CN116003251A - Production method of electronic grade acetate - Google Patents
Production method of electronic grade acetate Download PDFInfo
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- CN116003251A CN116003251A CN202211632512.0A CN202211632512A CN116003251A CN 116003251 A CN116003251 A CN 116003251A CN 202211632512 A CN202211632512 A CN 202211632512A CN 116003251 A CN116003251 A CN 116003251A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims description 49
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000005886 esterification reaction Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000004821 distillation Methods 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 230000032050 esterification Effects 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 19
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000007670 refining Methods 0.000 claims description 16
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 238000007667 floating Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000002168 ethanoic acid esters Chemical class 0.000 claims 3
- 235000019439 ethyl acetate Nutrition 0.000 abstract description 22
- 238000000926 separation method Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000000066 reactive distillation Methods 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 229960000583 acetic acid Drugs 0.000 description 29
- 238000000034 method Methods 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000007429 general method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of electronic grade acetic ester, which belongs to the technical field of acetic ester production, and realizes efficient continuous production of acetic ester, and acetic ester generated by reversible reaction is continuously distilled out of the top of a tower by utilizing reactive distillation, so that the conversion rate of the reaction is improved, the energy consumption is low, the yield is high, the product quality is high, the separation process is simplified, the separation cost is reduced, the coupling is realized by esterification reaction and distillation separation, the reaction and the separation can be realized in a single tower, the conversion rate is high, the purity is high, the separation energy consumption is low, trace moisture is separated, the separation efficiency is high, the product purity is high, impurity ions and water molecules in the acetic ester are fully separated, the processing quality of the acetic ester is ensured, and the purity of the acetic ester is improved.
Description
Technical Field
The invention belongs to the technical field of acetate production, and particularly relates to a production method of electronic grade acetate.
Background
At present, the industrialized production of the acetic ester mainly adopts an esterification method, is obtained by esterifying acetic acid and corresponding alcohol, and is a relatively traditional and mature production method. At present, four methods for synthesizing acetate are mainly reported in literature: the esterification method, the acetaldehyde condensation method, the ethanol dehydrogenation method and the ethylene addition method are the most widely applied in chemical industry, and the other two methods are relatively rare. Due to the development of ultra-large-scale integrated circuits, the requirements on the purity of various electronic-grade reagents are also higher and higher, and from the aspect of technical trend, the requirement of processing the nano-grade integrated circuits is the development direction of the electronic-grade reagents. The advantages of the esterification process are still quite obvious and more competitive in the future. At present, advanced production plants in the world adopt a continuous method, and a batch method is adopted by a plurality of small-sized production plants in China. The microporous filtering film is mainly used for filtering mobile phase and sample in chromatographic analysis, is easy to block, has unsatisfactory stability, has selective adsorption property, can be saturated in short time, has great regeneration energy consumption, and Japanese patent JP2008308500A, 12 months and 15 in 2008 discloses a production method of high-purity butyl acetate, and CN108675932A, 10 months and 19 in 2018 discloses a hollow fiber ultrafiltration film for ultrafiltering ethyl acetate. CN102417450a, 4 and 18A in 2012 discloses chromatographic grade butyl acetate obtained by filtration with a microporous filter membrane after rectification, CN107098810a, 8 and 29 a in 2017 discloses a separation and purification method for preparing electronic grade propylene glycol methyl ether acetate, and the acetate has the characteristics of good solubility, low melting point and the like, and has wide application fields. The high-purity acetate is successfully applied to the electrolyte of the lithium ion battery at present, so that the low-temperature performance of the battery can be effectively improved, and the capacity exertion problem of the battery in a low-temperature state is solved. Most industrial raw materials in the market have purity which does not meet the use requirement of the lithium ion battery, and trace impurities in the raw materials seriously reduce the performance of the lithium ion battery, and only electronic-grade acetate can be applied to the field of electronic appliances such as the lithium ion battery. Those skilled in the art are urgent to develop a method for producing electronic grade acetate to meet the existing application market and performance requirements.
Disclosure of Invention
In view of this, the present invention provides a method for producing electronic grade acetate.
