CN108191604B - Method for continuously preparing 2-methallyl alcohol - Google Patents
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- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000001632 sodium acetate Substances 0.000 claims abstract description 54
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 49
- 239000011780 sodium chloride Substances 0.000 claims abstract description 25
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 52
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000003444 phase transfer catalyst Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- -1 aluminium alkoxides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006199 crossed Cannizzaro oxidation reduction reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for continuously preparing 2-methallyl alcohol, which adopts a multi-stage series continuous stirring reactor to react sodium acetate solution, 2-methallyl chloride and sodium hydroxide to directly obtain the 2-methallyl alcohol, and a product is separated after being extracted from the upper part of the reactor. Except the product, the rest water and sodium acetate solution in the extracted substance at the upper part of the reactor can be reused in the reactor; meanwhile, by controlling the high-content sodium acetate and the pH value of the reaction, the sodium chloride generated in the reaction process can be automatically separated out, and the sodium acetate mother liquor can be reused in the reactor. The invention takes MAC and sodium hydroxide as raw materials, after continuous reaction and separation in sodium acetate solution with high molar ratio, only two products are produced: 2-methyl allyl alcohol and sodium chloride are crystallized, the reaction heat is used for the gradual temperature rise process of materials, no additional energy is needed, therefore, the energy consumption of the process is low, and the water in the reaction process can be used for circularly preparing a sodium hydroxide solution and adding the sodium hydroxide solution into the reaction.
Description
Technical Field
The invention relates to a continuous preparation method of 2-methallyl alcohol, belonging to the technical field of organic chemical industry.
Background
2-methallyl alcohol (MAOH for short) is an important organic intermediate, can be used as a polymer monomer, a resin and a perfume, and the most important application is the synthesis of methallyl polyoxyethylene ether. The methyl allyl polyoxyethylene ether is an important monomer for synthesizing the fourth-generation polycarboxylic acid concrete water reducing agent, and has a determining function on the high-efficiency performances of low mixing amount, high water reduction, low slump and the like of the polycarboxylic acid water reducing agent. The application of the methyl allyl polyoxyethylene ether can improve the fluidity and the flow retentivity of the concrete mixture and reduce the slump and the shrinkage rate, so that the polycarboxylic acid water reducing agent has wider application and stronger adaptability, and can be applied to important fields of water conservancy, nuclear power engineering and the like.
There are two main routes for synthesizing 2-methallyl alcohol: one is the 2-methacrolein reduction route, and the other is the 2-methallyl chloride alkaline hydrolysis route. Which are described separately below.
The following two methods are used for synthesizing 2-methallyl alcohol by using 2-methallyl aldehyde as a starting material and adopting a reduction reaction.
US2779801, US4731488, CN107365245, CN105061139, CN106278814 disclose a process for preparing the corresponding unsaturated alcohols by selective reduction of aldehyde groups by secondary alcohols in the presence of catalysts such as aluminium alkoxides, which produces by-products of equimolar amounts of other carbonyl compounds.
CN107032952 uses 2-methylacrolein and α -H-free aldehyde to perform crossed Cannizzaro reaction to generate ester, and then 2-methyl allyl alcohol and carboxylate are obtained through alkali saponification reaction.
CN106984356 uses a carrier tin compound as a catalyst, and 2-methylacrolein and ethanol are reacted to obtain 2-methyl allyl alcohol and acetal.
US2767221, CN102167657, CN103755523, CN106824221 and the like select different catalysts to selectively hydrogenate and reduce unsaturated aldehyde to prepare unsaturated alcohol. In the method, selective hydrogenation is needed on C ═ O without destroying C ═ C bonds, so that the method is difficult, saturated aldehyde or saturated alcohol is generated in the hydrogenation process, and the selectivity of unsaturated alcohol is generally poor.
The above-mentioned method for synthesizing 2-methallyl alcohol requires that 2-methacrolein, which is a raw material having poor stability, be obtained first, and the yield of 2-methacrolein prepared by catalytic oxidation of isobutylene is not high, and therefore, there is no advantage in producing 2-methacrolein alone by this method.
