CN102351665A - Preparation method of methylal - Google Patents
Preparation method of methylal Download PDFInfo
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- CN102351665A CN102351665A CN2011102358370A CN201110235837A CN102351665A CN 102351665 A CN102351665 A CN 102351665A CN 2011102358370 A CN2011102358370 A CN 2011102358370A CN 201110235837 A CN201110235837 A CN 201110235837A CN 102351665 A CN102351665 A CN 102351665A
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Abstract
The invention relates to a preparation method of methylal. According to the invention, modified resin is adopted as a catalyst. Two technologies, which are an extractive distillation technology and a catalytic distillation technology are coupled into a distillation tower. Water or an aqueous solution of formaldehyde is adopted as an extractant, and a catalytic reaction is carried out. The extraction of a product and the separation of the extractant are completed in the same distillation tower. When the raw materials are sufficiently subject to the reaction, an azeotrope formed by methanol, methylal and a small amount of water is subject to extractive distillation in a distillation section. High-purity methylal is obtained by distilling from the tower top. Tower bottom liquid with s small amount of raw material residue is collected for unified processing. Compared to traditional methods, with the method provided by the present invention, extractant recovering processes are reduced, an operation procedure is greatly simplified, and a fixed cost is reduced. Also, high-purity methylal can be continuously produced, and raw material residue is greatly reduced. Therefore, the method is a green method for continuously producing high-purity methylal.
Description
Technical field:
The present invention relates to a kind of preparation method who prepares the high purity methylal.
Background technology:
Along with the continuous development of Coal Chemical Industry, be that the technology of raw material synthesizing methanol is ripe with the coal, methylal because of its good physicochemical performance, has very wide application prospect as one of most important derived product of methyl alcohol.Methylal oxidation can make high-concentration formaldehyde; Because methylal has good ability of cleaning greasy dirt and volatility; Can be used as sanitising agent and substitute F11, F13 and chlorinated solvents; Be replacement fluorine Lyons, reduce volatile organic matter (VOCSs) discharging, reduce brand-new environmentally friendly machine (Lin Bin topsoil; A new generation's environmentally friendly solvent-methylal, 2008); Methylal itself is a kind of oxygenated fuel, when using as diesel-dope, can obviously reduce the discharging of diesel engine nuisance; Add a certain amount of methylal in the methanol gasoline and can improve its low-temperature startup performance (Li Zhengqing, methyl alcohol a new generation derived product methylal, 2006).
The method of traditional synthesizing dimethoxym ethane is under the katalysis of the vitriol oil; Methyl alcohol and formaldehyde generation aldol reaction prepare; Because the methylal purity low (about 55%wt) that this method is prepared into, vitriolic corrosion cause facility investment to increase greatly and can produce a large amount of organic waste waters; Do not meet with the sustainable CHEMICAL DEVELOPMENT of current green, do not re-use gradually.In recent years, used solid acid catalyst, prepared the focus that methylal becomes research through catalytic distillation.But this method often can only make the methylal that purity is 85%-93%; And can form the azeotrope of methylal and methyl alcohol; Azeotrope consists of methylal 93%wt; Methyl alcohol 7%wt (Zhou Wei; The application of catalytic distillation in synthesizing dimethoxym ethane; 1998), so this technology also is difficult to obtain highly purified methylal.
Though use extraction and distillation technology can destroy the azeotropic balance of methyl alcohol and methylal; Improve the purity of methylal; For example select glycerin or terepthaloyl moietie to make extraction agent (Gu Zhenggui; CN1807378A; 2006), but this technology must dispose special extraction agent recovery tower, and cost of equipment is higher; Running cost is high, energy consumption is big, and schedule of operation is complicated.Therefore,, be necessary to develop a kind of can simplifying procedures, be lowered into the product cost, the catalyzer and the method thereof of green again preparation high purity methylal from industry practice.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of methylal; This method adopts modified resins as catalyzer; Extracting rectifying and two kinds of technologies of catalytic distillation are coupled in the rectifying tower; Select water or formaldehyde as extraction agent; Make catalyzed reaction; Being separated in the same rectifying tower of product extraction and extraction agent accomplished; After raw material fully reacts in tower; The azeotrope that methyl alcohol, methylal and less water form carries out extracting rectifying at rectifying section; The highly purified methylal of product distillates from cat head, has the residual tower bottoms of micro material to collect Unified Treatment.This method is compared with traditional method, has reduced the operation that extraction agent reclaims, and has simplified schedule of operation greatly, has reduced fixed cost; Realized continuous production high purity methylal simultaneously, and the remaining quantity of raw material significantly reducing, is a kind of method of continuous production high purity methylal of green.
