CN108329207A - A kind of device and method producing fatty acid methyl ester using catalytic distillation technology - Google Patents
A kind of device and method producing fatty acid methyl ester using catalytic distillation technology Download PDFInfo
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- CN108329207A CN108329207A CN201810414255.0A CN201810414255A CN108329207A CN 108329207 A CN108329207 A CN 108329207A CN 201810414255 A CN201810414255 A CN 201810414255A CN 108329207 A CN108329207 A CN 108329207A
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- 238000004821 distillation Methods 0.000 title claims abstract description 94
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 76
- 235000019387 fatty acid methyl ester Nutrition 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 489
- 238000005886 esterification reaction Methods 0.000 claims abstract description 54
- 230000032050 esterification Effects 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 19
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 17
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 claims abstract description 8
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 47
- 239000000126 substance Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000002347 injection Methods 0.000 claims description 26
- 239000007924 injection Substances 0.000 claims description 26
- 150000007524 organic acids Chemical class 0.000 claims description 21
- 230000008676 import Effects 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 18
- 239000011973 solid acid Substances 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 230000002411 adverse Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000004332 deodorization Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003225 biodiesel Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 36
- 238000007747 plating Methods 0.000 description 23
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of device and method producing fatty acid methyl ester using catalytic distillation technology, design one or more fixed beds first before catalytic distillation tower, realize the pre- esterification of aliphatic acid, then pass through catalytic distillation tower, realize the complete esterification of aliphatic acid, methanol distillation column is devised behind catalytic distillation tower so that excessive methanol realizes recycling, recycles.The present invention uses the new technology of fixed bed+catalytic distillation tower, has started the technical strategies of (biodiesel) of a production fatty acid methyl ester, has realized the new method of methyl esterification of fatty acid；This route overcomes the defect of other technologies route, such as the drawbacks of product acid value is high, esterification cannot be fully and completely.The present invention is a kind of clean environment firendly, efficient low-consume, the new technique that investment is small, quick, income is big.
Description
Technical field
The present invention relates to a kind of device and method producing fatty acid methyl ester using catalytic distillation technology, are to use catalytic distillation
Technology realizes the complete reaction of aliphatic acid, belongs to field of fine chemical.
Background technology
Currently, the production technology of fatty acid methyl ester is to be in backward state mostly.For example it is still catalyzed with sulfuric acid, liquid caustic soda
Agent；It is produced using the stirred reactor of simple and crude backwardness, to find out its cause, mainly there are catalyst technology backwardness, reaction dresses
Set it is simple and crude, cannot meet cleaning, environmental protection, efficiently, the production technology new demand of low consumption.Therefore, through study for many years we have invented
The novel production process that methyl esterification of fatty acid is completed with fixed bed+catalytic distillation technology, changes existing, simple and crude production technology
Fall behind situation.
Invention content
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and a kind of utilize is provided and is fixed
The device and method that bed produces fatty acid methyl ester with catalytic distillation coupling technique, are a kind of skills using fixed bed+catalytic distillation
Art, the new technique method that biodiesel is produced by deodorised oil, are a kind of new methods for realizing methyl esterification of fatty acid.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of device producing fatty acid methyl ester using catalytic distillation technology, including sequentially connected fixed bed reactors,
Catalytic distillation tower, methanol distillation column, aliphatic acid and methanol in deodorised oil carry out esterification pre-reaction in fixed bed reactors,
It then passes in catalytic distillation tower and continues esterification reaction of organic acid and collect product, excessive methanol enters in methanol distillation column
It is recycled, it is characterised in that：
The fixed bed reactors are equipped with inlet port and outlet port；Feed inlet and the device that deodorised oil and methanol are provided
It is connected；
The catalytic distillation tower, tower top are equipped with water and methanol outlet, are equipped with refluxing opening at the upper side of tower wall, the other side is set
There is material inlet, gas-phase methanol supply port is equipped with below tower wall, bottom of tower is exported equipped with fatty acid methyl ester, wherein：The material
Import is connected with discharge port, and gas-phase methanol supply port is connected with the device for being capable of providing gas-phase methanol, fatty acid methyl ester outlet
It is connected with the device of acquisition fatty acid methyl ester；Water and methanol outlet are connected with jet pump, the injection pump discharge connection of jet pump
There are receiving tank, the outlet of receiving tank to be divided into two-way, is connected all the way with refluxing opening by chemical pump I, another way passes through chemical pump
II is connected with methanol distillation column；Realize that alcohol-water separation recycles methanol in methanol distillation column；
The methanol distillation column, tower top are exported equipped with high concentration methanol, and bottom of tower is equipped with waste water and arranges mouth, and tower wall center is equipped with
Water and methanol import, tower wall top are equipped with methanol eddy mouth, wherein：Water and methanol import are connected with the pump discharge of chemical pump II
It connects, waste water row's mouth is connected with waste water treatment system, and high concentration methanol outlet is connected with condenser, drainer and chemical pump in turn
The pump discharge of III, chemical pump III are divided into two-way, are connected all the way with methanol eddy mouth, pass through heater and gas-phase methanol all the way
Supply port is connected.
