CN102795964A - 20000-ton-annual-yield production technique of trimethylolpropane by calcium method - Google Patents
20000-ton-annual-yield production technique of trimethylolpropane by calcium method Download PDFInfo
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- CN102795964A CN102795964A CN2012103355995A CN201210335599A CN102795964A CN 102795964 A CN102795964 A CN 102795964A CN 2012103355995 A CN2012103355995 A CN 2012103355995A CN 201210335599 A CN201210335599 A CN 201210335599A CN 102795964 A CN102795964 A CN 102795964A
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Abstract
The invention discloses a 20000-ton-annual-yield production technique of trimethylolpropane by a calcium method, which is divided into condensation, filtration, evaporation, calcium separation and rectification. The production technique is characterized by comprising the following steps: by using n-butyl aldehyde and formaldehyde as raw materials and industrial calcium hydroxide as an alkaline catalyst, carrying out condensation and formic acid neutralization reaction to obtain a trimethylolpropane crude product reaction solution containing byproducts ditrimethylolpropane and calcium formate; in the filtration process, separating out solid-phase residues from the reaction solution in a horizontal spiral centrifugal filtration mode; evaporating with a climbing-film evaporator, and sending the evaporative condensate back to the condensation technique; after entering the settling tank, continuously scraping calcium formate from the bottom of the settling tank, and recycling the calcium formate with a band filter; and carrying out rectification to obtain the trimethylolpropane product, wherein rectification column uses column refluxing and climbing film heating techniques, the deflector plate in the column is controlled, and meanwhile, a gas-liquid separator is mounted on a vacuum tube of the rectification column. The invention has the advantages of simple technical process, high labor rate, low production cost, energy saving and emission reduction.
Description
Technical field
The invention belongs to chemical technology field, relate to the production technique of 20,000 tons of calcium method TriMethylolPropane(TMP)s of a kind of annual output, be specifically related to a kind of solution tower bias current in calcium method TriMethylolPropane(TMP) production technique, produce reaction, isolating novel process that the container increase brings.
Background technology
In industry, TMP mainly is to be main raw material with butyraldehyde-n and formaldehyde, and condensation reaction makes midbody dihydroxymethyl butyraldehyde under the basic catalyst effect, and this midbody further generates TriMethylolPropane(TMP) with formolite reaction.The production technique of at present domestic TriMethylolPropane(TMP) is divided into two kinds of sodium method and calcium methods, and promptly raw material uses sodium hydroxide or calcium hydroxide respectively.Calcium method technology is because of having that flow process is short, cost is low, labour intensity is low and advantage such as environmental protection and energy saving, replacement sodium method technology gradually.
The domestic production TriMethylolPropane(TMP) the nineties Shandong forever the fluidisation worker produce 300 tons per year, the Jiization introduction of foreign technology was carried product to 5000 ton/year afterwards.The technology of 05 year Hubei San Jiang introduction Korea S Sanyo is built up at home and is produced other production line of ton per year.
Existing 10,000 tons of production processes are: the condensation discrimination method reaction equation that with sodium hydroxide is catalyzer is following:
This method is to be raw material with butyraldehyde-n and formaldehyde, is catalyzer with sodium hydroxide, carries out aldol reaction at a lower temperature and generates 2; 2-dihydroxymethyl butyraldehyde; Generate TriMethylolPropane(TMP) with excessive formaldehyde and highly basic effect generation Cannizzaro reaction again, adopt the plate type pressure filter filtration process again, the condensated liquid that contains TriMethylolPropane(TMP) after the filtration is through pervaporation, SX; Extraction phase is through the Separation and Recovery solvent, in rectifying tower, purifies then three promptly to get product through methylpropane.
Existing technology is owing to mostly adopt above-mentioned technological process, and the solvent recuperation amount is big, so production capacity never has to such an extent that promote; Because, as simple on the basis of existing 10,000 tons of production lines productivity gain reach 20,000 tons, following situation can occur: 1, condensation reaction is a thermopositive reaction; Mix inhomogeneously during reaction, can cause local temperature too high, cause side reaction to increase; Impurity increases, and production brings difficulty to postorder, even the situation of local imitation frosted glass can occur.2, TriMethylolPropane(TMP) all has extraction process now, and the amount of extraction agent and reaction solution ratio are volume ratio 3:1.Extraction agent consumption is big, and production cost improves, and a large amount of extraction agents reclaims, skewness in the time of can causing the rectifying tower operation, and the rectifying tower bias current, product content descends, and situation such as colourity rising occur; 3, TriMethylolPropane(TMP) is high density, and content is more than 99.5%, and the TriMethylolPropane(TMP) high vacuum can not guarantee.
