CN101463021B - Method and equipment for automatically and continuously producing furfuryl alcohol - Google Patents
Method and equipment for automatically and continuously producing furfuryl alcohol Download PDFInfo
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- CN101463021B CN101463021B CN2008100808658A CN200810080865A CN101463021B CN 101463021 B CN101463021 B CN 101463021B CN 2008100808658 A CN2008100808658 A CN 2008100808658A CN 200810080865 A CN200810080865 A CN 200810080865A CN 101463021 B CN101463021 B CN 101463021B
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 419
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 78
- 238000009835 boiling Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000470 constituent Substances 0.000 claims description 14
- 230000008016 vaporization Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 8
- 230000001143 conditioned effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical group [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 description 23
- 238000005406 washing Methods 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000006210 lotion Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SLTNJGDECJATET-RIVJSTIKSA-N [(8r,9s,10r,13s,14s,17s)-10,13-dimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl] 4-methylpentanoate;[(8r,9s,10r,13s,14s,17s)-10,13-dimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CC)[C@@]1(C)CC2.C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CCC(C)C)[C@@]1(C)CC2.C([C@]1(C2CC[C@@H]1O)C)CC(C1=CC=3)C2CCC1=CC=3OC(=O)C1=CC=CC=C1.O([C@H]1CCC2C3C(C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1=CC=CC=C1.O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(CCC(=O)C=C4CC3)C)CC[C@@]21C)C(=O)CCC1=CC=CC=C1 SLTNJGDECJATET-RIVJSTIKSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
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- 238000005373 pervaporation Methods 0.000 description 1
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- 238000011085 pressure filtration Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
- Y02P90/02—Total factory control, e.g. smart factories, flexible manufacturing systems [FMS] or integrated manufacturing systems [IMS]
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention aims at providing a method for automatically and continuously producing furfuryl alcohol. The method comprises the following steps: delivering preheated mixture of the furfuryl alcohol and a catalyst together with hydrogen gas to a reactor with an automatic temperature control system for reaction; cooling the crude furfuryl alcohol from the reactor in a cooler, then performing gas-liquid separation in a separator to separate the hydrogen gas from the crude furfuryl alcohol; separating the crude furfuryl alcohol from the separator into clear liquid and the catalyst by a continuous filter; and directly sending the clear liquid obtained by the continuous filter to a light-ends removal column to remove light ends, and further sending the clear liquid to a rectification column for rectification to continuously produce the furfuryl alcohol. The invention further provides a device for automatically and continuously producing the furfuryl alcohol.
Description
Technical field
The invention belongs to the production technical field of furfuryl alcohol, be specifically related to the method and apparatus of automatically and continuously producing furfuryl alcohol.
Background technology
Furfuryl alcohol is a kind of important fine chemical material, is mainly used in to produce furfuryl alcohol resin, furane resin etc.Furfuryl alcohol mainly by furfural and hydrogen the reaction in the presence of catalyzer carry out suitability for industrialized production.
The reaction formula of furfural and H-H reaction is: C
5H
4O
2+ H
2→ C
5H
6O
2+ Q, Q are reaction heat.
In traditional furfuryl alcohol production method, furfuryl alcohol production is mainly reacted by tubular type or tank reactor, and the crude furfuryl alcohol that reflects freely precipitates and isolates catalyzer in settling bowl, obtains finished product through the rectifying still batch fractionating then.The typical process of this method is, enters the preheater preheating after furfural and catalyst mix and hydrogen are mixed, and enters the reaction of tubular reactor or reactor then, and temperature of reaction is regulated intake (or low-pressure steam) by manually (or variable valve) and controlled; The crude furfuryl alcohol that reflects enters the water cooler cooling, enters separator then, and hydrogen returns recycle, and crude furfuryl alcohol is introduced into whizzer and carries out the normal temperature and pressure filtration, owing to can not filter out catalyzer fully, still need enter subsider and carry out secondary settlement; Regular then labor cleaning; It is refining that the thick alcohol on subsider upper strata enters rectifying still, goes out light constituent earlier, goes out finished product then, when the observation cat head does not go out liquid, stops distillation, discharges high boiling material; It is refining to repeat next still again.
There are many shortcomings in above-mentioned traditional method.Show following aspect:
(1) manual shift water inlet or low-pressure steam are with control reaction temperature, and water inlet (or low-pressure steam) there is not rule, and by experience control, the result can cause temperature of reaction fluctuated, temperature of reaction vary within wide limits, the crude furfuryl alcohol quality instability that reflects; If the water inlet or advance excessive steam, can cause falling temperature.After reacting away temperature, need open reactor jacket or internal heat exchange tubes steam heats up again; Because temperature of reaction is wayward, everyone multipotency operation 1-2 cover reactor, and frequent operation, labor strength is big; Safety coefficient is low.Under the situation of cutting off the water supply suddenly or cutting off the power supply, need take emergency decompression and do the processing of stopping in emergency, otherwise, security incidents such as overtemperature can appear.
