CN115286486B - Method for removing azeotrope in recovered methanol - Google Patents
Method for removing azeotrope in recovered methanol Download PDFInfo
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- CN115286486B CN115286486B CN202211025685.6A CN202211025685A CN115286486B CN 115286486 B CN115286486 B CN 115286486B CN 202211025685 A CN202211025685 A CN 202211025685A CN 115286486 B CN115286486 B CN 115286486B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 235
- 238000000034 method Methods 0.000 title claims abstract description 36
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 6
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000005660 chlorination reaction Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 20
- 238000005086 pumping Methods 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical group ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000006735 epoxidation reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- -1 on one hand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- 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
- 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
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for removing azeotrope in recovered methanol, which comprises the steps of leaving impurity GME (1, 2-epoxy-3-methoxypropane) in a tower kettle through a methanol rectifying tower to obtain methanol containing AAL (allyl alcohol) and a small amount of water, adding a chlorinating agent into a fraction extracted from the methanol rectifying tower, chlorinating the AAL to generate chloropropene under the condition of absorbing tail gas under micro negative pressure, removing the chloropropene from the methanol through a light removal tower to obtain recovered methanol with the content of more than or equal to 99.9%, wherein the recovered methanol content meets the requirement of long-period recycling of the process of the epichlorohydrin by a hydrogen peroxide method on one hand, and chlorinating and recovering the AAL to obtain the chloropropene, namely the main raw material of the epichlorohydrin by the hydrogen peroxide method on the other hand.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, relates to a solvent recovery technology, and in particular relates to a method for removing and recovering azeotrope in methanol.
Background
Epoxy Chloropropane (ECH) is an important basic chemical raw material and is mainly applied to the production of various products such as epoxy resin, chlorohydrin rubber, glycerol and the like. At present, the industrial production methods of epoxy chloropropane mainly comprise two methods: chlorohydrin process and glycerol process. The chlorohydrin method has the defects of serious equipment corrosion and serious environmental pollution, and about 40 tons of salt-containing wastewater is produced per 1 ton of epichlorohydrin. The main reaction process of the glycerol method mainly comprises two steps of chlorination and saponification. The glycerol method has fewer byproducts and mild operating conditions, but the epichlorohydrin productivity is limited by raw material glycerol.
The development of a clean production process of epichlorohydrin has become a necessary requirement for the development of the times, wherein a process for synthesizing epichlorohydrin by taking a titanium silicon molecular sieve as a catalyst and hydrogen peroxide as an oxygen source becomes a research hot spot due to the advantages of high selectivity, less ineffective decomposition of hydrogen peroxide and the like.
The process needs to use Methanol (MA) as a solvent, on one hand, hydrogen peroxide is dissolved to form homogeneous reaction liquid, and on the other hand, a catalyst is activated, the activity of the catalyst is maintained, and the recovered methanol content is more than or equal to 99.9 percent and can be recycled. However, in scale-up experiments, it was found that the main impurities in the aqueous solution were AAL (allyl alcohol) and GME (1, 2-epoxy-3-methoxypropane), and that the difference in boiling point between the two impurities and methanol was > 30 ℃ from the boiling point, and when methanol was recovered by the rectifying column, GME was able to remain in the column bottom, but because of the azeotropic effect of AAL with water, the difference in boiling point between AAL and methanol was reduced, so that AAL entered the rectifying column top to make the methanol content lower, and the recovered methanol content was not more than 99.5%, and the methanol content could not be made to be equal to or higher than 99.9% even if the rectifying reflux ratio was increased to 5 or more.
Because methanol is a solvent and hardly participates in the reaction, the methanol needs to be recycled for a long period, the quality of recovered methanol directly influences the selectivity of epichlorohydrin synthesis, and finally influences the quality of finished products. Therefore, development of a method for removing and recovering azeotrope in methanol is urgently needed for the epichlorohydrin process by the hydrogen peroxide method.
Disclosure of Invention
In order to solve the problems, the invention provides the following technical scheme:
a process for removing azeotropes from recovered methanol comprising the steps of: continuously pumping aqueous phase solution into a methanol rectifying tower, rectifying, and pumping fractions into a reaction kettle; adding a chlorinating agent into the reaction kettle for chlorination reaction, performing micro negative pressure reaction, and absorbing the condensed tail gas by an alkaline washing tower; pumping a reaction liquid in a reaction kettle into a light component removal tower for rectification, obtaining chloropropene from the top of the tower, and obtaining recovered methanol from the tower kettle; the aqueous phase solution is produced by an epoxy chloropropane process by a hydrogen peroxide method, and comprises the following components: MA: 10-30%; AAL:0.25 to 1 percent; GME: 0.15-1%; ECH:0.01 to 0.3 percent; the balance of water and trace organic impurities; the components of the fraction extracted from the methanol rectifying tower are as follows: AAL:0.3 to 0.9 percent; water: 0.01 to 0.1 percent; the balance is MA.