The preparation method of a kind of methylal of the present invention, this method use modified resins as catalyzer, in catalytic distillation and rectifying tower device of extracting rectifying coupled, and catalysis methanol and prepared formaldehyde methylal, concrete operations follow these steps to carry out:
A, the resin after the modification is filled into rectifying tower (1) catalyst reaction section (3) as catalyzer locates; Be 1-5 with mol ratio again: 1 methyl alcohol and formaldehyde stock liquid get in the tower from catalyst reaction section (3); Extraction agent is that water or concentration are that the formalin of 0.5-37% gets in the tower from the rectifying section (2) of rectifying tower (1); The temperature of rectifying tower (1) cat head is 38-45 ℃; The temperature of rectifying tower (1) body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extraction agent and material benzenemethanol+formaldehyde is 0.1-5: 1;
B, material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section (2) under the catalysis of modified resin catalyst; Extraction agent is the methyl alcohol of the aqueous solution in rectifying section (2) extraction azeotrope of water or formaldehyde, destroys the azeotropic balance;
C, the non-azeotropic mixture in extraction back are purified at the rectifying section on extractant feed mouth top, and the product methylal after the purification distillates from cat head continuously, and the water that contains trace formaldehyde goes out from tower bottom flow, can obtain the methylal of purity 98-99%.
The mol ratio of step a methyl alcohol and formaldehyde raw material is 1.5-2.5: 1, and the volume ratio of extraction agent and material benzenemethanol+formaldehyde is 0.8-2.5: 1.
Modified resin catalyst repeatedly washes resin for using distilled water among the step a; Till the limpid nothing muddiness of the water that washes out, inclusion-free; Use concentration to be sodium hydroxide, yellow soda ash or ammoniacal liquor then as the alkaline solution of 5-20%; In ion exchange column, soaked 2-8 hour; Obtain the alkaline solution modified resins; Be washed till neutrality with a large amount of distilled water again; Use concentration to be hydrochloric acid, sulfuric acid or phosphoric acid drip washing 2-5 time as the acid solution of 5%-20%; Obtain the further modified resins of acid solution; Be washed till neutrality with distilled water again; Oven dry obtains the modified resins catalyzer.
The employed resin of step a modified resin catalyst is LSCA-30, D-001, LSA-10 type.
In the step a modified resin catalyst consumption of acid be the resin volume 1-5 doubly.
Step a rectifying tower device is catalytic distillation and extracting rectifying coupled rectifying tower (1); Be by the extracting rectifying section; Catalyst reaction section; Reboiler; The reboiler liquid outlet; The extractant feed mouth; Material inlet; Reflux ratio controller and condenser are formed; The aspect ratio of catalyst reaction section (3) and rectifying section (2) is 0.5-2: 1; The aspect ratio of catalyst reaction section (3) is 10-400: 1; The aspect ratio of rectifying section (2) is 5-15: 1; After mixing, catalyzer and the netted filler of Θ ring stainless steel fill in the catalyst reaction section (3) of tower; Rectifying section (2) is all loaded the netted filler of Θ ring stainless steel, and catalyst reaction section (3) temperature from top to bottom is a Gradient distribution.