Preferably, the jet pump is equipped with injection pump inlet, injection pump discharge and injection liquid entrance, wherein：Jet pump
Import is connected with the water of catalytic distillation tower and methanol outlet, and injection pump discharge is connected with receiving tank, sprays liquid entrance and chemical industry
Pump II is connected.
Preferably, the receiving tank is equipped with inlet and outlet, wherein：Import is connected with the injection pump discharge of jet pump
It connects, outlet is divided into two-way, is connected all the way with the pump inlet of chemical pump I, the reflux of the pump discharge of chemical pump I and catalytic distillation tower
Mouth is connected, and another way is connected with the pump inlet of chemical pump II.
Preferably, the pump discharge of chemical pump II is divided into two-way, is connected all the way with the water of methanol distillation column and methanol import
Alcohol-water separation is carried out to which material to be passed through in methanol distillation column, another way is connected with the injection liquid entrance of jet pump thus will
Material is passed through the power for providing and vacuumizing for jet pump in jet pump.
Preferably, the fixed bed reactors, feeding manner are fair current, and feed inlet is located at the top of fixed bed reactors
End, discharge port are located at the bottom ends of fixed bed reactors, i.e., charging suitable for reading, lower mouth are discharged.
Preferably, the fixed bed reactors, feeding manner are adverse current, and feed inlet is located at the bottom of fixed bed reactors
End, discharge port are located at the top of fixed bed reactors, that is, descend mouth charging, discharge suitable for reading.
Preferably, catalyst A is housed, catalyst A is solid acid catalyst, and type is this in the fixed bed reactors
Company production D006 or D008 in any one.
Preferably, the fixed bed reactors are one or more can not only connect but also simultaneously each other when being more
Connection.
Preferably, the catalytic distillation tower is designed by three sections, and epimere is rectifying section in tower, hypomere is stripping section, centre
For catalytic section.
Preferably, internals are filled in the rectifying section, stripping section, internals are sieve plate or structured packing：Filler is N
Section, 1≤N≤50, every section of height are 2000-4000mm, and the type of filler is stainless steel wave pit plate；Sieve plate is N layers, 5≤N≤
100, the spacing of layer and layer is 350-550mm, and sieve plate is high-efficient float valve sieve plate.
Preferably, catalyst B is filled in the catalytic section, catalyst B is solid acid catalyst, and type is our company
Produce any one in D006 or D008；Solid acid catalyst can be in bulk, may be designed in module catalysis dosage form
Formula；
Preferably, when the catalyst B is designed as module catalyst mode, with mould in patent CN201620189748.5
Block catalyst, including active catalyst, woven wire and wire weave plate：The module catalyst is by the wire
Net, the spaced and parallel setting of woven wire corrugated plating contain catalyst granules (namely this hair between two panels woven wire
Solid acid catalyst in bright) active catalyst layer, and the active catalyst particles in the catalyst layer are formed, it is described
Woven wire corrugated plating apart from；Active catalyst layer interval setting in the module catalyst；
The module catalyst is fixed in periphery by wire；
It is in geometry that the module catalyst outer profile wraps closing by the woven wire；Described is several
What shape is cube, cylinder；
One or two layers woven wire corrugated plating is spaced between the woven wire and woven wire；
The active catalyst layer interval one or two layers woven wire corrugated plating setting；The active catalyst layer
It is that one or two layers woven wire corrugated plating is arranged and the internal filling activity is urged by being spaced between two layers of woven wire
Catalyst particles；
The woven wire, woven wire corrugated plating are made of stainless steel material, the woven wire or metal
Screen waviness plate can also be replaced by stainless steel plate with holes；
The woven wire, woven wire corrugated plating are vertically arranged up and down；
Outer wall is reinforced in the active catalyst layer setting, and the woven wire and stainless steel corrugated plating with holes is double-deck
Outer wall as the catalyst layer；
Catalyst layer formed liquid channel, wire weave plate layer constitute gas phase channel, gas phase from lower part feed, liquid phase from
Top is fed, and two counter current contactings of gas-liquid to be reacted completely.
Preferably, internals are filled in the methanol distillation column, internals are sieve plate or structured packing, and filler is N sections,
1≤N≤50, every section of height are 2000-4000mm, and the type of filler is stainless steel wave card；Sieve plate is N layers, 5≤N≤100,
The spacing of layer and layer is 350-550mm, and sieve plate is high-efficient float valve sieve plate.