Further, the chlorinating agent comprises thionyl chloride, phosgene, methyl chloroformate and solid phosgene.
Further, the chlorinating agent is used in an amount of 1 to 1.05 times the AAL equivalent.
Further, the chlorination reaction conditions are: the reaction temperature is 55-70 ℃, the micro negative pressure is minus 2 to minus 0.02kPa, and the reaction time is 0.5-2 hours.
Further, the rectification reflux ratio of the light component removal tower is 1-4.
Further, the alkaline washing tower circularly absorbs tail gas by adopting 5% sodium hydroxide solution.
The invention has the beneficial effects that: the method comprises the steps of (1) adding a chlorinating agent into a fraction extracted from a methanol rectifying tower, chlorinating the AAL to generate chloropropene under the condition of absorbing tail gas under micro negative pressure, removing the chloropropene from the methanol by a light removal tower to obtain recovered methanol with the content of more than or equal to 99.9%, wherein the recovered methanol content meets the requirement of long-period recycling of a hydrogen peroxide epichlorohydrin process, and the AAL is chlorinated and recovered to obtain chloropropene, namely the main raw material of the hydrogen peroxide epichlorohydrin process.
Drawings
FIG. 1 is a schematic diagram of the chlorination reaction and the light component removal process.
In the figure, a 1-reaction kettle, a 2-light component removing tower, a 3-light component removing condenser, a 4-methanol storage tank, a 5-reboiler, a 6-chloropropene storage tank, a 7-chlorination condenser and an 8-alkali absorption tower.
Detailed Description
In order that the manner in which the above-recited features and advantages of the present invention are obtained, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which, as a result, all embodiments of the invention are illustrated in the appended drawings.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, adding the fraction extracted from the methanol rectifying tower into a reaction kettle 1, adding a chlorinating agent, introducing reaction tail gas into an alkali absorption tower 8 through a chlorination condenser 7, connecting the alkali absorption tower 8 with micro negative pressure, and keeping the chlorination reaction under the micro negative pressure; the chloridizing reaction liquid is pumped into the light component removing tower 2, chloropropene in the chloridizing reaction liquid is distilled out from the top of the light component removing tower 2 through the heating of the reboiler 5, the recovered chloropropene is collected into the chloropropene storage tank 6 after being condensed by the light component removing condenser 3, high-purity methanol is arranged in the tower bottom of the light component removing tower 2, and the high-purity methanol is pumped into the methanol storage tank 4 for storage.
The methanol rectifying towers adopted in the following examples are all conventional methanol rectifying towers, and the aqueous phase solution is produced by the process of epoxy chloropropane by a hydrogen peroxide method, and the components are as follows: MA: 10-30%; AAL:0.25 to 1 percent; GME: 0.15-1%; ECH:0.01 to 0.3 percent; the balance of water and trace organic impurities; rectifying the aqueous phase solution by a methanol rectifying tower, wherein the reflux ratio is 1-4, and the obtained fraction comprises the following components: AAL:0.3 to 0.9 percent; water: 0.01 to 0.1 percent; the rest is MA, and the process of rectifying the aqueous phase solution by the methanol rectifying tower in the following embodiments is not repeated.
Example 1:
3m 3 pumping 1200kg of methanol rectifying tower into a reaction kettle to extract fractions, wherein the components are as follows: MA99.35%; AAL 0.6%; adding 15kg of sulfoxide chloride into a reaction kettle, reacting for 1.5h at 65-68 ℃ and negative pressure of-0.15 kpa, and obtaining tail gas (the main component is SO) 2 And HCl) firstly passes through a chlorination condenser, then is pumped into an alkaline washing tower for absorption under negative pressure, the alkaline washing tower uses 5% sodium hydroxide solution for circulating absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 1.0, 9.5kg of chloropropene with the content of 99.15% is obtained at the tower top (the gas phase temperature is 43-44 ℃), the methanol with the content of 99.92% is obtained at the tower bottom, and the methanol content of the tower bottom meets the use requirement of an epoxidation raw material.
