CN117700325A - Ethyl acetate chromaticity treatment method - Google Patents
Ethyl acetate chromaticity treatment method Download PDFInfo
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- CN117700325A CN117700325A CN202311728582.0A CN202311728582A CN117700325A CN 117700325 A CN117700325 A CN 117700325A CN 202311728582 A CN202311728582 A CN 202311728582A CN 117700325 A CN117700325 A CN 117700325A
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- ethyl acetate
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003463 adsorbent Substances 0.000 claims abstract description 56
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229960000892 attapulgite Drugs 0.000 claims abstract description 34
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000465 moulding Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000013067 intermediate product Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 2
- 238000004042 decolorization Methods 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 16
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 229910052680 mordenite Inorganic materials 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000032050 esterification Effects 0.000 abstract description 7
- 238000005886 esterification reaction Methods 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 6
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000004927 clay Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 238000000053 physical method Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- -1 Iron ions Chemical class 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an ethyl acetate chromaticity treatment method, which comprises the steps of conveying a reaction kettle material at the bottom of an ethyl acetate esterification tower to an adsorption tank through a conveying pump, removing carbide and metal ions through a compound adsorbent, enabling the material to enter a decoloring reaction tank, removing carbonyl compounds through nucleophilic addition reaction, and finally returning the decolored material to the reaction tank, so that the chromaticity of the reaction kettle material at the bottom and crude ester at the top of the tower is reduced, and the chromaticity of an ethyl acetate product meets the requirements of national standard superior products. The method combines physical adsorption and chemical reaction, uses sulfuric acid and acetic acid to carry out acid washing pretreatment and molding preparation on attapulgite and mordenite, and then branches macromolecular cellulose to form the adsorbent, so that the adsorbent has excellent adsorption performance, and the decolorization rate of materials in a tower bottom reaction kettle after the physical adsorption and chemical reaction are combined, so that the ethyl acetate chromaticity treatment method has good decolorization effect on acidic materials in the reaction kettle, can be applied to industrial production of ethyl acetate, improves the product quality and reduces pollutant emission.
Description
Technical Field
The invention relates to the technical field of ethyl acetate production, in particular to an ethyl acetate chromaticity treatment method.
Background
Ethyl acetate is a colorless transparent flammable liquid with fluidity, has fruit fragrance, is easy to volatilize, is mainly used as a solvent, and is widely applied to the fields of pharmacy, dyes, rubber, coating, printing ink, adhesives and the like.
In the industrial process, acetic acid and ethanol are generally adopted for esterification to prepare ethyl acetate, as the esterification process uses concentrated sulfuric acid as a catalyst, organic matters are carbonized to generate colored matters so as to deepen the color of the matters in the tower, and too high reaction temperature or longer reaction time also can lead to carbonization and even oxidation of the matters, so that the chromaticity of the product is increased, and the quality of the product is influenced. Iron ions generated by the concentrated sulfuric acid corrosion equipment also develop color. Impurities contained in the raw materials and side reactions occur, so that some low-carbon carbonyl compounds such as butanedione, glutaraldehyde, 2, 3-pentanedione, 2, 4-pentanedione and the like are all chromogenic substances.
In addition to reducing the production of color-forming substances by controlling the reaction temperature and the reaction time while maintaining the process stability, a general treatment method is to increase the reflux ratio of the esterification distillation column so that the color-forming substances remain at the bottom of the column or to discharge the pot liquid periodically. The method can also be used for decoloring the color-forming substance by adopting an environment-friendly and energy-saving method. The common decoloring methods include a chemical method and a physical method, and the chemical method needs to introduce new substances such as acid, alkali and the like, so that the subsequent treatment difficulty is increased, and the environmental protection pressure is high. The use of strong oxidizing agents such as hypochlorous acid and hydrogen peroxide for decolorization can oxidize the esterification products, and the color is further deepened. The physical method mainly uses adsorbents such as activated carbon and the like to decolorize, which can cause that part of products remain in the activated carbon to cause product loss and increase the treatment capacity of waste residues. In addition, there are active alumina adsorption process, hydrogenation decolorizing process, bromoacid treating process, ion exchange resin process, zeolite molecular sieve process, liquid-liquid extraction process, etc. The decolorization technologies have advantages and disadvantages, and because the composition of the color-forming substances is complex in the production process of the ethyl acetate, the effect is poor by using a single decolorization method, and the methods are required to be screened and optimized according to the actual production situation and then combined.
