CN115160131B - Method for reducing crude ester moisture in ethyl acetate production process - Google Patents
Method for reducing crude ester moisture in ethyl acetate production process Download PDFInfo
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 366
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000002148 esters Chemical class 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003463 adsorbent Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005886 esterification reaction Methods 0.000 claims abstract description 40
- 230000032050 esterification Effects 0.000 claims abstract description 38
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 30
- 239000004005 microsphere Substances 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000001338 self-assembly Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 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 12
- 238000001914 filtration Methods 0.000 claims description 12
- 229930182830 galactose Natural products 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002904 solvent 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
- 238000009826 distribution Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 hydrogen ions Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 14
- 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 8
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 238000007273 lactonization reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 238000005373 pervaporation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012043 crude product Substances 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
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000011734 sodium Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to a method for reducing crude ester moisture in the production process of ethyl acetate, and belongs to the technical field of chemical industry. According to the invention, on the basis of the traditional process for producing ethyl acetate by an esterification method, the vapor 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 of the finally obtained purified ethyl acetate is less than or equal to 0.005%.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a method for reducing crude ester moisture in an ethyl acetate production process.
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 solutions for external use and gels, and is useful in edible printing inks for tablets. The current production methods of ethyl acetate mainly comprise an acetate method, an acetaldehyde condensation method, an ethanol dehydrogenation method and an acetic acid and ethylene addition method. In chemical production, a continuous esterification method is often adopted to produce ethyl acetate, namely raw material 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 the reaction products are separated by a series of rectifying towers to obtain an ethyl acetate product. In the process of purifying ethyl acetate, because the product water and ethanol can form binary and ternary azeotrope with ethyl acetate, the product water and the ethanol are partially mutually soluble at normal temperature, and great difficulty is brought to the purification of ethyl acetate. At present, the industrial purification of ethyl acetate by cyclic rectification, condensation, reflux dehydration mainly utilizes the difference of constant boiling composition of ethyl acetate, ethanol and water and mutual solubility at normal temperature, but the method has high energy consumption and the water content in the ethyl acetate product is still higher.
Patent CN112299999a discloses a refining method of high-purity ethyl acetate, crude ethyl acetate is firstly put into a mixed adsorbent for adsorption filtration to obtain ethyl acetate after preliminary impurity removal, then ethyl acetate after preliminary impurity removal is taken and added into a high-efficiency rectifying tower for normal pressure rectification reflux to obtain ethyl acetate after normal pressure rectification, and then ethyl acetate after normal pressure rectification is taken for secondary adsorption filtration to obtain high-purity ethyl acetate, but the impurity content of the ethyl acetate after purification is still not low.
Patent CN105712873a discloses a control method for synthesizing ethyl acetate by an esterification method, which comprises the steps of firstly controlling the mole ratio of acetic acid to ethanol in a mixer to be 1:1, conveying a uniformly stirred mixture to an esterification tower, arranging sulfuric acid at the bottom of the esterification tower and only at the bottom of the esterification tower, heating and esterifying by an esterification reboiler to generate gaseous ethyl acetate and water, and finally enabling the gaseous ethyl acetate and water to enter an esterification phase separator by an esterification condenser and an esterification cooler to obtain ethyl acetate. The invention mainly controls specific parameters in the process of synthesizing ethyl acetate by an esterification method so as to achieve the aim of purifying the ethyl acetate.
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, tower top steam is sent into a pervaporation separator for separation to obtain dehydrated crude ester and permeate liquid, 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, ethyl acetate crude product is extracted from the tower bottom, ethyl acetate crude product enters a refining tower for separation, heavy components are removed, and ethyl acetate finished product is obtained from the tower top. The invention mainly dehydrates crude ethyl acetate by a pervaporation separator consisting of a molecular sieve membrane, an amorphous silica membrane or a PVA membrane, and the amorphous silica membrane is mentioned, but the morphological structure is not specified, and the water content of dehydrated crude ester is still higher.
Patent publication No. CN112500292A discloses a method for purifying ethyl acetate, which comprises first dehydrating crude ethyl acetate to be treated through an acid-resistant permeable membrane, and then removing other impurities through a rectification technique. 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 dehydrated material.