The production method of the electronic grade acetic ester comprises the following steps of taking acetic acid and one of n-propanol or ethanol as raw materials:
(1) Pumping acetic acid into an acetic acid preheater for preheating, pumping normal propyl alcohol or ethanol into an alcohol preheater for preheating, mixing the normal propyl alcohol or ethanol with the alcohol preheater according to a set proportion, continuously entering the esterification kettle from the top of the esterification kettle, allowing a catalyst to flow into the esterification kettle from the top of the esterification kettle through a catalyst storage tank at a set flow rate, performing esterification pre-reaction in the esterification kettle, pumping the esterification kettle into a feeding tray between a rectifying section and a stripping section of the reaction rectifying tower through a feeding pump of the reaction rectifying tower, generating reflux liquid, and keeping total reflux for 5-10 minutes, wherein the molar ratio of acetic acid to normal propyl alcohol or ethanol is 1-1.2:1, the temperature control range of the top of the tower is 95-108 ℃, the pressure range is 0.12-0.13 MPa, the temperature control range of the bottom of the tower is 104-116 ℃, the pressure range is 0.13-0.116 MPa, the temperature of the esterification kettle is 104-0.12-0.6, continuously performing reaction rectifying to prepare crude acetate, the lower gas phase is fed into a light removal tower, the composition of a liquid phase of the reaction rectifying tower is crude acetate and sulfuric acid, the sulfuric acid is recycled to the high-boiling point acid/acid mixture of the acid ester is formed on the rectifying tower according to the high-boiling point acid/the acid mixture of the acid ester, and the acid mixture is recycled to the high-boiling point acid mixture is pumped to the rectifying section; (2) refining: the flow rate of 0.4-0.45T/h is controlled to be sent to a crude acetate light component removing tower for treatment, the acetate and the trace light component are condensed by a condenser and then enter a distilling tank, a part of the condensed liquid is pumped to flow back, a part of the condensed liquid is sent to a refined tower top buffer tank, the acetate and the trace heavy component are respectively contained in a light component removing tower kettle, the material of the light component removing tower kettle is treated by the heavy component removing tower by pumping, the gas phase of the heavy component removing tower is the acetate, the acetate in the gas phase of the heavy component removing tower is sent to a reboiler of the light component removing tower, the condensate after heat exchange is partially pumped to flow back, the reflux ratio is 0.6, a part of the condensed liquid is sent to the acetate heavy component removing tower distillation buffer tank after cooling, the electronic grade acetate is obtained in a tank area after inspection, and the acetate and the trace heavy component is sent to a refined tower kettle buffer tank after cooling.
Further, one of the ethyl acetate and n-propyl acetate.
Further, the temperature control range of the acetic acid preheater and the alcohol preheater is 97-108 ℃, and the pressure range is 125-150 kPa.
The purpose of the light component removing tower is to remove light components, namely low-boiling-point substances, in the acetate.
Further, the light component removing tower is a floating valve tower, the operation condition is that the temperature of the tower top is 74-99 ℃, and the pressure is 0.01-0.015 MPa.
The purpose of the de-weighting column is to remove the high boilers from the acetate. The tower top acetate is sent to an acetate light component removing tower reboiler as a heat source of the acetate light component removing tower, and after heat exchange, one part of the condensate is sent to the tower top as reflux liquid, and the rest part of the condensate is cooled and then sent to an acetate heavy component removing tower distillation buffer tank, and the tower bottom material is acetate containing heavy components and is sent to a refining tower kettle buffer tank.
Further, the weight removing tower is a floating valve tower, and the operating condition is that the temperature of the tower top is 82.5-106 ℃ and the pressure is 0.01-0.015 MPa.
In the liquid phase composition at the bottom of the reaction rectifying tower, sulfuric acid is deposited at the bottom, an acid-resistant pump is adopted to pump the acid/ester mixture with higher sulfuric acid content at the bottom to the upper part of the rectifying section of the reaction rectifying tower,
the gas phases at the top of the reactive distillation column directly enter the bottom of the light component removal column through a pipeline, and comprise components with high boiling point including acetic acid, and finally are sent to a buffer tank of a refining column kettle for further refining and then are used for esterification reaction.