The present invention also provides a kind of methods producing fatty acid methyl ester using catalytic distillation technology, include the following steps：
(1) esterification pre-reaction：After aliphatic acid and methanol mix in deodorised oil, first is carried out under catalyst A catalytic action
It is esterified pre-reaction；
(2) esterification reaction of organic acid：All materials in step (1) after esterification pre-reaction, together with gas-phase methanol,
Esterification reaction of organic acid is carried out under the catalytic action of catalyst B, obtains final product-fatty acid methyl ester；
(3) recycle and/or recycle methanol：In step (2) esterification reaction of organic acid generate water and reaction in excessive first
Alcohol, a part are back in step (2) and recycle；It is recycled after another part is condensed.
In above-mentioned technical proposal, method specifically includes following steps：
(1) esterification pre-reaction：After aliphatic acid and methanol mix in deodorised oil, fixed bed reactors are passed by feed inlet
In, the catalytic action of the catalyst A in it carries out esterification pre-reaction, generated in reaction process a part of fatty acid methyl ester and
A part of water；All materials are exported by discharge port and are passed into catalytic distillation tower by material inlet in fixed bed reactors；
The molar ratio of the deodorization fatty acid oil and methanol is 1.0：1.1-2.0；
The catalyst A is solid acid catalyst, and type is any one in the D006 or D008 of our company's production；
The quality Feed space velocities of the deodorised oil and methanol are 0.5-2.5h-1；
Reaction condition in the fixed bed reactors is：Pressure：60-100 DEG C of 0.1-1.5Mpa, temperature.
(2) esterification reaction of organic acid：Gas-phase methanol is passed into from gas-phase methanol supply port in catalytic distillation tower, warp in step (1)
All materials and gas-phase methanol after esterification pre-reaction are crossed, it is flat to break chemistry for the counter current contacting under the catalytic action of catalyst B
Weighing apparatus, is continuously finished esterification reaction of organic acid so that the aliphatic acid intimate 100% in deodorised oil reacts completely；It is exported from fatty acid methyl ester
Collect final product-fatty acid methyl ester；
The quality Feed space velocities of the gas-phase methanol are 0.2-1.5h-1；
All materials quality Feed space velocities in the step (1) after esterification pre-reaction are 0.5-2.0h-1；
The catalyst B solid acid catalysts, type are any one in the D006 or D008 of our company's production；
The catalytic distillation tower, tower top：Pressure：30-100 DEG C of -1.0-0.0Mpa, temperature；Tower reactor：Pressure 0.01-
50-200 DEG C of 1.5Mpa, temperature.
(3) recycle and/or recycle methanol：In step (2) esterification reaction of organic acid generate water and reaction in excessive first
Alcohol, in the case where jet pump vacuumizes the suction function to be formed, followed by water and methanol outlet, injection pump inlet, jet pump, injection
Pump discharge and enter in receiving tank；Material in receiving tank, a part are flowed out from outlet and under the action of chemical pump I by returning
Head piece is back in catalytic distillation tower and flows back, and another part is from outlet outflow and flows into chemical pump II；And chemical pump II
Pump discharge be divided into two-way, be connected all the way with injection liquid entrance G, material is back to provide for jet pump in jet pump vacuumizes
Power, another way is connected with water and methanol import, material is sent into methanol distillation column and realizes alcohol-water separation；Alcohol-water separation obtains
To waste water by waste water row mouth be expelled in waste water treatment system phase, obtained high concentration gas-phase methanol from high concentration methanol export
It is expelled in condenser and is condensed；Obtained liquid methanol is condensed to enter in drainer；Material is in chemical pump in drainer
Under the action of III, a part, which is back to by methanol eddy mouth in methanol distillation column, to flow back, the heated device gasification of another part
After be back in gas-phase methanol supply port and recycle；
The vacuum degree of the jet pump, formation is -1.0~0MPa；
The methanol distillation column, tower top：30-80 DEG C of pressure 0.05-0.35Mpa, temperature；Tower reactor：Pressure 0.1-
80-200 DEG C of 0.55Mpa, temperature；
The condenser, the temperature of condensation are the temperature of cooling water：20-40℃；
When in the feed back to catalytic distillation tower in receiving tank, reflux ratio 0.2-2.0；
When in the feed back to methanol distillation column in drainer, reflux ratio 0.5-2.0.
The advantages of technical solution of the present invention, is：
(1) of the invention, one or more fixed beds are designed before catalytic distillation tower first, realize the pre- methyl esters of aliphatic acid
Change, then by catalytic distillation tower, realizes the complete esterification of aliphatic acid, Methanol Recovery is devised behind catalytic distillation tower
Tower so that excessive methanol realizes recycling, recycles.
(2) present invention uses the new technology of fixed bed+catalytic distillation tower, has started (the life of a production fatty acid methyl ester
Object diesel oil) technical strategies, realize the new method of methyl esterification of fatty acid；This route overcomes lacking for other technologies route
It falls into, such as the drawbacks of product acid value is high, esterification cannot be fully and completely.