(2) energy consumption is big, and capacity usage ratio is low.In the traditional method, the charging furfural needs steam preheating, and the crude furfuryl alcohol that reflects need be at the water cooler circulating water cooling.
(3) natural subsidence is to isolate catalyzer in subsider for the crude furfuryl alcohol that reflects, and 50-100 ℃ crude furfuryl alcohol is volatilized in subsider, causes furfuryl alcohol loss and environmental pollution.
(4) in still formula batch fractionating method: 1. thick alcohol residence time in still is long, and high refuse produces many, and the high boiling material of the big more generation of still is many more, and product yield is low; 2. be not suitable for scale operation, the rectifier unit of a cover 20,000 t/a needs 5M
34 of rectifying stills, two people operation, facility investment is big; 3. frequently feed in raw material, open steam, row's high boiling material, labor strength is big; 4. the rectifying of still formula is because rectifying tower is lower, and product colour turns to be yellow, and furfuryl alcohol content is below 97%.
(5) spent catalyst in subsider needs regular labor cleaning's barrelling to sell, and does not have second stage employ, and the consumption of ton catalyst for furfural alcohol is more than 6kg.
Summary of the invention
The method and apparatus that the purpose of this invention is to provide a kind of automatically and continuously producing furfuryl alcohol is to overcome the problems referred to above of the prior art.
For achieving the above object, the invention provides following aspect.
1. the method for an automatically and continuously producing furfuryl alcohol comprises
(1) reactions steps: the furfural of preheating and catalyst mixture and hydrogen are sent in the reactor to react, and described reactor is equipped with automatic temperature control system, and described catalyzer comprises copper silicon or copper chromium catalyst for furfural alcohol;
(2) cooling and Hydrogen Separation step: will in water cooler, cool off by the crude furfuryl alcohol that reactor comes out, and in separator, carry out gas-liquid separation then, hydrogen is separated from crude furfuryl alcohol;
(3) catalyst separating step: will be divided into clear liquid and catalyzer by continuous filter by the crude furfuryl alcohol that separator comes out;
(4) take off light and rectification step: the clear liquid that obtains in the step (3) is directly sent into lightness-removing column, after lightness-removing column is sloughed light constituent, enter rectifying tower and rectifying in rectifying tower, thereby manufacture a finished product furfuryl alcohol continuously.
2. according to the method for the automatically and continuously producing furfuryl alcohol of item 1, wherein said automatic temperature control system comprises reactor jacket or built-in water cooler, in reactor jacket or built-in water cooler, be filled with the liquid of boiling point between 60-240 ℃, liquid level remains on chuck or built-in water cooler volumetrical 10-80%, and liquid feeding amount by automatic (or manual adjustment system) conditioned reaction device chuck of DCS automatic control system or built-in water cooler, pressure, temperature, liquid level remains on the temperature in chuck or the built-in water cooler constant pressure of 60-240 ℃ of steady temperature and 0.2-3.0MPa.
3. according to the method for the automatically and continuously producing furfuryl alcohol of item 2, the liquid first-selection of wherein said boiling point between 60-240 ℃ is water.
4. according to the method for the automatically and continuously producing furfuryl alcohol of item 2, also comprise the high-temperature gas behind the vaporizing liquid in reactor jacket or the built-in water cooler is delivered to steam pockets, as the thermal source that takes off the heating in light and the rectification step.
5. according to the method for item 1 each automatically and continuously producing furfuryl alcohol to the item 4, wherein the water cooler described in the step (2) is the preheater that is used for preheating furfural and catalyst mixture.
6. according to the method for item 1 each automatically and continuously producing furfuryl alcohol to the item 5, wherein the continuous filter described in the step (3) is filter plants such as whizzer or pressure filter.
7. according to the method for item 1 each automatically and continuously producing furfuryl alcohol to the item 6, comprise that also the catalyzer that will separate in (3) catalyst separating step washs with the good solvent of high boiling material solubleness, then recycling.
8. according to the method for the automatically and continuously producing furfuryl alcohol of item 7, the good solvent of wherein said high boiling material solubleness comprises furfural, furfuryl alcohol, methyl furan, aromatic hydrocarbons etc.
9. the equipment of an automatically and continuously producing furfuryl alcohol mainly comprises
(1) is used for the preheater of preheating furfural and catalyst mixture;
(2) the described reactor of reactor that is used to carry out the reaction of the furfural of preheating and catalyst mixture and hydrogen is equipped with automatic temperature control system;
(3) be used to cool off the water cooler of the crude furfuryl alcohol of coming out by reactor;
(4) be used for carrying out the separator of gas-liquid separation so that hydrogen is separated from crude furfuryl alcohol;
(5) be used for the continuous filter of the crude furfuryl alcohol that continuous filtration come out by separator;
(6) clear liquid that is used for being come out by continuous filter takes off light lightness-removing column;
(7) be used for the product rectifying after taking off gently to obtain the rectifying tower of finished product furfuryl alcohol.