Patent publication No. CN107986964A discloses a method for synthesizing ethyl acetate by membrane separation and dehydration, wherein ethanol and acetic acid are reboiled and enter an esterification kettle to carry out esterification reaction in the presence of a catalyst, reaction products enter an esterification tower to be separated, gas phase components are distilled out from the top of the tower to be condensed and separated into crude ethyl acetate by layering through a layering tank, the ethyl acetate enters a raw material pervaporation water permeable membrane assembly to be dehydrated and then is divided into two parts, one part of the ethyl acetate flows back to the esterification tower to serve as a water carrying agent, and the other part of the ethyl acetate enters a refining tower to be refined, so that purified ethyl acetate is obtained. The material adopted by the pervaporation permeable membrane component is a ceramic membrane, and is composed of silicate and SiO 2 、Al 2 O 3 、Na 2 One or more than two of O. There is also no mention of the related art regarding hydrophilic silica aerogel microspheres as a dehydrated material.
Patent publication No. CN102070444A discloses a dehydration and impurity removal method for ethyl acetate, wherein an impurity removing agent which is insoluble in ethyl acetate and can adsorb moisture, 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 dehydrated material.
Patent publication No. CN105037156A discloses a production method of ultra-clean high-purity ethyl acetate, which comprises the steps of sequentially preprocessing industrial-grade ethyl acetate by an adsorbent, filtering by a membrane to obtain an ethyl acetate semi-finished product, and purifying the semi-finished product by the steps of 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 dehydration and purification method of ethyl acetate, and the invention also achieves the aim of improving the purity of the ethyl acetate by controlling the technical parameters such as reaction temperature, reflux ratio and the like in the process of producing the ethyl acetate by an esterification method.
Disclosure of Invention
The invention aims to provide a method for reducing crude ester moisture in the ethyl acetate production process, which is based on the traditional process for producing ethyl acetate by an esterification method, wherein the top steam of an esterification tower is dehydrated through hydrophilic silica aerogel microspheres, and the rectified ethyl acetate is dehydrated and dealcoholized again 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 aim of the invention can be achieved by the following technical scheme:
a method for reducing crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Lactonizing acetic acid and ethanol in an esterification kettle, separating reaction steam in an esterification tower, and dehydrating 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 (3) pouring the rectified ethyl acetate into the mixed adsorbent B for further dehydration and dealcoholization to obtain the purified ethyl acetate.
As a preferable technical scheme of the 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 distribution is 10-15 um.
As a preferred technical scheme of the invention, the preparation method of the hydrophilic silica aerogel microspheres comprises the following steps:
1) Synthesis of siloxane prepolymer: stirring tetraethoxysilane and galactose with acetone until the mixture is transparent, adding a dilute hydrochloric acid solution, 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: adding alkali into the emulsion of 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) carrying out vacuum drying on the white precipitate obtained in the step (3) at 40-50 ℃ to obtain the hydrophilic silica 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 to tetraethoxysilane in the step 1) is 0.005-0.008:1.
As a preferred embodiment of the present invention, the weight ratio of tetraethoxysilane, galactose and acetone in step 1) is 100: 30-80:2-10.
As a preferable 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 Composition is prepared.
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, the weight ratio of tetraethoxysilane, galactose and acetone in the preparation process of the hydrophilic silica aerogel microspheres is controlled, the concentration of a dilute hydrochloric acid solution and the pH value of a white emulsion are controlled, the weight ratio of dilute hydrochloric acid to tetraethoxysilane is controlled, the temperature and the time of vacuum drying are controlled, the porosity of the final finished silica aerogel microspheres is controlled to be 90-95%, and the particle size distribution is controlled to be 10-15 mu m, so that the silica aerogel microspheres have more excellent hydrophilic performance and stronger dehydration capability of ethyl acetate serving as an adsorption material.