The invention has the beneficial effects that:
the invention utilizes the reversible reaction of esterification reaction under the action of sulfuric acid. The yield of the acetate is limited by the chemical balance of the reaction, and as the ternary minimum azeotrope exists among the ester, the water and the alcohol and the minimum azeotropic point is lower than the boiling point of ethanol and acetic acid, and the acetate is contained in the azeotrope, the acetate generated by the reversible reaction is continuously distilled out from the top of the tower by utilizing reactive distillation, and the reaction is carried out in the forward direction, so that the conversion rate of the reaction is increased. And removing light components and heavy components in the acetate by using a refining system consisting of the light component removing tower and the heavy component removing tower.
Compared with the prior art, the invention has the following advantages:
in the conventional process for producing acetate, concentrated sulfuric acid is used as a catalyst for batch production. And the catalytic reaction requires kettle washing and material pulling in the later stage, resulting in the generation of a large amount of kettle washing acid water. Meanwhile, water generated in the esterification reaction process can be azeotroped with ester and unreacted alcohol, the subsequent multi-step distillation or extraction is needed to remove the ester, the circulation amount of intermediate material flow generated by separation is large, a large amount of steam is needed to be consumed to obtain high-purity acetate, and the total energy consumption in the process is high. The coupling is carried out through the esterification reaction and the rectification separation, the reaction and the separation can be carried out in a single tower at the same time, the process is advanced, the conversion rate is high, the purity is high, and the separation energy consumption is low; the tower type rectification thermal coupling process is adopted to separate trace water, so that the separation efficiency is high, the product yield is high, the product purity is more than or equal to 99.99%, impurity ions and water molecules in the acetate are separated, the processing quality of the acetate is ensured, and the purity of the acetate is improved.
Drawings
FIG. 1 is a flow chart of the production process of the invention, wherein: 1-acetic acid preheater, 2-alcohol, 3-acetic acid preheater, 4-alcohol preheater, 5-mixer, 6-catalyst, 7-catalyst storage tank, 8-esterification kettle, 9-reaction rectifying tower, 10-reaction rectifying tower reboiler, 11-gas-liquid separator, 12-light component removing tower, 13-distillation tank, 14-refined tower top buffer tank, 15-light component removing tower reboiler, 16-heavy component removing tower distillation buffer tank, 17-heavy component removing tower distillation buffer tank, 18-refined tower kettle buffer tank and 19-condenser.
Detailed Description
Example 1
Wherein, the acetic acid accords with the specification of GB/T1628-2008 industrial glacial acetic acid, the acetic acid adopts a superior product with the main content of 99.8 percent, the ethanol adopts a superior product with the content of more than 99.5 percent, and the concentrated sulfuric acid adopts a superior product with the content of more than 98 percent. (1) Pumping acetic acid into an acetic acid preheater for preheating, pumping ethanol into an alcohol preheater for preheating, mixing the acetic acid and the alcohol according to a set proportion, wherein the temperature of the acetic acid preheater and the alcohol preheater is 108 ℃, the pressure range is 150kPa, the acetic acid and the alcohol preheater continuously enter from the top of an esterification kettle at the flow rate of 0.375T/h, the catalyst concentrated sulfuric acid flows into the esterification kettle from the top of the esterification kettle through a catalyst storage tank at the flow rate of 0.035T/h, the esterification pre-reaction is carried out in the esterification kettle, a feeding tray between a rectifying section and a stripping section of the reaction rectifying tower is pumped through a feeding pump of the reaction rectifying tower, reflux liquid is generated, total reflux is kept for 10 minutes, the temperature control range of the top of the acetic acid and the ethanol is 108 ℃, the pressure range is 0.13MPa, the temperature control range of the bottom of the tower is 116 ℃, the pressure range of the esterification kettle is 0.14MPa, the temperature of the esterification kettle is 0.15MPa and the reflux ratio of the catalyst concentrated sulfuric acid is 0.6, the composition of the liquid phase of the reaction rectifying tower is the crude acetic