10. according to the equipment of the automatically and continuously producing furfuryl alcohol of item 9, wherein said automatic temperature control system comprises reactor jacket or built-in water cooler, in reactor jacket or built-in water cooler, be filled with the liquid of boiling point between 60-240 ℃, liquid level remains on chuck or built-in water cooler volumetrical 10-80%, and liquid feeding amount by automatic (or manual adjustment system) conditioned reaction device chuck of DCS automatic control system or built-in water cooler, pressure, temperature, liquid level remains on the liquid in chuck or the built-in water cooler constant pressure of 60-240 ℃ of steady temperature and 0.2-3.0MPa.
11. according to the equipment of the automatically and continuously producing furfuryl alcohol of item 10, the liquid first-selection of wherein said boiling point between 60-240 ℃ is water.
12., also comprise being used to hold the steam pockets of the high-temperature gas behind the vaporizing liquid in reactor jacket or the built-in water cooler with the thermal source that heats when taking off light and rectifying according to the equipment of the automatically and continuously producing furfuryl alcohol of item 10.
13. according to the equipment of item 9 each automatically and continuously producing furfuryl alcohol to the item 12, the water cooler that wherein is used to cool off the crude furfuryl alcohol of being come out by reactor is the preheater that is used for preheating furfural and catalyst mixture.
14. according to the equipment of item 9 each automatically and continuously producing furfuryl alcohol to the item 13, the continuous filter that wherein is used for the crude furfuryl alcohol that continuous filtration come out by separator is filter plants such as whizzer or pressure filter.
Adopt the method and apparatus of automatically and continuously producing furfuryl alcohol of the present invention, solved following five key technical problems: the constant temperature and pressure of (1) reaction is controlled automatically.Mainly be to adopt the liquid of a kind of boiling point between 60-240 ℃, in reactor jacket or built-in water cooler, remain under the constant pressure of 60-240 ℃ of constant temp and 0.2-3.0MPa, liquid level remains on chuck or built-in refrigerating unit volume 10-80%, absorb big calorimetric by vaporizing liquid, thereby the realization response temperature is constant.(2) balance of reaction heat and comprehensive utilization.The one, the high-temperature gas devaporation bag in reactor jacket or the built-in water cooler behind the vaporizing liquid is as taking off the thermal source that heats in light and the rectification step; The 2nd, enter separator after material that reflects and the heat exchange of charging furfural, thereby the reaction liberated heat is fully utilized.(3) recovery and utilization technology of furfuryl alcohol spent catalyst.Spent catalyst in the crude furfuryl alcohol washs with the good solvent of high boiling material solubleness, the materials such as high boiling material on flush away spent catalyst surface, and the part activity of recovery catalyzer is returned system's recycling then.(4) furfuryl alcohol is from being reacted to the continuous of rectifying.Directly enter the lightness-removing column of distillation system after the crude furfuryl alcohol that separator comes out is filtered by the continous way filter plant, the temperature of charge that advances distillation system need not heat about 50-120 ℃.Both utilize the waste heat of reaction, realized being reacted to the continuous of rectifying again.(5) furfuryl alcohol continuous rectification technology.The crude furfuryl alcohol that reflects enters lightness-removing column continuously after isolating spent catalyst continuously, from the lightness-removing column into rectifying tower that comes out, go out finished product and high boiling material continuously from rectifying tower.
Description of drawings
Fig. 1. the flow diagram of automatically and continuously producing furfuryl alcohol method.
Fig. 2. the flow diagram of traditional furfuryl alcohol production method.
Fig. 3. furfuryl alcohol of the present invention is produced the figure of an embodiment of reactor.
Fig. 4. furfuryl alcohol of the present invention is produced the figure of another embodiment of reactor.
Fig. 5. furfuryl alcohol of the present invention is produced the figure of another embodiment of reactor.