Example 2
3m 3 Pumping 1000kg of methanol rectifying tower to extract fraction with the composition of MA99.24%; AAL0.75%; 0.01% of water, 12.5kg of phosgene is introduced, the reaction is carried out for 1h at 55-58 ℃ and-0.05 kpa, and the tail gas (the main component is CO) 2 And HCl) firstly pass through a chlorination condenser and then are pumped into an alkaline washing tower to be absorbed under negative pressure, and alkali is absorbedThe washing tower uses 5% sodium hydroxide solution for circulating absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 2.0, 10.0kg of chloropropene with 99.34% content is obtained at the top of the tower (the gas phase temperature is 43-44 ℃), the methanol with 99.90% content is obtained at the bottom of the tower, and the methanol content of the bottom of the tower meets the use requirement of an epoxidation raw material.
Example 3
3m 3 Pumping 900kg of methanol rectifying tower into a reaction kettle to extract fraction, wherein the composition of the fraction is MA99.11%; AAL0.8%; adding 6kg of methyl chloroformate into a reaction kettle with 0.09% of water, reacting for 2h at 60-62 ℃ under negative pressure of-0.12 kpa, and obtaining tail gas (the main component is CO) 2 And HCl) firstly passes through a chlorination condenser, then is pumped into an alkaline washing tower for absorption under negative pressure, the alkaline washing tower uses 5% sodium hydroxide solution for circulating absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 3.0, 9.6kg of chloropropene with 99.47% content is obtained at the tower top (the gas phase temperature is 43-44 ℃), the methanol with 99.93% content is obtained at the tower bottom, and the methanol content of the tower bottom meets the use requirement of an epoxidation raw material.
Example 4
3m 3 Pumping 1000kg of methanol rectifying tower to extract fraction with the composition of MA99.34%; AAL0.61%; adding 10.5kg of solid phosgene into a reaction kettle, reacting for 1h at 63-65 ℃ and negative pressure of-0.07 kpa, and obtaining tail gas (the main component is CO) 2 And HCl) firstly passes through a chlorination condenser, then is pumped into an alkaline washing tower for absorption under negative pressure, the alkaline washing tower uses 5% sodium hydroxide solution for circulating absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 1.5, 8kg of chloropropene with 99.24% content is obtained at the top of the tower (the gas phase temperature is 43-44 ℃), the methanol with 99.91% content is obtained at the bottom of the tower, and the methanol content of the bottom of the tower meets the use requirement of an epoxidation raw material.
Example 5
3m 3 Pumping 1000kg of methanol rectifying tower to extract fraction with the composition of MA99.08%; AAL0.9%; 0.02% of water, 15kg of phosgene is introduced, the reaction is carried out for 1.5 hours at the temperature of 62-64 ℃ and under the negative pressure of-0.1 kpa, and the tail gas (the main component is CO) 2 And HCl) firstly pass through a chlorination condenser, then are pumped into an alkaline washing tower for absorption under negative pressure, the alkaline washing tower uses 5% sodium hydroxide solution for circulating absorption, and the chlorination reaction liquid is subjected to light component removalRectifying the tower at normal pressure, wherein the reflux ratio is 4.0, 11.7kg of chloropropene with 99.54 percent of content is obtained at the tower top (the gas phase temperature is 43-44 ℃), and the methanol with 99.92 percent of content is obtained at the tower bottom, wherein the methanol content of the tower bottom meets the use requirement of an epoxidation raw material.
Example 6
3m 3 Pumping 1200kg of distilled fraction from a methanol rectifying tower into a reaction kettle, wherein the distilled fraction comprises 99.25% of MA and 0.7% of AAL; adding 17.2kg of thionyl chloride into a reaction kettle with 0.05% of water, reacting for 1h at 55-58 ℃ and negative pressure of-0.12 kpa, and obtaining tail gas (the main component is SO) 2 And HCl) firstly passes through a chlorination condenser, then is pumped into an alkaline washing tower for absorption under negative pressure, the alkaline washing tower uses 5% sodium hydroxide solution for circulating absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 2.5, 11kg of chloropropene with the content of 99.38% is obtained at the top of the tower (the gas phase temperature is 43-44 ℃), the methanol with the content of 99.9% is obtained at the bottom of the tower, and the methanol content of the bottom of the tower meets the use requirement of an epoxidation raw material.
Example 7
3m 3 Pumping 1000kg of methanol rectifying tower to extract fraction with the composition of MA99.05% and AAL0.85%; adding 14.5kg of methyl chloroformate into a reaction kettle with 0.1% of water, reacting at 68-70 ℃ under negative pressure of-0.20 kpa for 0.5h, and obtaining tail gas (the main component is CO) 2 And HCl) firstly passes through a chlorination condenser, then is pumped into an alkaline washing tower for absorption under negative pressure, the alkaline washing tower uses 5% sodium hydroxide solution for cyclic absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 2.0, 10.5kg of chloropropene with the content of 99.29% is obtained at the top of the tower (the gas phase temperature is 43-44 ℃), the methanol with the content of 99.93% is obtained at the bottom of the tower, and the methanol content of the bottom of the tower meets the use requirement of an epoxidation raw material.