Summary of the invention
The object of the invention just is to omit extraction process through the volume that promotes reaction vessel, the speed of response and the separating power of tower, thereby the production technique of 20,000 tons of calcium method TriMethylolPropane(TMP)s of a kind of annual output is provided.
Technical solution of the present invention: preparation technology is divided into condensation, centrifuging, evaporation, scraper plate and divides calcium and rectifying; It is characterized in that: with butyraldehyde-n and formaldehyde is raw material; Use technical grade calcium hydroxide to be basic catalyst; Through condensation process and formic acid neutralization reaction, obtain containing the TriMethylolPropane(TMP) bullion reaction solution that comprises ditrimethylolpropane and calcium formiate sub product; Centrifuging process using horizontal spiral centrifuging mode is carried out the separation of solid phase residue to reaction solution; The evaporation of employing rising-film evaporator, evaporation condensate is back to condensation process; Scraper plate divides calcium technology to inject subsider for containing calcium formiate solid liquid concentrator after will evaporate, scrapes calcium formiate from the bottom continuity of subsider, again through band filter recovery calcium formiate; Rectifying tower adopts tower self backflow and rises membrane type intensification technology in the rectification process, and the control techniques of the traverse baffle in the tower is installed gas-liquid separator simultaneously on the valve tube of rectifying tower; Get the TriMethylolPropane(TMP) product after the rectifying.
(1) condensation: adopt two condensation reaction stills; The effective volume of each condensation reaction still is designed to 35 cubic metres; Condensation process one feeding amount is 25-28kmol, and end water management is at 110-115g/l, and the stirring of condensation reaction still is increased to more than the 150 commentaries on classics/mir; 22 stills that feed intake every day, 25-28 cubic metres of reaction solutions of every still, speed of response is that every still reaction times is 120 minutes;
(2) centrifuging: in TriMethylolPropane(TMP) bullion reaction solution, add flocculation agent; The volume ratio of flocculation agent and TriMethylolPropane(TMP) bullion reaction solution is 1:580-650; The speed that adds flocculation agent is 30-32kg/h; After leaving standstill 5-8 minutes, adopt horizontal spiral centrifuging mode reaction solution to be carried out the separation of solid phase residue again; Filtration velocity is 22.5-25.5m
3/ h, producing the solid phase residue is 200-300kg/h;
(3) evaporation: with 22.5-25m
3The filtered liq of/h speed after the solid phase residue that the evaporator evaporation device drops into separates adopts rising-film evaporator, and effective heating zone of vaporizer is 8-12 square metres, and dehydration rate reaches 85-88%, and dewatering speed is 17-19m
3/ h, evaporation condensate is back to condensation process;
(4) scraper plate divides calcium: contain calcium formiate solid liquid concentrator after will evaporating and inject subsider, adopt the separation system that comprises scraper plate machine and band filter combination, scrape calcium formiate from the bottom continuity of subsider, again through band filter recovery calcium formiate;
Divide after the calcium technology 98.5-99% calcium formiate in the reaction solution is separated, remaining calcium adds phosphoric acid hydrolysis; Divide in the calcium technology and per hour separate 1.54-1.75 tons of calcium formiates;
(5) rectifying: with 4.5-5m
3/ h speed does not have the liquid concentrator of solid particulate to put in the rectifying tower at the top, and the tower diameter is 1750-1850,30-32 meters of height; Isolate the light constituent low-boiling point material; Get into the TriMethylolPropane(TMP) knockout tower, adopt the top condensation, per hour can produce 2.55-2.80 tons of TriMethylolPropane(TMP)s through rectifying; To directly send into pelleter cooling and slice packaging through the smart TriMethylolPropane(TMP) product of rectifying again;
According to calculating in 330 days, press minimum output and calculate 2.55 * 24 * 330=20196 ton, calculate 2.8 * 24 * 330=22176 ton by maximum production.
Said flocculation agent is a SEPIGEL 305.
