CN115160131A - Method for reducing water content of crude ester in ethyl acetate production process - Google Patents
Method for reducing water content of crude ester in ethyl acetate production process Download PDFInfo
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- CN115160131A CN115160131A CN202210947252.XA CN202210947252A CN115160131A CN 115160131 A CN115160131 A CN 115160131A CN 202210947252 A CN202210947252 A CN 202210947252A CN 115160131 A CN115160131 A CN 115160131A
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- ethyl acetate
- crude ester
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 369
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000002148 esters Chemical class 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003463 adsorbent Substances 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000005886 esterification reaction Methods 0.000 claims abstract description 42
- 230000032050 esterification Effects 0.000 claims abstract description 32
- 239000004005 microsphere Substances 0.000 claims abstract description 30
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000000926 separation method Methods 0.000 claims description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000001338 self-assembly Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229930182830 galactose Natural products 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000004964 aerogel Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- -1 hydrogen ions Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000005909 Kieselgur Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 238000005373 pervaporation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- FMYHFHVAPZDDPJ-UHFFFAOYSA-N ethanol;ethyl acetate;hydrate Chemical group O.CCO.CCOC(C)=O FMYHFHVAPZDDPJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for reducing the moisture of crude ester in the production process of ethyl acetate, belonging to the technical field of chemical industry. On the basis of the traditional process for producing ethyl acetate by an esterification method, steam at the top of an esterification tower is dehydrated through hydrophilic silica aerogel microspheres, and the rectified ethyl acetate is dehydrated and dealcoholized through a mixed adsorbent, so that the water content of the finally obtained purified ethyl acetate is less than or equal to 0.005 percent, and the ethanol content is less than or equal to 0.005 percent.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a method for reducing the moisture of crude ester in the production process of ethyl acetate.
Background
Ethyl acetate is an important chemical raw material, and pure ethyl acetate is colorless and clear liquid. In the pharmaceutical preparation, ethyl acetate is mainly used as a solvent, and can also be used as a spice and a flavoring. As a solvent, it is used in external solutions and gels, and can be used in edible printing inks for tablets. The current production methods of ethyl acetate mainly comprise an acetic acid esterification method, an acetaldehyde condensation method, an ethanol dehydrogenation method and an acetic acid and ethylene addition method. In chemical production, ethyl acetate is usually produced by a continuous esterification method, namely raw materials of acetic acid and ethanol are subjected to esterification reaction in a strong acid homogeneous catalyst at a certain temperature and under a certain pressure, and reaction products are separated by a series of rectifying towers to obtain an ethyl acetate product. In the process of purifying the ethyl acetate, the product water and the ethanol can form binary and ternary azeotrope with the ethyl acetate, and are partially mutually soluble at normal temperature, so great difficulty is brought to the purification of the ethyl acetate. At present, the difference between the constant boiling composition of ethyl acetate-ethanol-water and the mutual solubility at normal temperature is mainly used in industry to purify ethyl acetate by cyclic rectification-condensation-reflux dehydration, but the method has large energy consumption and the water content in the ethyl acetate product is still high.
Patent CN112299999A discloses a refining method of high-purity ethyl acetate, which comprises the steps of firstly putting crude ethyl acetate into a mixed adsorbent for adsorption and filtration to obtain ethyl acetate after primary impurity removal, then adding the ethyl acetate after the primary impurity removal into a high-efficiency rectifying tower for normal-pressure rectification reflux to obtain ethyl acetate after normal-pressure rectification, and then taking the ethyl acetate after the normal-pressure rectification for secondary adsorption and filtration to obtain the high-purity ethyl acetate.
Patent CN105712873A discloses a control method for synthesizing ethyl acetate by an esterification method, firstly controlling the molar ratio of acetic acid to ethanol in a mixer to be 1. The invention mainly achieves the purpose of purifying the ethyl acetate by controlling the specific parameters in the process of synthesizing the ethyl acetate by the esterification method.