Description of reference numerals in the accompanying drawing 3:
1. take over, connect the pressure fluid storage tank
2. descend chuck water inlet variable valve, regulate chuck liquid level down
3. go up chuck water inlet variable valve, chuck liquid level in the adjusting
4. descend the chuck safety valve
5. go up the chuck safety valve
6. go up chuck steam discharge variable valve, chuck pressure in the adjusting
7. descend chuck steam discharge variable valve, regulate chuck pressure down
8. vapor pipe connects steam pockets
9. reactor safety valve
10. water discharge valve
11. water shoot
12. following chuck water inlet and the chain control of following chuck liquid level
13. last chuck water inlet and the chain control of last chuck liquid level
14. last chuck steam discharge and the chain control of last chuck pressure
15. following chuck steam discharge and the chain control of following chuck pressure
Description of reference numerals in the accompanying drawing 4:
1. take over, connect the pressure fluid storage tank
2. chuck water inlet variable valve is regulated the chuck liquid level
3. chuck safety valve
4. chuck steam discharge variable valve, adjustable clamp cover pressure
5. vapor pipe connects steam pockets
6. reactor safety valve
7. water discharge valve
8. water shoot
9. the chain control of steam discharge and pressure
10. water inlet and the chain control of liquid level
Description of reference numerals in the accompanying drawing 5:
1. water inlet variable valve
2. water shoot connects the pressure container for storing liquid
3. exhaust regulating valve
4. vapor pipe connects steam pockets
5. safety valve
6. reactor safety valve
Embodiment
The method of automatically and continuously producing furfuryl alcohol
The method of automatically and continuously producing furfuryl alcohol of the present invention mainly comprises the steps: the furfural from storage tank is entered the batching still, and furfural and catalyst by proportion are mixed in the batching still; Mix the back and squeeze into preheater, utilize the crude furfuryl alcohol of coming out that mixture is preheating to 80--170 ℃ and hydrogen mixing by reactor with volume pump; Enter reactor then, at 3.0--15.0MPa, in reaction, react under the temperature 140--300 ℃ of condition with hydrogen, at this moment, liquid in chuck or the built-in water cooler is under the constant pressure of 60--240 ℃ of constant temp and 0.2--3.0MPa, liquid level remains on the volumetrical 10--80% of chuck or built-in water cooler, utilizes vaporizing liquid to absorb big calorimetric and produces steam, and steam enters steam pockets; Come out 140--280 ℃ thick alcohol of reactor enters after preheater and the furfural heat exchange self temperature and drops to about 50--140 ℃; Entered separator by the crude furfuryl alcohol after the cooling, hydrogen returns the utilization of hydrogen pressure machine; Crude furfuryl alcohol is regulated by automatic valve and is entered filter plant continuously; The 50--140 ℃ of furfuryl alcohol clear liquid that comes out from filter plant enters the lightness-removing column (need not heat substantially) of distillation system, lightness-removing column links to each other with reboiler, the thermal source of reboiler is provided by the reactive vapors bag, and lightness-removing column ejects light constituent, and tower still furfuryl alcohol and a small amount of high boiling material enter the rectifying tower vaporizer; Vaporizer links to each other with rectifying tower, sloughs high boiling material at the bottom of the tower, and cat head goes out the finished product furfuryl alcohol continuously; The spent catalyst that comes out from filter plant enters the washing lotion jar, enters filter plant after the washing, catalyzer reuse, clear liquid recycle.
The raw material furfural that uses among the present invention is commercially available furfural, purity: furfural content 〉=98.5%, moisture≤0.2%, acidity≤0.008mol/l.
The catalyzer that uses among the present invention comprises: the copper silicon of Xiao Shouing, copper chromium catalyst for furfural alcohol in the market, domestic manufacturer has Xia County, Shanxi, Jiaozhuo universal love to converge catalyst for furfural alcohol manufacturers such as Longhua worker, Qingdao etc.
The blending ratio of furfural and catalyzer is that the amount of the catalyzer of per 100 parts of furfurals is 0.2-0.8 part, preferred 0.3-0.6 part, more preferably 0.4-0.5 part.Can use the mixture of raw catalyst and old catalyzer (catalyzer of recovery).
In preheater mixture is preheating to 80--1700 ℃, temperature is too high, and coking or resinifying can take place in preheater, and temperature is low can the influence reaction.
The pressure of hydrogen is at 3.0--15MPa, and temperature 140--300 ℃, reaction time is between 20-50min.
Liquid in chuck or the built-in water cooler is the liquid of boiling point between 60--240 ℃, though industrial the most frequently used be water, but also can be liquid such as other heat-eliminating medium or the raw material that needs heating, reactant, temperature is remained under the constant pressure of 60--240 ℃ of constant temp and 0.2--3.0MPa, liquid level remains on the volume 10--80% of chuck or built-in water cooler.Liquid level is crossed and low can be caused the bad control of temperature, and the too high meeting of liquid level cause the vapour space little, easily fall temperature.Utilize vaporizing liquid to absorb heat and come control reaction temperature, vaporizing liquid produces steam simultaneously, and steam enters steam pockets, can be used as and takes off in light and the rectification step or the thermal source that is used to heat in other technology.
Use continuous filter among the present invention, realized being reacted to the continuous production of rectifying.Continuous filter comprises filter, snubber assembly, regulates feeding unit, superpressure automatic regulating device etc. automatically.Continuous filter principle of work: the liquid level that relies on automatic regulating valve control separator from the crude furfuryl alcohol of separating tank; keep discharging stable; filter import superpressure is adjusted pressure valve automatically the raised area pressure is derived; guarantee filtering equipment safety; after wherein a filter plant filter cake reaches the design volume; variable valve automaticallyes switch (because the pressure and the variable valve of filter are chain control) to another filter plant; this filter plant protection of inert gas gas inlet valve is opened automatically by the DCS system; automatically the displacement filter plant is discharged to filter cake the program that enters down one in the washing lotion jar then automatically.The solvent that is used to wash spent catalyst in the washing lotion jar is furfural, furfuryl alcohol, methyl furan, aromatic hydrocarbons etc.
The catalyzer that joins the recovery in the material-compound tank mixes with raw catalyst, forms mixed catalyst, and in mixed catalyst, the catalyzer proportion of recovery is 90%, and surpassing 90% influences catalytic effect.Take all factors into consideration catalytic effect and production cost, the catalyzer proportion of recovery is preferably 20-50%.