The synthesis of 2-methallyl alcohol by alkaline hydrolysis using 2-methallyl chloride as the starting material was the most developed industrial process.
US2072015 proposes hydrolysis reaction under strong stirring at 100-150 deg.C in the presence of alkali metal hydroxide or sodium carbonate, alkaline earth metal hydroxide or carbonate to obtain 2-methallyl alcohol with a yield of 94-96%.
US2313767 teaches adding an alkali solution to a vertical reactor in the presence of a surfactant dusting, passing 2-methallyl chloride as a vapor to the bottom of the reactor and performing a cyclic hydrolysis after condensation at the top to obtain 2-methallyl alcohol. When the reaction is carried out for 3 hours by using a sodium hydroxide solution, the conversion rate is 84 percent; if the reaction is carried out for 5.5 hours with a sodium carbonate solution, the conversion is 83% and the ether content is 0.2%.
US2323781 uses electrolytic copper to catalyze the reaction of 2-methallyl chloride with potassium hydroxide or potassium carbonate to produce 2-methallyl alcohol. When potassium hydroxide solution is reacted with 2-methylallyl chloride, the yield is 88%; when potassium carbonate is reacted with 2-methylallyl chloride, the yield is close to theoretical. The reaction process, however, produces copper-containing wastewater that is difficult to treat.
Schale et al (Chemische Berichte., Vol.70 (1937); p.116, 121) proposed the synthesis of 2-methylallyl alcohol by reacting 2-methylallyl chloride with potassium hydroxide, which resulted in severe etherification side reactions, resulting in lower yields of the desired product and greater difficulty in product isolation.
CN101759528 adopts water, solid alkali, 2-methyl allyl chloride and polyethylene glycol to be added into a reaction container in turn, then 1-50% alkali liquor is dripped to carry out intermittent hydrolysis under the condition of reflux, standing and layering are carried out after the reaction is finished, an oil layer is dehydrated and decolored to obtain 2-methyl allyl alcohol, the content of the 2-methyl allyl alcohol is lower than 98.5%, and the content of the byproduct 2-methyl allyl alcohol ether is 1.3-1.6%; the water layer is filtered to remove salt and then is used.
CN104447206 adopts low concentration sodium hydroxide solution (3-8%) to react for 0.3-5 hours at 80-120 ℃, an oil layer is separated, an azeotrope of 2-methallyl alcohol and water is distilled out from a water layer through azeotropic distillation, and then solvent is removed through cyclohexane extraction and distillation, so that high-content 2-methallyl alcohol is obtained, and the yield is 97.2-98.5%. Because of the low concentration of alkali, the amount of saline wastewater is large.
CN104341255 adopts non-polar solvent as diluent, halogenated olefin, catalyst and water are put into a reaction kettle, alkali solution is dripped at 20-150 ℃, pH value is controlled to be 5-7, yield is 92%, and 2-methallyl alcohol content is 97.2%.
CN103588622 adopts a continuous hydrolysis method to synthesize 2-methallyl alcohol. Preparing a catalyst and alkali into an aqueous solution, continuously introducing the aqueous solution into the bottom of a tower reactor, introducing 2-methylallyl chloride into the bottom of the tower, reacting vaporized 2-methylallyl chloride with circulating alkali liquor on a filler at the reaction temperature of 90-100 ℃ for about 18 hours, wherein the conversion rate of 2-methylallyl alcohol is 88.0-97.6%, and the selectivity is 92.1-97.5%.
The main disadvantages of the one-step direct hydrolysis method are that etherification side reactions are easy to occur, so that the yield is not high and the separation and purification difficulty of crude products is high.
In order to solve the problem that the one-step method is easy to generate etherification side reaction, the literature proposes a process for producing 2-methallyl alcohol by using 2-methallyl chloride as a starting material and adopting an esterification hydrolysis two-step method.