CN107597057a discloses an attapulgite clay decolorizing adsorbent for regenerating used engine oil and a preparation method, and discloses a composite use of zeolite molecular sieve and attapulgite clay after sintering molding, so that the modified attapulgite clay decolorizing adsorbent has strong adsorption capacity and good decolorizing effect. However, the invention does not mention adding nano carbon powder as pore-forming agent to improve the pore structure of the adsorbent, nor does it mention acid washing pretreatment of zeolite molecular sieve and attapulgite clay.
CN1126197a discloses a process for removing carbonyl-containing impurities from alpha, beta unsaturated carboxylic acids using bisulphite to react with carbonyl groups to form the corresponding water-soluble sulfonate salts, effecting removal of carbonyl-containing impurities. The invention is only suitable for removing carbonyl compounds, but can not remove carbide and metal ions.
Therefore, a technical solution is needed to perfect the defects of the prior art.
Disclosure of Invention
The invention aims to solve the problem of complex composition of color-forming substances in ethyl acetate production, and provides an ethyl acetate chromaticity treatment method which gradually removes various color-forming substances through matching of a physical method and a chemical method, and has the characteristics of strong applicability, high decoloring efficiency and simple process.
The temperature of a tower bottom reaction kettle of the ethyl acetate production device is higher, materials are easy to carbonize to generate colored substances, the temperature of the lower part of the tower body is higher, the colored substances are easier to generate, the colored substances with the boiling point lower than the temperature of the tower bottom can be gasified and enter the tower body, the colored substances with the higher boiling point are easy to be entrained to the tower top to influence the chromaticity of crude ester, and the chromaticity of the final ethyl acetate product is unqualified. The high boiling point chromophoric substances can be left at the bottom of the tower and separated from the top light component products by controlling the distillation temperature and the reflux ratio of the ethyl acetate esterification tower, and the color of the crude ester reaches or is near colorless. However, when the boiling point of the generated chromogenic substance is close to that of ethyl acetate, separation by distillation is difficult, and the generation of the chromogenic substance has an influence on the quality of the product. Therefore, the chroma of the ethyl acetate can be obviously improved by decoloring the material of the reaction kettle at the bottom of the tower, and the material has complex composition, contains organic matters such as acetic acid, ethanol, ethyl acetate and the like and also contains water, and is a homogeneous oil-water mixture with stronger acidity.
The attapulgite is a magnesium-rich fibrous mineral, and mainly comprises silicon dioxide, and has fine and smooth soil quality and grey or off-white appearance. The attapulgite has good decoloring effect, and compared with activated clay, the attapulgite has the advantages of less consumption, less oil loss and low price. The problem is that the filtration is difficult, and the fineness of the soil should be properly coarsened.
The chemical composition of the zeolite adsorbent is mainly silicon dioxide, and then aluminum oxide. The zeolite has better decoloring effect, can reduce the acid value and the moisture of grease during decoloring, has cheaper price than active clay, and is a new material for decoloring grease.
The adsorbent prepared by adopting the attapulgite and zeolite compound forming method is granular, has the advantages of both the attapulgite and the zeolite, and has lower price, lower dosage and good decoloring effect compared with clay and active carbon. On the basis, the attapulgite and zeolite are further modified, and cellulose with a macromolecular structure is grafted, wherein a large number of hydroxyl groups are arranged on the cellulose, so that the adsorption of organic matters and metal ions, namely polar matters, is facilitated; and the macromolecules such as cellulose can well permeate into each pore, so that the adsorption area is larger. Thereby improving the adsorption efficiency of the adsorbent and removing impurities as much as possible.
