CN108329207B - Device and method for producing fatty acid methyl ester by catalytic distillation technology - Google Patents
Device and method for producing fatty acid methyl ester by catalytic distillation technology Download PDFInfo
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- CN108329207B CN108329207B CN201810414255.0A CN201810414255A CN108329207B CN 108329207 B CN108329207 B CN 108329207B CN 201810414255 A CN201810414255 A CN 201810414255A CN 108329207 B CN108329207 B CN 108329207B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 64
- 238000004821 distillation Methods 0.000 title claims abstract description 57
- 235000019387 fatty acid methyl ester Nutrition 0.000 title claims abstract description 36
- 238000005516 engineering process Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 48
- 230000032050 esterification Effects 0.000 claims abstract description 29
- 239000000194 fatty acid Substances 0.000 claims abstract description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 22
- 229930195729 fatty acid Natural products 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 495
- 239000003054 catalyst Substances 0.000 claims description 123
- 239000000463 material Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 51
- 239000012071 phase Substances 0.000 claims description 44
- 238000011084 recovery Methods 0.000 claims description 43
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000010992 reflux Methods 0.000 claims description 35
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011973 solid acid Substances 0.000 claims description 15
- 230000001502 supplementing effect Effects 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 15
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000004064 recycling Methods 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 10
- 238000012856 packing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004332 deodorization Methods 0.000 claims description 7
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003225 biodiesel Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 description 13
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
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- 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 device and a method for producing fatty acid methyl ester by utilizing a catalytic distillation technology. The invention adopts a new technology of a fixed bed and a catalytic distillation tower, creates a new technical route for producing fatty acid methyl ester (biodiesel) and realizes a new method of fatty acid methyl esterification; the method overcomes the defects of other technical routes, such as high acid value of products and incomplete esterification reaction. The invention is a novel technology which is clean, environment-friendly, efficient, low in consumption, small in investment, fast in effect and high in benefit.
Description
Technical Field
The invention relates to a device and a method for producing fatty acid methyl ester by utilizing a catalytic distillation technology, which realize complete reaction of fatty acid by utilizing the catalytic distillation technology and belong to the field of fine chemical industry.
Background
At present, the production technology of fatty acid methyl ester is mostly in a lag state. Such as still using sulfuric acid, liquid base as catalyst; the reason why the stirring type reaction device is adopted for production is that the catalyst technology is behind, the reaction device is crude, and the novel production technical requirements of cleanness, environmental protection, high efficiency and low consumption cannot be met. Therefore, through many years of research, we invented a novel production process for completing fatty acid methyl esterification by using a fixed bed and catalytic distillation technology, and the existing and crude production technology is changed into a lagging situation.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, provides a device and a method for producing fatty acid methyl ester by utilizing a fixed bed and catalytic distillation coupling technology, is a novel technical method for producing biodiesel from deodorized oil by utilizing a fixed bed and catalytic distillation technology, and is a novel method for realizing fatty acid methyl esterification.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the utility model provides an utilize device of catalytic distillation technique production fatty acid methyl ester, includes fixed bed reactor, catalytic distillation tower, the methyl alcohol recovery tower that connects gradually, and fatty acid and the methyl alcohol in the deodorization oil carry out methyl esterification pre-reaction in fixed bed reactor, then pass into catalytic distillation tower and continue to carry out methyl esterification and collect the product, and excessive methyl alcohol enters into the methyl alcohol recovery tower and carries out recovery, its characterized in that:
the fixed bed reactor is provided with a feed inlet and a discharge outlet; the feed inlet is connected with a device for providing deodorization oil and methanol;
the catalytic distillation tower, the top of the tower is equipped with water and methyl alcohol export, tower wall top one side is equipped with the backward flow mouth, the opposite side is equipped with the material import, tower wall below is equipped with gaseous phase methyl alcohol and supplements the mouth, the bottom of the tower is equipped with fatty acid methyl ester export, wherein: the material inlet is connected with the discharge port, the gas-phase methanol supplementing port is connected with a device capable of providing gas-phase methanol, and the fatty acid methyl ester outlet is connected with a device for collecting fatty acid methyl ester; the water and methanol outlets are connected with a jet pump, the jet pump outlet of the jet pump is connected with a receiving tank, the outlet of the receiving tank is divided into two paths, one path is connected with a reflux port through a chemical pump I, and the other path is connected with a methanol recovery tower through a chemical pump II; realizing alcohol-water separation in a methanol recovery tower to recover methanol;
the methanol recovery tower, the top of the tower is equipped with high concentration methanol outlet, the bottom of the tower is equipped with waste water outlet, tower wall central authorities are equipped with water and methanol inlet, tower wall top is equipped with the methanol reflux mouth, wherein: the water and methanol inlet is connected with the pump outlet of the chemical pump II, the wastewater outlet is connected with the wastewater treatment system, the high-concentration methanol outlet is sequentially connected with the condenser, the condensing tank and the chemical pump III, the pump outlet of the chemical pump III is divided into two paths, one path is connected with the methanol reflux outlet, and the other path is connected with the gas-phase methanol supplementing port through the heater.