Horizontal spiral centrifuging mode is:, squeezes in the rotary drum of horizontal spiral centrifuge TriMethylolPropane(TMP) bullion reaction solution through transferpump, and powerful through the rotary drum generation of high speed rotating
Cf-The solid phase particles big density is deposited to drum inner wall; Because the rotating speed of spiral and rotary drum is different; The two has relative movement, utilizes the relative movement of spiral and rotary drum to push the solid phase that is deposited on drum inner wall the discharge of to rotary drum exit, and the clear liquid after the separation is discharged from the whizzer the other end; Thereby accomplished the separation of solid phase residue in the TriMethylolPropane(TMP) bullion reaction solution; The rotating speed of horizontal spiral centrifuge high speed rotating is more than the 3000 commentaries on classics/min, and the filter pore of the built-in filtering net of horizontal spiral centrifuge is 500-1000 orders.
The method of separating calcium formiate is:
1. will contain the successional injection subsider of calcium formiate solid liquid concentrator, solid formic acid calcium receives the influence of gravity to be deposited to the bottom of subsider, and the top does not have the liquid concentrator of solid particulate to get into the rectification process of TriMethylolPropane(TMP);
2. the bottom of scraper plate machine links to each other with the bottom of subsider, the burying scraper plate when operation of scraper plate machine, and the successional calcium formiate that will be deposited in the subsider bottom scrapes;
3. bury the scraper plate wash-down water to what be in uncovered position, scraper plate machine top, dash above the band filter on the transition band will burying calcium formiate that scraper plate scrapes under the drive of current;
4. the below of top transition band is with negative pressure or vacuum tank suction, and the filter pore of transition band is 500 orders-1000 orders; Water separates with the calcium formiate solid through filter opening under the dual power effect of gravity and suction, gets the calcium formiate solid, and wash-down water returns in the flushed channel again;
5. separating the back calcium formiate directly packs or packs after the process pneumatic dryer drying.
Condensation reaction still in the condensation process adopts the various stirring of multilayer, and the first layer adopts three leaves pusher, and the second layer adopts double-deck hinged joint slurry, and layer adopts three leaves pusher for the third time.
Condensation reaction cooling in the condensation process adopts full chuck to add coil arrangement, guarantees that maintain is at the 50-70 degree.
Condensation feed intake reacted after, residual aldehyde 7g/l is in sampling, constant temperature kept 25 minutes; Do the residual aldehyde of condensated liquid once more; If the residual aldehyde of fruit then adds ydrogen peroxide 50 and unnecessary formolite reaction when 3.5g/l-3.7g/l, the add-on calculating of ydrogen peroxide 50: residual aldehyde concentration * condensated liquid volume * constant 3.2; When if residual aldehyde is higher than 3.7g/l, continue constant temperature and keep up to residual aldehyde during to 3.7g/l, if when residual aldehyde is lower than 3.5g/l, then add formaldehyde; The residual alkali of having thrown material is at 6g/l; After adding ydrogen peroxide 50, be warming up to 80 degree, need 40 minutes when rising to 80 degree from constant temperature 39.5 degree, the residual aldehyde of sampling analysis, if when residual aldehyde is higher than 0.3g/l, the continuation activation; When residual aldehyde is lower than 0.3g/l, add 30-32 flocculation agent SEPIGEL 305s, sedimentation 5 minutes.
Beneficial effect of the present invention:
1, centrifuging of the present invention is owing to adopting horizontal spiral centrifuging mode, settling process before minimizing separates and the extraction process after the separation.Save the setting of subsider, reduced the floor space of whole technology, saved the settling time more than 2 hours; Stopped the generation of a large amount of wash waters in the production process; The minimizing of extraction, the consumption of having practiced thrift extraction agent.
2, scraper plate of the present invention divides burying scraper plate when operation of calcium middle scraper machine, and the successional calcium formiate that will be deposited in the subsider bottom scrapes, and the top does not have the liquid concentrator of solid particulate to get into the rectification working process of TriMethylolPropane(TMP); Promptly reach the purpose of separating calcium formiate, do not influenced TriMethylolPropane(TMP) preparation technology again, guaranteed calcium method TriMethylolPropane(TMP) preparation technology's continuity.
Therefore, but the present invention's operate continuously is suitable for more massive suitability for industrialized production, is particularly suitable for 20,000 tons of calcium method TriMethylolPropane(TMP) suitability for industrialized production.