The clear liquid that comes out from continuous filtration equipment enters the clear liquid jar, after the process buffering becomes normal pressure, squeezes into lightness-removing column from the clear liquid jar with pump, and light constituent goes out to the light constituent jar from cat head; Furfuryl alcohol and high boiling material enter the falling-film evaporator of rectifying tower at the bottom of the tower, and behind pervaporation, gas-liquid mixed enters rectifying tower, and the rectifying tower cat head goes out finished product, goes out high boiling material at the bottom of the tower.
The light constituent that is ejected by lightness-removing column mainly comprises methyl furan, water etc.
High boiling material mainly comprises furancarboxylic acid, furfuryl alcohol resin and micro-furfuryl alcohol etc.
The equipment of automatically and continuously producing furfuryl alcohol
The equipment of the method for automatically and continuously producing furfuryl alcohol of the present invention mainly comprises: material-compound tank, preheater, pressure vessel, automatic valve, frequency transformer, DCS Controlling System, washing lotion jar, continuous filter, lightness-removing column, rectifying tower, well heater, condenser, various pump and pipeline.Describe some major equipments below in detail.
(1) raw material furfural and preparation of catalysts jar
The material-compound tank that uses among the present invention is the mixing kettle that band commonly used in this area stirs, and its volume is at 1-10M
3All can.Material-compound tank also comprises agitator, speed regulator etc., in that furfural and catalyzer are added in the material-compound tank in the 100:0.2-0.5 ratio, opens and stirs, and furfural and catalyzer are mixed in material-compound tank.The upstream of material-compound tank links to each other with the furfural test tank, and the downstream links to each other with preheater by volume pump.
(2) reactor
Reactor is that volume is the tubular reactor (or tank reactor) of 50-2000L, is made by carbon steel (or stainless steel) material.Reactor also comprises chuck or built-in water cooler, safety valve, prevents blank pipe, temperature measuring equipment and measuring pressure device.The furfural of preheating and catalyst mixture and hydrogen react in reactor, and the crude furfuryl alcohol that reaction obtains is come out by reactor, cools off in water cooler.Under situation of the present invention, the water cooler that is used to cool off crude furfuryl alcohol is exactly the preheater that is used for preheating furfural and catalyst mixture.
(3) reaction regulation system
Comprise: compositions such as pressure fluid hold-up vessel, automatic valve, DCS automatic control system (or manual control mode), liquid feeding pump, frequency transformer, tensimeter.This regulation system is used for the liquid feeding amount of automatic conditioned reaction device chuck or built-in water cooler, pressure, temperature, liquid level, come the conditioned reaction temperature, concrete regulate process: pour rare gas element 0.2-0.8MPa to wet tank earlier, open the frequency conversion fresh feed pump then, pressure reaches 0.2--3.0MPa, and (this force value is higher than the pressure of reactor jacket or built-in cooler liquid, with the chain control of system), when temperature of reaction rises, the feed system variable valve is opened automatically to reactor jacket or built-in water cooler feed liquor, vent valve is opened to drum automatically and is supplied gas simultaneously, thus the realization response temperature auto control.
(4) preheater (water cooler)
The preheater that uses among the present invention (water cooler) is a preheater (its structure is telescoping or shell and tube) commonly used in this area.Preheater tube, shell side can both withstand voltage 15MPa, and heat interchanging area is at 50M
2
Among the present invention, the preheating of preheater and the cooling of crude furfuryl alcohol realize simultaneously, that is, utilize the heat of 140--280 ℃ the crude furfuryl alcohol that reactor comes out to heat the into furfural and the mixture of catalysts of reactor, thereby reach the cooling effect of thick alcohol itself.
(5) catalyst separating and recycle device
This device mainly comprises continuous filter and washing lotion jar.The crude furfuryl alcohol of being come out by separator under the effect of certain centrifugal force or pressure, makes crude furfuryl alcohol pass through filter cloth in continuous filter, and spent catalyst is left, and clear liquid comes out to enter the clear liquid jar.Spent catalyst and furfural (furfuryl alcohol) are added the washing lotion jar, open and stir, stirred about about 1 hour, the materials such as high boiling material of flush away catalyst surface, the part activity of recovery catalyzer is returned system's recycling then.
(6) rectifier unit
Rectifier unit comprises: (furfuryl alcohol and light constituent are in tower, and according to the difference of volatility, its lower boiling light constituent (carrying a small amount of furfuryl alcohol secretly) under the effect of trim the top of column liquid, is all separated extraction for reboiler, lightness-removing column.The extraction at the bottom of the tower of the material of high boiling point such as furfuryl alcohol and high boiling material), (furfuryl alcohol and high boiling material are in tower for rectifying tower, difference according to volatility, its furfuryl alcohol is carried a small amount of high boiling material secretly, and under the effect of trim the top of column liquid, furfuryl alcohol content reaches more than 98.5% and all separated extraction.The extraction at the bottom of the tower of the material of high boiling points such as high refuse), condenser, reflux ratio sparger (are equivalent to a T-valve, adjust discharging and quantity of reflux), recycle pump, light constituent jar, finished product tundish at the bottom of the falling-film evaporator (feed liquid enters the back and is membranaceous by the divider feed liquid along the heat exchange tube wall and flows down from top, gas-liquid mixture is from the bottom into rectifying tower that comes out), tower.Link to each other with reaction unit before the rectifier unit.Be used to reflect the refining of crude furfuryl alcohol, make it reach the qualified product-furfuryl alcohol that meets national standard.