Preferably, the jet pump is provided with a jet pump inlet, a jet pump outlet and a jet liquid inlet, wherein: the inlet of the jet pump is connected with the water and methanol outlets of the catalytic distillation tower, the outlet of the jet pump is connected with the receiving tank, and the inlet of the jet liquid is connected with the chemical pump II.
Preferably, the receiving tank is provided with an inlet and an outlet, wherein: the inlet is connected with the jet pump outlet of the jet pump, the outlet is divided into two paths, one path is connected with the pump inlet of the chemical pump I, the pump outlet of the chemical pump I is connected with the reflux outlet of the catalytic distillation tower, and the other path is connected with the pump inlet of the chemical pump II.
Preferably, the pump outlet of the chemical pump II is divided into two paths, one path is connected with the water and methanol inlet of the methanol recovery tower so as to introduce materials into the methanol recovery tower for alcohol-water separation, and the other path is connected with the injection liquid inlet of the injection pump so as to introduce the materials into the injection pump for providing vacuumizing power for the injection pump.
Preferably, the feeding mode of the fixed bed reactor is concurrent, the feeding port is positioned at the top end of the fixed bed reactor, and the discharging port is positioned at the bottom end of the fixed bed reactor, namely, the feeding port is positioned at the upper port, and the discharging port is positioned at the lower port.
Preferably, the feeding mode of the fixed bed reactor is countercurrent, the feeding port is positioned at the bottom end of the fixed bed reactor, and the discharging port is positioned at the top end of the fixed bed reactor, namely, the feeding port is positioned at the lower port, and the discharging port is positioned at the upper port.
Preferably, the fixed bed reactor is provided with a catalyst A, wherein the catalyst A is a solid acid catalyst, and the type of the catalyst A is any one of D006 or D008 produced by the company.
Preferably, the fixed bed reactors are one or more, and when the fixed bed reactors are a plurality of fixed bed reactors, the fixed bed reactors can be connected in series or in parallel.
Preferably, the catalytic distillation tower is designed according to three sections, wherein the upper section in the tower is a rectifying section, the lower section is a stripping section, and the middle is a catalytic section.
Preferably, the rectifying section and the stripping section are filled with internal parts, and the internal parts are sieve plates or structured packing: the filler is N sections, N is less than or equal to 1 and less than or equal to 50, the height of each section is 2000-4000mm, and the types of the filler are stainless steel corrugated pore plates; the sieve plate is N layers, N is more than or equal to 5 and less than or equal to 100, the spacing between the layers is 350-550mm, and the sieve plate is an efficient float valve sieve plate.
Preferably, the catalyst section is filled with a catalyst B, wherein the catalyst B is a solid acid catalyst, and the type of the catalyst B is any one of D006 or D008 produced by the company; the solid acid catalyst can be in bulk or in the form of a modular catalyst;
preferably, the catalyst B is designed as a modular catalyst, which, like the modular catalyst in CN201620189748.5, comprises an active catalyst, a wire mesh and a corrugated wire plate: the module catalyst is formed by arranging the wire mesh and the wire mesh corrugated plates in parallel at intervals, wherein the two wire mesh plates are filled with the catalyst particles (namely the solid acid catalyst in the invention) to form an active catalyst layer, and the active catalyst particles in the catalyst layer are arranged by the wire mesh corrugated plates at intervals; the active catalyst layers in the module catalyst are arranged at intervals;
the module catalyst is fixed on the periphery by metal wires;
the outer contour of the module catalyst is wrapped and fixed by the wire mesh to form a geometric shape; the geometric shape is a cube and a cylinder;
one or two layers of wire mesh corrugated plates are arranged between the wire mesh and the wire mesh at intervals;
the active catalyst layer is arranged at intervals by one or two layers of metal wire mesh corrugated plates; the active catalyst layer is formed by spacing one or two layers of metal wire mesh corrugated plates between two layers of metal wire mesh, and the active catalyst particles are filled in the active catalyst layer;
the wire mesh and the wire mesh corrugated plate are made of stainless steel materials, and the wire mesh or the wire mesh corrugated plate can be replaced by a stainless steel plate with holes;
the wire mesh and the wire mesh corrugated plate are vertically arranged up and down;
the active catalyst layer is provided with a reinforced outer wall, and the double layers of the wire mesh and the stainless steel belt pore corrugated plate are used as the outer wall of the catalyst layer;
the catalyst layer forms a liquid phase channel, the metal wire corrugated plate layer forms a gas phase channel, the gas phase is fed from the lower part, the liquid phase is fed from the upper part, and the gas phase and the liquid phase are in countercurrent contact so as to carry out complete reaction.