Patent CN105439855A discloses a refining method for esterification synthesis of ethyl acetate, acetic acid and ethanol are reacted in an esterification kettle, reaction steam enters an esterification tower for separation, overhead steam is sent into a pervaporation separator for separation to obtain dehydrated crude ester and penetrating fluid, one part of the dehydrated crude ester flows back to the top of the esterification tower, the other part of the dehydrated crude ester enters a dealcoholization tower for dealcoholization separation, crude ethyl acetate is collected from the bottom of the tower, the crude ethyl acetate enters a refining tower for separation to remove heavy components, and a finished ethyl acetate product is obtained from the top of the tower. The invention dehydrates crude ethyl acetate mainly by a pervaporation separator consisting of a molecular sieve membrane, an amorphous silica membrane or a PVA membrane, and although the amorphous silica membrane is mentioned, the morphological structure is not specified, and the water content of the dehydrated crude ester is still high.
Patent publication No. CN112500292A discloses a method for purifying ethyl acetate, in which crude ethyl acetate to be treated is first dehydrated through an acid-resistant permeable membrane, and then other impurities are removed by a rectification technique. The acid-resistant permeable membrane comprises a zeolite molecular sieve membrane, a silicon dioxide membrane or a polymer membrane, and the invention also discloses a T/NaY zeolite molecular sieve composite membrane and a preparation method thereof. There is no mention of the related art regarding hydrophilic silica aerogel microspheres as a dehydrating material.
Patent publication No. CN107986964A discloses a method for synthesizing ethyl acetate by membrane separation dehydration, in which ethanol and acetic acid are reboiled and then enter an esterification kettle to carry out esterification reaction in the presence of a catalyst, the reaction product enters an esterification tower to be separated, a gas phase component is distilled off from the top of the tower and condensed, and then crude ethyl acetate is separated by layers through a layering tankAnd (3) evaporating and vaporizing ethyl acetate, then feeding the evaporated and vaporized ethyl acetate into the raw material pervaporation permeable membrane component for dehydration, and then dividing the raw material pervaporation permeable membrane component into two parts, wherein one part of the ethyl acetate is refluxed to the esterification tower to be used as a water-carrying agent, and the other part of the ethyl acetate is fed into a refining tower for refining to obtain purified ethyl acetate. The pervaporation permeable membrane component is made of ceramic membrane made of silicate and SiO 2 、Al 2 O 3 、Na 2 One or more than two of O. Nor is there any mention of the related art concerning hydrophilic silica aerogel microspheres as a dehydrating material.
Patent publication No. CN102070444A discloses a method for removing impurities by ethyl acetate dehydration, wherein an impurity removing agent which is insoluble in ethyl acetate and can absorb water, alcohols, aldehydes and small molecular impurities thereof is added into the ethyl acetate, and the impurity removing agent can be one or more of spherical low-sodium molecular sieves such as 3A, 4A, 5A, 10X, 13X and the like, activated alumina, activated carbon, silica gel, calcium oxide, calcium chloride and the like. The patent also does not mention the related art regarding hydrophilic silica aerogel microspheres as a dehydrating material.
Patent publication No. CN105037156A discloses a method for producing ultra-clean high-purity ethyl acetate, which comprises the steps of sequentially subjecting industrial-grade ethyl acetate to adsorbent pretreatment and membrane filtration to obtain a semi-finished product of ethyl acetate, and purifying the semi-finished product by sequentially subjecting the semi-finished product to molecular sieve dehydration, ion exchange resin and circulating filtration to obtain the ultra-clean high-purity ethyl acetate. The adsorbent is a mixture of diatomite and fine-pore silica gel, the membrane is a porous silica gel membrane or a polyimide membrane, and the ion exchange resin is gel weak base acrylic resin.
Patent CN100357250C discloses a method for dehydrating and purifying ethyl acetate, and the invention also achieves the purpose of improving the purity of ethyl acetate by controlling the technical parameters such as reaction temperature, reflux ratio and the like in the process of producing ethyl acetate by an esterification method.