The preparation method of a kind of methylal of the present invention, this method is compared with traditional method for preparing methylal, and the substantive distinguishing features that has is:
(1), equipment is simple, technical process is short, schedule of operation is simplified greatly;
(2), catalyzer, product separate easily with extraction agent, be convenient to amplify and industrial application;
(3), reduce production costs greatly, significantly reduced the remaining quantity of raw material simultaneously.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1:
At first use distilled water that the LSCA-30 resin is repeatedly washed; Be washed till till the limpid nothing muddiness of water outlet, the inclusion-free, the NaOH with 5% soaked in ion exchange column 4 hours, obtained the alkaline solution modified resins; Carry out drip washing to neutrality with deionized water again; Hydrochloric acid drip washing with 5% 3 times, the consumption of each acid is 3 times of resin volume, drains acid solution; Can be for use with clear water drip washing to neutrality; Be washed till neutrality with distilled water again, dry, obtain the LSCA-30 resin catalyst of modification;
The rectifying tower device is catalytic distillation and extracting rectifying coupled rectifying tower 1; Be by the extracting rectifying section; Catalyst reaction section; Reboiler; The reboiler liquid outlet; The extractant feed mouth; Material inlet; Reflux ratio controller and condenser are formed; The top of rectifying tower 1 is rectifying section 2; Its underpart is a catalyst reaction section 3; Be provided with opening for feed 6 in rectifying section 2 one sides; Be provided with opening for feed 7 in catalyst reaction section 3 one sides; Be provided with condenser 9 is connected with the reflux ratio controller 8 that is fixed on rectifying tower 1 top one side at the top of rectifying tower 1; Be provided with reboiler 4 in the bottom of rectifying tower 1; The aspect ratio of catalyst reaction section 3 and rectifying section 2 is 0.5-2: 1; The aspect ratio of catalyst reaction section 3 is 10-400: 1; The aspect ratio of rectifying section 2 is 5-15: 1; After mixing, catalyzer and the netted filler of Θ ring stainless steel fill in the catalyst reaction section 3 of tower; Rectifying section 2 is all loaded the netted filler of Θ ring stainless steel, and catalyst reaction section 3 temperature from top to bottom is a Gradient distribution;
LSCA-30 resin after the 150g modification is filled into rectifying tower 1 catalyst reaction section 3 as catalyzer from material inlet 7; Using volume pump is that 2.5: 1 methyl alcohol is squeezed in the catalyst reaction section 3 entering towers from opening for feed 7 with the speed of 60mL/h with the formaldehyde stock liquid continuously with mol ratio; With volume pump extraction agent water being squeezed into rectifying section 2 with the speed of 100mL/h from opening for feed 6 again gets in the tower; The temperature of rectifying tower 1 cat head is 38 ℃; The temperature of rectifying tower 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extraction agent and material benzenemethanol+formaldehyde is 0.1: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98% through rectifying tower 1 bottom.
At first use distilled water that the D-001 resin is repeatedly washed; It is muddy to be washed till the limpid nothing of water outlet; Till the inclusion-free; Using concentration is that 10% yellow soda ash soaked in ion exchange column 2 hours; Obtain the alkaline solution modified resins; Carry out drip washing to water outlet near neutral with a large amount of deionized waters again; Using concentration is 10% sulfuric acid drip washing 2 times; The consumption of each acid is 1 times of resin volume, obtains the further modified resins of acid solution, and then soaks in ion exchange column with 10% yellow soda ash; Use pickling again; 3 times repeatedly, use sour drip washing for the last time after, be washed till neutrality with distilled water again; Oven dry obtains D-001 modified resins catalyzer;
The rectifying tower device carries out according to embodiment 1;
D-001 resin after the 100g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 1: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 25% formalin is squeezed in the rectifying section 2 entering towers from charging aperture 6 with the speed of 100mL/h with measuring pump with extractant concentration again; The temperature of rectifying column 1 cat head is 40 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 0.5: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98.2% through rectifying tower 1 bottom.
