CN102351666A - Method for continuous production of high-concentration methylal - Google Patents
Method for continuous production of high-concentration methylal Download PDFInfo
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- CN102351666A CN102351666A CN2011102747631A CN201110274763A CN102351666A CN 102351666 A CN102351666 A CN 102351666A CN 2011102747631 A CN2011102747631 A CN 2011102747631A CN 201110274763 A CN201110274763 A CN 201110274763A CN 102351666 A CN102351666 A CN 102351666A
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Abstract
The invention relates to a method for continuous production of high-concentration methylal. The method is characterized by adopting methanol and formaldehyde for feeding respectively, controlling the content of each of formaldehyde and the methanol in each reactor and enabling the lowermost side reactor to adopt the process of enabling reactants of feed material of an upper-stage column plate to enter a lower-stage column plate; and the method comprises the following steps: a) a reaction rectification column is a packed column, formaldehyde is fed at the upper part of the reaction section, and methanol is fed through an inlet of the uppermost side reactor and the inlet of the lowermost side reactor; b) the reaction temperature of the side reactors is 60-80 DEG C from top to bottom, and liquid-phase reaction is performed on methanol and formaldehyde in the reactors to generate methylal; c) except for the lowermost side reactor, each reactor adopts the way of enabling extracted liquid from the lower-stage column plate of the rectification column to enter the reactor, and enabling reactor products to enter the upper-stage column plate of the rectification column; d) the lowermost side reactor adopts the way of enabling the extracted liquid from the upper-stage column plate of the rectification column to enter the reactor and enabling the reaction products to enter the lower-stage column plate of the rectification column; and e) the gas phase at the top of the column is condensed, then part of the condensed gas phase refluxes into the rectification column, and the other part of the condensed gas phase is extracted and introduced into a methylal intermediate storage tank; and liquid discharged from a column kettle is returned into a formaldehyde preparation unit for recycling or discharged after the liquid is treated to achieve the standard.
Description
Technical field
The present invention relates to technical field of organic synthesis, be a kind of method of continuous production high density methylal; Especially a kind of technique for synthesizing methylal of utilizing catalytic rectifying tower for reaction unit.
Background of invention
Methylal is as a kind of important derived product of formaldehyde, and its working method and utilisation technology are all in constantly development and perfect.Especially today of being becoming tight in petroleum resources day; Methylal is as one of the important derived prods in methyl alcohol downstream; Except that as the solvent, be widely used in fields such as methanol-based fuel, oil dope, fuel cell and liquid fuel, all caused extensive concern both domestic and external.
Laboratory initial preparation methylal is that formaldehyde, methyl alcohol add thermal synthesis in the presence of liquid acid such as the vitriol oil.The industrial making method of methylal mainly comprises with the vitriol oil to be methyl alcohol and the formaldehyde liquid phase condensation method of catalyzer and to be the reaction rectification method of catalyzer with the storng-acid cation exchange resin.As far back as 1993, it was catalyzer that company of Asahi Chemical Industry just proposes in patent CN1020450C with macropore or gel type cation exchange resin, and it is seated in the auxiliary reactor, and the method through reactive distillation is the raw material synthesizing dimethoxym ethane with methyl alcohol, formaldehyde solution.After this, the lot of domestic and foreign researchers are studied synthesizing dimethoxym ethane technology and catalyzer.Proposing with HZSM-5 like CN 1301688A is catalyzer, and methyl alcohol and formalin are the method for prepared in reaction methylal under 20～100 ℃ the condition in temperature in batch reactor.CN101857533A proposes with SO
4 -/ SnO-ZrO
2-γ-Al
2O
3The method of producing methylal by composite solid-acid catalyst.Comprehensively it seems; Liquid phase condensation method production methylal is simple to operate, reaction conditions is gentle; But the vitriol oil as catalyzer all gets in the reaction solution; Be difficult for separating from product; The acid of trace also can make product decompose, and produce a large amount of acid-bearing wastewater contaminate environment simultaneously, and methylal content only is 85%～90% (massfraction); Therefore, this method will be eliminated gradually.In the reaction rectification method, adopt the solid acid as catalyst, water insoluble; The preparation of product is carried out with separating simultaneously; Reduced follow-up separating device, reduced equipment investment cost, simultaneously; Solid acid can be recycled; Also significantly reduced production cost, and the purity of the methylal that makes of this method is high, it is few to produce waste water; Therefore, reaction rectification method has become the major industry working method of synthesizing dimethoxym ethane.