acid ethyl ester, the crude acetic acid and sulfuric acid is formed by the reaction rectifying the sulfuric acid, the composition of the liquid phase of the reaction rectifying tower is the crude acetic acid and sulfuric acid is the acid, the acid is formed by the acid-containing the acid with high acid/acid mixture in the acid precipitation amount on the rectifying section and the high in the rectifying section is the catalyst in the rectification pump of the reaction rectifying section according to the molar ratio of the high pressure ratio; (2) refining: and (3) controlling the flow of 0.42T/h to be sent to a crude ethyl acetate light component removing tower for treatment, wherein the light component removing tower is a floating valve tower, and the operating condition is that the tower top temperature is 74 ℃ and the pressure is 0.015MPa. The method comprises the steps of condensing ethyl acetate and trace light components at the top of a light component removing tower through a condenser, feeding the condensed materials into a distillation tank, pumping a part of the condensed materials into a reflux ratio of 0.5, feeding a part of the condensed materials into a refining tower top buffer tank, cooling the condensed materials into an ethyl acetate light component removing tower, feeding the condensed materials into a tank area after inspection, and feeding the condensed materials into a refining tower kettle buffer tank after the condensed materials are qualified, wherein the operation condition of the light component removing tower is that the temperature of the top of the tower is 82.5 ℃ and the pressure of the condensed materials is 0.015MPa, the condensed materials are treated by the light component removing tower, the gas phase of the light component removing tower is ethyl acetate, feeding the ethyl acetate into a light component removing tower reboiler, feeding the condensed materials into the ethyl acetate light component removing tower after heat exchange, feeding the condensed materials into the ethyl acetate light component removing tower after cooling, and feeding the condensed materials into the ethyl acetate light component removing tower after inspection.
The yield of the ethyl acetate is more than 98%, the purity of the product is more than or equal to 99.99%, the purity of silver Ag is less than or equal to 0.001ppm, the purity of aluminum Al is less than or equal to 0.005ppm, the purity of calcium Ca is less than or equal to 0.01ppm, the purity of cadmium Cd is less than or equal to 0.001ppm, the purity of chromium Cr is less than or equal to 0.001ppm, the purity of copper Cu is less than or equal to 0.005ppm, the purity of iron Fe is less than or equal to 0.05ppm, the purity of potassium K is less than or equal to 0.005ppm, the purity of magnesium Mg is less than or equal to 0.005ppm, the purity of manganese Mn is less than or equal to 0.001ppm, the purity of sodium Na is less than or equal to 0.001ppm, the purity of nickel Ni is less than or equal to 0.001ppm, the purity of lead Pb is less than or equal to 300ppm, the purity of zinc Zn is less than or equal to 0.002ppm, the evaporation residue is less than or equal to 3Mg/kg, and the acidity is less than or equal to 0.05mmol/100g.
Example 2
Wherein acetic acid accords with the specification of GB/T1628-2008 industrial glacial acetic acid, and n-propanol accords with T/SACE 009-2020
The industrial n-propanol is regulated to have acetic acid as the first grade product with the main content of 99.5%, the n-propanol as the first grade product with the content of more than 99.5%, and the concentrated sulfuric acid as the first grade product with the content of more than 98%, wherein the flow is 0.03T/h. (1) Pumping acetic acid into an acetic acid preheater for preheating, pumping normal propyl alcohol into an alcohol preheater for preheating, mixing the acetic acid and normal propyl alcohol according to a set proportion, wherein the temperature control range of the acetic acid preheater and the alcohol preheater is 95 ℃, the pressure range is 125kPa, the continuous 0.375T/h flow enters from the top of an esterification kettle, the catalyst concentrated sulfuric acid flows into the esterification kettle from the top of the esterification kettle through a catalyst storage tank, esterification pre-reaction is carried out in the esterification kettle, reflux liquid is generated and kept for 8 minutes after reflux liquid is generated, wherein the molar ratio of acetic acid to normal propyl alcohol is 1.1:1, the temperature control range of the top of the tower is 100 ℃, the pressure range of the bottom of the tower is 125kPa, the pressure range of the esterification kettle is 135kPa, the pressure of the esterification kettle is 0.13MPa and the reflux