3, with respect to existing 10,000 tons of calcium method TriMethylolPropane(TMP) production technique, the present invention
1. same output, operator reduce half the, have improved work rate, reduce cost of labor.
2. same output, the sewage of production is less 70%-75%, has also reduced the introducing amount of former water, reduces the waste and the sewage load of water resources, reduces cost of sewage disposal.
3. same output, power consumption is low, practices thrift 70%-80% power consumption.
4. same output, the ground area reduces, and significantly reduces land wastage, guarantees the availability in soil.
5. the material that stops in tower and the groove jar in the middle of dropping in the production technique of 20,000 tons of calcium method TriMethylolPropane(TMP) production technique than 10,000 tons reduces 75%-80%, reduces the operation fund reduction that enterprise drops into.
6. build 20,000 tons of calcium method TriMethylolPropane(TMP) production technique of a cover and reduce by 70%-80%, reduce the infusion of financial resources of enterprise than the production technique cost of investment of building 10,000 tons.
Description of drawings
Fig. 1 is the embodiment of the invention 1 process flow sheet.
Fig. 2 is the structural representation of the embodiment of the invention 1 calcium formiate separation system.
Embodiment
The present invention can do further description to the present invention through following embodiment, yet scope of the present invention is not limited to following embodiment.
Embodiment 1:
(1) condensation: adopt two condensation reaction stills; The effective volume of each condensation reaction still is designed to 30 cubic metres; Condensation process one feeding amount is 25kmol, and end water concentration is controlled at 110-115g/l, and the stirring of condensation reaction still is increased to more than the 150 commentaries on classics/mir; Butyraldehyde-n: formaldehyde: calcium hydroxide is 1:3.0:0.6, stirs to be warmed up to 50-70 ℃ and to carry out condensation reaction, obtains 2,2-dihydroxymethyl butyraldehyde in the reaction process, and formaldehyde carries out Cannizzaro reaction again, and every mole of above-mentioned butyraldehyde-n adds 0.2 mole formaldehyde again; Then in reaction kettle, add formic acid and neutralize and reach pH value 5-7, promptly obtain containing the TriMethylolPropane(TMP) bullion reaction solution that comprises ditrimethylolpropane and calcium formiate sub product; TriMethylolPropane(TMP) accounts for about 12%-12.5% in the TriMethylolPropane(TMP) bullion reaction solution.
Wherein:
The condensation reaction still adopts the various stirring of multilayer; The first layer adopts three leaves pusher; The second layer adopts double-deck hinged joint to starch, and three leaves of layer employing for the third time are pusher, and the liquid that bottom or dead angle are located sucks out it once more through the pusher stirring of three leaves to be broken up it through two layers of hinged joints slurry; Make the molecular contact of material amass increase, react complete as much as possible;
Condensation feed intake reacted after, residual aldehyde 7g/l is in sampling, constant temperature kept 25 minutes; Do the residual aldehyde of condensated liquid once more; If the residual aldehyde of fruit then adds ydrogen peroxide 50 and unnecessary formolite reaction when 3.5g/l-3.7g/l, the add-on calculating of ydrogen peroxide 50: residual aldehyde concentration * condensated liquid volume * constant (3.2); When if residual aldehyde is higher than 3.7g/l, continue constant temperature and keep up to residual aldehyde during to 3.7g/l, if when residual aldehyde is lower than 3.5g/l, then add formaldehyde; The residual alkali of having thrown material is at 6g/l; After adding ydrogen peroxide 50, be warming up to 80 degree, need 40 minutes when rising to 80 degree from constant temperature 39.5 degree, the residual aldehyde of sampling analysis, if when residual aldehyde is higher than 0.3g/l, the continuation activation.When residual aldehyde is lower than 0.3g/l, add 30Kg flocculation agent sedimentation 5 minutes, reduce formaldehyde to the impurity that subsequent technique produces, improved yield, guarantee quality product;
The condensation reaction cooling is used full chuck instead and is added coil pipe, makes the cooling area increase, and guarantee that maintain at the 50-70 degree, solves localized hyperthermia in the reaction process, and it is many to produce by product;
Every still reaction times is 120 minutes; Every still 25m
3Reaction solution, 22 stills feed intake every day;
(2) centrifuging: the speed of in TriMethylolPropane(TMP) bullion reaction solution, pressing 30kg/h adds SEPIGEL 305, accelerates the flocculation of suspended substance, leave standstill 5 minutes after, adopt horizontal spiral centrifuging mode reaction solution to be carried out the separation of solid phase residue again; Filtration velocity is 22.5m