(2) In the method, the crude ethyl acetate is dehydrated by the adsorbent A, rectified and dehydrated and dealcoholized by the mixed adsorbent B, and 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%.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
Example 1
A method for reducing crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Acetic acid and ethanol are subjected to lactonization reaction in an esterification kettle, reaction steam enters an esterification tower for separation, tower top steam is dehydrated through an adsorbent A to obtain dehydrated crude ester, and the adding amount of the adsorbent A is 5% 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 is put into a reactor composed of 25 weight parts of diatomite, 38 weight parts of activated carbon, 6 weight parts of CaO and 5 weight parts of Al 2 O 3 Further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the adding amount of the mixed adsorbent B is as follows13% by weight of ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100:35:8, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution with a hydrogen ion concentration of 3mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.005:1, 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: adding alkali into the emulsion of the step 2) to adjust the pH to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step (3) in vacuum at 42 ℃ for 5 hours 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 distribution is 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 crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Acetic acid and ethanol are subjected to lactonization reaction in an esterification kettle, reaction steam enters an esterification tower for separation, tower top steam is dehydrated through an adsorbent A to obtain dehydrated crude ester, and the adding 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 is put into a reactor composed of 30 weight parts of diatomite, 42 weight parts of activated carbon, 7 weight parts of CaO and 8 weight parts of Al 2 O 3 Further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the mixed adsorbent B is added withThe amount was 15% by weight of ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100:33:7, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution with a hydrogen ion concentration of 2mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.007:1 by weight ratio of the dilute hydrochloric acid to the tetraethoxysilane, 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: adding alkali into the emulsion of the step 2) to adjust the pH to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step (3) in vacuum at 40 ℃ for 3h 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 distribution is 10-12 um.
The purified ethyl acetate of this example had a water content of 0.003% and an ethanol content of 0.004%.
Example 3
A method for reducing crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Acetic acid and ethanol are subjected to lactonization reaction in an esterification kettle, reaction steam enters an esterification tower for separation, tower top steam is dehydrated through an adsorbent A to obtain dehydrated crude ester, and the adding 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 is put into a reactor composed of 29 parts by weight of diatomite, 32 parts by weight of activated carbon, 8 parts by weight of CaO and 5 parts by weight of Al 2 O 3 Further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the mixed adsorbent BThe addition amount was 17% by weight of ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100:77:5, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution with a hydrogen ion concentration of 5mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.008:1, 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: adding alkali into the emulsion of the step 2) to adjust the pH to 9.5-10.5, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH is 6-7;
4) And (3) drying: and (3) drying the white precipitate obtained in the step (3) in vacuum at 50 ℃ for 6 hours 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 distribution is 12-15 um.
The purified ethyl acetate of this example had a water content of 0.004% and an ethanol content of 0.004%.
Comparative example 1
A method for reducing crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Acetic acid and ethanol are subjected to lactonization reaction in an esterification kettle, reaction steam enters an esterification tower for separation, tower top steam is dehydrated through an adsorbent A to obtain dehydrated crude ester, and the adding 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 is put into a reactor composed of 25 weight parts of diatomite, 38 weight parts of activated carbon, 6 weight parts of CaO and 5 weight parts of Al 2 O 3 Further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the mixed adsorbent isThe addition amount of the agent B is 17% of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of siloxane prepolymer: mixing tetraethoxysilane, galactose and acetone according to a weight ratio of 100:27:11, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution with a hydrogen ion concentration of 7mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.01:1, 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: adding alkali into the emulsion of the step 2) to adjust the pH to 8.5-9.0, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH is 5-6;
4) And (3) drying: and (3) drying the white precipitate obtained in the step (3) in vacuum at 39 ℃ for 7h 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 distribution is 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 crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Acetic acid and ethanol are subjected to lactonization reaction in an esterification kettle, reaction steam enters an esterification tower for separation, tower top steam is dehydrated through an adsorbent A to obtain dehydrated crude ester, and the adding 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 is put into a reactor composed of 25 weight parts of diatomite, 38 weight parts of activated carbon, 6 weight parts of CaO and 5 weight parts of Al 2 O 3 Further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the mixed adsorbent isThe addition amount of the additive B is 17% of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of siloxane prepolymer: stirring tetraisopropoxysilane, galactose and acetone according to a weight ratio of 100:81:1 until the mixture is transparent, adding a dilute hydrochloric acid solution with a hydrogen ion concentration of 1.5mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.004:1, and removing a solvent after the reaction is complete 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: adding alkali into the emulsion of the step 2) to adjust the pH to 8.5-9.0, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH is 5-6;
4) And (3) drying: and (3) drying the white precipitate obtained in the step (3) in vacuum at 39 ℃ for 7h 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 distribution 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 crude ester moisture in an ethyl acetate production process, comprising the steps of:
(1) Acetic acid and ethanol are subjected to lactonization reaction in an esterification kettle, reaction steam enters an esterification tower for separation, tower top steam is dehydrated through an adsorbent A to obtain dehydrated crude ester, and the adding 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 is put into a reactor composed of 25 weight parts of diatomite, 38 weight parts of activated carbon, 6 weight parts of CaO and 5 weight parts of Al 2 O 3 Further dehydrating and dealcoholizing the mixed adsorbent B to obtain purified ethyl acetate, wherein the mixed adsorbent B comprisesThe amount of the adsorbent B added is 17% of the weight of the ethyl acetate.