The present invention has the following advantages and active effect:
(1) reactive system DCS constant temperature and pressure is controlled automatically.1. the temperature of reaction fluctuating range is smaller, thick pure steady quality; When 2. temperature of reaction was high, unnecessary heat was taken away by heat transferring medium vaporization heat; When temperature of reaction is hanged down, heated up by heat transferring medium, reaction process temperature can not occur falling; 3. because temperature of reaction is stable, everyone can operate the above reactor of 8 covers, and without frequent operation, labor strength reduces greatly; 4. safety coefficient height.Under the situation of cutting off the water supply suddenly or cutting off the power supply, the reacting replacing heat system imports and exports automatic valve and opens automatically, and cold liquid enters, the gas or the high-temp liquid that are vaporized are discharged automatically, play the purpose of reactive system cooling, system's automatic safety parking does not need to take emergency decompression and does the processing of stopping in emergency.
(2) reaction heat makes full use of, and the used heating source of total system is provided by reaction heat.Whole device uses the steam except that driving first, and ordinary production is used steam hardly.
(3) temperature of reaction is stable, and by product is few, and crude furfuryl alcohol master's content is on average more than 97%.
(4) the furfuryl alcohol spent catalyst is through carrying out washing treatment, and recycling not only reduces catalyst consumption, and reduces the generation of spent catalyst, has good economic and social benefit.
(5) owing to the successful utilization of continuous filter, realized being reacted to the continuous production of rectifying, avoid crude furfuryl alcohol in subsider, to volatilize, cause the pollution of furfuryl alcohol loss and environment.
(6) the successful utilization of continuous rectification technology in purification of furfuryl alcohol.1. thick alcohol is short at the rectifying dwell time in the tower, and high refuse produces few, and product yield is more than 99%; 2. be fit to scale operation, the furfuryl alcohol device of a cover 0.2-10 ten thousand t/a, the facility investment expense is 1/3rd of same scale device batch fractionating facility investment; 3. be fed to out the operation of finished product autostable.The furfuryl alcohol rectifier unit of one cover 0.2-10t/a only needs two people operation; Labour intensity is little, and level of automation height 4. rectifying product colour is colourless, and furfuryl alcohol content is in (gas chromatograph analysis) more than 98.5%.
Embodiment
Embodiment 1
Furfural (purity: furfural content 〉=98.5% from head tank, moisture≤0.2%, acidity≤0.008mol/l) enters the batching still, furfural and catalyst for furfural alcohol were by 100: 0.3 mixed in the batching still, mix the back and squeeze into preheater with about 600L/h with volume pump, be preheating to about 100 ℃ by the crude furfuryl alcohol that reflects, enter reactor after mixing with hydrogen then, the about 6.0MPa reaction pressure of maintenance, temperature of reaction are under 170 ℃, the condition of the residence time at about 20-40min in reaction.Water in chuck or the built-in water cooler, in about 240 ℃ of constant temp scopes and in the constant pressure pressure range about 2.0MPaMPa, liquid level remains on that the volumetrical of chuck or built-in water cooler is about 30%, and vaporizing liquid absorbs big calorimetric and produces steam, and steam enters the steam bag.The about 140 ℃ thick alcohol that comes out from reactor enters after preheater and the furfural heat exchange self temperature and drops to about about 90 ℃, is entered separator by the crude furfuryl alcohol after lowering the temperature, and hydrogen returns the utilization of hydrogen pressure machine; Crude furfuryl alcohol is regulated by automatic valve and is entered filter plant continuously, the about 90 ℃ of furfuryl alcohol clear liquids that come out from filter plant enter the lightness-removing column (need not heat substantially) of distillation system, lightness-removing column links to each other with reboiler, the thermal source of reboiler is provided by the reactive vapors bag, lightness-removing column ejects light constituent, and tower still furfuryl alcohol and a small amount of high boiling material enter the rectifying tower vaporizer.Vaporizer links to each other with rectifying tower, sloughs high boiling material at the bottom of the tower, and cat head goes out finished product furfuryl alcohol (furfuryl alcohol purity is more than 98.5%, and productive rate is more than 99%) continuously.The spent catalyst that comes out from filter plant enters the washing lotion jar, enters filter plant after the washing, catalyzer reuse, clear liquid recycle.
The quality determining method of finished product furfuryl alcohol is according to the gas chromatography in the GB/T14022.1-92 country furfuryl alcohol quality standard.