Aiming at the characteristic that the carbonyl compound is not easy to be adsorbed and removed, the invention uses a chemical method to remove the carbonyl compound, and can rapidly remove the carbonyl compound with color development through nucleophilic addition reaction, thus having short reaction time, high removal efficiency and easy separation of products.
The invention discloses an ethyl acetate chromaticity treatment method, which comprises the following steps:
the material is treated by an adsorbent in an adsorption tank and then decolorized to obtain a finished product;
wherein the adsorbent is a blend of modified attapulgite and modified zeolite,
the adsorbent is prepared by the following steps:
s1, immersing a blend of attapulgite and zeolite into a solution of sulfuric acid and acetic acid, cleaning and drying, blending and molding by an extruder, and calcining at a high temperature to obtain an intermediate product 1;
s2, cleaning the intermediate product 1, immersing the intermediate product into a mixed solution of sodium hydroxide and hydrogen peroxide, heating, stirring, washing and drying to obtain a surface hydroxylated intermediate product 2;
and S3, immersing the product obtained in the step S2 into carboxymethyl cellulose solution, heating and ultrasonic treatment, and washing and drying to obtain the adsorbent.
Specifically, the reaction kettle materials to be treated are conveyed to an adsorption tank through a conveying pump, carbide and metal ions are removed through a compound adsorbent, then the materials enter a decoloring reaction tank to remove carbonyl compounds through nucleophilic addition reaction, and finally the decolored materials are returned to the reaction kettle, so that the chromaticity of the materials at the bottom of the reaction kettle is reduced.
The adsorption tank and the decoloring reaction tank are operated at normal temperature and normal pressure, and no additional heating is needed.
The specific decoloring operation process is as follows:
F1. solid carbide and metal ion adsorption: the materials in the tower bottom reaction kettle pass through the fixed bed layer of the adsorption tank from top to bottom through a conveying pump.
F2. Carbonyl compound removal: the material after passing through the adsorption tank enters a decoloring reaction tank, when the liquid level in the tank reaches 2/3 of the height, the prepared saturated sodium bisulphite solution (more than 40%wt) is added into the decoloring reaction tank to be fully mixed with the material according to the weight ratio of 10%wt of the material at the tower bottom in the decoloring reaction tank, the decolored mixture is sent to a phase separator for oil-water separation after 2-20 minutes, water phase is discharged, wastewater is sent to a wastewater treatment system, and the decolored oil phase material is directly returned to the tower bottom reaction tank. The saturated sodium bisulphite solution used should be freshly prepared, not allowed to stand for a long time, and easily oxidized to sodium bisulphite.
The chromaticity of the materials is measured according to the national standard GB/T3728-2007, and the decoloring rate is calculated according to the following formula:
wherein:
y-decolorization rate of the materials in the reaction kettle;
B 0 -raw colour of the reactor material;
B 1 chromaticity of the reaction kettle material after decolorization.
Wherein,
the volume of the adsorption tank is 3-10m 3 The flow rate of the materials in the reaction kettle is 1-3m 3 /h；
The volume of the compound adsorbent filled in the adsorption tank is 2-4m 3 The compound adsorbent is scattered in a tank to form a fixed bed layer;
the compound adsorbent is prepared by compounding and molding attapulgite and mordenite, mixing the attapulgite powder and the mordenite powder according to a certain proportion, adding a certain amount of 30% silica sol and nano carbon powder, uniformly mixing, extruding and cutting into cylinders, drying at 105 ℃ for 2 hours, placing into a muffle furnace for high-temperature roasting for a certain time, and cooling to room temperature to obtain an adsorbent finished product, wherein the attapulgite, the mordenite, the silica sol and the nano carbon powder are all common products sold in the market.