Preferably, the methanol recovery tower is filled with internal parts, wherein the internal parts are sieve plates or structured packing, the packing is N sections, N is more than or equal to 1 and less than or equal to 50, the height of each section is 2000-4000mm, and the type of the packing is stainless steel corrugated plates; the sieve plate is N layers, N is more than or equal to 5 and less than or equal to 100, the spacing between the layers is 350-550mm, and the sieve plate is an efficient float valve sieve plate.
The invention also provides a method for producing fatty acid methyl ester by utilizing the catalytic distillation technology, which comprises the following steps:
(1) Methyl esterification pre-reaction: mixing fatty acid in the deodorized oil with methanol, and performing methyl esterification pre-reaction under the catalysis of a catalyst A;
(2) Methyl esterification reaction: all materials after methyl esterification pre-reaction in the step (1) are subjected to methyl esterification reaction together with gas-phase methanol under the catalysis of a catalyst B to obtain a final product, namely fatty acid methyl ester;
(3) Recycling and/or recovering methanol: water generated by the methyl esterification reaction in the step (2) and excessive methanol in the reaction, and part of the water is refluxed to the step (2) for recycling; the other part is recycled after condensation.
In the technical scheme, the method specifically comprises the following steps:
(1) Methyl esterification pre-reaction: after fatty acid and methanol in the deodorized oil are mixed, the mixture is introduced into a fixed bed reactor through a feed inlet, and methyl esterification pre-reaction is carried out under the catalysis of a catalyst A in the mixture, and part of fatty acid methyl ester and part of water are generated in the reaction process; all materials in the fixed bed reactor are led out from a discharge port and are led into a catalytic distillation tower from a material inlet;
the mol ratio of the deodorization oil fatty acid to the methanol is 1.0:1.1 to 2.0;
the catalyst A is a solid acid catalyst, and the type of the catalyst A is any one of D006 or D008 produced by the company;
the space velocity of the mass feed of the deodorized oil and the methanol is 0.5-2.5h -1 ；
The reaction conditions in the fixed bed reactor are as follows: pressure: 0.1-1.5Mpa and 60-100 deg.c.
(2) Methyl esterification reaction: introducing gas-phase methanol into a catalytic distillation tower from a gas-phase methanol supplementing port, and enabling all materials subjected to methyl esterification pre-reaction in the step (1) to be in countercurrent contact with the gas-phase methanol under the catalytic action of a catalyst B, so that chemical balance is broken, methyl esterification reaction is continuously completed, and fatty acid in deodorized oil is almost 100% completely reacted; collecting from the fatty acid methyl ester outlet to obtain final product fatty acid methyl ester;
the mass feeding airspeed of the gas-phase methanol is 0.2-1.5h -1 ；
The feeding airspeed of all materials after the methyl esterification pre-reaction in the step (1) is 0.5-2.0h -1 ；
The type of the catalyst B solid acid catalyst is any one of D006 or D008 produced by the company;
the catalytic distillation tower, the top of which is: pressure: -1.0-0.0Mpa and 30-100 ℃; and (3) tower kettle: the pressure is 0.01-1.5Mpa and the temperature is 50-200 ℃.