(3) present invention is a kind of clean environment firendly, efficient low-consume, the new technique that investment is small, quick, income is big.
Description of the drawings
Fig. 1 is the flow chart of the method for the present invention；
Fig. 2 is the structural schematic diagram of apparatus of the present invention；
Wherein：1, fixed bed reactors, 1A, feed inlet, 1B, discharge port；2, catalytic distillation tower, 2A, water and methanol outlet,
2B, refluxing opening, 2C, material inlet, 2D, gas-phase methanol supply port, 2E, fatty acid methyl ester outlet；3, methanol distillation column, 3A, height
Concentration methanol outlet, 3B, waste water arrange mouth, 3C methanol eddy mouths, 3D, water and methanol import；4, jet pump, L, injection pump inlet,
F, pump discharge is sprayed, G is injection liquid entrance；5, receiving tank；6, condenser；7, drainer；8, heater；I, chemical pump I；II、
Chemical pump II；III, chemical pump III.
Specific implementation mode
The specific implementation mode of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold：
The present invention provides a kind of device producing fatty acid methyl ester using catalytic distillation technology, including sequentially connected fixation
Bed reactor 1, catalytic distillation tower 2, methanol distillation column 3, aliphatic acid and methanol in deodorised oil carry out in fixed bed reactors
Esterification pre-reaction then passes in catalytic distillation tower and continues esterification reaction of organic acid and collect product, and excessive methanol enters
To being recycled in methanol distillation column, as shown in Figure 2：
The fixed bed reactors are equipped with feed inlet 1A and discharge port 1B；Feed inlet with deodorised oil and methanol are provided
Device is connected；
The catalytic distillation tower, tower top are equipped with water and methanol outlet 2A, and refluxing opening 2B, another is equipped at the upper side of tower wall
Side is equipped with material inlet 2C, and gas-phase methanol supply port 2D is equipped with below tower wall, and bottom of tower is equipped with fatty acid methyl ester and exports 2E, wherein：
The material inlet 2C is connected with discharge port 1B, gas-phase methanol supply port 2D and the device phase for being capable of providing gas-phase methanol
Even, fatty acid methyl ester exports 2E and is connected with the device for acquiring fatty acid methyl ester；Water and methanol outlet 2A are connected with jet pump 4,
The injection pump discharge of jet pump is connected with receiving tank 5, and the outlet of receiving tank is divided into two-way, passes through chemical pump I and refluxing opening all the way
2B is connected, and another way is connected by chemical pump II with methanol distillation column；Alcohol-water separation recycling is realized in methanol distillation column
Methanol；
The methanol distillation column 3, tower top are equipped with high concentration methanol and export 3A, and bottom of tower is equipped with waste water and arranges mouth 3B, in tower wall
Centre is equipped with water and methanol import 3D, and methanol eddy mouth 3C is equipped with above tower wall, wherein：Water and methanol import 3D are with chemical pump II's
Pump discharge is connected, and waste water row mouth 3B is connected with waste water treatment system, and high concentration methanol outlet 3A is connected with condenser in turn
6, the pump discharge of drainer 7 and chemical pump III, chemical pump III are divided into two-way, are connected all the way with methanol eddy mouth 3C, all the way
It is connected with gas-phase methanol supply port 2D by heater 8.
Preferably, the jet pump 4 is equipped with jet pump imported L, injection pump discharge F and injection liquid entrance G, wherein：Spray
It penetrates pump inlet L with the water of catalytic distillation tower and methanol outlet 2A to be connected, injection pump discharge F is connected with receiving tank, and injection liquid enters
Mouth G is connected with chemical pump II.
Preferably, the receiving tank 5 is equipped with inlet and outlet, wherein：The injection pump discharge F phases of import and jet pump
Connection, outlet are divided into two-way, are connected all the way with the pump inlet of chemical pump I, time of the pump discharge of chemical pump I and catalytic distillation tower
Head piece 2B is connected, and another way is connected with the pump inlet of chemical pump II.
Preferably, the pump discharge of chemical pump II is divided into two-way, is connected all the way with the water of methanol distillation column 3 and methanol import 3D
It connects material being passed through in methanol distillation column 3 to carry out alcohol-water separation, another way is connected with the injection liquid entrance G of jet pump 4
To which material is passed through the power for providing and vacuumizing for jet pump in jet pump.
Preferably, the fixed bed reactors, feeding manner are fair current, and feed inlet is located at the top of fixed bed reactors
End, discharge port are located at the bottom ends of fixed bed reactors, i.e., charging suitable for reading, lower mouth are discharged.
Preferably, the fixed bed reactors, feeding manner are adverse current, and feed inlet is located at the bottom of fixed bed reactors
End, discharge port are located at the top of fixed bed reactors, that is, descend mouth charging, discharge suitable for reading.
