CN1052113A - The production method of Thiovanic acid and device - Google Patents
The production method of Thiovanic acid and device Download PDFInfo
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- CN1052113A CN1052113A CN 90103698 CN90103698A CN1052113A CN 1052113 A CN1052113 A CN 1052113A CN 90103698 CN90103698 CN 90103698 CN 90103698 A CN90103698 A CN 90103698A CN 1052113 A CN1052113 A CN 1052113A
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Abstract
The invention provides Sodium sulfhydrate and monochloroacetic acid and react technology and the device thereof of producing Thiovanic acid.Pulse reaction, reduce pressure discharging, non-scaling, noncoking technology have automatically been used; Device has then adopted blank pipe and filling pipe tandem reactor, turntable extracting tower, rotary film evaporator that ripple net and waved plate are housed, but the Thiovanic acid of continuous production 300～4000T/Y.
Description
The invention belongs to vitochemical category, be specially adapted to produce Thiovanic acid.
People know that in the structure of Thiovanic acid, existing sulfydryl has carboxyl again, so have purposes widely.And its derivative can be used for aspects such as setting lotion, trichogen, nontoxic polyvinyl chloride stablizer, metal conditioner, analytical reagent.Become most important fine chemical product at present, for this reason, about preparing the method for Thiovanic acid, people have done many work.As: Japan special permission 51-29440 has introduced monochloroacetic acid salt and the sulfenyl choline prepares Thiovanic acid under normal pressure, in reaction process and feed hydrogen sulfide; 53-147026 has proposed in the reactor of stirring is housed with monochloroacetic acid and Sodium sulfhydrate prepared in reaction Thiovanic acid; Germany 2711876 patents then propose monochloroacetic acid and an alkali metal salt at CO
2The following preparation Thiovanic acid of pressure.In these schemes, it is in the majority to prepare Thiovanic acid with sodium monochloracetate and Sodium sulfhydrate reactant aqueous solution, the shortcoming that they all exist, and transformation efficiency is low, side reaction is many.Though the mode that has also proposed the adding rare gas element and the operate continuously of pressurizeing that has prepares Thiovanic acid, also inevitable equipment is huge, cost is high, and the drawback of contaminate environment.
The purpose of this invention is to provide a kind of high continuous production method and device of industrialization, less energy-consumption, product purity height, product yield of producing Thiovanic acid with Sodium sulfhydrate and monochloroacetic acid reaction.
A kind of method with Sodium sulfhydrate and monochloroacetic acid prepared in reaction Thiovanic acid is characterized in that:
A) adopt the pulse reaction technology;
B) adopt decompression discharging technology automatically;
C) adopt noncoking, non-scaling technology;
D) adopt automatic operation system.
The device of Sodium sulfhydrate and monochloroacetic acid prepared in reaction Thiovanic acid constitutes reactor by static mixer and blank pipe, and extraction tower, pump and thin-film evaporator are formed, and it is characterized in that:
A) pulse type reactor that is composed in series of blank pipe and static mixer, this pulse type reactor is by the wire rod of molybdenum, titanium, tantalum, niobium or their alloy or sheet material is formed the ripple net or waved plate is filled;
B) turntable extracting tower;
C) climbing-film evaporator;
D) falling-film evaporator;
E) XZ-rotary film evaporator.
Prepare the method for Thiovanic acid with Sodium sulfhydrate and monochloroacetic acid, use ether, ethyl acetate, butylacetate, isooctyl alcohol as solvent.The invention is characterized in not to be only applicable to ether, ethyl acetate, butylacetate, isooctyl alcohol, and be to be best with isobutyl acetate, diethylene glycol ethyl ether acetic ester.
The present invention is the embodiment that has proposed us on the basis of the whole bag of tricks of having studied current preparation Thiovanic acid and operational path, with regard to its method, we think that it is feasible adopting monochloroacetic acid and Sodium sulfhydrate reaction to produce Thiovanic acid, but must fully take into account rationality of technological process, produce side reaction as much as possible less, improve the purity of product.For this reason, we adopt the pulse fed technology, and its purpose is to improve transformation efficiency; Adopted automatic decompression discharging technology, production can be carried out in serialization; Having adopted noncoking, non-scaling technology, is to realize by our reactor of design, though also use blank pipe, we have been connected in series the garden pipe that has ripple net or waved plate again with it, and realization response is even, and noncoking, non-scaling.In order to make technical process reliable and stable, we have also adopted automatic operation system, are made of a plurality of micro-chips and main control microcomputer.Its software is then designed by well-known programable and control supervisor language.Realized whole automatic operation system.