JP2009107949 proposes that DMF is used as a solvent, 2-methylallyl chloride is firstly reacted with sodium acetate to form 2-methylallyl alcohol acetate, sodium chloride is removed by filtration, alkali is added for saponification, sodium acetate is removed by filtration, and 2-methylallyl alcohol is obtained by rectification, wherein the yield is 97.5 percent at most and the content is 99 percent. DMF is needed as a solvent in the reaction process, the boiling point of 2-methylallyl alcohol is closer to that of DMF, and the separation difficulty is higher; in addition, the sodium chloride obtained by filtration needs a solvent removal process, and the process is relatively complex.
CN103242139A discloses a two-step esterification and hydrolysis process, namely, 2-methallyl alcohol carboxylate is synthesized, and then low-concentration strong base is added for hydrolysis to obtain 2-methallyl alcohol. The reaction yield of the method can reach more than 98 percent, the content can reach 99 percent, but the method needs a phase transfer catalyst, so that the reaction system is difficult to layer, and a large amount of waste salt and waste water containing sodium acetate are generated in the reaction.
CN105037097A proposes that in the presence of an excessive phase transfer catalyst and 2-methallyl chloride, solid sodium acetate reacts with 2-methallyl chloride to fully react the sodium acetate, reactants are simply distilled to obtain a mixture of 2-methallyl alcohol acetate and unreacted raw materials, the mixture is rectified to obtain the unreacted raw materials and the 2-methallyl alcohol acetate, the unreacted raw materials are used indiscriminately, the 2-methallyl alcohol acetate is subjected to alkali liquor saponification reaction to obtain 2-methallyl alcohol, and water in a water phase is removed to obtain the sodium acetate which can be directly used indiscriminately for reaction. However, the esterification reaction of the process involves a phase transfer catalyst, the esterification reaction is intermittent, the saponification reaction is carried out after the product is treated, the two steps of reactions are completely separated, and the operation is troublesome.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for continuously preparing 2-methallyl alcohol, which adopts a two-step method and has no waste liquid discharge in the continuous production process. The invention has the advantages of high yield, good product quality, complex process, high operation cost and high equipment investment cost.
A process for the continuous preparation of 2-methallyl alcohol comprising the steps of:
(1) adding a sodium acetate solution, 2-methallyl chloride and sodium hydroxide into a multistage serial continuous stirring reactor for reaction to directly obtain 2-methallyl alcohol, wherein the stage number of the multistage serial stirring reactor is 6-15, the amount of the sodium acetate is 6-10 mol based on 1mol of 2-methallyl chloride, the introduction amount of the sodium hydroxide is such that the pH value of a reaction solution is 9-11, and the reaction temperature in the multistage serial continuous stirring reactor is preferably 100-120 ℃;
(2) after the continuous reaction is carried out for a period of time, the reaction mixture flowing out from the outlet at the upper part of the reactor is separated to obtain the product 2-methallyl alcohol, sodium chloride crystals, and water and sodium acetate solution are recovered;
(3) and recycling the recovered water and the sodium acetate solution.
And introducing the sodium acetate solution and the 2-methylallyl chloride into the first stage of the multistage series continuous stirring reactor, and introducing the solution prepared from sodium hydroxide into each stirring stage respectively.
Each stirring stage is provided with an online pH meter to control the addition amount of the sodium hydroxide solution.
The residence time of the continuous reaction is 1-4 hours.
And (3) recycling the recycled water in the step (3) for preparing the sodium hydroxide solution to be recycled in the step (1), and directly recycling the sodium acetate solution in the step (1) or recycling the sodium acetate solution in the step (1).