Disclosure of Invention
The invention aims to provide a method for reducing the moisture of crude ester in the production process of ethyl acetate, which is characterized in that on the basis of the traditional process for producing ethyl acetate by an esterification method, steam at the top of an esterification tower is dehydrated through hydrophilic silica aerogel microspheres, and the rectified ethyl acetate is dehydrated and dealcoholized through a mixed adsorbent, so that the water content of the finally obtained purified ethyl acetate is less than or equal to 0.005%, and the ethanol content is less than or equal to 0.005%.
The purpose of the invention can be realized by the following technical scheme:
a method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, introducing reaction steam into an esterification tower for separation, and dehydrating the tower top steam through an adsorbent A to obtain dehydrated crude ester;
(2) Feeding the dehydrated crude ester into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) And putting the rectified ethyl acetate into the mixed adsorbent B for further dehydration and dealcoholization to obtain purified ethyl acetate.
As a preferred technical solution of the present invention, the adsorbent a is a hydrophilic silica aerogel microsphere.
As a more preferable technical scheme of the invention, the porosity of the hydrophilic silica aerogel microspheres is 90-95%, and the particle size is distributed in the range of 10-15 um.
As a preferred technical scheme of the present invention, the preparation method of the hydrophilic silica aerogel microspheres comprises the following steps:
1) Synthesis of a siloxane prepolymer: adding acetone into tetraethoxysilane and galactose, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution, and removing a solvent after the reaction is completed to obtain a siloxane prepolymer;
2) Self-assembly: adding the siloxane prepolymer obtained in the step 1) into water for self-assembly to obtain a white emulsion;
3) Washing with water: adding alkali into the emulsion obtained in the step 2) to adjust the pH value to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value in the water is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 40-50 ℃ in vacuum to obtain the hydrophilic silicon dioxide aerogel microspheres.
As a preferable technical scheme of the invention, the concentration of hydrogen ions in the dilute hydrochloric acid solution in the step 1) is 2-6 mol/L.
As a preferable technical scheme of the invention, the weight ratio of the dilute hydrochloric acid solution in the step 1) to the tetraethoxysilane is 0.005-0.008.
As a preferred technical solution of the present invention, the weight ratio of the tetraethoxysilane, the galactose and the acetone in the step 1) is 100: 30-80.
As a preferred technical scheme of the invention, the vacuum drying time in the step 4) is 2-6 h.
As a preferable technical scheme of the invention, the mixed adsorbent B consists of 20 to 35 weight parts of diatomite, 30 to 50 weight parts of activated carbon, 5 to 9 weight parts of CaO and 3 to 8 weight parts of Al 2 O 3 And (4) forming.
As a preferable technical scheme of the invention, the adding amount of the adsorbent A is 5-8% of the weight of the ethyl acetate.
As a preferable technical scheme of the invention, the adding amount of the mixed adsorbent B is 12-20% of the weight of the ethyl acetate.
The invention has the beneficial effects that:
(1) According to the invention, by controlling the weight ratio of tetraethoxysilane, galactose and acetone, the concentration of dilute hydrochloric acid solution, the pH value of white emulsion, the weight ratio of dilute hydrochloric acid to tetraethoxysilane, the vacuum drying temperature and time in the preparation process of the hydrophilic silica aerogel microspheres, the porosity of the final finished product of silica aerogel microspheres is controlled to be 90-95%, and the particle size is distributed between 10-15 mu m, so that the hydrophilic silica aerogel microspheres have more excellent hydrophilic performance and have stronger dewatering capacity on ethyl acetate as an adsorbing material.
(2) In the method, the crude ethyl acetate is subjected to dehydration by an adsorbent A, rectification and dehydration and dealcoholization by a mixed adsorbent B in sequence, and the water content and the ethanol content of the finally obtained purified ethyl acetate are respectively less than or equal to 0.005% and less than or equal to 0.005%.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be provided in conjunction with the embodiments.
