A kind of methyl acetate catalysis rectification hydrolysis technique
Technical field
The present invention relates to a kind of methyl acetate catalysis rectification hydrolysis technique.
Background technology
Ritalin is a kind of common Chemical Manufacture by product, colourless transparent liquid, savory, be slightly soluble in water, be soluble in most of organic solvents such as ethanol, 56.9 ℃ of boiling points, density are 0.932g/ml, generally appear in the Industrial processes of pure terephthalic acid (PTA) and polyvinyl alcohol (PVA).
In the PTA production process, what adopt at present is high-temperature oxidation mostly, and this technology is solvent with acetic acid, is oxygenant with the air that PTA is produced in the reaction of liquid phase high temperature oxidation, and this technology accounts for more than 90% of present PTA production.In the side reaction that acetic acid takes place, about 75% acetic acid generates CO, CO
2And water, 25% generates ritalin etc.PVA also is a kind of very important and common Chemicals, and during industrial synthetic PVA, owing to PVA can not be got by the monomer direct polymerization, so what adopt mostly is technology by the Vinyl Acetate Copolymer alcoholysis, the alcohol that wherein is used for alcoholysis is generally methyl alcohol.The alcoholysis under catalyst action of Vinyl Acetate Copolymer solution generates PVA and a large amount of pure hydrolysis mother liquors, contains a large amount of ritalin by products in the pure hydrolysis mother liquor, is about 1.7 times of PVA by weight approximately.
At the processing of ritalin, in PTA produces, generally it is recycled in the oxidation reactor and is used; In PVA produces, generally be hydrolyzed and generate acetic acid and methyl alcohol.Because acetic acid and methyl alcohol are important chemical material, compare with ritalin, marketable value is higher, therefore, the processing that is hydrolyzed of Dichlorodiphenyl Acetate methyl esters not only can solve the recycling problem of ritalin by product, also can be other Chemical Manufacture and provide important material, remarkable in economical benefits.
In recent years, the hydrolysis treatment of Dichlorodiphenyl Acetate methyl esters has been carried out a large amount of research both at home and abroad.CN1333204A utilizes water and ritalin in the reactor that possesses the fixed catalytic layer behind the hydrolysis reaction, enter in the ritalin knockout tower, ritalin knockout tower cat head is unreacted ritalin, Returning reactor after the condensation, the tower still is acetic acid, methyl alcohol and less water, deliver to recovery tower, separating acetic acid and methyl alcohol.But adopt reactor hydrolysis ritalin in this technology, hydrolysis conversion is lower.The methyl acetate catalysis rectification hydrolysis technique of reports such as CN1927792A comprises catalytic rectifying tower, extractive distillation column, dealcoholize column, takes off ester tower and extracting tower.All materials of catalytic rectifying tower are only from the discharging of tower still, tower still water content is higher, because water and ritalin, ritalin and methyl alcohol can form azeotrope, separation difficulty must and be taken off the ester tower and ritalin, water and methyl alcohol could be separated fully through extractive distillation column, dealcoholize column.Because all materials of catalytic rectifying tower are only in the discharging of tower still, not discharging of cat head, thus make the later separation difficulty increase, flow process is tediously long, equipment cost increases, energy consumption is higher.CN101012162A Dichlorodiphenyl Acetate methyl esters hydrolysate tripping device is studied, comprise acetic acid separated tower, ritalin extraction tower, methyl alcohol knockout tower, packing tower all adopts regular packed tower, filler is the metal corrugated plate filler, because there are defectives such as flow process is tediously long, equipment cost is high, energy consumption height in all materials of catalytic rectifying tower equally only in the discharging of tower still.CN1213014C has introduced the method that is obtained carboxylic acid and alcohol by corresponding carboxylic acid ester and water hydrolysis.The fluid that contains carboxylicesters enters into pre-reactor, react with water under the first hydrolyst effect, part reacts, and resulting hydrolysate enters into reactive distillation column again, under the second hydrolyst effect, remaining carboxylate moiety is converted into carboxylic acid and alcohol.More volatile compound is derived from the reaction distillation top of tower as top stream, and more difficult evaporable compound is collected as bottom fraction at the reaction distillation tower bottom, but its not the whole technological process of Dichlorodiphenyl Acetate methyl esters hydrolysis study.
Summary of the invention
The objective of the invention is deficiency, a kind of methyl acetate catalysis rectification hydrolysis technique is provided at existing hydrolysis process of methyl acetate.
Technical scheme of the present invention: a kind of methyl acetate catalysis rectification hydrolysis technique, adopt catalytic rectifying tower T1, dealcoholize column T2 and extracting tower T3 three-column process flow technology, its concrete steps are as follows:
A: catalytic rectifying tower T1 is divided into rectifying section, conversion zone and stripping section from top to down, and water enters from the conversion zone top, and ritalin enters from the conversion zone bottom, and the discharging of catalytic distillation column overhead is methyl alcohol, ritalin and less water, and the discharging of tower still is acetic acid and water;
B: the overhead product of catalytic rectifying tower T1 is introduced dealcoholize column T2 and is separated, and dealcoholysis Tata still obtains methyl alcohol, and cat head is unreacted ritalin and less water, methyl alcohol, returns the catalytic rectifying tower circulating reaction again; The tower kettle product of catalytic rectifying tower T1 is introduced extracting tower T3 and is separated, and depickling Tata still obtains acetic acid, and cat head is a water.
Wherein said ritalin generally is the by product that produces in pure terephthalic acid or the polyvinyl alcohol production process.
The water among the above-mentioned steps A and the raw materials components mole ratio of ritalin are (1~10): 1, reflux ratio is (1~8): 1, the ritalin superficial velocity be 0.1~1 cubic metre/(cubic meter reaction zone volume hour), the catalyzer of filling in the conversion zone is a strongly acidic cation-exchange, 1~2 year work-ing life of catalyzer.
