic absorption peak of C = O bond exists, which indicates that the modified PVDF ultrafiltration membrane prepared in example 1 contains madecassoside.
Test example 2:
methyl iodide purity test
Preparing 10 colorimetric tubes, respectively measuring and adding 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0mL of iodomethane standard solution, and then adding absolute ethyl alcohol to 5.0mL to prepare a standard series solution; respectively measuring 0.1mL of 1,2-naphthoquinone-4-sodium sulfonate solution with the concentration of 3g/L, adding the solution into each standard tube, and shaking up; adding 0.2mL of 350g/L sodium nitrite solution, and shaking up; heating in 80 deg.C water bath for 20min, cooling, adding 0.1mL sodium hydroxide solution with concentration of 0.035mol/L, and shaking for 1min; colorimetrically measuring the absorbance at the wavelength of 570nm, repeatedly measuring each concentration for 3 times, drawing a standard curve by plotting the content of the iodomethane to the absorbance; the samples were weighed and the sample and blank were assayed for absorption using the operating conditions of the assay standard series. Subtracting the blank absorbance value from the measured sample absorbance value, and obtaining the amount of the iodomethane from the standard curve, wherein the calculation formula of the purity of the iodomethane is as follows:
R/%=（m1/m0）×100%
wherein m1 is the measured mass of methyl iodide; m0 is the mass of the sample.
TABLE 1 purity of methyl iodide
| Grouping | Purity/%) |
| Example 1 | 96.4 |
| Example 2 | 97.2 |
| Example 3 | 96.8 |
| Example 4 | 94.5 |
| Example 5 | 94.9 |
| Example 6 | 92.6 |
The results of the above tests on the purified methyl iodide of examples 1 to 6 are shown in Table 1. As can be seen from table 1, the purity of methyl iodide is significantly improved in examples 1 and 4, and examples 5 and 6, which indicates that the use of 4-methyl-7-trimethylsiloxy coumarin has an accelerating effect on the purification of the crude methyl iodide; the purity of the methyl iodide is also increased in the embodiment 1 compared with the embodiment 5 and the embodiment 4 compared with the embodiment 6, which shows that the addition of the madecassoside improves the purification effect of the PVDF ultrafiltration membrane on the methyl iodide.
Test example 3:
adsorption activity test of ZSM-12 molecular sieve
The adsorption activity of the ZSM-12 molecular sieve is expressed by the adsorption rate of 2,4-dihydroxy benzophenone in the adsorbent, and the formula is as follows:
S/%=[(A0-A1)/A0]×100%
wherein A0 is the concentration of 2,4-dihydroxy benzophenone before adsorption; a1 is the concentration of 2,4-dihydroxybenzophenone after adsorption.
TABLE 2 adsorption rates of molecular sieves with 2,4-dihydroxybenzophenone
| Grouping | Adsorption rate/%) |
| Example 1 | 72.3 |
| Example 2 | 75.8 |
| Example 3 | 73.1 |
| Example 4 | 58.6 |
The modified ZSM-12 molecular sieves prepared in examples 1-4 were tested as described above, and the results are shown in Table 2. As can be seen from Table 2, the adsorption rates of the modified ZSM-12 molecular sieve prepared in example 1 and 2,4-dihydroxybenzophenone are obviously higher than that of example 4, which shows that the addition of 4-methyl-7-trimethylsiloxycoumarin improves the activity of the modified ZSM-12 molecular sieve and the adsorption capacity of the modified ZSM-12 molecular sieve on 2,4-dihydroxybenzophenone.
Test example 4:
ultrafiltration membrane surface roughness test
Intercepting a membrane sample on the surface of the sample ultrafiltration membrane, putting the membrane sample on a glass slide and fixing the membrane sample, sucking water on the surface of the sample by using filter paper, observing the sample by using an atomic force microscope, and analyzing and calculating the surface roughness of the membrane.
TABLE 3 roughness of the Ultrafiltration Membrane surface
| Grouping | roughness/Ra |
| Example 1 | 189.6 |
| Example 2 | 193.1 |
| Example 3 | 191.5 |
| Example 5 | 148.2 |
The modified PVDF ultrafiltration membranes prepared in examples 1 to 3 and 5 were subjected to the above-described test, and the results are shown in table 3. As can be seen from table 3, the roughness of the modified PVDF ultrafiltration membrane prepared in example 1 is significantly greater than that of example 5, which indicates that the addition of madecassoside increases the roughness of the surface of the PVDF ultrafiltration membrane, further increases the effective filtration area of the membrane, and enhances the purity of high-purity methyl iodide for LED materials.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. A method for purifying high-purity methyl iodide for an LED material comprises the following steps:
(1) Obtaining dried crude iodomethane liquid;
(2) Passing the dried crude iodomethane liquid through a modified ZSM-12 molecular sieve adsorbent;
(3) Obtaining high-purity iodomethane for the LED material;
the modified ZSM-12 molecular sieve adsorbent is prepared by depositing and modifying a ZSM-12 molecular sieve by using 4-methyl-7-trimethylsiloxy coumarin and then performing impregnation treatment;
the preparation method of the modified ZSM-12 molecular sieve comprises the following steps:
adding a ZSM-12 molecular sieve into a cyclohexane solvent, adding tetraethoxysilane and 4-methyl-7-trimethylsiloxy coumarin, stirring at room temperature for 2-3h, drying after the solvent is evaporated, heating to 520-570 ℃ at the heating rate of 2-3 ℃/min, and roasting for 5-7h to obtain the modified ZSM-12 molecular sieve;
the dipping liquid for dipping treatment is prepared by mixing 2,4-dihydroxy benzophenone, salicylaldehyde, acetylacetone and ethanol.
2. The method for purifying high-purity methyl iodide used for LED materials according to claim 1, wherein the method comprises the following steps: the mass ratio of the 4-methyl-7-trimethylsiloxy coumarin to the ZSM-12 molecular sieve is as follows: 1:25-30.
3. The method for purifying high-purity methyl iodide used for LED materials according to claim 1, wherein the method comprises the following steps: the weight ratio of 2,4-dihydroxy benzophenone to salicylaldehyde is as follows: 1:0.1-0.3.
4. The method for purifying high-purity methyl iodide for the LED material as claimed in claim 1, wherein the method comprises the following steps: the 2,4-dihydroxy benzophenone and acetylacetone have the mass ratio of: 1:5-8.
5. The method for purifying high-purity methyl iodide for the LED material as claimed in claim 1, wherein the method comprises the following steps: the 2,4-dihydroxy benzophenone and ethanol have the mass ratio of: 1:2.5-3.
6. The method for purifying high-purity methyl iodide for the LED material as claimed in claim 1, wherein the method comprises the following steps: the step (3) comprises ultrafiltration treatment; the ultrafiltration treatment adopts a PVDF ultrafiltration membrane.
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