Embodiment 3:
At first use distilled water that the LSA-10 resin is repeatedly washed; It is muddy to be washed till the limpid nothing of water outlet; Till the inclusion-free; Using concentration is that 15% ammoniacal liquor soaked in ion exchange column 6 hours; Obtain the alkaline solution modified resins; Carry out drip washing to water outlet near neutral with a large amount of deionized waters again; Using concentration is 15% phosphoric acid drip washing 4 times; The consumption of each acid is 4 times of resin volume, obtains the further modified resins of acid solution, and then soaks in ion exchange column with 15% ammoniacal liquor; Use pickling again; 3 times repeatedly, use sour drip washing for the last time after, be washed till neutrality with distilled water again; Oven dry obtains LSA-10 modified resins catalyzer;
The rectifying tower device carries out according to embodiment 1;
LSA-10 resin after the 150g modification is filled into rectifying tower 1 catalyst reaction section 3 as catalyzer from material inlet 7; Using volume pump is that 1.5: 1 methyl alcohol is squeezed in the catalyst reaction section 3 entering towers from opening for feed 7 with the speed of 60mL/h with the formaldehyde stock liquid continuously with mol ratio; With volume pump extraction agent water being squeezed into rectifying section 2 with the speed of 100mL/h from opening for feed 6 again gets in the tower; The temperature of rectifying tower 1 cat head is 42 ℃; The temperature of rectifying tower 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extraction agent and material benzenemethanol+formaldehyde is 1: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 99% through rectifying tower 1 bottom.
Embodiment 4
At first use distilled water that the LSCA-30 resin is repeatedly washed; Be washed till till the limpid nothing muddiness of water outlet, the inclusion-free, the yellow soda ash with 20% soaked in ion exchange column 7 hours, obtained the alkaline solution modified resins; Carry out drip washing to neutrality with deionized water again; Sulfuric acid drip washing with 20% 3 times, the consumption of each acid is 5 times of resin volume, drains acid solution; Can be for use with clear water drip washing to neutrality; Be washed till neutrality with distilled water again, dry, obtain the LSCA-30 resin catalyst of modification;
The rectifying tower device carries out according to embodiment 1;
LSCA-30 resin after the 150g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 3.5: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 0.5% formalin is squeezed into rectifying section 2 with the speed of 100mL/h from charging aperture 6 and got in the towers with extractant concentration with measuring pump again; The temperature of rectifying column 1 cat head is 45 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 3: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98.5% through rectifying tower 1 bottom.
At first use distilled water that the D-001 resin is repeatedly washed; It is muddy to be washed till the limpid nothing of water outlet; Till the inclusion-free; Using concentration is that 18% NaOH soaked in ion exchange column 3 hours; Obtain the alkaline solution modified resins; Carry out drip washing to water outlet near neutral with a large amount of deionized waters again; Using concentration is 18% hydrochloric acid drip washing 5 times; The consumption of each acid is 2 times of resin volume, obtains the further modified resins of acid solution, and then soaks in ion exchange column with 18% NaOH; Use pickling again; 3 times repeatedly, use sour drip washing for the last time after, be washed till neutrality with distilled water again; Oven dry obtains D-001 modified resins catalyzer;
The rectifying tower device carries out according to embodiment 1;
D-001 resin after the 100g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 5: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 15% formalin is squeezed in the rectifying section 2 entering towers from charging aperture 6 with the speed of 100mL/h with measuring pump with extractant concentration again; The temperature of rectifying column 1 cat head is 43 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 5: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98.6% through rectifying tower 1 bottom.
At first use distilled water that the LSA-10 resin is repeatedly washed; It is muddy to be washed till the limpid nothing of water outlet; Till the inclusion-free; Using concentration is that 12% yellow soda ash soaked in ion exchange column 4 hours; Obtain the alkaline solution modified resins; Carry out drip washing to water outlet near neutral with a large amount of deionized waters again; Using concentration is 12% sulfuric acid drip washing 5 times; The consumption of each acid is 2.5 times of resin volume, obtains the further modified resins of acid solution, and then soaks in ion exchange column with 12% yellow soda ash; Use pickling again; 3 times repeatedly, use sour drip washing for the last time after, be washed till neutrality with distilled water again; Oven dry obtains LSA-10 modified resins catalyzer;
The rectifying tower device carries out according to embodiment 1;
LSA-10 resin after the 150g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 5: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 30% formalin is squeezed into rectifying section 2 with the speed of 100mL/h from charging aperture 6 and got in the towers with extractant concentration with measuring pump again; The temperature of rectifying column 1 cat head is 39 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 0.8: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98.7% through rectifying tower 1 bottom.