The separation in the step (2) comprises the following steps: (A) the reaction mixture enters a delayer, an oil layer at the upper part of the delayer enters a continuous rectifying tower, and the lower layer of the delayer enters a flash evaporator; (B) separating a lower water layer from a condensate liquid at the top of the rectifying tower through a water separator, refluxing an upper layer to the top of the rectifying tower, collecting a product 2-methallyl alcohol from the lower part of the rectifying tower in a gas phase discharging mode, recovering water from the water layer separated by the water separator, and taking sodium acetate solution as a rectifying tower kettle liquid; (C) condensing the upper gas phase of the flash evaporator to obtain a mixed solution of 2-methallyl alcohol and water as recovered moisture; and filtering, separating and washing a lower salt water phase to obtain sodium chloride crystals and a mother solution, wherein the mother solution is a sodium acetate solution.
The inventor of the invention discovers through a great deal of research that the raw material 2-methyl allyl chloride (MAC for short) is dispersed in a sodium acetate aqueous solution with a high molar ratio through multi-stage stirring, the reaction speed of the MAC and the sodium hydroxide can be greatly improved, a phase transfer catalyst does not need to be added, the reaction can be carried out at a satisfactory speed, and the solubility of a by-product sodium chloride formed by the reaction in high-concentration sodium acetate is small and is only 7-8%, so that the by-product sodium chloride can be separated out in a crystallization form by recycling the sodium acetate solution more than 2 times and can be separated through filtration; the solubility of the product 2-methallyl alcohol in a high-concentration sodium acetate solution is low and is only 1-2%. In the multi-stage stirring reactor, esterification reaction and saponification reaction simultaneously occur, and due to different boiling points, the upper part of the reactor is a mixture of 2-methallyl alcohol and water, and the bottom part of the reactor is reaction raw materials of 2-methallyl chloride and sodium acetate. Therefore, most of the product exists in the form of oil layer, the crude product of the 2-methallyl alcohol can be obtained by layering, and the 2-methallyl alcohol can be obtained after the crude product is subjected to azeotropic distillation to remove contained moisture and remove a small amount of dissolved sodium acetate. Sodium acetate participates in esterification reaction, and a byproduct sodium acetate is obtained after saponification reaction, so that the amount of the added sodium acetate is recycled in the continuous reaction process and is not changed greatly, and only sodium hydroxide (solution) needs to be supplemented continuously to maintain the pH value required by the reaction.
In addition, the inventor of the invention finds that the reaction of the 2-methallyl chloride and the sodium hydroxide is a strong exothermic reaction, the reaction heat is up to 370Kcal calculated by 1Kg of 2-methallyl alcohol, if a multi-kettle series reactor is adopted for continuous reaction, the material can be heated gradually by the reaction heat, and the heating gradually is very beneficial to improving the selectivity of the reaction. Separating the material leaving the reactor into a water layer and an oil layer by an automatic layering device, and rectifying the oil layer to obtain 2-methallyl alcohol; the water layer is subjected to reduced pressure flash evaporation to obtain a cooled brine layer, the brine layer is filtered to obtain sodium chloride crystals and a sodium acetate solution, and the sodium acetate solution can be directly recycled and used in the reaction process; the steam obtained by flash evaporation can be used for preparing sodium hydroxide solution after condensation.
The invention takes MAC and sodium hydroxide as raw materials, after continuous reaction and separation in sodium acetate solution with high molar ratio, only two products are produced: 2-methyl allyl alcohol and sodium chloride are crystallized, the reaction heat is used for the gradual temperature rise process of materials, no additional energy is needed, therefore, the energy consumption of the process is low, and the water in the reaction process can be used for circularly preparing a sodium hydroxide solution and adding the sodium hydroxide solution into the reaction.
The invention has the advantages that:
1) the reaction process can be continuously carried out, the energy consumption is low, and the yield is high.
2) The step-by-step heating process naturally formed in the multistage stirring reactor meets the requirement of reaction kinetics, the reaction selectivity is high, and the byproducts are few.
3) The process only obtains 2-methallyl alcohol product and sodium chloride crystallization byproduct, and no other three wastes are discharged.