The reactor that the present invention adopts is to be made up of at interval pulse type reactor (comprising static mixer: be Φ 24mm, the ripple net of interior dress Φ 20mm or waved plate element) and blank pipe, and a meter pulse reactor and one meter blank pipe are formed a unit, totally five unit.Static mixer disperses the reacting fluid short mix, can make temperature of reaction even; Mobile the comparing with blank pipe of fluidic is bordering on piston flow, so the fluid retention amount is few, makes the resultant of reaction quality even, adds with blank pipe and assemble at interval that its effect is better.The report use blank pipe reaction solution residence time is 8～10 minutes among the day disclosure special permission 49-75526, and reaction solution of the present invention only needs 3 minutes residence time can reach ideal effect.
Pulse type reactor, its unit is assembled by ripple net or waved plate, this pulse type reactor is by the wire rod of molybdenum, titanium, tantalum, niobium or their alloy or sheet material is formed the ripple net or waved plate is filled, the unit of the making tubular inner casing of packing into, this reactor can become very little drop with immiscible liquid dispersion, reach good mixing by this, strengthen reaction.When linear velocity W=0.7[meter per second] time, the mass transfer coefficient of pulse mixer is 7 times of blank pipe.
For guaranteeing to be reflected at the pressure operation down of setting,, done many work, thereby determined the scale of this device nominal diameter, component units number, the thrust of pump of the pulse mixer that adopts.
In relevant patent, only be conceived to composite part, and the present invention studies to composite part not only, and the purification of product is studied, compare, adopt route of the same race can improve the purity of product, reduce product cost with previous patent.
After synthesis procedure, as solvent, and be to be best with ether, ethyl acetate, butylacetate, isooctyl alcohol with isobutyl acetate, diethylene glycol ethyl ether acetic ester, synthetic liquid is carried out extracting operation, to remove impurity and most water, inorganic salt etc.In this operation, designed advanced extraction equipment-rotating disc type extraction tower, be achieved serialization thereby make to produce.Whole apparatus structure is simple, turndown ratio is big, adaptability is strong, power consumption is low, balance easy and simple to handle, easy, regulate rapidly, operate steadily reliable, solvent consumption is little, facility investment is few, use the danger of inflammable and explosive medium to reduce greatly.
Extraction tower is made up of garden column-shaped barrel, set collar and rotating disk, comprises upper and lower two settling sections and middle extraction section; Acidizing fluid enters in the tower from the cat head end, solvent enters in the tower from tower bottom, borrow both difference in specific gravity, by each extraction cells, solvent is that external phase is full of tower body upstream, and acidizing fluid is a disperse phase, shearing action by the rotating disk of horizontal distribution, the droplet-like that is the about 1～2mm of diameter is scattered in external phase-solvent equably, and this state has greatly increased the two-phase contact area.At the contrary mobile two alternate mass transfers that carry out,, synthetic acidizing fluid is purified by choice of Solvent; Both pass through settling section up and down respectively, then become extraction liquid and raffinate and discharge.The turntable extracting tower of our design through trial production, has reached design requirements safely.