Further, the mass ratio of the sulfuric acid to the acetic acid is 1:1-1:3.
Specifically, before use, the attapulgite and mordenite are subjected to acid washing pretreatment and water washing, 10-30wt% of sulfuric acid aqueous solution and 65-85wt% of acetic acid aqueous solution are mixed, the attapulgite and mordenite are completely soaked, and the temperature is raised to 60-80 ℃ and then fully mixed for 30-60min; filtering, washing with distilled water to neutrality, drying for 2 hr, and further treating.
Further, the particle size of the attapulgite is 40-60 meshes; the particle size of the zeolite is 0.5-20nm.
Further, the mass ratio of the attapulgite to the zeolite is 2-4:1.
Further, the intermediate product is a cylinder, the particle size is 5mm in diameter and 5-10mm in length.
Further, the calcination temperature is 250-550 ℃ and the calcination time is 2-6h.
Further, in the decoloring treatment, sodium bisulphite solution is adopted to react with impurities in the material.
Further, the mass ratio of the sodium bisulfite solution to the materials is 0.1:10-1:10.
Further, the sodium bisulfite solution is a saturated solution.
Further, the adsorbent also comprises silica sol and nano carbon powder.
Compared with the prior art, the invention has the beneficial effects that:
1. the chromaticity treatment method adopts a compound technology to prepare the adsorbent, and the adsorbent is prepared by kneading and forming attapulgite and mordenite according to a certain proportion and then roasting. The attapulgite has good adsorption decolorizing capacity due to a unique crystal structure, holes are formed after nano carbon powder is added and baked, on the basis, the attapulgite and zeolite are further modified, cellulose with a macromolecular structure is grafted, and the adsorbent formed after modification has strong adsorption capacity on carbide and metal ions. In addition, the prepared adsorbent can be used for a long time at a higher temperature, and has good decoloring effect and less material loss in the adsorption process.
2. Surprisingly, it has been found that both sulfuric acid and acetic acid are present in the reaction kettle bottom material, and that the acid washing pretreatment using a mixture of both can remove impurities such as metal ions, which are easily soluble in acidic substances, in attapulgite and mordenite, thereby increasing the number of micropores and increasing the surface area, and thus improving the adsorption performance. If the acid is not washed or other types of acid are used for acid washing, metal ion impurities dissolved in sulfuric acid or acetic acid can be generated when the bottom material of the reaction kettle containing sulfuric acid and acetic acid contacts the adsorbent, and the adsorption decolorization effect is affected. The mixed acid washing can play the synergistic effect of two acids, has high acid washing speed, and can reduce the acid concentration and the treatment temperature required by single acid washing.
3. According to the invention, carbide and metal ions are removed by physical adsorption, so that adverse effects of impurities on a subsequent chemical method can be reduced, and rapid phase separation after subsequent carbonyl compound reaction is facilitated. The physical method and the chemical method are combined to reduce the chromaticity of the ethyl acetate tower bottom reaction kettle material, reduce the production of reaction kettle waste, save pollution discharge treatment cost, ensure the product quality, ensure that the chromaticity of the ethyl acetate product meets the requirements of national standard superior products, and have simple operation, and can be operated continuously or intermittently.
Drawings
Fig. 1: a flow diagram of decoloring the ethyl acetate tower bottom reaction kettle material;
reference numerals: 1 is a tower bottom reaction kettle, 2 is an esterification tower, 3 is an adsorption tank, 4 is a decoloring reaction tank, and 5 is a phase separator.
Detailed Description
In order to more clearly illustrate the technical aspects of the present invention, the following examples are set forth, but the present invention is not limited thereto.
The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
In the examples and comparative examples of the present invention, the parts refer to parts by mass.
Example 1
An ethyl acetate colorimetric treatment method comprising the steps of:
and conveying the reaction kettle materials to be treated to an adsorption tank through a conveying pump, removing carbide and metal ions by using a compound adsorbent, then feeding the materials into a decoloring reaction tank, removing carbonyl compounds by a nucleophilic addition reaction mechanism, and finally returning the decolored materials to the reaction kettle to reduce the chromaticity of the materials at the bottom of the reaction kettle.