Comparative example 1
Furfural (purity: furfural content 〉=98.5% from head tank, moisture≤0.2%, acidity≤0.008mol/l) enters the batching still, furfural and catalyst for furfural alcohol were by 100: 0.5 (all being raw catalyst) mixed in the batching still, mix the back and enter mixing tank with 500L/h with volume pump, enter preheater after the mixing, after being preheating to 140 ℃, enter reactor, in reaction, keep the 6.0MPa reaction pressure, temperature of reaction is at 170 ℃, the residence time is regulated water inlet (or low-pressure steam) by manual (or variable valve) and carries out control reaction temperature under the condition of 50min; The crude furfuryl alcohol that reflects enters water cooler (the cooling medium is a water) cooling, enters separator then, and hydrogen returns recycle, and crude furfuryl alcohol is introduced into whizzer, filters out the part catalyzer, is entering subsider then; Spent catalyst is natural subsidence in subsider, regular then labor cleaning; The thick alcohol on subsider upper strata is squeezed into rectifying still volumetrical 3/4ths with pump and is stopped charging, open the water coolant of overhead condenser earlier, and then the steam valve of the chuck of unlatching still kettle or reboiler begins heating, the control tower top temperature goes out light constituent at 60 ℃, when rising to, tower top temperature begins finished product more than 100 ℃, when the observation cat head does not go out liquid, stop distillation, discharge high boiling material; It is refining to repeat next still again.
The quality determining method of finished product furfuryl alcohol detects according to the gas chromatography in the GB/T14022.1-92DE country furfuryl alcohol quality standard: furfuryl alcohol content 97%, moisture 0.3% acidity 0.05mol/L.Product colour is faint yellow; Product yield 96%.
The result's of table 1, embodiment and comparative example contrast
| Project | The present invention | Traditional method |
| Ton product furfural unit consumption t/t | 1.01-1.015 | 1.025-1.05 |
| Ton product steam mono-consumption t/t | 0.2 | 0.8 |
| Ton product electricity unit consumption kwh/t | 140 | 250 |
| Furfuryl alcohol content % | 98.5-99 | 97 |
| Moisture content % | 0.1 | 0.3 |
| Acidity mol/L | 0.005 | 0.01 |
| Outward appearance | Colourless transparent liquid | Light yellow transparent liquid |
Claims (13)
1. the method for an automatically and continuously producing furfuryl alcohol comprises
(1) reactions steps: the furfural of preheating and mixture of catalysts and hydrogen are sent in the reactor to react, and described reactor is equipped with automatic temperature control system, and described catalyzer is copper silicon or copper chromium catalyst for furfural alcohol;
(2) cooling and Hydrogen Separation step: will in water cooler, cool off by the crude furfuryl alcohol that reactor comes out, and in separator, carry out gas-liquid separation then, hydrogen is separated from crude furfuryl alcohol;
(3) catalyst separating step: will be divided into clear liquid and catalyzer by continuous filter by the crude furfuryl alcohol that separator comes out;
(4) take off light and rectification step: the clear liquid that obtains in the step (3) is directly sent into lightness-removing column, after lightness-removing column is sloughed light constituent, enter rectifying tower and rectifying in rectifying tower, thereby manufacture a finished product furfuryl alcohol continuously.
2. according to the method for the automatically and continuously producing furfuryl alcohol of claim 1, wherein said automatic temperature control system comprises reactor jacket or built-in water cooler, in reactor jacket or built-in water cooler, be filled with the liquid of boiling point between 60-240 ℃, liquid level remains on chuck or built-in water cooler volumetrical 10-80%, and liquid feeding amount by DCS automatic control system automatic or manual regulation system conditioned reaction device chuck or built-in water cooler, pressure, temperature, liquid level, with the liquid in chuck or the built-in water cooler remain on 60-240 ℃ in the scope steady temperature and the constant pressure in the 0.2-3.0MPa scope.
3. according to the method for the automatically and continuously producing furfuryl alcohol of claim 2, the liquid of wherein said boiling point between 60-240 ℃ is water.
4. according to the method for the automatically and continuously producing furfuryl alcohol of claim 2, also comprise the high-temperature gas behind the vaporizing liquid in reactor jacket or the built-in water cooler is delivered to steam pockets, as the thermal source that takes off the heating in light and the rectification step.
5. according to the method for the automatically and continuously producing furfuryl alcohol of claim 1, wherein the water cooler described in the step (2) is the preheater that is used for preheating furfural and catalyst mixture.
6. according to the method for the automatically and continuously producing furfuryl alcohol of claim 1, wherein the continuous filter described in the step (3) is whizzer, pressure filter filter plant.
7. according to the method for the automatically and continuously producing furfuryl alcohol of claim 1, comprise that also the catalyzer that will separate in (3) catalyst separating step washs with the good solvent of high boiling material solubleness, recycling then, the good solvent of wherein said high boiling material solubleness comprises furfural, furfuryl alcohol, methyl furan, aromatic hydrocarbons.