Preferably, catalyst A is housed, catalyst A is solid acid catalyst, and type is this in the fixed bed reactors
Company production D006 or D008 in any one.
Preferably, the fixed bed reactors are one or more can not only connect but also simultaneously each other when being more
Connection.
Preferably, the catalytic distillation tower is designed by three sections, and epimere is rectifying section in tower, hypomere is stripping section, centre
For catalytic section.
Preferably, internals are filled in the rectifying section, stripping section, internals are sieve plate or structured packing：Filler is N
Section, 1≤N≤50, every section of height are 2000-4000mm, and the type of filler is stainless steel wave pit plate；Sieve plate is N layers, 5≤N≤
100, the spacing of layer and layer is 350-550mm, and sieve plate is high-efficient float valve sieve plate.
Preferably, catalyst B is filled in the catalytic section, catalyst B is solid acid catalyst, and type is our company
Produce any one in D006 or D008；Solid acid catalyst can be in bulk, may be designed in module catalysis dosage form
Formula；
Preferably, when the catalyst B is designed as module catalyst mode, with mould in patent CN201620189748.5
Block catalyst, including active catalyst, woven wire and wire weave plate：The module catalyst is by the wire
Net, the spaced and parallel setting of woven wire corrugated plating contain catalyst granules (namely this hair between two panels woven wire
Solid acid catalyst in bright) active catalyst layer, and the active catalyst particles in the catalyst layer are formed, it is described
Woven wire corrugated plating apart from；Active catalyst layer interval setting in the module catalyst；
The module catalyst is fixed in periphery by wire；
It is in geometry that the module catalyst outer profile wraps closing by the woven wire；Described is several
What shape is cube, cylinder；
One or two layers woven wire corrugated plating is spaced between the woven wire and woven wire；
The active catalyst layer interval one or two layers woven wire corrugated plating setting；The active catalyst layer
It is that one or two layers woven wire corrugated plating is arranged and the internal filling activity is urged by being spaced between two layers of woven wire
Catalyst particles；
The woven wire, woven wire corrugated plating are made of stainless steel material, the woven wire or metal
Screen waviness plate can also be replaced by stainless steel plate with holes；
The woven wire, woven wire corrugated plating are vertically arranged up and down；
Outer wall is reinforced in the active catalyst layer setting, and the woven wire and stainless steel corrugated plating with holes is double-deck
Outer wall as the catalyst layer；
Catalyst layer formed liquid channel, wire weave plate layer constitute gas phase channel, gas phase from lower part feed, liquid phase from
Top is fed, and two counter current contactings of gas-liquid to be reacted completely.
Preferably, internals are filled in the methanol distillation column, internals are sieve plate or structured packing, and filler is N sections,
1≤N≤50, every section of height are 2000-4000mm, and the type of filler is stainless steel wave card；Sieve plate is N layers, 5≤N≤100,
The spacing of layer and layer is 350-550mm, and sieve plate is high-efficient float valve sieve plate.
The present invention also provides it is a kind of using above-mentioned apparatus carry out production fatty acid methyl ester method, as shown in Figure 1, include with
Lower step：
(1) esterification pre-reaction：After aliphatic acid and methanol mix in deodorised oil, fixed bed reaction is passed by feed inlet 1A
In device, the catalytic action of the catalyst A in it carries out esterification pre-reaction, and a part of fatty acid methyl ester is generated in reaction process
With a part of water；All materials are passed into catalysis steaming by discharge port 1B export and by material inlet 2C in fixed bed reactors
It evaporates in tower；
(2) esterification reaction of organic acid：Gas-phase methanol is passed into from gas-phase methanol supply port 2D in catalytic distillation tower, in step (1)
All materials after esterification pre-reaction and gas-phase methanol, the counter current contacting under the catalytic action of catalyst B, break chemistry
Balance, is continuously finished esterification reaction of organic acid so that the aliphatic acid intimate 100% in deodorised oil reacts completely；Go out from fatty acid methyl ester
Mouth 2E collects final product-fatty acid methyl ester；
(3) recycle and/or recycle methanol：In step (2) esterification reaction of organic acid generate water and reaction in excessive first
Alcohol, in the case where jet pump vacuumizes the suction function to be formed, followed by water and methanol outlet 2A, jet pump imported L, jet pump 4,
It sprays pump discharge F and enters in receiving tank 5；Material in receiving tank, a part is from outlet outflow and in the effect of chemical pump I
Under be back in catalytic distillation tower and flow back by refluxing opening 2B, another part is from outlet outflow and flows into chemical pump II；And
The pump discharge of chemical pump II is divided into two-way, is connected all the way with injection liquid entrance G, material is back in jet pump is carried for jet pump
The power for for vacuumizing, another way are connected with water and methanol import 3D, material are sent into methanol distillation column and realizes alcohol-water separation；
The waste water that alcohol-water separation obtains is expelled to by waste water row mouth 3B in waste water treatment system phase, and obtained high concentration gas-phase methanol is from height
Concentration methanol outlet 3A, which is expelled in condenser 6, to be condensed；Obtained liquid methanol is condensed to enter in drainer 7；Condensation
Under the action of chemical pump III, a part is back to by methanol eddy mouth 3C in methanol distillation column to flow back material, separately in tank
A part of heated device 8 is back in gas-phase methanol supply port 2D after gasifying and recycles.