3/ h, producing the solid phase residue is 200kg/h;
Horizontal spiral centrifuging mode is:, squeezes in the rotary drum of horizontal spiral centrifuge TriMethylolPropane(TMP) bullion reaction solution through transferpump, and powerful through the rotary drum generation of high speed rotating
Cf-The solid phase particles big density is deposited to drum inner wall; Because the rotating speed of spiral and rotary drum is different; The two has relative movement, utilizes the relative movement of spiral and rotary drum to push the solid phase that is deposited on drum inner wall the discharge of to rotary drum exit, and the clear liquid after the separation is discharged from the whizzer the other end; Thereby accomplished the separation of solid phase residue in the TriMethylolPropane(TMP) bullion reaction solution;
(3) evaporation: during evaporation, with 22.5m
3The filtered liq of/h speed after the solid phase residue that the evaporator evaporation device drops into separates adopts rising-film evaporator, and effective heating zone of vaporizer is 8-12 square metres, and dehydration rate reaches 85%, and dehydration by evaporation speed is 17m
3/ h, evaporation condensate is back to condensation process;
Carry out filtration membrane vaporizer control vacuum-95KPa, vaporization temperature 90 degree, it is high to control its dehydration rate, and reduces material in the hot conditions residence time, guarantees not imitation frosted glass, guarantees quality product.The evaporation pan feeding is 22.5m
3/ h, TriMethylolPropane(TMP) content are about 12%.
Be TriMethylolPropane(TMP) and calcium formiate liquid concentrator at the bottom of the tower of rising-film evaporator, the rising-film evaporator column bottom temperature is controlled to be 120-135 when spending, and the calcium formiate crystallization is separated out;
The evaporation later stage adds phosphoric acid, guarantees in decalcification, to fail the calcium formiate removed fully, influence the blocking pipe tower, and phosphoric acid produces calcium phosphate with the calcium reaction, can remove the calcium of material fully through filtration, and assurance calcium is less than the normal running that influences tower.
(4) scraper plate divides calcium: contain calcium formiate solid liquid concentrator after will evaporating and inject subsider, adopt the separation system that comprises scraper plate machine and band filter combination, scrape calcium formiate from the bottom continuity of subsider, from but reach the purpose of separation calcium formiate;
The method of separating calcium formiate is:
1. will contain the successional injection subsider of calcium formiate solid liquid concentrator, solid formic acid calcium receives the influence of gravity to be deposited to the bottom of subsider, and the top does not have the liquid concentrator of solid particulate to get into the rectification process of TriMethylolPropane(TMP);
2. the bottom of scraper plate machine links to each other with the bottom of subsider, the burying scraper plate when operation of scraper plate machine, and the successional calcium formiate that will be deposited in the subsider bottom scrapes;
3. bury the scraper plate wash-down water to what be in uncovered position, scraper plate machine top, dash above the band filter on the transition band will burying calcium formiate that scraper plate scrapes under the drive of current;
4. the below of top transition band is with negative pressure or vacuum tank suction, and the filter pore of transition band is 500 orders-1000 orders; Water separates with the calcium formiate solid through filter opening under the dual power effect of gravity and suction, gets the calcium formiate solid, and wash-down water returns in the flushed channel again;
5. separating the back calcium formiate directly packs or packs after the process pneumatic dryer drying.
Divide after the calcium technology 99% calcium formiate in the reaction solution is separated, remaining calcium adds phosphoric acid hydrolysis; Per hour separate 1.54 tons of calcium formiates;
Like Fig. 2; The calcium formiate separation system adopts and comprises subsider 3, scraper plate machine 5 and band filter 6, and the bottom notch of subsider 3 is connected with the communication port of scraper plate machine 5 bottoms, and scraper plate machine 5 is obliquely installed; The below, top of scraper plate machine 5 is provided with band filter 6; Be provided with transport tape in the scraper plate machine 5, the transport tape outside is connected with some scraper plates that bury, the power wheel of transport tape with scrape board motor and be connected; The top of scraper plate machine 5 is provided with flushing tank 10, and the flush position of flushing tank 10 forms the tangential flushing with the transport tape that is in scraper plate machine 5 top ports.