The preparation method of the adsorbent A comprises the following steps:
1) Synthesis of siloxane prepolymer: mixing tetramethoxysilane, galactose and acetone according to a weight ratio of 100:27:13, stirring until the mixture is transparent, adding a dilute hydrochloric acid solution with a hydrogen ion concentration of 1mol/L, controlling the adding amount of the dilute hydrochloric acid to be 0.02:1, 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: adding alkali into the emulsion of the step 2) to adjust the pH to 8.5-9.0, stirring, standing to obtain white precipitate, filtering to remove water, and washing with water until the pH is 5-6;
4) And (3) drying: and (3) drying the white precipitate obtained in the step (3) in vacuum at 39 ℃ for 1h 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 distribution is 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%.
From the comparison of the data of the above examples 1 and comparative examples 1 to 3, it was found that the comparative examples 1 to 3 were adjusted in terms of the parameters in the production process of the 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, and the tetraethoxysilane was replaced with tetramethoxysilane and tetraisopropoxysilane, respectively, and the porosity and particle size of the finally obtained hydrophilic silica aerogel microspheres were not in the range of example 1, and the water content and alcohol content in the purified ethyl acetate in the comparative examples 1 to 3 were higher than those in example 1.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (4)
1. A method for reducing the water content of crude ester in the process of producing ethyl acetate, which is characterized by comprising the following steps:
lactonizing acetic acid and ethanol in an esterification kettle, separating reaction steam in an esterification tower, and dehydrating tower top steam through an adsorbent A to obtain dehydrated crude ester;
feeding the dehydrated crude ester into a rectifying tower for rectification and separation to obtain rectified ethyl acetate;
adding the rectified ethyl acetate into the mixed adsorbent B for further dehydration and dealcoholization to obtain purified ethyl acetate;
the adsorbent A is a hydrophilic silica aerogel microsphere;
the porosity of the hydrophilic silica aerogel microspheres is 90-95%, and the particle size distribution is 10-15 um;
the preparation method of the hydrophilic silica aerogel microspheres comprises the following steps:
1) Synthesis of siloxane prepolymer: stirring tetraethoxysilane and galactose with acetone until the mixture is transparent, adding a dilute hydrochloric acid solution, 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: adding alkali into the emulsion 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: vacuum drying the white precipitate obtained in the step 3) at 40-50 ℃ to obtain hydrophilic silica aerogel microspheres;
the concentration of hydrogen ions in the dilute hydrochloric acid solution is 2-6 mol/L;
the weight ratio of the dilute hydrochloric acid solution to tetraethoxysilane in the step 1) is 0.005-0.008:1;
the weight ratio of tetraethoxysilane, galactose and acetone in the step 1) is 100: 30-80:2-10;
the mixed adsorbent B consists of 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 Composition is prepared.
2. The method for reducing the water content of crude ester in the production process of ethyl acetate according to claim 1, wherein the vacuum drying time in the step 4) is 2-6 hours.
3. The method for reducing crude ester moisture in an ethyl acetate production process according to claim 1, wherein the amount of the adsorbent A added is 5-8% of the weight of ethyl acetate.
4. The method for reducing the water content of crude ester in the production process of ethyl acetate according to claim 1, wherein the adding amount of the mixed adsorbent B is 12-20% of the weight of ethyl acetate.
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| 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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| 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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