Apparatus and method of the present invention is illustrated with reference to specific embodiment：
Embodiment 1：
A method of fatty acid methyl ester being produced using catalytic distillation technology, is included the following steps：
(1) esterification pre-reaction：After deodorised oil PAF and methanol mix, it is passed into fixed bed reactors by feed inlet 1A,
The catalytic action of catalyst A in it carries out esterification pre-reaction, and a part of fatty acid methyl ester and one are generated in reaction process
Part water；All materials by discharge port 1B export and are passed into catalytic distillation tower by material inlet 2C in fixed bed reactors
In；
The molar ratio of the deodorization fatty acid oil, methanol is 1.0：1.3；
The catalyst A is D006；
The quality Feed space velocities of the deodorised oil and methanol are 0.8h-1；
The fixed bed reactors are one, and reaction condition is：Pressure is 0.2, temperature 70 C；
The fixed bed reactors feeding manner is fair current.
(2) esterification reaction of organic acid：Gas-phase methanol is passed into from gas-phase methanol supply port 2D in catalytic distillation tower, in step (1)
All materials after esterification pre-reaction and gas-phase methanol, counter current contacting breaks chemistry under the catalytic action of catalyst B
Balance, is continuously finished esterification reaction of organic acid so that the aliphatic acid intimate 100% in deodorised oil reacts completely；Go out from fatty acid methyl ester
Mouth 2E collects the fatty acid methyl ester of product, and the conversion ratio of methyl esterification of fatty acid is 99.9%.
The quality Feed space velocities of the gas-phase methanol are 0.8h-1；
The Feed space velocities of all materials in the step (1) after esterification pre-reaction are 1.0h-1；
The catalytic distillation tower, tower top：Pressure -0.05Mpa, temperature 50 C；Tower reactor：Pressure 0.15Mpa, temperature 80
℃。
The catalytic distillation tower is designed by three sections, and epimere is rectifying section in tower, hypomere is stripping section, centre is catalysis
Section：
Internals are filled in the rectifying section, stripping section, internals are that regular stainless steel wave card is filled out in this implementation
Material loads 5 sections, every section of 2000mm；
It is D006 that the catalyst B is loaded in the catalytic section, to be designed to module catalyst in this implementation, with specially
Module catalyst in sharp CN201620189748.5, including catalyst, woven wire and wire weave plate：Module catalyst by
Woven wire, the spaced and parallel setting of woven wire corrugated plating form catalyst layer after containing D006 between two panels woven wire, and
Catalyst granules in the catalyst layer by woven wire corrugated plating apart from；Catalyst layer interval in module catalyst is set
It sets.It is in geometry that module catalyst outer profile wraps closing by woven wire, and geometry is cube (see the patent
Fig. 2)；One metal wire layer net corrugated plating is spaced between woven wire and woven wire；Catalyst layer interval double layer of metal silk screen
Corrugated plating is arranged；Catalyst layer is by being spaced the setting of one metal wire layer net corrugated plating and internal filling work between double layer of metal silk screen
Property catalyst granules；Woven wire, woven wire corrugated plating are made of stainless steel material；Woven wire, woven wire ripple
Plate is vertically arranged up and down；Outer wall is reinforced in active catalyst layer setting, using woven wire and stainless steel corrugated plating bilayer with holes as
The outer wall of catalyst layer.