4) The reaction process does not need a phase transfer catalyst, the reaction solution is easy to layer, the content of the byproduct sodium chloride is high, and the organic matter residue is less.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Example 1
A solution of sodium acetate (containing 36.0% of sodium acetate and 7.5% of sodium chloride, at a temperature of about 75 ℃) which is continuously used to reach equilibrium is introduced at 136 Kg/h into the bottom of a 6-stage stirring series reactor 1 with a total volume of 500L shown in FIG. 1, and MAC is introduced at 9.05 Kg/h; a total of 9.8 Kg/h of sodium hydroxide solution (41% sodium hydroxide) was fed into each of the 6 stirring stages, and the amount of the solution fed into each stage was controlled in terms of pH (pH 11), and the residence time was about 4 hours. At the outlet of the upper part of the reactor 1, the temperature of the reaction product is about 100 ℃, the reaction product is layered by a continuous layering device 2, an oil layer enters the middle part of a continuous azeotropic distillation tower 7, and a water layer enters a flash evaporator 3.
Under the condition that a reboiler 11 provides a heat source, in the top of a rectifying tower 7, an azeotrope is condensed by a condenser 8 and then enters a water separator 9, an oil layer at the upper part of the water separator 9 is used as the top of the rectifying tower 7 to flow back, and a water layer at the lower part is sent to an alkali preparation kettle 5 at a rate of about 0.4 Kg/h; 2-methylallyl alcohol steam is extracted from the lower side line of the rectifying tower 7, and after being condensed by a condenser 10, 2-methylallyl alcohol products are obtained by about 7.2 Kg/h (the content is 99.76 percent by GC detection); the still liquid containing a small amount of sodium acetate is also sent to the alkali preparation kettle at about 0.2 Kg/h in the rectifying tower 7.
Steam distilled from the water layer of the demixer 2 by the flash evaporator 3 is condensed by the condenser 6 and then enters the alkali preparation kettle 5 at a flow rate of about 5.1 Kg/h; the temperature of the water layer after flash evaporation is reduced to about 77 ℃, the water layer is continuously centrifuged and filtered by a filter 4, and the filter cake is washed by 0.3 Kg/h of water to obtain about 6.1 Kg/h of sodium chloride crystals (containing about 5 percent of water); the filtrate and washing liquid are sodium acetate solution containing a small amount of sodium chloride, and are mixed and directly applied to the reaction process.
Example 2
315 Kg/h of sodium acetate solution (containing 38.5% of sodium acetate and 7.3% of sodium chloride, and having a temperature of about 89 ℃) which is continuously used to reach equilibrium is introduced into the bottom of a 10-stage stirring series reactor 1 with a total volume of 500L shown in FIG. 1, and 18.1 Kg/h of MAC is introduced at the same time; sodium hydroxide solution (containing 40% sodium hydroxide) was introduced into each of 10 stirring stages in a total amount of 20.0 Kg/hr, and the amount of the solution introduced into each stage was controlled in terms of pH (pH was controlled at 10), and the residence time was about 2 hours. At the outlet of the reactor 1, the temperature of the reaction product is about 110 ℃, the reaction product is layered by a continuous layering device 2, an oil layer enters the middle part of a continuous azeotropic distillation tower 7, and a water layer enters a flash evaporator 3.
Under the condition that a reboiler 11 provides a heat source, in the top of a rectifying tower 7, an azeotrope is condensed by a condenser 8 and then enters a water separator 9, an oil layer at the upper part of the water separator 9 is used as the top of the rectifying tower 7 to flow back, and a water layer at the lower part is sent to an alkali preparation kettle 5 at a rate of about 0.8 Kg/h; 2-methylallyl alcohol steam is extracted from the lower side line of the rectifying tower 7, and after being condensed by a condenser 10, a 2-methylallyl alcohol product is obtained by 14.4 Kg/h (the GC content is 99.83%); the distillation tower 7 is a still containing a small amount of sodium acetate, and the still is also added with alkali at a rate of about 0.4 Kg/h.