Said band filter 6 is horizontally disposed with, and an end of band filter 6 is inboard below the top of scraper plate machine 5, and the filter pore of transition band is 500 orders-1000 orders; The below of the top transition band 9 of band filter 6 is provided with rubber sealing coat 12, and rubber sealing coat 12 is connected with band filter vacuum tank 7 through the suction pipe 13 of bottom, and the power wheel of band filter 6 is connected with the filtration motor.
The other end below of band filter 6 is provided with pneumatic dryer 11, and the discharging direction of band filter 6 is corresponding with the opening for feed of pneumatic dryer 11.Like this with water sepn after calcium formiate directly get in the pneumatic dryer 11 dry.
The transport tape that is provided with in the said scraper plate machine 5 is connected with scraper plate chain bar 8 or the transport tape inboard is provided with scraper plate chain bar 8, and power wheel is a sprocket wheel.
The angle that the water (flow) direction of wash-down water and horizontal direction form is 90 °-120 °.
The top of said scraper plate machine 5 is higher than the interior top 2m-4m of groove of subsider 3.
The angle of inclination that said scraper plate machine 5 is obliquely installed is 40 °.
The top of said subsider 3 is provided with agitator motor 2 and opening for feed 1, and the cell body top of subsider 3 is provided with riser 4, and the paddle wheel that is provided with in agitator motor 2 and the subsider 3 is connected, and paddle wheel leaves the minimum interval of communication port of scraper plate machine 5 bottoms between 15cm.
(5) rectifying: with 4.5 m
3/ h speed does not have the liquid concentrator of solid particulate to put in the rectifying tower at the top, and TriMethylolPropane(TMP) content is about 58%, and the tower diameter is 1800,30 meters of height; Isolate the light constituent low-boiling point material, get into the TriMethylolPropane(TMP) knockout tower, adopt the top condensation, per hour can produce 2.55 tons of TriMethylolPropane(TMP)s, will directly send into pelleter cooling and slice packaging through the smart TriMethylolPropane(TMP) product of rectifying again through rectifying;
At rectification process; In order to guarantee the normal separation of tower; We install gas-liquid separator on the valve tube of rectifying tower; Can guarantee that so incondensible liquid is carrying out condensation at gas-liquid separator in the tower, guarantee the normal operation of unimpeded, the vacuum apparatus of vacuum pipe, thereby guaranteed that 2.55 tons/h TriMethylolPropane(TMP) finished product produces.Thereby guarantee the normal operation of tower, help the separation of material in the tower, guaranteed the good of quality product.
The production efficiency abridged table
| ? | Device parameter | Process time | Speed | Output |
| Condensation | 35 cubic metres of useful volumes/individual | Operation in 24 hours | Every still 120 minutes (two still) | Be equivalent to reaction solution 23m 3/h? |
| Filter | LW-450 whizzer | Operation in 24 hours | 200kg/h solid phase residue | 22.5m 3/ h reacts the stillness of night |
| Evaporation | Two in diameter 800 vaporizers | Operation in 24 hours | Dehydration rate 85% | 4.5m 3/ h evaporated liquor |
| Divide calcium | 10 square meter band filters | Operation in 24 hours | ? | 1.54 ton/h calcium formiate |
| Rectifying | Two on diameter 1800 rectifying tower | Operation in 24 hours | ? | 2.55 ton/h TriMethylolPropane(TMP) |
Calculated 2.55 * 24 * 330=20196 ton, the actual annual output per year according to 330 days above 20,000 tons of TriMethylolPropane(TMP)s.
With respect to existing 10,000 tons of calcium method TriMethylolPropane(TMP) production technique, the scale of pressing present embodiment, operator of the present invention reduce about 50; Practice thrift 2,500,000 yuan of labor costs every year, saved about 400 tons, the consumption of the extraction agent about 6,000,000 yuan; Reduce the waste of water resources, stopped the generation of about 50,000 side's wash waters in the production process, practice thrift the power consumption of about 4,000,000 degree; Land area reduces about 30 mu; Cost of investment reduces by 70%-80%, and the TriMethylolPropane(TMP) per ton cost 1500-2000 unit/ton that descended has improved production efficiency widely.