ratio of the catalyst concentrated sulfuric acid, the lower gas phase is sent to a light component of the crude acetic acid n-propyl ester and sulfuric acid, the sulfuric acid is deposited at the bottom, the acid is formed by acid/acid mixture with higher acid content and the acid/ester is recycled to the rectification section of the reaction rectification pump; (2) refining: and (3) controlling the flow of 0.45T/h to be sent to a crude ethyl acetate light component removing tower for treatment, wherein the light component removing tower is a floating valve tower, and the operating condition is that the tower top temperature is 99 ℃ and the pressure is 0.013MPa. The method comprises the steps of condensing n-propyl acetate and trace light components at the top of a light component removing tower through a condenser, feeding the condensed liquid into a distillation tank, pumping a part of the condensed liquid into a reflux ratio of 0.6, feeding a part of the condensed liquid into a refining tower top buffer tank, feeding the condensed liquid into a tank area after inspection, cooling the condensed liquid into the refining tower top buffer tank, and feeding the condensed liquid into the refining tower bottom buffer tank after inspection, wherein the operation condition of the light component removing tower is that the temperature of the top of the light component removing tower is 106 ℃ and the pressure is 0.012MPa, the material of the light component removing tower is treated by the light component removing tower, the gas phase of the heavy component removing tower is n-propyl acetate, feeding the n-propyl acetate into a light component removing tower reboiler, feeding the condensed liquid into the n-propyl acetate after heat exchange into the distillation buffer tank after the condensed liquid is cooled, and feeding the condensed liquid into the refining tower bottom buffer tank after inspection.
The purity of the n-propyl acetate product is more than or equal to 99.9 percent, silver Ag is less than or equal to 0.001ppm, aluminum Al is less than or equal to 0.005ppm, calcium Ca is less than or equal to 0.01ppm, cadmium Cd is less than or equal to 0.001ppm, chromium Cr is less than or equal to 0.001ppm, copper Cu is less than or equal to 0.005ppm, iron Fe is less than or equal to 0.05ppm, potassium K is less than or equal to 0.005ppm, magnesium Mg is less than or equal to 0.005ppm, manganese Mn is less than or equal to 0.001ppm, sodium Na is less than or equal to 0.05ppm, nickel Ni is less than or equal to 0.001ppm, lead Pb is less than or equal to 0.001ppm, water is less than or equal to 500ppm, zinc Zn is less than or equal to 0.002ppm, evaporation residue is less than or equal to 3Mg/kg, and acidity is less than or equal to 0.05mmol/100g.
Note that: reference GB/T601-2002 standard titration solution of chemical reagent is prepared; preparing a standard solution for measuring GB/T602-2002 chemical reagent impurities; preparation of all formulations and preparations in GB/T603-2002 chemical reagent test method; HG/T3498-2014 chemical reagent butyl acetate; GB/T605-2006 general method for measuring chromaticity of chemical reagent; GB/T606-2003 general method for moisture determination of chemical reagents (Karl Fischer method); GB/T611-2006 chemical reagent density determination general method; GB/T6682-2008 analysis laboratory water specification and test method; GB/T9722-2006 general rules for chemical reagent gas chromatography; GB/T9736-2008 general method for measuring acidity and alkalinity of chemical reagent; GB/T9740-2008 general method for measuring chemical reagent evaporation residue; GB/T12589-2007 chemical reagent ethyl acetate; wherein the content of the gas chromatography is measured, and the condition detector is as follows: FID detector, nitrogen 191.21ml/min air flow rate 400ml/min, hydrogen flow rate 30ml/min, chromatographic column HP-5,5% phenyl methyl SiOxane column 30m×320 μm×0.25 μm, column temperature 35 ℃, vaporization chamber temperature 200 ℃, detection chamber temperature 300 ℃, sample injection amount 0.4 μl, split ratio 50:1, moisture determination using Karl-Fischer method according to GB/T606-2003 rule. Metal ion content measurement (ICP-MS) 50ml of the sample to be measured was placed in a clean quartz evaporation pan, placed on a water bath and evaporated to dryness, the evaporated residue was dissolved in 5ml of nitric acid solution (2+98), filtered with a 0.45 μm pore size aqueous microporous filter membrane, and finally measured in a 50ml volumetric flask with the nitric acid solution (2+98) to volume, an instrument of us Angilent company 7500cs, detector Shan Siji rod, resolution 0.85amu, argon pressure 725KPa, circulating water temperature 20 ℃, and exhaust air volume 10m/s.