(3) Recycling and/or recovering methanol: the water generated by the methyl esterification reaction in the step (2) and excessive methanol in the reaction flow through the water and methanol outlet, the jet pump inlet, the jet pump and the jet pump outlet in sequence under the negative pressure effect formed by the vacuum pumping of the jet pump, and then enter the receiving tank; one part of the materials in the receiving tank flows out from the outlet and returns to the catalytic distillation tower for reflux through the reflux port under the action of the chemical pump I, and the other part flows out from the outlet and flows into the chemical pump II; the pump outlet of the chemical pump II is divided into two paths, one path is connected with the injection liquid inlet G, the material is returned to the injection pump to provide vacuumizing power for the injection pump, and the other path is connected with the water and methanol inlet to send the material into the methanol recovery tower to realize alcohol-water separation; the wastewater obtained by alcohol-water separation is discharged into a wastewater treatment system phase through a wastewater discharge port, and the obtained high-concentration gas-phase methanol is discharged into a condenser from a high-concentration methanol outlet for condensation; the liquid methanol obtained by condensation enters a condensation tank; under the action of a chemical pump III, one part of materials in the condensing tank returns to the methanol recovery tower from the methanol reflux port for reflux, and the other part returns to the gas-phase methanol supplementing port for recycling after being gasified by the heater;
the vacuum degree of the jet pump is-1.0-0 MPa;
the methanol recovery tower is characterized in that the top of the tower is provided with: the pressure is 0.05-0.35Mpa and the temperature is 30-80 ℃; and (3) tower kettle: the pressure is 0.1-0.55Mpa and the temperature is 80-200 ℃;
the condenser is characterized in that the condensing temperature is the temperature of cooling water: 20-40 ℃;
when the materials in the receiving tank are refluxed to the catalytic distillation tower, the reflux ratio is 0.2-2.0;
when the materials in the condensing tank are refluxed to the methanol recovery tower, the reflux ratio is 0.5-2.0.
The technical scheme of the invention has the advantages that:
(1) According to the invention, one or more fixed beds are designed in front of the catalytic distillation tower to realize the pre-methyl esterification of fatty acid, then the catalytic distillation tower is used for realizing the complete methyl esterification of fatty acid, and a methanol recovery tower is designed behind the catalytic distillation tower to realize the recovery and recycling of excessive methanol.
(2) The invention adopts a new technology of a fixed bed and a catalytic distillation tower, creates a new technical route for producing fatty acid methyl ester (biodiesel) and realizes a new method of fatty acid methyl esterification; the method overcomes the defects of other technical routes, such as high acid value of products and incomplete esterification reaction.
(3) The invention is a novel technology which is clean, environment-friendly, efficient, low in consumption, small in investment, fast in effect and high in benefit.
Drawings
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is a schematic diagram of the structure of the device of the present invention;
wherein: 1. a fixed bed reactor, 1A, a feed inlet, 1B and a discharge outlet; 2. the catalytic distillation tower comprises a catalytic distillation tower, a 2A, a water and methanol outlet, a 2B, a reflux port, a 2C, a material inlet, a 2D, a gas-phase methanol supplementing port, a 2E and a fatty acid methyl ester outlet; 3. the device comprises a methanol recovery tower, a 3A high-concentration methanol outlet, a 3B wastewater outlet, a 3C methanol reflux port, a 3D water and methanol inlet; 4. the jet pump is L, the jet pump inlet, F, the jet pump outlet, G is the jet liquid inlet; 5. a receiving tank; 6. a condenser; 7. a condensing tank; 8. a heater; I. a chemical pump I; II. A chemical pump II; III, chemical pump III.