Wherein,
the volume of the adsorption tank is 3m 3 The flow rate of the reaction kettle material is 2m 3 /h；
The volume of the adsorbent filled in the adsorption tank is 2m 3 The adsorbent is scattered in the tank to form a fixed bed layer (the height of the bed layer is 2/3 of the height of the tank body).
The adsorbent is a blend of modified attapulgite and modified zeolite, and is prepared by the following steps:
s1, carrying out acid washing pretreatment and water washing on 60 parts of attapulgite (with the particle size of 40 meshes) and 20 parts of mordenite (with the particle size of 10 nm) before use, mixing with a 20wt% sulfuric acid aqueous solution and a 80wt% acetic acid aqueous solution according to the mass ratio of 1:1, completely soaking the attapulgite and the mordenite, and fully mixing for 50min after heating to 70 ℃; filtering, washing with distilled water to neutrality, drying for 2h, adding 10 parts of 30wt% silica sol and 15 parts of nano carbon powder, and uniformly blending; then adding the mixture into a double-screw extruder, extruding and molding at high temperature, and cutting the obtained strip-shaped material into regular cylinders with the particle size of 5mm in diameter and 5mm in length. Finally, placing the mixture into a muffle furnace for roasting for 4 hours at 400 ℃ to obtain an intermediate product 1;
s2, washing the intermediate product 1 by deionized water, and immersing 1 part of the intermediate product 1 into 100 parts of NaOH/H 2 O 2 In the mixed solution, heating, stirring and refluxing for 2 hours at 80 ℃, filtering, washing with ethanol and deionized water, and vacuum drying for 8 hours at 70 ℃ to obtain an intermediate product 2 with a modified surface by hydroxylation;
s3, immersing the intermediate product 2 in the step S2 into carboxymethyl cellulose solution (50 wt%) and heating to 80 ℃ and carrying out ultrasonic treatment for 2 hours, and washing and drying with clear water and ethanol to obtain the adsorbent.
The adsorption tank and the decoloring reaction tank are operated at normal temperature and normal pressure, and no additional heating is needed;
the NaOH/H 2 O 2 In the mixed solution, naOH, H 2 O 2 The concentration of (2) is 0.5wt% and 2wt%, respectively.
The specific decoloring operation process is as follows:
F1. solid carbide and metal ion adsorption: and conveying the tower bottom reaction kettle material through a fixed bed layer of the adsorption tank from top to bottom by a conveying pump, wherein the residence time is 1h.
F2. Carbonyl compound removal: the material after passing through the adsorption tank enters a decoloring reaction tank, when the liquid level in the tank reaches 2/3 of the height, the newly prepared saturated sodium bisulphite solution (40 wt%) is added into the decoloring reaction tank to be fully mixed with the material according to the proportion of 10wt% of the material in the tower bottom in the decoloring reaction tank, the decolored mixture after 5min is sent to a phase separator for oil-water separation, the water phase is discharged, the wastewater is sent to a wastewater treatment system, and the decolored oil phase material is directly returned to the tower bottom reaction tank.
Example 2
An ethyl acetate colorimetric treatment method comprising the steps of:
and conveying the reaction kettle materials to be treated to an adsorption tank through a conveying pump, removing carbide and metal ions by using a compound adsorbent, then feeding the materials into a decoloring reaction tank, removing carbonyl compounds by a nucleophilic addition reaction mechanism, and finally returning the decolored materials to the reaction kettle to reduce the chromaticity of the materials at the bottom of the reaction kettle.
Wherein,
the volume of the adsorption tank is 3m 3 The flow rate of the reaction kettle material is 2m 3 /h；
The volume of the adsorbent filled in the adsorption tank is 2m 3 The adsorbent is scattered in the tank to form a fixed bed layer (the height of the bed layer is 2/3 of the height of the tank body).