(3) recycle and/or recycle methanol：In step (2) esterification reaction of organic acid generate water and reaction in excessive first
Alcohol, in the case where jet pump vacuumizes the suction function to be formed (vacuum degree be -1.0~0MPa), followed by water and methanol outlet 2A,
Jet pump imported L, sprays pump discharge F and enters receiving tank 5 jet pump 4；Material in receiving tank, it is a part of from outlet stream
Go out and is back in catalytic distillation tower flowed back (reflux ratio 0.6) by refluxing opening 2B under the action of chemical pump I, another portion
Divide from outlet outflow and enters realization alcohol moisture in methanol distillation column by water and methanol import 3D under the action of chemical pump II
From；Isolated waste water is expelled to by waste water row mouth 3B in waste water treatment system phase, and obtained high concentration gas-phase methanol is from height
Concentration methanol outlet 3A, which is expelled in condenser 6, to be condensed；Obtained liquid methanol is condensed to enter in drainer 7；Condensation
Under the action of chemical pump III, a part is back to by methanol eddy mouth 3C in methanol distillation column to be flowed back and (be returned material in tank
Stream is than for 0.8), another part is back in gas-phase methanol supply port 2D and recycles；
The methanol distillation column, tower top：65 DEG C of pressure 0.1Mpa, temperature；Tower reactor：90 DEG C of pressure 0.2Mpa, temperature；
The condenser (6), 35 DEG C of the temperature of cooling water；
The methanol distillation column is filled with internals, and internals are high-efficient float valve sieve plate, and sieve plate is 10 layers, between layer and layer
Away from for 450mm.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of method producing fatty acid methyl ester using catalytic distillation technology, which is characterized in that include the following steps：
(1) esterification pre-reaction：After aliphatic acid and methanol mix in deodorised oil, in fixed bed under the catalytic action of catalyst A
Carry out esterification pre-reaction；
(2) esterification reaction of organic acid：All materials in step (1) after esterification pre-reaction are being catalyzed together with gas-phase methanol
Esterification reaction of organic acid is carried out under the catalytic action of agent B, obtains final product-fatty acid methyl ester；
(3) recycle and/or recycle methanol：In step (2) esterification reaction of organic acid generate water and reaction in excessive methanol, one
It is partly refluxed in step (2) and recycles；It is recycled after another part is condensed.
2. according to the method described in claim 1, it is characterized in that, method specifically includes following steps：
(1) esterification pre-reaction：After aliphatic acid and methanol mix in deodorised oil, fixed bed reactors are passed by feed inlet (1A)
In, the catalytic action of the catalyst A in it carries out esterification pre-reaction, generated in reaction process a part of fatty acid methyl ester and
A part of water；All materials are exported by discharge port (1B) and are passed into catalysis by material inlet (2C) in fixed bed reactors
In destilling tower；
(2) esterification reaction of organic acid：Gas-phase methanol is passed into from gas-phase methanol supply port (2D) in catalytic distillation tower, warp in step (1)
All materials and gas-phase methanol after esterification pre-reaction are crossed, it is flat to break chemistry for the counter current contacting under the catalytic action of catalyst B
Weighing apparatus, is continuously finished esterification reaction of organic acid so that the aliphatic acid intimate 100% in deodorised oil reacts completely；It is exported from fatty acid methyl ester
(2E) collects final product-fatty acid methyl ester；
(3) recycle and/or recycle methanol：In step (2) esterification reaction of organic acid generate water and reaction in excessive methanol,
Jet pump vacuumizes under the suction function to be formed, followed by water and methanol outlet (2A), injection pump inlet (L), jet pump
(4), it sprays pump discharge (F) and enters in receiving tank (5)；Material in receiving tank, a part is from outlet outflow and in chemical industry
It is back in catalytic distillation tower and is flowed back by refluxing opening (2B) under the action of pump I, another part is flowed out from outlet and inflowization
Work pumps in II；And the pump discharge of chemical pump II is divided into two-way, is connected all the way with injection liquid entrance G, material is back to jet pump
In the power vacuumized is provided for jet pump, another way is connected with water and methanol import (3D), material is sent into methanol distillation column
Middle realization alcohol-water separation；The waste water that alcohol-water separation obtains is expelled to by waste water row's mouth (3B) in waste water treatment system phase, is obtained
High concentration gas-phase methanol is expelled in condenser (6) from high concentration methanol outlet (3A) and is condensed；Condense obtained liquid first
Alcohol enters in drainer (7)；Material under the action of chemical pump III, by methanol eddy mouth (3C) returned by a part in drainer
It is back in methanol distillation column and flows back, the heated device 8 of another part is back in gas-phase methanol supply port (2D) after gasifying and follows
Ring utilizes.
3. according to the method described in claim 2, it is characterized in that：In step (1), the described deodorization fatty acid oil and methanol
Molar ratio is 1.0：1.1-2.0；The catalyst A is solid acid catalyst；The quality of the deodorised oil and methanol is fed
Air speed is 0.5-2.5h-1；Reaction condition in the fixed bed reactors is：Pressure：0.1-1.5Mpa, temperature 60-100
℃。
4. according to the method described in claim 2, it is characterized in that：In step (2), the quality charging of the gas-phase methanol is empty
Speed is 0.2-1.5h-1；All materials quality Feed space velocities in the step (1) after esterification pre-reaction are 0.5-
2.0h-1；The catalyst B solid acid catalysts；The catalytic distillation tower, tower top：Pressure：- 1.0-0.0Mpa, temperature
30-100℃；Tower reactor：50-200 DEG C of pressure 0.01-1.5Mpa, temperature.
5. according to the method described in claim 2, it is characterized in that：In step (3), the jet pump, the vacuum degree of formation
For -1.0~0MPa；The methanol distillation column, tower top：30-80 DEG C of pressure 0.05-0.35Mpa, temperature；Tower reactor：Pressure 0.1-
80-200 DEG C of 0.55Mpa, temperature；The condenser (6), the temperature of condensation are the temperature of cooling water：20-40℃；Receiving tank
(5) when in the feed back to catalytic distillation tower in, reflux ratio 0.2-2.0；Feed back in drainer (7) is to Methanol Recovery
When in tower, reflux ratio 0.5-2.0.