Example 1
A method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, feeding reaction steam into an esterification tower for separation, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester, wherein the addition amount of the adsorbent A is 5% of the weight of ethyl acetate;
(2) The dehydrated crude ester is sent into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) The ethyl acetate after rectification was charged into a reactor containing 25 parts by weight of diatomaceous earth, 38 parts by weight of activated carbon, 6 parts by weight of CaO and 5 parts by weight of Al 2 O 3 And further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the addition amount of the mixed adsorbent B is 13 percent of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of a siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100;
2) Self-assembly: adding the siloxane prepolymer obtained in the step 1) into water for self-assembly to obtain a white emulsion;
3) Washing with water: adding alkali into the emulsion obtained in the step 2) to adjust the pH value to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 42 ℃ for 5 hours in vacuum to obtain the adsorbent A.
The prepared adsorbent A is a hydrophilic silica aerogel microsphere, the porosity of the hydrophilic silica aerogel microsphere is 90-92%, and the particle size is distributed between 11-13 um.
The purified ethyl acetate of this example had a water content of 0.004% and an ethanol content of 0.005%.
Example 2
A method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, feeding reaction steam into an esterification tower for separation, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester, wherein the addition amount of the adsorbent A is 7% of the weight of ethyl acetate;
(2) Feeding the dehydrated crude ester into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) The ethyl acetate after rectification was charged with a mixture of 30 parts by weight of diatomaceous earth, 42 parts by weight of activated carbon, 7 parts by weight of CaO and 8 parts by weight of Al 2 O 3 And further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the addition amount of the mixed adsorbent B is 15 percent of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of a siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100;
2) Self-assembly: adding the siloxane prepolymer in the step 1) into water for self-assembly to obtain white emulsion;
3) Washing with water: adding alkali into the emulsion obtained in the step 2) to adjust the pH value to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value is 6-7;
4) And (3) drying: and (4) drying the white precipitate obtained in the step 3) at 40 ℃ for 3 hours in vacuum to obtain the adsorbent A.
The prepared adsorbent A is a hydrophilic silica aerogel microsphere, the porosity of the hydrophilic silica aerogel microsphere is 93-95%, and the particle size is distributed between 10-12 um.
In this example, the purified ethyl acetate contained 0.003% water and 0.004% ethanol.
Example 3
A method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, introducing reaction steam into an esterification tower for separation, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester, wherein the addition amount of the adsorbent A is 6% of the weight of ethyl acetate;
(2) The dehydrated crude ester is sent into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) The ethyl acetate after rectification was charged into a reactor containing 29 parts by weight of diatomaceous earth, 32 parts by weight of activated carbon, 8 parts by weight of CaO and 5 parts by weight of Al 2 O 3 And further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the addition amount of the mixed adsorbent B is 17 percent of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of a siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100;
2) Self-assembly: adding the siloxane prepolymer obtained in the step 1) into water for self-assembly to obtain a white emulsion;
3) Washing with water: adding alkali into the emulsion obtained in the step 2) to adjust the pH value to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 50 ℃ for 6 hours in vacuum to obtain the adsorbent A.
The prepared adsorbent A is a hydrophilic silica aerogel microsphere, the porosity of the hydrophilic silica aerogel microsphere is 93-95%, and the particle size is distributed between 12-15 um.
In this example, the purified ethyl acetate contained 0.004% of water and 0.004% of ethanol.
Comparative example 1
A method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, introducing reaction steam into an esterification tower for separation, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester, wherein the addition amount of the adsorbent A is 6% of the weight of ethyl acetate;
(2) The dehydrated crude ester is sent into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) The ethyl acetate after rectification was charged into a reactor containing 25 parts by weight of diatomaceous earth, 38 parts by weight of activated carbon, 6 parts by weight of CaO and 5 parts by weight of Al 2 O 3 And further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the addition amount of the mixed adsorbent B is 17 percent of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of a siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100;
2) Self-assembly: adding the siloxane prepolymer in the step 1) into water for self-assembly to obtain white emulsion;
3) Washing with water: adding alkali into the emulsion obtained in the step 2) to adjust the pH value to 8.5-9.0, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value is 5-6;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 39 ℃ for 7 hours in vacuum to obtain the adsorbent A.