8. the equipment of an automatically and continuously producing furfuryl alcohol mainly comprises
(1) is used for the preheater of preheating furfural and catalyst mixture;
(2) be used to carry out the reactor of the reaction of the furfural of preheating and catalyst mixture and hydrogen, described reactor is equipped with temperature, pressure automatic control system;
(3) be used to cool off the water cooler of the crude furfuryl alcohol of coming out by reactor;
(4) be used for carrying out the separator of gas-liquid separation so that hydrogen is separated from crude furfuryl alcohol;
(5) be used for the continuous filter of the crude furfuryl alcohol that continuous filtration come out by separator;
(6) be used for the clear liquid that is come out by continuous filter is sloughed the lightness-removing column of light constituent;
(7) be used for and slough product rectifying behind the light constituent to obtain the rectifying tower of finished product furfuryl alcohol.
9. the equipment of automatically and continuously producing furfuryl alcohol according to Claim 8, wherein said automatic temperature control system comprises reactor jacket or built-in water cooler, in reactor jacket or built-in water cooler, be filled with the liquid of boiling point between 60-240 ℃, liquid level remains on chuck or built-in water cooler volumetrical 10-80%, and liquid feeding amount by DCS automatic control system automatic or manual regulation system conditioned reaction device chuck or built-in water cooler, pressure, temperature, liquid level, with the liquid in chuck or the built-in water cooler remain on 60-240 ℃ in the scope steady temperature and the constant pressure in the 0.2-3.0MPa scope.
10. according to the equipment of the automatically and continuously producing furfuryl alcohol of claim 9, the liquid of wherein said boiling point between 60-240 ℃ is water.
11., also comprise being used to hold the steam pockets of the high-temperature gas behind the vaporizing liquid in reactor jacket or the built-in water cooler with the thermal source that heats when taking off light and rectifying according to the equipment of the automatically and continuously producing furfuryl alcohol of claim 9.
12. the equipment of automatically and continuously producing furfuryl alcohol according to Claim 8, the water cooler that wherein is used to cool off the crude furfuryl alcohol of being come out by reactor is the preheater that is used for preheating furfural and catalyst mixture.
13. the equipment of automatically and continuously producing furfuryl alcohol according to Claim 8, the continuous filter that wherein is used for the crude furfuryl alcohol that continuous filtration come out by separator is whizzer, pressure filter filter plant.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101863863A (en) * | 2010-06-28 | 2010-10-20 | 宏业生化股份有限公司 | Refining method for crude furfuryl alcohol |
| CN102417494A (en) * | 2011-12-09 | 2012-04-18 | 宁夏共享集团有限责任公司 | Production method of high-purity furfuryl alcohol |
| CN102688726A (en) * | 2012-05-30 | 2012-09-26 | 山东一诺生化科技有限公司 | Equipment and technology for preparing furfuryl alcohol by liquid phase hydrogenation of furfural |
| CN102964278B (en) * | 2012-11-27 | 2015-02-18 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| WO2015034964A1 (en) | 2013-09-03 | 2015-03-12 | Virdia, Inc. | Methods for extracting and converting hemicellulose sugars |
| CN104174403B (en) * | 2014-07-22 | 2016-04-20 | 石家庄恒昌环保科技有限公司 | A kind of recycling method of useless catalyst for furfural alcohol |
| CN104536485A (en) * | 2014-12-20 | 2015-04-22 | 安徽神剑新材料股份有限公司 | Top temperature controlling device of constant temperature cooling source |
| CN105056823B (en) * | 2015-06-15 | 2017-10-20 | 河南心连心化肥有限公司 | The automatic recipe maker and its distribution of furfural hydrogenation production furfuryl alcohol |
| CN105233754B (en) * | 2015-09-16 | 2017-10-20 | 河南心连心化肥有限公司 | Furfuryl alcohol production injection proportioner and its distribution |
| CN106966879B (en) * | 2017-02-20 | 2021-05-04 | 山东一诺生物质材料有限公司 | Equipment and process for producing acetyl n-propanol by kettle type continuous hydrogenation |
| CN109020929B (en) * | 2018-07-30 | 2023-11-17 | 河南心连心化学工业集团股份有限公司 | Crude furfuryl alcohol separating device and separating process thereof |
| CN110563674B (en) * | 2019-07-25 | 2023-05-05 | 宏业生物科技股份有限公司 | Device and method for preparing furfuryl alcohol |
| CN112546969B (en) * | 2020-12-07 | 2022-12-23 | 安徽贝克制药股份有限公司 | Catalytic hydrogenation continuous production device and preparation method of ritonavir intermediate |
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| CN1990476A (en) * | 2005-12-28 | 2007-07-04 | 中国科学院兰州化学物理研究所 | Method for preparing furfuryl alcohol by furfural selective hydrogenation reaction in liquid phase |
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| CN1990476A (en) * | 2005-12-28 | 2007-07-04 | 中国科学院兰州化学物理研究所 | Method for preparing furfuryl alcohol by furfural selective hydrogenation reaction in liquid phase |
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