Extraction tower has related parameter as follows:
Tower diameter: Φ 350～1000mm
Tower height: the H=10m(height overall)
Extraction cells height: H
1=110～200mm
Axle rotating speed: n=167rpm～100rpm
Solvent ratio: 1: 3～5
Solvent flux: Wc=360～1000Kg/hr
Two-phase void tower speed ratio: Ud/Uc=1.51
Disperse phase hold-up: ε F=0.363
Driving power: N=2.2～10Kw
Traditional material filling type extraction tower, the tower height of every theoretical stage is bigger, at tower height (referring to virtual height) is 1 meter, tower diameter is among the contrast experiment of 50mm, when operational condition is identical, extracting phase concentration is 0.09% at the bottom of the rotating disc type extraction Tata, and at the bottom of the tower of material filling type extraction tower extracting phase concentration up to 0.56%, in addition, the free flow sectional area of material filling type extraction tower is much smaller than the rotating disc type extraction tower, thereby, throughput obviously reduces, and the dispersed phase drop size was inhomogeneous when the performance of packing tower itself had determined extraction, and it is even that the distribution in external phase also can not show a candle to the rotating disc type extraction tower; The packing tower of same throughput and performance is about 3: 1 with rotating disc contactor cost ratio.For centrifugal extractor,, relatively harsher to the requirement of material because the system corrodibility in this process of producing product is stronger, cause the device fabrication difficulty, facility investment is big, and centrifugal in addition extractor rotating speed is very high, processing request precision height is also very high to pressing reload request.Contrast, in the extracting operation that product is purified, it is advanced, economical selecting the rotating disc type extraction tower for use.
The distillation of product: raffinate through double effect evaporator remove desolvate and a spot of low-boiling-point substance after, enter the XZ-rotary film evaporator and make with extra care, to remove a spot of high boiling material, obtain purified Thiovanic acid product.This unit design advanced evaporation equipment-rotary film evaporator, this equipment has that evaporation capacity is big, power consumption less,, characteristics such as turndown ratio big, residence time of material very short, facility investment few, maintenance easy, life-span long strong to the adaptation of product, and floor space is little, is easy to realize the serialization of producing and the automatization of control.
Rotary film evaporator is made up of the drive part on top and the evaporation section of bottom, at axle envelope place, adopts double mechanical seal to guarantee the vacuum tightness of equipment; Evaporation section by the cylindrical shell of rotor, strap clamp cover, and separator forms, rotor is made up of sparger, mist eliminator, main shaft, groove scraper plate and support, the groove scraper plate can radially slip in the U of support type groove; Material enters vaporizer by inlet, under the centrifugation of sparger, be evenly distributed on the cylinder inboard wall and flow downward, the groove scraper plate is pressed to an inwall under action of centrifugal force, when it rotates, treatment solution is spread to uniform film along tube inwall-generating surface, the heat of being supplied with by chuck passes to liquid film by barrel, material is evaporated rapidly, and the product steam that steams is upwards by mist eliminator, remove droplets entrained after, discharge from the secondary steam outlet, be condensed into liquid product in condenser, remaining high boiling point residue is pushed away evaporating area rapidly by scraper plate, discharges from base of evaporator; This rapid evaporation, the quick result of deslagging make this vaporizer more be applicable to heat-sensitive material, and non-scaling, noncoking, and Thiovanic acid is subjected to thermally labile for a long time, and easily polymerization is so this equipment of employing is very reasonable.Investigate through trial production, this vaporizer meets the requirements fully.
Vaporizer has related parameter as follows:
Evaporation area: 0.5m
Working pressure: 0.065MPa
Power of motor: 1.5Kw
Material processing power: 50～80Kg/h
Accompanying drawing and accompanying drawing simple declaration:
Fig. 1 Thiovanic acid technological process of production figure:
1-sulfuric acid basin; 2-Sodium sulfhydrate material-compound tank;
3-monochloroacetic acid material-compound tank; The 4-filter for molten;
The 5-synthesis reactor; 6-decomposes jar;
7-alkali pot; 8-hydrogen sulfide absorption jar;
9-Sodium sulfhydrate basin; The 10-solvent tanker;
The 11-extraction tower; 12-extraction liquid receiver;
13-I level vaporizer; The 14-separator;
The 15-condenser; 16-solvent receiver;
17-II level vaporizer; The 18-separator;
The 19-basin; The 20-condenser;
21-hangs down the fraction receiver; 22-finished product distiller;
23-residue receiver; The 24-separator;
The 25-condenser; 26-finished product receiver;
27～33-transferpump.