The prepared adsorbent A is a hydrophilic silica aerogel microsphere, the porosity of the hydrophilic silica aerogel microsphere is 80-85%, and the particle size is distributed between 20-30 um.
The purified ethyl acetate of this comparative example had a water content of 0.018% and an ethanol content of 0.021%.
Comparative example 2
A method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, introducing reaction steam into an esterification tower for separation, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester, wherein the addition amount of the adsorbent A is 6% of the weight of ethyl acetate;
(2) Feeding the dehydrated crude ester into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) The ethyl acetate after rectification was charged with a mixture of 25 parts by weight of diatomaceous earth, 38 parts by weight of activated carbon, 6 parts by weight of CaO and 5 parts by weight of Al 2 O 3 And further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the addition amount of the mixed adsorbent B is 17 percent of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of a siloxane prepolymer: stirring tetraisopropoxysilane, galactose and acetone according to a weight ratio of 100 to 1 until the mixture is transparent, adding a dilute hydrochloric acid solution with the hydrogen ion concentration of 1.5mol/L, controlling the adding amount of the dilute hydrochloric acid until the weight ratio of the dilute hydrochloric acid to tetraethoxysilane is 0.004;
2) Self-assembly: adding the siloxane prepolymer in the step 1) into water for self-assembly to obtain white emulsion;
3) Washing with water: adding alkali into the emulsion in the step 2) to adjust the pH value to 8.5-9.0, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value is 5-6;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 39 ℃ for 7 hours in vacuum to obtain the adsorbent A.
The prepared adsorbent A is a hydrophilic silica aerogel microsphere, the porosity of the hydrophilic silica aerogel microsphere is 80-83%, and the particle size is 20-25 um.
The purified ethyl acetate of this comparative example had a water content of 0.015% and an ethanol content of 0.02%.
Comparative example 3
A method for reducing the moisture of crude ester in the production process of ethyl acetate comprises the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, introducing reaction steam into an esterification tower for separation, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester, wherein the addition amount of the adsorbent A is 6% of the weight of ethyl acetate;
(2) The dehydrated crude ester is sent into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) The ethyl acetate after rectification was charged with a mixture of 25 parts by weight of diatomaceous earth, 38 parts by weight of activated carbon, 6 parts by weight of CaO and 5 parts by weight of Al 2 O 3 And further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the addition amount of the mixed adsorbent B is 17 percent of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of a siloxane prepolymer: mixing and stirring tetramethoxysilane, galactose and acetone according to a weight ratio of 100 to 13 until the mixture is transparent, adding a dilute hydrochloric acid solution with the concentration of hydrogen ions of 1mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.02 of the weight ratio of the dilute hydrochloric acid to the tetraethoxysilane, and removing the solvent after the reaction is completed to obtain a siloxane prepolymer;
2) Self-assembly: adding the siloxane prepolymer in the step 1) into water for self-assembly to obtain white emulsion;
3) Washing with water: adding alkali into the emulsion in the step 2) to adjust the pH value to 8.5-9.0, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value is 5-6;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 39 ℃ for 1h in vacuum to obtain the adsorbent A.
The prepared adsorbent A is a hydrophilic silica aerogel microsphere, the porosity of the hydrophilic silica aerogel microsphere is 78-82%, and the particle size is distributed between 22-32 um.
The purified ethyl acetate of this comparative example had a water content of 0.018% and an ethanol content of 0.02%.