At first use distilled water that the D-001 resin is repeatedly washed; It is muddy to be washed till the limpid nothing of water outlet; Till the inclusion-free; Using concentration is that 8% ammoniacal liquor soaked in ion exchange column 2.5 hours; Obtain the alkaline solution modified resins; Carry out drip washing to water outlet near neutral with a large amount of deionized waters again; Using concentration is 8% phosphoric acid drip washing 5 times; The consumption of each acid is 3.5 times of resin volume, obtains the further modified resins of acid solution, and then soaks in ion exchange column with 8% ammoniacal liquor; Use pickling again; 3 times repeatedly, use sour drip washing for the last time after, be washed till neutrality with distilled water again; Oven dry obtains D-001 modified resins catalyzer;
The rectifying tower device carries out according to embodiment 1;
D-001 resin after the 120g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 3.5: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 35% formalin is squeezed in the rectifying section 2 entering towers from charging aperture 6 with the speed of 100mL/h with measuring pump with extractant concentration again; The temperature of rectifying column 1 cat head is 45 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 2.5: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98.1% through rectifying tower 1 bottom.
At first use distilled water that the LSA-10 resin is repeatedly washed; It is muddy to be washed till the limpid nothing of water outlet; Till the inclusion-free; Using concentration is that 10% NaOH soaked in ion exchange column 4.5 hours; Obtain the alkaline solution modified resins; Carry out drip washing to water outlet near neutral with a large amount of deionized waters again; Using concentration is 10% hydrochloric acid drip washing 3 times; The consumption of each acid is 4.5 times of resin volume, obtains the further modified resins of acid solution, and then soaks in ion exchange column with 10% NaOH; Use pickling again; 3 times repeatedly, use sour drip washing for the last time after, be washed till neutrality with distilled water again; Oven dry obtains LSA-10 modified resins catalyzer;
The rectifying tower device carries out according to embodiment 1;
LSA-10 resin after the 150g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 3.5: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 10% formalin is squeezed into rectifying section 2 with the speed of 100mL/h from charging aperture 6 and got in the towers with extractant concentration with measuring pump again; The temperature of rectifying column 1 cat head is 38 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 1.5: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 99% through rectifying tower 1 bottom.
At first use distilled water that the LSCA-30 resin is repeatedly washed; Be washed till till the limpid nothing muddiness of water outlet, the inclusion-free, the ammoniacal liquor with 10% soaked in ion exchange column 4 hours, obtained the alkaline solution modified resins; Carry out drip washing to neutrality with deionized water again; Hydrochloric acid drip washing with 10% 4 times, the consumption of each acid is 2 times of resin volume, drains acid solution; Can be for use with clear water drip washing to neutrality; Be washed till neutrality with distilled water again, dry, obtain the LSCA-30 resin catalyst of modification;
The rectifying tower device carries out according to embodiment 1;
LSCA-30 resin after the 120g modification is filled into rectifying column 1 catalyst reaction section 3 as catalyst from material inlet 7; Be that 1.5: 1 methyl alcohol and formaldehyde material liquid squeezed into catalyst reaction section 3 from charging aperture 7 continuously with the speed of 60mL/h and got in the towers with measuring pump with mol ratio; Be that 37% formalin is squeezed into rectifying section 2 with the speed of 100mL/h from charging aperture 6 and got in the towers with extractant concentration with measuring pump again; The temperature of rectifying column 1 cat head is 45 ℃; The temperature of rectifying column 1 body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extractant and material benzenemethanol+formaldehyde is 5: 1;
Material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section 2 under the catalysis of modified resin catalyst, extraction agent is the methyl alcohol of water in rectifying section 2 extraction azeotropes, destruction azeotropic balance;
The non-azeotropic mixture in extraction back is purified at the rectifying section 2 on extractant feed mouth 6 tops; Product methylal after the purification flows out than controller 8 from trim the top of column continuously; Contain of reboiler 4 outflows of the water of trace formaldehyde, can obtain the methylal of purity 98.5% through rectifying tower 1 bottom.