Claims (8)
1. production technique of producing 20000 tons of calcium method TriMethylolPropane(TMP)s per year; Preparation technology is divided into condensation, centrifuging, evaporation, scraper plate and divides calcium and rectifying; It is characterized in that: with butyraldehyde-n and formaldehyde is raw material; Use technical grade calcium hydroxide to be basic catalyst,, obtain containing the TriMethylolPropane(TMP) bullion reaction solution that comprises ditrimethylolpropane and calcium formiate sub product through condensation process and formic acid neutralization reaction; Centrifuging process using horizontal spiral centrifuging mode is carried out the separation of solid phase residue to reaction solution; The evaporation of employing rising-film evaporator, evaporation condensate is back to condensation process; Scraper plate divides calcium technology to inject subsider for containing calcium formiate solid liquid concentrator after will evaporate, scrapes calcium formiate from the bottom continuity of subsider, again through band filter recovery calcium formiate; Rectifying tower adopts tower self backflow and rises membrane type intensification technology in the rectification process, and the control techniques of the traverse baffle in the tower is installed gas-liquid separator simultaneously on the valve tube of rectifying tower; Get the TriMethylolPropane(TMP) product after the rectifying.
2. production technique as claimed in claim 1 is characterized in that:
(1) condensation: adopt two condensation reaction stills; The effective volume of each condensation reaction still is designed to 35 cubic metres; Condensation process one feeding amount is 25-28kmol, and end water management is at 110-115g/l, and the stirring of condensation reaction still is increased to more than the 150 commentaries on classics/mir; 22 stills that feed intake every day, 25-28 cubic metres of reaction solutions of every still, speed of response is that every still reaction times is 120 minutes;
(2) centrifuging: in TriMethylolPropane(TMP) bullion reaction solution, add flocculation agent; The volume ratio of flocculation agent and TriMethylolPropane(TMP) bullion reaction solution is 1:580-650; The speed that adds flocculation agent is 30-32kg/h; After leaving standstill 5-8 minutes, adopt horizontal spiral centrifuging mode reaction solution to be carried out the separation of solid phase residue again; Filtration velocity is 22.5-25.5m
3/ h, producing the solid phase residue is 200-300kg/h;
(3) evaporation: with 22.5-25m
3The filtered liq of/h speed after the solid phase residue that the evaporator evaporation device drops into separates adopts rising-film evaporator, and effective heating zone of vaporizer is 8-12 square metres, and dehydration rate reaches 85-88%, and dewatering speed is 17-19m
3/ h, evaporation condensate is back to condensation process;
(4) scraper plate divides calcium: contain calcium formiate solid liquid concentrator after will evaporating and inject subsider, adopt the separation system that comprises scraper plate machine and band filter combination, scrape calcium formiate from the bottom continuity of subsider, again through band filter recovery calcium formiate;
Divide after the calcium technology 98.5-99% calcium formiate in the reaction solution is separated, remaining calcium adds phosphoric acid hydrolysis; Divide in the calcium technology and per hour separate 1.54-1.75 tons of calcium formiates;
(5) rectifying: with 4.5-5m
3/ h speed does not have the liquid concentrator of solid particulate to put in the rectifying tower at the top, and the tower diameter is 1750-1850,30-32 meters of height; Isolate the light constituent low-boiling point material; Get into the TriMethylolPropane(TMP) knockout tower, adopt the top condensation, per hour can produce 2.55-2.80 tons of TriMethylolPropane(TMP)s through rectifying; To directly send into pelleter cooling and slice packaging through the smart TriMethylolPropane(TMP) product of rectifying again;
According to calculating in 330 days, press minimum output and calculate 2.55 * 24 * 330=20196 ton, calculate 2.8 * 24 * 330=22176 ton by maximum production.
3. production technique as claimed in claim 2 is characterized in that: said flocculation agent is a SEPIGEL 305.
4. according to claim 1 or claim 2 production technique; It is characterized in that horizontal spiral centrifuging mode is: through transferpump with TriMethylolPropane(TMP) bullion reaction solution; Squeeze in the rotary drum of horizontal spiral centrifuge; The powerful cf-of rotary drum generation through high speed rotating is deposited to drum inner wall to the big solid phase particles of density, because the rotating speed of spiral and rotary drum is different, the two has relative movement; Utilize the relative movement of spiral and rotary drum to push the solid phase that is deposited on drum inner wall the discharge of to rotary drum exit, the clear liquid after the separation is discharged from the whizzer the other end; Thereby accomplished the separation of solid phase residue in the TriMethylolPropane(TMP) bullion reaction solution; The rotating speed of horizontal spiral centrifuge high speed rotating is more than the 3000 commentaries on classics/min, and the filter pore of the built-in filtering net of horizontal spiral centrifuge is 500-1000 orders.