Detailed Description
The following detailed description of the technical scheme of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention provides a device for producing fatty acid methyl ester by utilizing a catalytic distillation technology, which comprises a fixed bed reactor 1, a catalytic distillation tower 2 and a methanol recovery tower 3 which are sequentially connected, wherein fatty acid and methanol in deodorized oil are subjected to methyl esterification pre-reaction in the fixed bed reactor, then are introduced into the catalytic distillation tower for continuous methyl esterification reaction, and products are collected, and excessive methanol is introduced into the methanol recovery tower for recovery, as shown in figure 2:
the fixed bed reactor is provided with a feed inlet 1A and a discharge outlet 1B; the feed inlet is connected with a device for providing deodorization oil and methanol;
the catalytic distillation tower, the top of the tower is equipped with water and methyl alcohol export 2A, tower wall top one side is equipped with the backward flow mouth 2B, the opposite side is equipped with material import 2C, tower wall below is equipped with gaseous phase methyl alcohol and supplements mouthful 2D, the tower bottom is equipped with fatty acid methyl ester export 2E, wherein: the material inlet 2C is connected with the discharge port 1B, the gas-phase methanol supplementing port 2D is connected with a device capable of providing gas-phase methanol, and the fatty acid methyl ester outlet 2E is connected with a device for collecting fatty acid methyl ester; the water and methanol outlet 2A is connected with a jet pump 4, the jet pump outlet of the jet pump is connected with a receiving tank 5, the outlet of the receiving tank is divided into two paths, one path is connected with a return port 2B through a chemical pump I, and the other path is connected with a methanol recovery tower through a chemical pump II; realizing alcohol-water separation in a methanol recovery tower to recover methanol;
the methanol recovery tower 3, the top of the tower is equipped with high concentration methanol outlet 3A, the bottom of the tower is equipped with waste water outlet 3B, tower wall central authorities are equipped with water and methanol inlet 3D, tower wall top is equipped with methyl alcohol reflux mouth 3C, wherein: the water and methanol inlet 3D is connected with the pump outlet of a chemical pump II, the wastewater outlet 3B is connected with a wastewater treatment system, the high-concentration methanol outlet 3A is sequentially connected with a condenser 6, a condensation tank 7 and a chemical pump III, the pump outlet of the chemical pump III is divided into two paths, one path is connected with a methanol reflux port 3C, and the other path is connected with a gas-phase methanol supplementing port 2D through a heater 8.
Preferably, the jet pump 4 is provided with a jet pump inlet L, a jet pump outlet F and a jet liquid inlet G, wherein: the jet pump inlet L is connected with the water and methanol outlet 2A of the catalytic distillation tower, the jet pump outlet F is connected with the receiving tank, and the jet liquid inlet G is connected with the chemical pump II.
Preferably, the receiving tank 5 is provided with an inlet and an outlet, wherein: the inlet is connected with the jet pump outlet F of the jet pump, the outlet is divided into two paths, one path is connected with the pump inlet of the chemical pump I, the pump outlet of the chemical pump I is connected with the reflux port 2B of the catalytic distillation tower, and the other path is connected with the pump inlet of the chemical pump II.
Preferably, the pump outlet of the chemical pump II is divided into two paths, one path is connected with the water of the methanol recovery tower 3 and the methanol inlet 3D so as to introduce materials into the methanol recovery tower 3 for alcohol-water separation, and the other path is connected with the injection liquid inlet G of the injection pump 4 so as to introduce the materials into the injection pump for providing vacuumizing power for the injection pump.
Preferably, the feeding mode of the fixed bed reactor is concurrent, the feeding port is positioned at the top end of the fixed bed reactor, and the discharging port is positioned at the bottom end of the fixed bed reactor, namely, the feeding port is positioned at the upper port, and the discharging port is positioned at the lower port.
Preferably, the feeding mode of the fixed bed reactor is countercurrent, the feeding port is positioned at the bottom end of the fixed bed reactor, and the discharging port is positioned at the top end of the fixed bed reactor, namely, the feeding port is positioned at the lower port, and the discharging port is positioned at the upper port.
Preferably, the fixed bed reactor is provided with a catalyst A, wherein the catalyst A is a solid acid catalyst, and the type of the catalyst A is any one of D006 or D008 produced by the company.
Preferably, the fixed bed reactors are one or more, and when the fixed bed reactors are a plurality of fixed bed reactors, the fixed bed reactors can be connected in series or in parallel.
Preferably, the catalytic distillation tower is designed according to three sections, wherein the upper section in the tower is a rectifying section, the lower section is a stripping section, and the middle is a catalytic section.
Preferably, the rectifying section and the stripping section are filled with internal parts, and the internal parts are sieve plates or structured packing: the filler is N sections, N is less than or equal to 1 and less than or equal to 50, the height of each section is 2000-4000mm, and the types of the filler are stainless steel corrugated pore plates; the sieve plate is N layers, N is more than or equal to 5 and less than or equal to 100, the spacing between the layers is 350-550mm, and the sieve plate is an efficient float valve sieve plate.