Example 8
3m 3 Pumping 1000kg of methanol rectifying tower to extract fraction with the composition of MA99.62% and AAL0.30%; adding 5.4kg of solid phosgene into a reaction kettle, reacting for 2 hours at 60-62 ℃ and negative pressure of-0.12 kpa, and obtaining tail gas (the main component is CO) 2 And HCl) is pumped into an alkaline washing tower for absorption by a chlorination condenser under negative pressure, the alkaline washing tower uses 5 percent sodium hydroxide solution for circulating absorption, the chlorination reaction liquid is rectified by a light component removal tower under normal pressure, the reflux ratio is 3.0, and the tower top (gas phase temperature)3.7kg of chloropropene with the content of 99.42 percent is obtained at the temperature of 43-44 ℃, and the methanol with the content of 99.9 percent is obtained at the tower kettle, wherein the methanol content of the tower kettle meets the use requirement of the epoxidation raw material.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modifications or equivalent substitutions made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (5)
1. A process for removing azeotropes from recovered methanol comprising the steps of: continuously pumping aqueous phase solution into a methanol rectifying tower, rectifying, and pumping fractions into a reaction kettle; adding a chlorinating agent into a reaction kettle for chlorination reaction, wherein the chlorinating agent is thionyl chloride, the reaction is carried out under micro negative pressure, and the condensed tail gas is absorbed by an alkaline washing tower; pumping a reaction liquid in a reaction kettle into a light component removal tower for rectification, obtaining chloropropene from the top of the tower, and obtaining recovered methanol from the tower kettle; the aqueous phase solution is produced by an epoxy chloropropane process by a hydrogen peroxide method, and comprises the following components: methanol: 10-30%; allyl alcohol: 0.25-1%; 1, 2-epoxy-3-methoxypropane: 0.15-1%; epichlorohydrin: 0.01-0.3%; the balance of water and trace organic impurities; the components of the fraction extracted from the methanol rectifying tower are as follows: allyl alcohol: 0.3-0.9%; water: 0.01-0.1%; the balance of methanol.
2. The method for removing and recovering an azeotrope from methanol as claimed in claim 1, wherein the chlorinating agent is used in an amount of 1 to 1.05 times the equivalent of allyl alcohol.
3. The method for removing azeotropes from recovered methanol according to claim 1, wherein said chlorination reaction conditions are: the reaction temperature is 55-70 ℃, the micro negative pressure is minus 0.2-minus 0.02kPa, and the reaction time is 0.5-2 hours.
4. The method for removing and recovering an azeotrope from methanol as claimed in claim 1, wherein the reflux ratio of the distillation of the light component removal column is 1 to 4.
5. The method for removing azeotropes from methanol as set forth in claim 1, wherein the alkaline washing tower uses 5% sodium hydroxide solution to circularly absorb tail gas.
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|---|---|---|---|---|
| US4899000A (en) * | 1989-01-27 | 1990-02-06 | Stauffer John E | Production of allyl chloride |
| JPH0733698A (en) * | 1993-07-22 | 1995-02-03 | Showa Denko Kk | Purification of 2,3-dichloro-1-propanol |
| CN1362942A (en) * | 2000-02-15 | 2002-08-07 | 昭和电工株式会社 | Process for production of allyl chloride |
| CN103664505A (en) * | 2013-12-24 | 2014-03-26 | 山东海益化工科技有限公司 | Chloropropene production technology |
| CN103980124A (en) * | 2014-05-09 | 2014-08-13 | 天津大学 | Synthetic method of diphenyl carbonate from propylene carbonate by catalysis of ionic liquid |
| CN111662178A (en) * | 2020-06-10 | 2020-09-15 | 湖南国发精细化工科技有限公司 | Method for synthesizing allyl chloroformate by phosgene method |
| CN111875478A (en) * | 2020-07-07 | 2020-11-03 | 江苏扬农化工集团有限公司 | Method for refining methanol recovered by epoxy chloropropane process by hydrogen peroxide method |
| CN112778080A (en) * | 2021-01-12 | 2021-05-11 | 江苏扬农化工集团有限公司 | Method for recovering 3-chloropropene from solution containing 3-chloropropene and methanol |
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