Reflux ratio is (0.5~5) among the preferred dealcoholize column T2: 1, and stage number 20~60; Reflux ratio is (3~10) among the preferred extracting tower T3: 1, and stage number 30~100.
The present invention is described in further detail below in conjunction with accompanying drawing.
Catalytic rectifying tower T1 is divided into three parts: upper rectifying section 1, intermediate reaction section 2, bottom stripping section 3, wherein filler is the metal corrugated plate filler in rectifying section and the stripping section, conversion zone filling male ion-exchange resin catalyzer is tied up bag, and described catalyzer is generally selected macroporous network type or gel type cation exchange resin catalyst.Dealcoholize column and depickling inner-tower filling material are the metal corrugated plate filler.
Material water autoreaction section top enters catalytic rectifying tower T1, and ritalin autoreaction section bottom enters, and after the conversion zone reaction, part generates acetic acid and methyl alcohol.Ritalin, water, acetic acid and methyl alcohol are after rectifying separation, and methyl alcohol, ritalin and less water are discharged from the T1 cat head, after the condenser cooling, and partial reflux, part enters dealcoholize column T2; Heavy constituent acetic acid and water are discharged from T1 tower still, enter extracting tower T3.
After material C entered dealcoholize column T2, after rectifying separation, cat head was unreacted ritalin and less water, methyl alcohol, after the condenser cooling, and partial reflux, part is returned catalytic rectifying tower T1 as material E and is continued circulating reaction; Tower still product methyl alcohol is discharged as material F.
After material D entered extracting tower T3, after rectifying separation, cat head was a water, after the condenser cooling, and partial reflux, part is discharged as material G; Tower still product acetic acid is discharged as material H.
Beneficial effect
(1) because the present invention adopts catalytic rectifying tower, extracting tower and dealcoholize column three-column process flow technology, more existing catalytic rectifying tower, extractive distillation column (or extraction tower), dealcoholize column and take off ester tower four-column process flow technology, flow process shortens, and equipment reduces.Compare with existing hydrolysis process, on the basis that guarantees the methyl acetate hydrolysis quality product, the present invention can reduce facility investment, reduces operation energy consumption and operation easier, thereby reduces production costs.
(2) under the operational condition of optimizing, the ritalin total conversion rate reaches more than 98%, and methyl alcohol and acetic acid mass concentration are respectively 99.9% and 95.0%, satisfies the specification of quality of PTA production to solvent acetic acid and fuel methanol substantially.
(3) hydrolysis process of methyl acetate proposed by the invention is not only applicable to the ritalin that produces in PTA and the polyvinyl alcohol production process, is applicable to the ritalin that produces in other production process yet.
Description of drawings
Fig. 1 is a methyl acetate catalysis rectification hydrolysis technique schematic flow sheet provided by the invention;
Wherein, T1 is a catalytic rectifying tower, and T2 is a dealcoholize column, and T3 is an extracting tower; 1 is the catalytic rectifying tower rectifying section, and 2 is the catalytic rectifying tower conversion zone, and 3 is the catalytic rectifying tower stripping section, and 4 is condenser, and 5 is reboiler; A is a feed water, and B is the charging ritalin, and C is the discharging of catalytic distillation column overhead, and D is the discharging of catalytic distillation Tata still, and E is unreacted ritalin and less water, methyl alcohol, and F is a methyl alcohol, and G is a water, and H is an acetic acid.
Embodiment
Concrete application of the present invention is described by the following examples, but range of application of the present invention is not subjected to the restriction of the following example.
Embodiment 1
Water and ritalin enter reactor in table 1 ratio, implement the hydrolysis of ritalin, among the embodiment 1, water and ritalin mol ratio are 2 among the T1, reflux ratio is 2, the ritalin superficial velocity be 0.2 cubic metre/(cubic meter reaction zone volume hour), catalyzer is a D002 type Zeo-karb; The T2 reflux ratio is 5; The T3 reflux ratio is 8.
Embodiment 2
Among the embodiment 2, water and ritalin mol ratio are 8 among the T1, and reflux ratio is 4, the ritalin superficial velocity be 0.6 cubic metre/(cubic meter reaction zone volume hour), catalyzer is an Amberlyst 35wet type Zeo-karb; The T2 reflux ratio is 3; The T3 reflux ratio is 5.
Embodiment 3
Among the embodiment 3, water and ritalin mol ratio are 4 among the T1, and reflux ratio is 7, the ritalin superficial velocity be 0.9 cubic metre/(cubic meter reaction zone volume hour), catalyzer is a D002 type Zeo-karb; The T2 reflux ratio is 1; The T3 reflux ratio is 4.
Table 1
Detailed |
Example 1 |
Example 2 |
Example 3 |
Water and ritalin mol ratio among the T1 |
2 |
8 |
4 |
The T1 reflux ratio |
2 |
4 |
7 |
Ritalin superficial velocity among the T1 |
0.2 |
0.6 |
0.9 |
The T1 catalyzer |
D002 type Zeo-karb |
Amberlyst 35wet type Zeo-karb |
D002 type Zeo-karb |
The T2 reflux ratio |
5 |
3 |
1 |
Detailed |
Example 1 |
Example 2 |
Example 3 |
The T2 stage number |
20 |
32 |
50 |
The T3 reflux ratio |
8 |
5 |
4 |
The T3 stage number |
32 |
45 |
70 |
Methanol quality concentration/% |
99.9 |
99.9 |
99.7 |
Quality concentration/% |
99.9 |
99.9 |
99.9 |
Acetic acid mass concentration/% |
96.4 |
95.8 |
95.1 |