Preferably, the catalyst section is filled with a catalyst B, wherein the catalyst B is a solid acid catalyst, and the type of the catalyst B is any one of D006 or D008 produced by the company; the solid acid catalyst can be in bulk or in the form of a modular catalyst;
preferably, the catalyst B is designed as a modular catalyst, which, like the modular catalyst in CN201620189748.5, comprises an active catalyst, a wire mesh and a corrugated wire plate: the module catalyst is formed by arranging the wire mesh and the wire mesh corrugated plates in parallel at intervals, wherein the two wire mesh plates are filled with the catalyst particles (namely the solid acid catalyst in the invention) to form an active catalyst layer, and the active catalyst particles in the catalyst layer are arranged by the wire mesh corrugated plates at intervals; the active catalyst layers in the module catalyst are arranged at intervals;
the module catalyst is fixed on the periphery by metal wires;
the outer contour of the module catalyst is wrapped and fixed by the wire mesh to form a geometric shape; the geometric shape is a cube and a cylinder;
one or two layers of wire mesh corrugated plates are arranged between the wire mesh and the wire mesh at intervals;
the active catalyst layer is arranged at intervals by one or two layers of metal wire mesh corrugated plates; the active catalyst layer is formed by spacing one or two layers of metal wire mesh corrugated plates between two layers of metal wire mesh, and the active catalyst particles are filled in the active catalyst layer;
the wire mesh and the wire mesh corrugated plate are made of stainless steel materials, and the wire mesh or the wire mesh corrugated plate can be replaced by a stainless steel plate with holes;
the wire mesh and the wire mesh corrugated plate are vertically arranged up and down;
the active catalyst layer is provided with a reinforced outer wall, and the double layers of the wire mesh and the stainless steel belt pore corrugated plate are used as the outer wall of the catalyst layer;
the catalyst layer forms a liquid phase channel, the metal wire corrugated plate layer forms a gas phase channel, the gas phase is fed from the lower part, the liquid phase is fed from the upper part, and the gas phase and the liquid phase are in countercurrent contact so as to carry out complete reaction.
Preferably, the methanol recovery tower is filled with internal parts, wherein the internal parts are sieve plates or structured packing, the packing is N sections, N is more than or equal to 1 and less than or equal to 50, the height of each section is 2000-4000mm, and the type of the packing is stainless steel corrugated plates; the sieve plate is N layers, N is more than or equal to 5 and less than or equal to 100, the spacing between the layers is 350-550mm, and the sieve plate is an efficient float valve sieve plate.
The invention also provides a method for producing fatty acid methyl ester by using the device, as shown in figure 1, comprising the following steps:
(1) Methyl esterification pre-reaction: after fatty acid and methanol in the deodorized oil are mixed, the mixture is introduced into a fixed bed reactor through a feed inlet 1A, and methyl esterification pre-reaction is carried out under the catalysis of a catalyst A in the mixture, and part of fatty acid methyl ester and part of water are generated in the reaction process; all materials in the fixed bed reactor are led out from a discharge hole 1B and are led into a catalytic distillation tower from a material inlet 2C;
(2) Methyl esterification reaction: introducing gas-phase methanol into a catalytic distillation tower from a gas-phase methanol supplementing port 2D, and enabling all materials subjected to methyl esterification pre-reaction in the step (1) to be in countercurrent contact with the gas-phase methanol under the catalysis of a catalyst B, so that chemical balance is broken, methyl esterification reaction is continuously completed, and fatty acid in deodorized oil is almost 100% completely reacted; collecting from the fatty acid methyl ester outlet 2E to obtain the final product-fatty acid methyl ester;
(3) Recycling and/or recovering methanol: the water generated by the methyl esterification reaction in the step (2) and excessive methanol in the reaction flow through the water and methanol outlet 2A, the jet pump inlet L, the jet pump 4 and the jet pump outlet F in sequence under the negative pressure effect formed by the vacuum pumping of the jet pump, and enter the receiving tank 5; one part of the materials in the receiving tank flows out from the outlet and returns to the catalytic distillation tower for reflux through the reflux port 2B under the action of the chemical pump I, and the other part flows out from the outlet and flows into the chemical pump II; the pump outlet of the chemical pump II is divided into two paths, one path is connected with the injection liquid inlet G, the material is returned to the injection pump to provide vacuumizing power for the injection pump, the other path is connected with the water and methanol inlet 3D, and the material is sent into the methanol recovery tower to realize alcohol-water separation; the wastewater obtained by alcohol-water separation is discharged into a wastewater treatment system phase through a wastewater discharge port 3B, and the obtained high-concentration gas-phase methanol is discharged into a condenser 6 from a high-concentration methanol outlet 3A for condensation; the liquid methanol obtained by condensation enters a condensation tank 7; and under the action of a chemical pump III, one part of materials in the condensing tank returns to the methanol recovery tower from the methanol reflux port 3C for reflux, and the other part of materials is gasified by the heater 8 and then returns to the gas-phase methanol supplementing port 2D for recycling.