As is apparent from comparison of the data of example 1 and comparative examples 1 to 3 above, comparative examples 1 to 3 were found to adjust the parameters of the preparation process of hydrophilic silica aerogel microspheres, including the weight ratio of tetraalkoxysilane, galactose and acetone, the concentration of dilute hydrochloric acid, the weight ratio of dilute hydrochloric acid to tetraethoxysilane, the vacuum drying temperature and time, on the basis of example 1, and to replace tetraethoxysilane with tetramethoxysilane and tetraisopropoxysilane, respectively, and the porosity and particle size of the finally obtained hydrophilic silica aerogel microspheres did not reach the range of example 1, and the water content and alcohol content of purified ethyl acetate in comparative examples 1 to 3 were higher than those in example 1.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for reducing the moisture of crude ester in the production process of ethyl acetate is characterized by comprising the following steps:
(1) Carrying out esterification reaction on acetic acid and ethanol in an esterification kettle, introducing reaction steam into an esterification tower for separation, and dehydrating the tower top steam through an adsorbent A to obtain dehydrated crude ester;
(2) Feeding the dehydrated crude ester into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
(3) Putting the rectified ethyl acetate into a mixed adsorbent B for further dehydration and dealcoholization to obtain purified ethyl acetate;
the adsorbent A is a hydrophilic silicon dioxide aerogel microsphere.
2. The method for reducing the moisture of the crude ester in the production process of the ethyl acetate, according to claim 1, wherein the porosity of the hydrophilic silica aerogel microspheres is 90-95%, and the particle size is 10-15 um.
3. The method for reducing the moisture of the crude ester in the ethyl acetate production process according to claim 2, wherein the preparation method of the hydrophilic silica aerogel microspheres comprises the following steps:
1) Synthesis of a siloxane prepolymer: adding acetone into tetraethoxysilane and galactose, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution, and removing a solvent after the reaction is completed to obtain a siloxane prepolymer;
2) Self-assembly: adding the siloxane prepolymer in the step 1) into water for self-assembly to obtain white emulsion;
3) Washing with water: adding alkali into the emulsion obtained in the step 2) to adjust the pH value to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH value in the water is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step 3) at 40-50 ℃ in vacuum to obtain the hydrophilic silicon dioxide aerogel microspheres.
4. The method for reducing the moisture content of the crude ester in the ethyl acetate production process according to claim 3, wherein the concentration of the hydrogen ions in the dilute hydrochloric acid solution in the step 1) is 2-6 mol/L.
5. The method for reducing the moisture of the crude ester in the production process of the ethyl acetate, according to the claim 3, characterized in that the weight ratio of the dilute hydrochloric acid solution in the step 1) to the tetraethoxysilane is 0.005-0.008.
6. The method for reducing the moisture of the crude ester in the ethyl acetate production process according to claim 3, wherein the weight ratio of the tetraethoxysilane, the galactose and the acetone in the step 1) is 100: 30-80 parts of.
7. The method for reducing the moisture of the crude ester in the production process of the ethyl acetate, according to the claim 3, characterized in that the vacuum drying time in the step 4) is 2-6 h.
8. The method for reducing the moisture content of the crude ester in the ethyl acetate production process according to claim 1, wherein the mixed adsorbent B comprises 20-35 parts by weight of diatomite, 30-50 parts by weight of activated carbon, 5-9 parts by weight of CaO and 3-8 parts by weight of Al 2 O 3 And (4) forming.
9. The method for reducing the moisture content of the crude ester in the ethyl acetate production process according to claim 1, wherein the addition amount of the adsorbent A is 5-8% of the weight of the ethyl acetate.
10. The method for reducing the moisture content of the crude ester in the ethyl acetate production process according to claim 1, wherein the addition amount of the mixed adsorbent B is 12-20% of the weight of the ethyl acetate.
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| CN105439855A (en) * | 2015-12-31 | 2016-03-30 | 江苏九天高科技股份有限公司 | Refinement method and device for synthesizing ethyl acetate through esterification |
| CN107055556A (en) * | 2017-03-21 | 2017-08-18 | 上海特栎材料科技有限公司 | A kind of hydrophilic silicon dioxide aerogel microball and preparation method thereof |
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| CN105439855A (en) * | 2015-12-31 | 2016-03-30 | 江苏九天高科技股份有限公司 | Refinement method and device for synthesizing ethyl acetate through esterification |
| CN107055556A (en) * | 2017-03-21 | 2017-08-18 | 上海特栎材料科技有限公司 | A kind of hydrophilic silicon dioxide aerogel microball and preparation method thereof |
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