Process flow sheet of the present invention, referring to Fig. 1, at material-compound tank 2, in 3 Sodium sulfhydrate and sodium monochloracetate are made into 25%(Wt) the aqueous solution, squeeze into reactor 5 through transferpump, reaction solution enters acid hydrolysis tank 6 after decompression, with entering extraction tower top behind hydrochloric acid or the sulfuric acid solution, solvent is squeezed into the extraction tower bottom through pump 31 in basin 10, raffinate discards, extraction liquid enters basin 12, squeeze into vaporizer 13 through pump 32 again, steam most of solvent by the top, evaporation section does not enter grade vaporizer 17, to hang down fraction and deviate from back inflow basin 19, squeeze into finished product vaporizer 22 by pump 33 again, finished product Thiovanic acid steam is steamed after condenser 25 condensations by the top and is collected in receiver 26, is collected in the receiver 23 by the effusive distillation residue in vaporizer 22 bottoms.
The explanation of Fig. 2 reactor:
This reactor is made up of static mixer and blank pipe
1-Sodium sulfhydrate inlet; 2-monochloroacetic acid inlet;
The 3-static mixer; The 4-blank pipe.
Sodium sulfhydrate and sodium monochloracetate enter pulse type reactor 3 after pump 28,29 is squeezed into premixer, reaction solution is discharged by 4.
The explanation of Fig. 3 I level vaporizer:
This vaporizer is the multitube rising-film evaporator
1-extraction liquid inlet; The outlet of 2-secondary steam;
The 3-residul discharging port.
Extraction liquid enters the vaporizer bottom by 1, and through steam heating, material is film like along tube wall and rises, evaporates, and gas-liquid mixture is discharged by outlet 2 and entered separator.
The explanation of Fig. 4 II level vaporizer:
This vaporizer is the multitube falling film evaporator, and the liquid that comes out from I level separator bottom enters vaporizer top by 1, after distributing, evaporates along tube wall decline, and the vapour-liquid mixture enters II level separator by outlet 3.
The explanation of Fig. 5 finished product vaporizer:
The 1-material inlet; 2-finished product vapor outlet port;
The outlet of 3-raffinate; The 4-steam inlet;
5-lacks water out.
This vaporizer is the rotary film evaporator of belt scraping plate, thick Thiovanic acid enters vaporizer by inlet 1, after distributing, flow down along inner tube wall, effect through rotating blade descends in the shape of a spiral, and evaporate through jacket steam heating, finished product steam is discharged by outlet 2 and is entered condenser, and residue is discharged by outlet 3.
Embodiment 1
With concentration 25% the sodium monochloracetate and the Sodium sulfhydrate aqueous solution, its inlet amount respectively is 240L/h, squeeze into respectively through every pump and to enter in the pulse type reactor after giving mixer, mole ratio is 1.14～1.6, in 90 ℃, react under 1～1.5MPa pressure, reaction conversion ratio counts 90% with monochloroacetic acid.
Synthetic liquid cools off under 40 ℃, carries out acidifying with hydrochloric acid or sulfuric acid then, makes in the synthetic liquid Thioglycolic acid sodium salt acidolysis awkward, and reaction end control pH value is 7～8.
With 200Kg/h solvent feed amount per hour and per hour the acidizing fluid inlet amount of 400Kg/h squeeze into the rotating disc contactor two ends and under normal pressure, extract, Thiovanic acid content is 0.14% in the raffinate,
Thiovanic acid content is 15～18% in the extraction liquid, for obtaining high-load Thiovanic acid more than 90%, need through distillation and refining, the distillation of product is carried out at climbing-film evaporator and falling-film evaporator series connection, the vapor phase temperature of I level vaporizer is 40～50 ℃, 90～100 ℃ of II level vapor phase temperatures, vacuum tightness are 0.32MPa, and inlet amount is 40～100L/h.
The refining of product carries out in rotary film evaporator, and its working pressure is 0.0065MPa, and service temperature is 105 ℃, per hour can get product 70Kg, and purity is 95%.
By the resulting product Thiovanic acid of above-mentioned production process index be:
Outward appearance: colourless or light yellow oily liquid
Content: 〉=90%
Iron level:＜0.5ppm
Turbidity: 10% aqueous solution is as clear as crystal
Smell: can accept
With concentration is 40% the sodium monochloracetate and the Sodium sulfhydrate aqueous solution, and inlet amount is 210L/h, in 60 ℃, carries out building-up reactions under the 1.6MPa pressure, and reaction conversion ratio still counts 92% with monochloroacetic acid.