Present reaction rectification method synthesizing dimethoxym ethane mainly comprises two kinds of tower (tradition) catalytic reaction rectification and auxiliary reactor formula catalytic reaction rectifications.The conventional catalyst rectification method is that catalyst loading is loaded in mixture on the rectifying tower sieve tray or with filler, will react with separating to be coupling in the tower and carry out, and has high-conversion rate, less energy-consumption, easy to operate, advantage that investment of devices is few.But also there is comparatively significantly inferior position in this method: sieve-tray tower then catalyzer is prone to cause catalyzer to contact insufficient reactivity worth decline with reaction medium; Then to tie up packet technology not perfect because of the catalyzer that uses body series for packing tower, perishable damage.Auxiliary reactor formula catalytic reaction rectification method is that catalyzer is placed the outer reactor of tower; Adopt pipeline that neighbouring or alternate column plate is imported and exported the clustered aggregates that links to each other with reactor; This method reaction efficiency is up to 70% of traditional reaction fractionating tower, and formaldehyde and methanol content are higher in the tower still liquid effluent.The main inferior position of this method is: reaction efficiency is low, and material loss is high, and formaldehyde, methyl alcohol exceed standard and are difficult to and handles in the waste water.
Be subjected to methyl alcohol-methylal-formaldehyde-steam liquid balance influence, adopt above-mentioned two kinds of reaction fractionating towers be difficult to not only to control methylal concentration be higher than 98% but also simultaneously the control tower still get rid of in the liquid formaldehyde and methanol content less than 200ppm.Formaldehyde and methanol content are carried methylal dense to more than 98% through azeotropic distillation less than 200ppm (this moment, cat head methylal content 85～90%) again in the current technology employing methyl alcohol overflow method control catalytic rectifying tower tower still eliminating liquid.Its equipment synoptic diagram is seen accompanying drawing 1.
Summary of the invention
The problem that the present invention will solve is: solve preparation high density methylal and need pass through catalytic reaction rectification and azeotropic distillation twice technology; Only just can synthesize 98% methylal through catalytic reaction rectification, and in the assurance tower still liquid effluent formaldehyde and methanol content less than 200ppm.
The present invention is a kind of method of continuous production high density methylal, it is characterized in that:
Adopt methyl alcohol, formaldehyde charging respectively, control formaldehyde, methanol content in each reactor, a bottom auxiliary reactor adopts higher level's column plate feed reactants to get into subordinate's column plate technology; Concrete processing step is following:
A. reaction fractionating tower is a packing tower, adopts formaldehyde in the charging of conversion zone top, and methyl alcohol is auxiliary reactor import and bottom auxiliary reactor inlet feed in the top;
B. the auxiliary reactor temperature of reaction is 60～80 ℃ from top to bottom, and methyl alcohol and formaldehyde carry out liquid phase reaction and generates methylal in reactor;
C. except that bottom auxiliary reactor, all adopt rectifying tower subordinate column plate Extract to get into reactor, reaction product gets into rectifying tower higher level column plate;
D. bottom auxiliary reactor adopts rectifying tower higher level column plate Extract to get into reactor, and reaction product gets into rectifying tower subordinate column plate;
E. the cat head gas phase is partly refluxed in the rectifying tower after condensation, and the methylal relay tank is advanced in all the other extraction; Tower still liquid effluent returns the prepared formaldehyde unit and recycles or handle back up to standard discharging.
According to the method described in the present invention, it is characterized in that:
A) auxiliary reactor A temperature of reaction is 60～62 ℃, 65～70 ℃ of auxiliary reactor B temperature of reaction, 70～75 ℃ of auxiliary reactor C temperature of reaction;
B) methyl alcohol mole of feed amount is 1.95～2.05: 1 with the ratio of formaldehyde mole of feed amount;
C) 40% of the methyl alcohol total feed get into auxiliary reactor A import, all the other 60% entering auxiliary reactor C imports;
D) 37～38 ℃ of trim the top of column section temperature, 101～102 ℃ of tower stills, control of reflux ratio are 5: (2～3);
E) in the tower still liquid effluent formaldehyde, methanol content less than 200ppm.