Claims (5)
1. The production method of the electronic grade acetate comprises the steps of taking acetic acid and one of n-propanol or ethanol as raw materials, and reacting to produce the acetate, and is characterized by comprising the following steps:
(1) Pumping acetic acid into an acetic acid preheater for preheating, pumping normal propyl alcohol or ethanol into an alcohol preheater for preheating, mixing the normal propyl alcohol or ethanol with the alcohol preheater according to a set proportion, continuously entering the esterification kettle from the top of the esterification kettle, allowing a catalyst to flow into the esterification kettle from the top of the esterification kettle through a catalyst storage tank at a set flow rate, performing esterification pre-reaction in the esterification kettle, pumping the esterification kettle into a feeding tray between a rectifying section and a stripping section of the reaction rectifying tower through a feeding pump of the reaction rectifying tower, generating reflux liquid, and keeping total reflux for 5-10 minutes, wherein the molar ratio of acetic acid to normal propyl alcohol or ethanol is 1-1.2:1, the temperature control range of the top of the tower is 95-108 ℃, the pressure range is 0.12-0.13 MPa, the temperature control range of the bottom of the tower is 104-116 ℃, the pressure range is 0.13-0.116 MPa, the temperature of the esterification kettle is 104-0.12-0.6, continuously performing reaction rectifying to prepare crude acetate, the lower gas phase is fed into a light removal tower, the composition of a liquid phase of the reaction rectifying tower is crude acetate and sulfuric acid, the sulfuric acid is recycled to the high-boiling point acid/acid mixture of the acid ester is formed on the rectifying tower according to the high-boiling point acid/the acid mixture of the acid ester, and the acid mixture is recycled to the high-boiling point acid mixture is pumped to the rectifying section; (2) refining: and (3) conveying the crude acetate to a light component removing tower for treatment, wherein acetate and a trace amount of light components are arranged at the top of the light component removing tower, condensed by a condenser, enter a distillation tank, are partially refluxed by a pump, and are partially conveyed to a refining tower top buffer tank, acetate and trace amount of heavy components are arranged at the bottom of the light component removing tower, the material at the bottom of the light component removing tower is treated by a heavy component removing tower by a pump, the gas phase at the top of the heavy component removing tower is acetate, the acetate is conveyed to a reboiler of the light component removing tower, condensate after heat exchange is partially refluxed by a pump, the reflux ratio is 0.4-0.6, and part of condensate is conveyed to an acetate heavy component removing tower distillation buffer tank after being inspected to be qualified and is conveyed to a tank area, and the acetate and trace amount of heavy components are conveyed to a refining tower kettle buffer tank after being cooled.
2. The method for producing electronic grade acetic acid ester according to claim 1, wherein the acetic acid ester is one of ethyl acetate and n-propyl acetate.
3. The method for producing electronic grade acetic acid ester according to claim 1, wherein the temperature control range of the acetic acid preheater and the alcohol preheater is 100-108 ℃ and the pressure range is 125-150 kpa.
4. The method for producing electronic grade acetate according to claim 1, wherein the light component removing tower is a floating valve tower, and the operation condition is that the temperature of the tower top is 78-80 ℃ and the pressure is 0.01-0.015 mpa.
5. The method for producing electronic grade acetate according to claim 1, wherein the de-weight tower is a floating valve tower, the operation condition is that the temperature of the tower top is 85-88 ℃, and the pressure is 0.01-0.015 mpa.
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| CN1844076A (en) * | 2006-03-20 | 2006-10-11 | 江阴市百川化学工业有限公司 | Method for mass producing butyl acetate by reactive distillation method and using sulfuric acid as catalyst |
| CN109369396A (en) * | 2018-11-30 | 2019-02-22 | 福州大学 | A kind of method that direct esterification prepares high-purity ethylene acetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1844076A (en) * | 2006-03-20 | 2006-10-11 | 江阴市百川化学工业有限公司 | Method for mass producing butyl acetate by reactive distillation method and using sulfuric acid as catalyst |
| CN109369396A (en) * | 2018-11-30 | 2019-02-22 | 福州大学 | A kind of method that direct esterification prepares high-purity ethylene acetate |
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