The steam distilled from the water layer of the delayer 2 by the flash evaporator 3 is condensed by the condenser 6 and then enters the alkali preparation kettle 5 at the flow rate of about 10.6 Kg/h; the temperature of the water layer after flash evaporation is reduced to about 91 ℃, the water layer is continuously centrifuged and filtered by a filter 4, and the filter cake is washed by 0.6 Kg/h of water to obtain about 12.2 Kg/h of sodium chloride crystals (containing about 5 percent of water); the filtrate and washing liquid are sodium acetate solution containing a small amount of sodium chloride, and are mixed and directly applied to the reaction process.
Example 3
A sodium acetate solution (containing 41.2 percent of sodium acetate and 7.0 percent of sodium chloride and with the temperature of about 101 ℃) which is continuously recycled to reach the equilibrium is introduced into the bottom of a 15-stage stirring series reactor 1 with the total volume of 500L shown in figure 1 at 597 Kg/h, and meanwhile, 27.15 Kg/h MAC is introduced; a total of 30.9 Kg/h of sodium hydroxide solution (39% sodium hydroxide) was fed into each of the 15 stirring stages, and the amount of sodium hydroxide fed into each stage was controlled in terms of pH (pH was controlled at 9), and the residence time was about 1 hour. At the outlet of the reactor, the temperature of the reaction product is about 120 ℃, the reaction product is layered by the continuous delayer 2, the oil layer enters the middle part of the continuous azeotropic distillation tower 7, and the water layer enters the flash evaporator 3.
Under the condition that a reboiler 11 provides a heat source, in the top of a rectifying tower 7, an azeotrope is condensed by a condenser 8 and then enters a water separator 9, an oil layer at the upper part of the water separator 9 is used as the top of the rectifying tower 7 to flow back, and a water layer at the lower part is sent to an alkali preparation kettle 5 at a rate of about 1.2 Kg/h; 2-methylallyl alcohol steam is extracted from the lower side line of the rectifying tower 7, condensed by a condenser 10 and then obtained by 21.6 Kg/h (the GC content is 99.91 percent) to obtain a 2-methylallyl alcohol product; the still liquid containing a small amount of sodium acetate is also added into an alkali preparation kettle at about 0.6 Kg/h in the rectifying tower 7.
The steam distilled from the water layer of the demixer 2 by the flash evaporator 3 is condensed by the condenser 6 and then enters the alkali preparation kettle 5 at the flow rate of about 17.1 Kg/h; the temperature of the water layer after flash evaporation is reduced to about 101 ℃, the water layer is continuously centrifuged and filtered by a filter 4, and the filter cake is washed by hot water of 0.9 Kg/h to obtain sodium chloride crystals (containing about 5 percent of water) of about 18.3 Kg/h; the filtrate and washing liquid are sodium acetate solution containing a small amount of sodium chloride, and are mixed and directly applied to the reaction process.
Claims (7)
1. A process for the continuous preparation of 2-methallyl alcohol comprising the steps of:
(1) adding a sodium acetate solution, 2-methallyl chloride and sodium hydroxide into a multistage series continuous stirring reactor for reaction to directly obtain 2-methallyl alcohol, wherein the stage number of the multistage series continuous stirring reactor is 6-15, the amount of sodium acetate is 6-10 mol based on 1mol of 2-methallyl chloride, the introduction amount of sodium hydroxide is such that the pH value of a reaction solution is 9-11, and the reaction temperature in the multistage series continuous stirring reactor is 100-120 ℃;
(2) after the continuous reaction is carried out for a period of time, the reaction mixture flowing out from the outlet at the upper part of the reactor is separated to obtain the product 2-methallyl alcohol, sodium chloride crystals, and water and sodium acetate solution are recovered;
(3) and recycling the recovered water and the sodium acetate solution.
2. The method as claimed in claim 1, wherein the sodium acetate solution and the 2-methallyl chloride are introduced into a first-stage continuous stirring reactor of a multi-stage series continuous stirring reactor, and the sodium hydroxide is prepared into solutions which are respectively introduced into stirring reactors of different stages.