The apparatus and method of the present invention are described below in conjunction with specific embodiments:
example 1:
a method for producing fatty acid methyl esters using catalytic distillation techniques, comprising the steps of:
(1) Methyl esterification pre-reaction: after the deodorization oil PAF and methanol are mixed, the mixture is introduced into a fixed bed reactor through a feed inlet 1A, and methyl esterification pre-reaction is carried out under the catalysis of a catalyst A in the mixture, and part of fatty acid methyl ester and part of water are generated in the reaction process; all materials in the fixed bed reactor are led out from a discharge hole 1B and are led into a catalytic distillation tower from a material inlet 2C;
the mol ratio of the fatty acid to the methanol of the deodorized oil is 1.0:1.3;
the catalyst A is D006;
the mass feeding airspeed of the deodorized oil and the methanol is 0.8h -1 ；
The fixed bed reactor is one, and the reaction conditions are as follows: the pressure is 0.2 and the temperature is 70 ℃;
the feeding mode of the fixed bed reactor is concurrent.
(2) Methyl esterification reaction: introducing gas-phase methanol into a catalytic distillation tower from a gas-phase methanol supplementing port 2D, and enabling all materials subjected to methyl esterification pre-reaction in the step (1) to be in countercurrent contact with the gas-phase methanol under the catalytic action of a catalyst B to break chemical equilibrium, so that methyl esterification reaction is continuously completed, and fatty acid in deodorized oil is almost 100% completely reacted; the fatty acid methyl ester of the product was obtained from fatty acid methyl ester outlet 2E, and the conversion rate of fatty acid methyl esterification was 99.9%.
The mass feeding airspeed of the gas-phase methanol is 0.8h -1 ；
The feeding airspeed of all materials after the methyl esterification pre-reaction in the step (1) is 1.0h -1 ；
The catalytic distillation tower, the top of which is: the pressure is-0.05 Mpa and the temperature is 50 ℃; and (3) tower kettle: the pressure is 0.15Mpa and the temperature is 80 ℃.
The catalytic distillation tower is designed according to three sections, wherein the upper section in the tower is a rectifying section, the lower section is a stripping section, and the middle is a catalytic section:
the rectifying section and the stripping section are filled with internal parts, and in the implementation, the internal parts are regular stainless steel corrugated plate fillers, and 5 sections are filled with 2000mm of each section;
the catalyst B filled in the catalytic section is D006, and in this embodiment, the catalyst B is designed into a module catalyst, and the module catalyst in the same patent CN201620189748.5 comprises a catalyst, a wire mesh and a wire corrugated plate: the modular catalyst is formed by arranging wire mesh and wire mesh corrugated plates in parallel at intervals, a catalyst layer is formed after D006 is contained between the two wire mesh plates, and catalyst particles in the catalyst layer are arranged at intervals by the wire mesh corrugated plates; the catalyst layers in the module catalyst are arranged at intervals. The outer contour of the modular catalyst is wrapped and fixed by a wire mesh to form a geometrical shape, and the geometrical shape is a cube (see fig. 2 of the patent); a layer of wire mesh corrugated plate is arranged between the wire mesh and the wire mesh; the catalyst layer is provided with two layers of metal wire mesh corrugated plates at intervals; the catalyst layer is formed by spacing a layer of metal wire mesh corrugated plates between two layers of metal wire meshes, and active catalyst particles are filled in the catalyst layer; the wire mesh and the wire mesh corrugated plate are made of stainless steel materials; the wire mesh and the wire mesh corrugated plate are vertically arranged up and down; the active catalyst layer is provided with a reinforced outer wall, and a double layer of a wire mesh and a stainless steel belt hole corrugated plate is used as the outer wall of the catalyst layer.