5. according to claim 1 or claim 2 production technique is characterized in that the method for separating calcium formiate is:
1. will contain the successional injection subsider of calcium formiate solid liquid concentrator, solid formic acid calcium receives the influence of gravity to be deposited to the bottom of subsider, and the top does not have the liquid concentrator of solid particulate to get into the rectification process of TriMethylolPropane(TMP);
2. the bottom of scraper plate machine links to each other with the bottom of subsider, the burying scraper plate when operation of scraper plate machine, and the successional calcium formiate that will be deposited in the subsider bottom scrapes;
3. bury the scraper plate wash-down water to what be in uncovered position, scraper plate machine top, dash above the band filter on the transition band will burying calcium formiate that scraper plate scrapes under the drive of current;
4. the below of top transition band is with negative pressure or vacuum tank suction, and the filter pore of transition band is 500 orders-1000 orders; Water separates with the calcium formiate solid through filter opening under the dual power effect of gravity and suction, gets the calcium formiate solid, and wash-down water returns in the flushed channel again;
5. separating the back calcium formiate directly packs or packs after the process pneumatic dryer drying.
6. according to claim 1 or claim 2 production technique is characterized in that the condensation reaction still in the condensation process adopts the various stirring of multilayer, and the first layer adopts three leaves pusher, and the second layer adopts double-deck hinged joint slurry, and layer adopts three leaves pusher for the third time.
7. according to claim 1 or claim 2 production technique is characterized in that the condensation reaction cooling in the condensation process adopts full chuck to add coil arrangement, guarantees that maintain is at the 50-70 degree.
8. production technique as claimed in claim 2; It is characterized in that condensation feed intake reacted after, residual aldehyde 7g/l is in sampling, constant temperature kept 25 minutes; Do the residual aldehyde of condensated liquid once more; If the residual aldehyde of fruit then adds ydrogen peroxide 50 and unnecessary formolite reaction when 3.5g/l-3.7g/l, the add-on calculating of ydrogen peroxide 50: residual aldehyde concentration * condensated liquid volume * constant 3.2; When if residual aldehyde is higher than 3.7g/l, continue constant temperature and keep up to residual aldehyde during to 3.7g/l, if when residual aldehyde is lower than 3.5g/l, then add formaldehyde; The residual alkali of having thrown material is at 6g/l; After adding ydrogen peroxide 50, be warming up to 80 degree, need 40 minutes when rising to 80 degree from constant temperature 39.5 degree, the residual aldehyde of sampling analysis, if when residual aldehyde is higher than 0.3g/l, the continuation activation; When residual aldehyde is lower than 0.3g/l, add 30-32 flocculation agent SEPIGEL 305s, sedimentation 5 minutes.
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| CN108997082A (en) * | 2018-09-10 | 2018-12-14 | 武汉中能恒信工程技术有限公司 | A method of catalysis trimethylolpropane condensation reaction |
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| CN109485544A (en) * | 2017-09-11 | 2019-03-19 | 中国科学院大连化学物理研究所 | A method of continuously preparing trimethylolpropane |
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| CN109369333A (en) * | 2018-11-27 | 2019-02-22 | 濮阳市永安化工有限公司 | The method of trimethylolpropane is isolated from trimethylolpropane light component |
| CN110357761A (en) * | 2019-07-25 | 2019-10-22 | 江西科顶化学材料有限公司 | A kind of production technology of trimethylolethane |
| CN115536491A (en) * | 2021-09-30 | 2022-12-30 | 湖北宜化化工科技研发有限公司 | Production method for producing trimethylolpropane by recycling carbide slag |
| CN115536491B (en) * | 2021-09-30 | 2024-04-12 | 湖北宜化化工科技研发有限公司 | Production method for producing trimethylolpropane by recycling carbide slag |
| CN115745742A (en) * | 2022-12-16 | 2023-03-07 | 赤峰瑞阳化工有限公司 | Method for recycling residual aldehyde from calcium-method trimethylolpropane condensation liquid |
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