Claims (6)
1. the preparation method of a methylal is characterized in that using modified resins as catalyzer, in catalytic distillation and rectifying tower device of extracting rectifying coupled, and catalysis methanol and prepared formaldehyde methylal, concrete operations follow these steps to carry out:
A, the resin after the modification is filled into rectifying tower (1) catalyst reaction section (3) as catalyzer locates; Be 1-5 with mol ratio again: 1 methyl alcohol and formaldehyde stock liquid get in the tower from catalyst reaction section (3); Extraction agent is that water or concentration are that the formalin of 0.5-37% gets in the tower from the rectifying section (2) of rectifying tower (1); The temperature of rectifying tower (1) cat head is 38-45 ℃; The temperature of rectifying tower (1) body of the tower is reduced to 98-38 ℃ from top to bottom gradually, and wherein the volume ratio of extraction agent and material benzenemethanol+formaldehyde is 0.1-5: 1;
B, material benzenemethanol and formaldehyde react the methylal that generates and methyl alcohol and form azeotrope and move up and get into rectifying section (2) under the catalysis of modified resin catalyst; Extraction agent is the methyl alcohol of the aqueous solution in rectifying section (2) extraction azeotrope of water or formaldehyde, destroys the azeotropic balance;
C, the non-azeotropic mixture in extraction back are purified at the rectifying section on extractant feed mouth top, and the product methylal after the purification distillates from cat head continuously, and the water that contains trace formaldehyde goes out from tower bottom flow, can obtain the methylal that purity is 98-99%.
2. method according to claim 1, the mol ratio that it is characterized in that step a methyl alcohol and formaldehyde raw material is 1.5-2.5: 1, the volume ratio of extraction agent and material benzenemethanol+formaldehyde is 0.8-2.5: 1.
3. method according to claim 2; It is characterized in that modified resin catalyst repeatedly washes resin for using distilled water among the step a; Muddy until the limpid nothing of the water that washes out; Till the inclusion-free; Use concentration to be sodium hydroxide then as the alkaline solution of 5-20%; Yellow soda ash or ammoniacal liquor; In ion exchange column, soaked 2-8 hour; Obtain the alkaline solution modified resins; Be washed till neutrality with a large amount of distilled water again; Use concentration to be hydrochloric acid as the acid solution of 5%-20%; Sulfuric acid or phosphoric acid drip washing 2-5 time; Obtain the further modified resins of acid solution; Be washed till neutrality with distilled water again, oven dry obtains the modified resins catalyzer.
4. method according to claim 3 is characterized in that the employed resin of step a modified resin catalyst is LSCA-30, D-001, LSA-10 type.
5. method according to claim 4, the consumption that it is characterized in that acid in the step a modified resin catalyst are 1-5 times of resin volume.
6. method according to claim 1; It is characterized in that step a rectifying tower device is catalytic distillation and extracting rectifying coupled rectifying tower (1); Be by the extracting rectifying section; Catalyst reaction section; Reboiler; The reboiler liquid outlet; The extractant feed mouth; Material inlet; Reflux ratio controller and condenser are formed; The aspect ratio of catalyst reaction section (3) and rectifying section (2) is 0.5-2: 1; The aspect ratio of catalyst reaction section (3) is 10-400: 1; The aspect ratio of rectifying section (2) is 5-15: 1; After mixing, catalyzer and the netted filler of Θ ring stainless steel fill in the catalyst reaction section (3) of tower; Rectifying section (2) is all loaded the netted filler of Θ ring stainless steel, and catalyst reaction section (3) temperature from top to bottom is a Gradient distribution.