With 300L/h solvent feed amount per hour and per hour the acidizing fluid inlet amount of 400L/h extract, operational condition is with example 1, solvent is 0.15% in the raffinate, Thiovanic acid content is 18% in the extraction liquid.
The purification condition of product is with example 1, and the product purity that obtains is 93%.
With concentration is 20% the sodium monochloracetate and the Sodium sulfhydrate aqueous solution, and its inlet amount respectively is 200L/h and 240L/h, in 70 ℃, carries out building-up reactions under the 1.2MPa pressure, and transformation efficiency still counts 95% with monochloroacetic acid.
Extraction, distillation and purification condition are with example 1, and product purity is 96%.
Explanation and example by the front are not difficult to find out, although still adopting monochloroacetic acid and Sodium sulfhydrate to react, our invention prepares Thiovanic acid, because technological process is more reasonable, has adopted advanced technology and corresponding device thereof again, thereby has made product purity up to more than 95%, continuous automatic operation, output is big, and therefore, we declare, produce Thiovanic acid, the present invention provides a kind of very ideal method and apparatus far and away.
Claims (3)
1, a kind of method with Sodium sulfhydrate and monochloroacetic acid prepared in reaction Thiovanic acid is characterized in that:
A) adopt the pulse reaction technology;
B) adopt decompression discharging technology automatically;
C) adopt noncoking, non-scaling technology;
D) adopt automatic operation system.
2, the device of Sodium sulfhydrate and monochloroacetic acid prepared in reaction Thiovanic acid constitutes reactor by static mixer and blank pipe, and extraction tower, pump and thin-film evaporator are formed, and it is characterized in that:
A) pulse type reactor that is composed in series of blank pipe and static mixer, this pulse type reactor is by the wire rod of molybdenum, titanium, tantalum, niobium or their alloy or sheet material is formed the ripple net or waved plate is filled;
B) turntable extracting tower;
C) climbing-film evaporator;
D) falling-film evaporator;
E) XZ-rotary film evaporator.
3, the method for preparing Thiovanic acid with Sodium sulfhydrate and monochloroacetic acid uses ether, ethyl acetate, butylacetate, isooctyl alcohol as solvent.The invention is characterized in not to be only applicable to ether, ethyl acetate, butylacetate, isooctyl alcohol, and be to be best with isobutyl acetate, diethylene glycol ethyl ether acetic ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103698 CN1052113A (en) | 1990-05-25 | 1990-05-25 | The production method of Thiovanic acid and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90103698 CN1052113A (en) | 1990-05-25 | 1990-05-25 | The production method of Thiovanic acid and device |
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| Publication Number | Publication Date |
|---|---|
| CN1052113A true CN1052113A (en) | 1991-06-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 90103698 Pending CN1052113A (en) | 1990-05-25 | 1990-05-25 | The production method of Thiovanic acid and device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229548A (en) * | 2011-05-16 | 2011-11-02 | 潍坊益华化工有限公司 | Method for producing thioglycollic acid |
| CN104370783A (en) * | 2014-10-30 | 2015-02-25 | 天津河清化学工业有限公司 | Hydrogen sulfide recycling method and hydrogen sulfide recycling system for continuously producing mercaptoacetic acid by adopting sodium hydrosulfide method |
| CN106167458A (en) * | 2016-07-05 | 2016-11-30 | 山东沾化金嘉利化工科技有限公司 | The method separating TGA from TGA aqueous solution |
-
1990
- 1990-05-25 CN CN 90103698 patent/CN1052113A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229548A (en) * | 2011-05-16 | 2011-11-02 | 潍坊益华化工有限公司 | Method for producing thioglycollic acid |
| CN104370783A (en) * | 2014-10-30 | 2015-02-25 | 天津河清化学工业有限公司 | Hydrogen sulfide recycling method and hydrogen sulfide recycling system for continuously producing mercaptoacetic acid by adopting sodium hydrosulfide method |
| CN106167458A (en) * | 2016-07-05 | 2016-11-30 | 山东沾化金嘉利化工科技有限公司 | The method separating TGA from TGA aqueous solution |
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