3. The method of claim 2, wherein each stage of the stirring reactor is provided with an online pH meter to control the addition amount of the sodium hydroxide solution.
4. The method of claim 1, wherein the continuous reaction has a residence time of 1 to 4 hours.
5. The method of claim 1, wherein the water recovered in step (3) is used for preparing the sodium hydroxide solution and is recycled to step (1), and the sodium acetate solution can be directly recycled to step (1) or used for preparing the sodium hydroxide solution and is recycled to step (1).
6. The method of claim 1, the separating in step (2) comprising the steps of: (A) the reaction mixture enters a delayer, an oil layer at the upper part of the delayer enters a continuous rectifying tower, and the lower layer of the delayer enters a flash evaporator; (B) separating a lower water layer from a condensate liquid at the top of the rectifying tower through a water separator, refluxing an upper layer to the top of the rectifying tower, collecting a product 2-methallyl alcohol from the lower part of the rectifying tower in a gas phase discharging mode, recovering water from the water layer separated by the water separator, and taking sodium acetate solution as a rectifying tower kettle liquid; (C) condensing the upper gas phase of the flash evaporator to obtain a mixed solution of 2-methallyl alcohol and water as recovered moisture; and filtering, separating and washing a lower salt water phase to obtain sodium chloride crystals and a mother solution, wherein the mother solution is a sodium acetate solution.
7. The method according to claim 1, wherein the step (2) further comprises the treatment of the reaction liquid at the lower part of the reactor, the reaction liquid is cooled and filtered, sodium chloride crystals and a sodium acetate solution are separated out, and the sodium acetate solution is recycled in the step (1).
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| CN201711400139.5A CN108191604B (en) | 2017-12-22 | 2017-12-22 | Method for continuously preparing 2-methallyl alcohol |
| KR1020207010732A KR102364274B1 (en) | 2017-12-22 | 2018-10-10 | Continuous process for the preparation of 2-methylallyl alcohol |
| RU2020112924A RU2734548C1 (en) | 2017-12-22 | 2018-10-10 | Method for continuous production of 2-methylallyl alcohol |
| PCT/CN2018/109595 WO2019119934A1 (en) | 2017-12-22 | 2018-10-10 | Method for continuous preparation of 2-methyl allyl alcohol |
| JP2020554344A JP7029740B2 (en) | 2017-12-22 | 2018-10-10 | Method for continuously producing 2-methylallyl alcohol |
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| CN111099990B (en) * | 2019-12-31 | 2023-12-26 | 山东广通新材料有限公司 | Recycling method of long carbon chain dicarboxylic acid refined crystallization mother liquor |
| CN111170828B (en) * | 2020-01-17 | 2023-01-03 | 浙江大学宁波理工学院 | Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst |
| CN111499515A (en) * | 2020-04-28 | 2020-08-07 | 南京简迪环境工程有限公司 | Process for synthesizing sodium nitrophenolate by continuous hydrolysis of nitrochlorobenzene |
| CN112546658A (en) * | 2020-11-13 | 2021-03-26 | 南通百川新材料有限公司 | Novel 2-methoxy-1-propanol acetate de-esterification rectification purification method |
| CN114015034A (en) * | 2021-12-08 | 2022-02-08 | 江苏奥克化学有限公司 | Preparation method and application of sodium alkoxide catalyst for synthesizing water reducer polyether |
| CN114560752A (en) * | 2022-02-24 | 2022-05-31 | 浙江皇马科技股份有限公司 | Synthetic method of 2-methallyl alcohol |
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| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by two-step esterification and hydrolysis |
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| CN105037097A (en) * | 2015-06-23 | 2015-11-11 | 浙江绿科安化学有限公司 | Synthetic method of 2-methallyl alcohol |
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| CN104341255A (en) * | 2014-09-19 | 2015-02-11 | 江苏省建筑科学研究院有限公司 | Preparation method of unsaturated alcohol |
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