A kind of device of realizing above-mentioned processing step by: rectifying tower, auxiliary reactor, condenser, recycle pump and storage tank are formed.Rectifying tower inside comprises from bottom to top: tower still, reboiler, stripping section, conversion zone, rectifying section, condenser and reflux.Stripping section, conversion zone and rectifying section are filled Stainless Steel Helices; The rectifying section outlet connects condenser, phlegma part extraction partial reflux; Auxiliary reactor is a calandria type fixed bed reactor, adopts the chuck heating in water bath, is installed in the rectifying tower outside, and its import and export have pipeline to be connected with the distillation column reactor section.
Described Stainless Steel Helices can be structured packing commonly used or dumped packing.
Described catalyzer is highly acidic resin or solid acid catalyst.
Beneficial effect of the present invention is embodied in following 2 points:
1. methyl alcohol and formaldehyde separate charging.Control formaldehyde, water, methyl alcohol and the concentration distribution of methylal in rectifying tower finally form methylal-water azeotropic system, preparation high density methylal.
Methyl alcohol mole of feed amount is 1.8～2.2: 1 with the ratio of formaldehyde mole of feed amount, preferred 1.95～2.05: 1.
Formaldehyde is positioned at the conversion zone top at the higher position of rectifying tower; Can utilize the azeotropic system (methylal: methyl alcohol=93: 7) of methylal-methyl alcohol in the water destruct rectifying tower in the formaldehyde solution; Form methylal-water azeotropic system (methylal: water=99: 1) replace methylal-methanol azeotropic system, thereby improve cat head methylal concentration.
Methanol feeding is divided into two-way: top-down first auxiliary reactor of auxiliary reactor extraction mouth and last auxiliary reactor; First auxiliary reactor methanol feeding amount accounts for methyl alcohol total feed 20～50%, preferred 30～40%; Last auxiliary reactor methanol feeding amount accounts for 50～80% of methyl alcohol total feed, preferred 60～70%.
2. rectifying tower from top to bottom last auxiliary reactor be: rectifying tower higher level column plate Extract gets into reactor, and reaction product gets into the rectifying tower Ta Jie of subordinate.Utilizing the people is that the methyl alcohol higher concentration that causes distributes, and improves the transformation efficiency of formaldehyde in the reactor, to reach the purpose that reduces tower still formaldehyde content.
Description of drawings
The present invention is further specified with embodiment below in conjunction with accompanying drawing 2.
Fig. 1 is an auxiliary reactor formula catalytic rectifying tower structural representation commonly used at present: 1-rectifying section, 2-conversion zone, 3-stripping section, 4-condenser, 5-methylal relay tank, 6-reboiler, 7-head tank, A, B, C---auxiliary reactor.
Fig. 2 is a catalytic rectifying tower structural scheme of mechanism of the present invention: 1-rectifying section, 2-conversion zone, 3-stripping section, 4-condenser, 5-methylal relay tank, 6-reboiler, 7-methanol feedstock jar, 8-formaldehyde head tank, A, B, C---auxiliary reactor.
Auxiliary reactor is 3 but be not limited only to 3 among Fig. 1 and Fig. 2, can increase according to the needs of producing.
Embodiment and embodiment
Combine 2 couples of the present invention of accompanying drawing to explain further details at present.This figure is the synoptic diagram of simplifying, and the basic technology structure of the inventive method only is described with the mode of signal, only shows that therefore the equipment relevant with the inventive method constitutes.
Methylal production equipment shown in accompanying drawing 2 is made up of rectifying tower, auxiliary reactor, condenser, recycle pump and storage tank.
Rectifying tower inside comprises from bottom to top: tower still, reboiler, stripping section, conversion zone, rectifying section, condenser and reflux.Stripping section, conversion zone and rectifying section are filled Stainless Steel Helices; The rectifying section outlet connects condenser, phlegma part extraction partial reflux; Auxiliary reactor is a calandria type fixed bed reactor, adopts the chuck heating in water bath, is installed in the rectifying tower outside, and its import and export have pipeline to be connected with the distillation column reactor section.
The formaldehyde solution opening for feed is between conversion zone and rectifying section, and the concentration of formaldehyde solution can be controlled between 10～37%.Formaldehyde solution, fully contacts with gas phase in the rectifying tower after volume pump is squeezed into rectifying tower through suitable preheating.