6. a kind of device producing fatty acid methyl ester using catalytic distillation technology, including sequentially connected fixed bed reactors (1),
Catalytic distillation tower (2), methanol distillation column (3), aliphatic acid and methanol in deodorised oil carry out esterification in fixed bed reactors
Pre-reaction then passes in catalytic distillation tower and continues esterification reaction of organic acid and collect product, and excessive methanol enters methanol
It is recycled in recovery tower, it is characterised in that：
The fixed bed reactors are equipped with feed inlet (1A) and discharge port (1B)；Feed inlet with deodorised oil and methanol are provided
Device is connected；
The catalytic distillation tower, tower top are equipped with water and methanol outlet (2A), and refluxing opening (2B), another is equipped at the upper side of tower wall
Side is equipped with material inlet (2C), and gas-phase methanol supply port (2D) is equipped with below tower wall, and bottom of tower is equipped with fatty acid methyl ester and exports (2E),
Wherein：The material inlet (2C) is connected with discharge port (1B), gas-phase methanol supply port (2D) and is capable of providing gas phase first
The device of alcohol is connected, and fatty acid methyl ester exports (2E) and is connected with the device for acquiring fatty acid methyl ester；Water and methanol outlet (2A)
It is connected with jet pump (4), the injection pump discharge of jet pump is connected with receiving tank (5), and the outlet of receiving tank is divided into two-way, a-road-through
It crosses chemical pump I (I) with refluxing opening (2B) to be connected, another way is connected by chemical pump II (II) with methanol distillation column；In first
Realize that alcohol-water separation recycles methanol in alcohol recovery tower；
The methanol distillation column (3), tower top are equipped with high concentration methanol and export (3A), and bottom of tower is equipped with waste water row's mouth (3B), tower wall
Center is equipped with water and methanol import (3D), and methanol eddy mouth (3C) is equipped with above tower wall, wherein：Water and methanol import (3D) and change
The pump discharge of work pump II is connected, and waste water row's mouth (3B) is connected with waste water treatment system, and high concentration methanol exports (3A) successively
The pump discharge for being connected with condenser (6), drainer (7) and chemical pump III (III), chemical pump III is divided into two-way, all the way with first
Alcohol reflux mouth (3C) is connected, and is connected all the way with gas-phase methanol supply port (2D) by heater (8)；
The jet pump (4) is equipped with injection pump inlet (L), injection pump discharge (F) and jet logistics entrance (G), wherein：Spray
Pump inlet (L) is penetrated with the water of catalytic distillation tower and methanol outlet (2A) to be connected；
The receiving tank (5) is equipped with inlet and outlet, wherein：Import is connected with the injection pump discharge (F) of jet pump, goes out
Mouth is divided into two-way, is connected all the way with the pump inlet of chemical pump I, the refluxing opening of the pump discharge of chemical pump I and catalytic distillation tower
(2B) is connected, and another way is connected with the pump inlet of chemical pump II；
The pump discharge of chemical pump II is divided into two-way, be connected all the way with the water of methanol distillation column (3) and methanol import (3D) to
Material is passed through in methanol distillation column (3) and carries out alcohol-water separation, another way is connected with the jet logistics entrance (G) of jet pump (4)
It connects and provides the power vacuumized to import jet logistics in jet pump for jet pump.
7. device according to claim 6, it is characterised in that：The fixed bed reactors, feeding manner be fair current or
It is inverse, wherein：Fair current refers to the bottom end that feed inlet is located at the top of fixed bed reactors, discharge port is located at fixed bed reactors；
Adverse current refers to the top that feed inlet is located at the bottom end of fixed bed reactors, discharge port is located at fixed bed reactors.
8. device according to claim 6, it is characterised in that：The fixed bed reactors are one or more, are more
When platform, can not only it connect each other but also in parallel；Catalyst A is housed, catalyst A urges for solid acid in the fixed bed reactors
Agent.
9. device according to claim 6, it is characterised in that：The catalytic distillation tower is designed by three sections, epimere in tower
For rectifying section, hypomere be stripping section, centre is catalytic section, wherein：Internals are filled in rectifying section, stripping section, internals are sieve plate
Or structured packing；Catalyst B is housed, catalyst B is solid acid catalyst, and solid acid catalyst is in bulk or sets in catalytic section
It is calculated as module catalyst mode；When catalyst B is designed as module catalyst mode, with module in patent CN201620189748.5
Catalyst.
10. device according to claim 6, it is characterised in that：Internals are filled in the methanol distillation column, internals are
Sieve plate or structured packing.
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