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| CN102627536A (en) * | 2012-03-23 | 2012-08-08 | 济南大学 | Batch extractive distillation separation method of methylal-methanol azeotropic mixture |
| CN103664551A (en) * | 2013-12-03 | 2014-03-26 | 惠州市利而安化工有限公司 | Synthesis method of methylal |
| CN107986947A (en) * | 2017-12-28 | 2018-05-04 | 四川鑫达新能源科技有限公司 | A kind of dimethoxym ethane heat integration synthesis system and preparation method |
| CN108424358A (en) * | 2018-05-22 | 2018-08-21 | 凯瑞环保科技股份有限公司 | A kind of device and method producing high-purity dimethoxym ethane using catalytic distillation coupling technique |
| CN108640823A (en) * | 2018-05-04 | 2018-10-12 | 南京师范大学 | A kind of device of recycling technical grade diethoxymethane and its method of recycling |
| CN109851483A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of extraction catalytic rectification method preparing dimethoxym ethane |
| CN111454135A (en) * | 2020-04-26 | 2020-07-28 | 青岛迈特达新材料有限公司 | Device and process for preparing high-concentration methylal |
| CN111909011A (en) * | 2020-07-13 | 2020-11-10 | 北洋国家精馏技术工程发展有限公司 | Separation process of polymethoxy dimethyl ether system containing formaldehyde, methanol and water |
| CN111909010A (en) * | 2020-07-13 | 2020-11-10 | 天津大学 | Method and device for separating methylal in polymethoxy dimethyl ether system |
| CN115260147A (en) * | 2022-08-22 | 2022-11-01 | 凯瑞环保科技股份有限公司 | Process device and method for synthesizing dioxolane by using extractive catalytic distillation |
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| CN102627536B (en) * | 2012-03-23 | 2014-07-09 | 济南大学 | Batch extractive distillation separation method of methylal-methanol azeotropic mixture |
| CN102627536A (en) * | 2012-03-23 | 2012-08-08 | 济南大学 | Batch extractive distillation separation method of methylal-methanol azeotropic mixture |
| CN103664551A (en) * | 2013-12-03 | 2014-03-26 | 惠州市利而安化工有限公司 | Synthesis method of methylal |
| CN109851483A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of extraction catalytic rectification method preparing dimethoxym ethane |
| CN109851483B (en) * | 2017-11-30 | 2020-08-07 | 中国科学院大连化学物理研究所 | Extraction catalytic rectification method for preparing methylal |
| CN107986947A (en) * | 2017-12-28 | 2018-05-04 | 四川鑫达新能源科技有限公司 | A kind of dimethoxym ethane heat integration synthesis system and preparation method |
| CN108640823A (en) * | 2018-05-04 | 2018-10-12 | 南京师范大学 | A kind of device of recycling technical grade diethoxymethane and its method of recycling |
| CN108424358A (en) * | 2018-05-22 | 2018-08-21 | 凯瑞环保科技股份有限公司 | A kind of device and method producing high-purity dimethoxym ethane using catalytic distillation coupling technique |
| CN108424358B (en) * | 2018-05-22 | 2023-12-26 | 凯瑞环保科技股份有限公司 | Device and method for producing high-purity methylal by utilizing catalytic distillation coupling technology |
| CN111454135A (en) * | 2020-04-26 | 2020-07-28 | 青岛迈特达新材料有限公司 | Device and process for preparing high-concentration methylal |
| CN111454135B (en) * | 2020-04-26 | 2022-11-04 | 青岛迈特达新材料有限公司 | Device and process for preparing high-concentration methylal |
| CN111909011A (en) * | 2020-07-13 | 2020-11-10 | 北洋国家精馏技术工程发展有限公司 | Separation process of polymethoxy dimethyl ether system containing formaldehyde, methanol and water |
| CN111909010A (en) * | 2020-07-13 | 2020-11-10 | 天津大学 | Method and device for separating methylal in polymethoxy dimethyl ether system |
| CN115260147A (en) * | 2022-08-22 | 2022-11-01 | 凯瑞环保科技股份有限公司 | Process device and method for synthesizing dioxolane by using extractive catalytic distillation |
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