The adsorbent is a blend of modified attapulgite and modified zeolite, and is prepared by the following steps:
s1, carrying out acid washing pretreatment and water washing on 70 parts of attapulgite (with the particle size of 40 meshes) and 20 parts of mordenite (with the particle size of 10 nm) before use, mixing with a 20wt% sulfuric acid aqueous solution and a 80wt% acetic acid aqueous solution according to the mass ratio of 1:1.5, completely soaking the attapulgite and the mordenite, and fully mixing for 30min after heating to 75 ℃; filtering, washing with distilled water to neutrality, drying for 2h, adding 10 parts of 30wt% silica sol and 15 parts of nano carbon powder, and uniformly blending; then adding the mixture into a double-screw extruder, extruding and molding at high temperature, and cutting the obtained strip-shaped material into regular cylinders with the particle size of 5mm in diameter and 5mm in length. Finally, placing the mixture into a muffle furnace for roasting for 4 hours at the temperature of 410 ℃ to obtain an intermediate product 1;
s2, washing the intermediate product 1 by deionized water, and immersing 1 part of the intermediate product 1 into 100 parts of NaOH/H 2 O 2 In the mixed solution, heating, stirring and refluxing for 2 hours at 80 ℃, filtering, washing with ethanol and deionized water, and vacuum drying for 8 hours at 70 ℃ to obtain an intermediate product 2 with a modified surface by hydroxylation;
s3, immersing the product obtained in the step S2 into carboxymethyl cellulose solution (50 wt%) and heating to 85 ℃ and carrying out ultrasonic treatment for 3 hours, and washing and drying with clear water and ethanol to obtain the adsorbent.
The adsorption tank and the decoloring reaction tank are operated at normal temperature and normal pressure, and no additional heating is needed.
The NaOH/H 2 O 2 In the mixed solution, naOH, H 2 O 2 The concentration of (2) is 0.5wt% and 2wt%, respectively.
The specific decoloring operation process is as follows:
F1. solid carbide and metal ion adsorption: and conveying the tower bottom reaction kettle material through a fixed bed layer of the adsorption tank from top to bottom by a conveying pump, wherein the residence time is 1h.
F2. Carbonyl compound removal: the material after passing through the adsorption tank enters a decoloring reaction tank, when the liquid level in the tank reaches 2/3 of the height, the newly prepared saturated sodium bisulphite solution (40 wt%) is added into the decoloring reaction tank to be fully mixed with the material according to the proportion of 10wt% of the material in the tower bottom in the decoloring reaction tank, the decolored mixture after 5min is sent to a phase separator for oil-water separation, the water phase is discharged, the wastewater is sent to a wastewater treatment system, and the decolored oil phase material is directly returned to the tower bottom reaction tank.
Example 3
The adsorbent preparation method and the material decolorization procedure of example 3 were the same as those of example 1, except that the calcination temperature in the adsorbent preparation process of example 3 was 300℃and the calcination time was 4 hours.
Comparative example 1
The adsorbent preparation method and the material decolorization flow of comparative example 1 are the same as those of example 1, except that nano carbon powder is not added in the adsorbent preparation process of comparative example 1.
Comparative example 2
The adsorbent preparation method and the material decolorization flow of comparative example 2 are the same as in example 1, except that steps S2 to S3 are not included in the adsorbent preparation process in comparative example 2.
Comparative example 3
The adsorbent preparation method and the material decolorization scheme of comparative example 3 were the same as in example 1, except that the decolorization reaction tank in comparative example 3 was not charged with a saturated sodium bisulfite solution.
Test results
The effect test was conducted on the decoloring treatment of examples 1 to 3 and comparative examples 1 to 3, that is, the chromaticity of the materials before and after decoloring was compared, and the decoloring ratio was calculated. The test results obtained are shown in Table 1.