The methanol feeding mouth has two, lays respectively at the import of auxiliary reactor A and auxiliary reactor C.Auxiliary reactor A import methanol feeding amount accounts for 30～40% of methyl alcohol total feed; Make the ratio of formaldehyde molar weight and methyl alcohol molar weight among the auxiliary reactor A greater than 2; Can promote that methyl alcohol transforms fully; Reduce methanol content in the rectifying section gas phase; Reduce the trend that forms methylal-methanol azeotropic, help improving the purity of cat head methylal.
Auxiliary reactor A and B adopt subordinate's column plate to extract out; Return the Recycle design of higher level's column plate after the reaction; The product methylal was effectively separated, helped unreacted formaldehyde and methyl alcohol again and repeatedly get in the auxiliary reactor and react, improve the transformation efficiency of methyl alcohol and formaldehyde.
Auxiliary reactor C adopts higher level's column plate to extract out, the Recycle design that the reaction back gets into adjacent next stage column plate.Simultaneously, the methyl alcohol that accounts for total feed 60～70% is introduced from Reactor inlet, improves methyl alcohol and formaldehyde mole ratio among the auxiliary reactor C, and formaldehyde is almost all transformed, and helps reducing formaldehyde content in the tower still liquid effluent.
The filler that rectifying tower uses can be structured packing commonly used.
Industrial methanol and formaldehyde solution 1.95～2.05 ratio are in molar ratio used the volume pump charging respectively; 40% of methanol feeding amount gets into auxiliary reactor A import, all the other 60% entering auxiliary reactor C imports.
Auxiliary reactor A temperature of reaction is 60～62 ℃, 65～70 ℃ of auxiliary reactor B temperature of reaction, 70～75 ℃ of auxiliary reactor C temperature of reaction; 37～38 ℃ of trim the top of column section temperature, 101～102 ℃ of tower stills, control of reflux ratio are 5: (2～3).
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 12.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 18.1Kg/h simultaneously with volume pump; 37 ℃ of trim the top of column section controlled temperature, 102 ℃ of tower still controlled temperature, reflux ratio is 5: 1.
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 12.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 18.1Kg/h simultaneously with volume pump; 38 ℃ of trim the top of column section controlled temperature, 102 ℃ of tower still controlled temperature, reflux ratio is 5: 1.
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 12.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 18.1Kg/h simultaneously with volume pump; 37 ℃ of trim the top of column section controlled temperature, 102 ℃ of tower still controlled temperature, reflux ratio is 5: 2.
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 12.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 18.1Kg/h simultaneously with volume pump; 37 ℃ of trim the top of column section controlled temperature, 102 ℃ of tower still controlled temperature, reflux ratio is 5: 3.
Comparative example 1
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 12.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 18.1Kg/h simultaneously with volume pump; 39 ℃ of trim the top of column section controlled temperature, 102 ℃ of tower still controlled temperature, reflux ratio is 5: 1.
Comparative example 2
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 12.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 18.1Kg/h simultaneously with volume pump; 37 ℃ of trim the top of column section controlled temperature, 95 ℃ of tower still controlled temperature, reflux ratio is 5: 1.
Comparative example 3
Industrial formol solution with 37% is preheating to 40 ℃, joins reaction fractionating tower formaldehyde opening for feed with volume pump with 75.7Kg/h speed; 99% industrial methanol is preheating to 40 ℃, joins auxiliary reactor A ingress methanol feeding mouth with the speed of 15.1Kg/h, join auxiliary reactor C ingress methanol feeding mouth with volume pump with the speed of 15.1Kg/h simultaneously with volume pump; 37 ℃ of trim the top of column section controlled temperature, 102 ℃ of tower still controlled temperature, reflux ratio is 5: 1.
Reaction result is listed in table 1.
The reaction result of table 1 preparation methylal
| Catalyzer | Methylal concentration (%) | Tower still formaldehyde (ppm) | Tower still methyl alcohol (ppm) |
| |
98.7 | 120 | 20 |
| |
98.1 | 122 | 20 |
| |
98.5 | 120 | 22 |
| |
98.3 | 123 | 22 |
| Comparative example 1 | 97.5 | 122 | 25 |
| Comparative example 2 | 96.5 | 150 | 65 |
| Comparative example 3 | 95.3 | 158 | 67 |
Claims (2)
1. the method for a continuous production high density methylal is characterized in that:
Adopt methyl alcohol, formaldehyde charging respectively, control formaldehyde, methanol content in each reactor, a bottom auxiliary reactor adopts higher level's column plate feed reactants to get into subordinate's column plate technology; Concrete processing step is following:
A. reaction fractionating tower is a packing tower, adopts formaldehyde in the charging of conversion zone top, and methyl alcohol is auxiliary reactor import and bottom auxiliary reactor inlet feed in the top;
B. the auxiliary reactor temperature of reaction is 60～80 ℃ from top to bottom, and methyl alcohol and formaldehyde carry out liquid phase reaction and generates methylal in reactor;
C. except that bottom auxiliary reactor, all adopt rectifying tower subordinate column plate Extract to get into reactor, reaction product gets into rectifying tower higher level column plate;
D. bottom auxiliary reactor adopts rectifying tower higher level column plate Extract to get into reactor, and reaction product gets into rectifying tower subordinate column plate;
E. the cat head gas phase is partly refluxed in the rectifying tower after condensation, and the methylal relay tank is advanced in all the other extraction; Tower still liquid effluent returns the prepared formaldehyde unit and recycles or handle back up to standard discharging.
2. according to the described method of claim 1, it is characterized in that:
A) auxiliary reactor A temperature of reaction is 60～62 ℃, 65～70 ℃ of auxiliary reactor B temperature of reaction, 70～75 ℃ of auxiliary reactor C temperature of reaction;
B) methyl alcohol mole of feed amount is 1.95～2.05: 1 with the ratio of formaldehyde mole of feed amount;
C) 40% of the methyl alcohol total feed get into auxiliary reactor A import, all the other 60% entering auxiliary reactor C imports;
D) 37～38 ℃ of trim the top of column section temperature, 101～102 ℃ of tower stills, control of reflux ratio are 5: [2～3];
E) in the tower still liquid effluent formaldehyde, methanol content less than 200ppm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669452A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for preparing methyl formate and coproducing dimethyl ether |
| CN107686745A (en) * | 2017-09-26 | 2018-02-13 | 丹东明珠特种树脂有限公司 | A kind of Etherification of Light FCC Gasoline system and its Etherification of Light FCC Gasoline process |
| CN109173310A (en) * | 2018-08-29 | 2019-01-11 | 张家港市科华化工装备制造有限公司 | Dimethoxym ethane rectifying column |
| CN111807940A (en) * | 2020-07-21 | 2020-10-23 | 安徽金轩科技有限公司 | Method for recycling waste methanol in galaxolide production |
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| CN1036755A (en) * | 1988-02-03 | 1989-11-01 | 旭化成工业株式会社 | The method for preparing formaldehyde and derivative thereof |
| US6379507B1 (en) * | 1998-08-03 | 2002-04-30 | Asahi Kasei Kabushiki Kaisha | Process for producing methylal |
| CN101863746A (en) * | 2010-04-01 | 2010-10-20 | 江苏恒茂机械制造有限公司 | Dimethoxymethane production process and device thereof |
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| CN1036755A (en) * | 1988-02-03 | 1989-11-01 | 旭化成工业株式会社 | The method for preparing formaldehyde and derivative thereof |
| US6379507B1 (en) * | 1998-08-03 | 2002-04-30 | Asahi Kasei Kabushiki Kaisha | Process for producing methylal |
| CN101863746A (en) * | 2010-04-01 | 2010-10-20 | 江苏恒茂机械制造有限公司 | Dimethoxymethane production process and device thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669452A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for preparing methyl formate and coproducing dimethyl ether |
| CN105669452B (en) * | 2014-11-17 | 2018-08-24 | 中国科学院大连化学物理研究所 | A method of preparing methyl formate combined producing dimethyl ether |
| CN107686745A (en) * | 2017-09-26 | 2018-02-13 | 丹东明珠特种树脂有限公司 | A kind of Etherification of Light FCC Gasoline system and its Etherification of Light FCC Gasoline process |
| CN107686745B (en) * | 2017-09-26 | 2020-06-12 | 丹东明珠特种树脂有限公司 | Light gasoline etherification system and light gasoline etherification process method thereof |
| CN109173310A (en) * | 2018-08-29 | 2019-01-11 | 张家港市科华化工装备制造有限公司 | Dimethoxym ethane rectifying column |
| CN111807940A (en) * | 2020-07-21 | 2020-10-23 | 安徽金轩科技有限公司 | Method for recycling waste methanol in galaxolide production |
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Application publication date: 20120215 |