TABLE 1 decolorization results for examples 1-3, comparative examples 1-3
From table 1 it can be derived that:
the preparation methods and the decolorization process flows of the adsorbents in the examples 1-3 are basically consistent, but the raw material proportion, the roasting temperature and the like of the adsorbents are slightly different, and the decolorization rate of the tower kettle materials after decolorization in the three examples is more than 80%, so that the appearance color is greatly improved, which shows that the technical scheme provided by the invention has obvious advantages.
In comparative example 1, no nano carbon powder is added in the preparation process of the adsorbent, the decolorization rate of tower kettle materials is reduced, which shows that the adsorption performance of the compound adsorbent is closely related to the pore structure of the compound adsorbent, the pore structure of the adsorbent can be improved by using the nano carbon powder as a pore-forming agent, and the decolorization effect of the adsorbent prepared after no nano carbon powder is added is poor.
In comparative example 2, however, the adsorption force to organic matters and metal ions was remarkably reduced because the adsorbent was not modified with cellulose, so that the decoloring effect was remarkably poor.
In comparative example 3, saturated sodium bisulphite solution (more than 40 wt%) is not added into the decoloring reaction tank, nucleophilic addition reaction of the carbonyl compound which is colored in the tower kettle material cannot occur, and the carbonyl compound still remains in the material and cannot be removed, so that the decoloring rate of the material is low.
In summary, the compound adsorbent and the chromaticity treatment method have better decoloring effect in the chromaticity treatment process of the ethyl acetate. Compared with other comparative examples, the ethyl acetate chroma treatment method has higher decoloring rate of the material of the tower bottom reaction kettle of the ethyl acetate after use, has good application prospect and can be widely applied to the ethyl acetate production process.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A chromaticity treatment method of ethyl acetate is characterized in that the material is decolorized after being treated by an adsorbent in an adsorption tank to obtain a finished product;
wherein the adsorbent is a blend of modified attapulgite and modified zeolite,
the adsorbent is prepared by the following steps:
s1, immersing a blend of attapulgite and zeolite into a solution of sulfuric acid and acetic acid, cleaning and drying, blending and molding by an extruder, and calcining at a high temperature to obtain an intermediate product 1;
s2, cleaning the intermediate product 1, immersing the intermediate product into a mixed solution of sodium hydroxide and hydrogen peroxide, heating, stirring, washing and drying to obtain a surface hydroxylated intermediate product 2;
s3, immersing the intermediate product 2 in the step S2 into carboxymethyl cellulose solution, heating and ultrasonic treatment, and washing and drying to obtain the adsorbent.
2. The ethyl acetate colorimetric treatment process according to claim 1, wherein the mass ratio of sulfuric acid to acetic acid is 1:1 to 1:3.
3. The ethyl acetate colorimetric treatment method according to claim 1, wherein the attapulgite has a particle diameter of 40 to 60 mesh; the particle size of the zeolite is 0.5-20nm.
4. The ethyl acetate colorimetric treatment process according to claim 1, wherein the mass ratio of the attapulgite to the zeolite is 2-4:1.
5. The ethyl acetate colorimetric treatment process according to claim 1, wherein the intermediate product is a cylinder having a particle diameter of 5mm and a length of 5 to 10mm.
6. The ethyl acetate colorimetric treatment method according to claim 1, wherein the calcination temperature is 250 to 550 ℃ and the calcination time is 2 to 6 hours.
7. The method for treating ethyl acetate according to claim 1, wherein sodium bisulphite solution is used for reaction with impurities in the material in the decoloring treatment.
8. The ethyl acetate color treatment method according to claim 7, wherein the mass ratio of the sodium bisulphite solution to the materials is 0.1:10-1:10.
9. The ethyl acetate color treatment method according to claim 8, wherein the sodium bisulphite solution is a saturated solution.
10. The ethyl acetate colorimetric treatment method according to claim 1, wherein the adsorbent further comprises silica sol and nano carbon powder.
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