(3) Recycling and/or recovering methanol: the water generated by the methyl esterification reaction in the step (2) and excessive methanol in the reaction flow through the water and methanol outlet 2A, the jet pump inlet L, the jet pump 4 and the jet pump outlet F in sequence under the negative pressure effect (the vacuum degree is-1.0-0 MPa) formed by the vacuum of the jet pump, and then enter the receiving tank 5; one part of the materials in the receiving tank flows out from the outlet and returns to the catalytic distillation tower from the reflux port 2B under the action of the chemical pump I for reflux (reflux ratio is 0.6), and the other part flows out from the outlet and enters the methanol recovery tower from the water and methanol inlet 3D under the action of the chemical pump II for realizing alcohol-water separation; the separated wastewater is discharged into a wastewater treatment system phase through a wastewater discharge port 3B, and the obtained high-concentration gas-phase methanol is discharged into a condenser 6 from a high-concentration methanol outlet 3A for condensation; the liquid methanol obtained by condensation enters a condensation tank 7; under the action of a chemical pump III, one part of materials in the condensing tank returns to the methanol recovery tower from a methanol reflux port 3C for reflux (reflux ratio is 0.8), and the other part returns to the gas-phase methanol supplementing port 2D for recycling;
the methanol recovery tower is characterized in that the top of the tower is provided with: the pressure is 0.1Mpa and the temperature is 65 ℃; and (3) tower kettle: the pressure is 0.2Mpa and the temperature is 90 ℃;
the temperature of the cooling water in the condenser (6) is 35 ℃;
the methanol recovery tower is filled with internal parts, the internal parts are high-efficiency float valve sieve plates, the sieve plates are 10 layers, and the interval between the layers is 450mm.
The foregoing examples are merely illustrative of the technical concept and technical features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the essence of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for producing fatty acid methyl ester by utilizing a catalytic distillation technology, which is characterized by comprising the following steps:
(1) Methyl esterification pre-reaction: after fatty acid and methanol in the deodorized oil are mixed, the mixture is introduced into a fixed bed reactor through a feed inlet (1A), and methyl esterification pre-reaction is carried out under the catalysis of a catalyst A in the mixture, and part of fatty acid methyl ester and part of water are generated in the reaction process; all materials in the fixed bed reactor are led out from a discharge hole (1B) and are led into a catalytic distillation tower from a material inlet (2C);
(2) Methyl esterification reaction: introducing gas-phase methanol into a catalytic distillation tower from a gas-phase methanol supplementing port (2D), and enabling all materials subjected to methyl esterification pre-reaction in the step (1) to be in countercurrent contact with the gas-phase methanol under the catalysis of a catalyst B, so that chemical balance is broken, methyl esterification reaction is continuously completed, and fatty acid in deodorized oil is almost 100% completely reacted; collecting the final product-fatty acid methyl ester from a fatty acid methyl ester outlet (2E);
(3) Recycling and/or recovering methanol: the water generated by the methyl esterification reaction in the step (2) and excessive methanol in the reaction flow through a water and methanol outlet (2A), a jet pump inlet (L), a jet pump (4) and a jet pump outlet (F) in sequence under the action of negative pressure formed by the vacuumizing of a jet pump, and enter a receiving tank (5); one part of the materials in the receiving tank flows out from the outlet and returns to the catalytic distillation tower for reflux through the reflux port (2B) under the action of the chemical pump I, and the other part flows out from the outlet and flows into the chemical pump II; the pump outlet of the chemical pump II is divided into two paths, one path is connected with the injection liquid inlet G, the material is returned to the injection pump to provide vacuumizing power for the injection pump, the other path is connected with the water and methanol inlet (3D), and the material is sent into the methanol recovery tower to realize alcohol-water separation; the wastewater obtained by alcohol-water separation is discharged into a wastewater treatment system phase through a wastewater discharge port (3B), and the obtained high-concentration gas-phase methanol is discharged into a condenser (6) from a high-concentration methanol outlet (3A) for condensation; the liquid methanol obtained by condensation enters a condensation tank (7); and under the action of a chemical pump III, one part of materials in the condensing tank returns to the methanol recovery tower from the methanol reflux port (3C) for reflux, and the other part returns to the gas-phase methanol supplementing port (2D) for recycling after being gasified by the heater 8.
2. The method according to claim 1, characterized in that: in the step (1), the mol ratio of the deodorized oil fatty acid to methanol is 1.0:1.1 to 2.0; the catalyst A is a solid acid catalyst; the space velocity of the mass feed of the deodorized oil and the methanol is 0.5-2.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction conditions in the fixed bed reactor are as follows: pressure: 0.1-1.5Mpa and 60-100 deg.c.
3. The method according to claim 1, characterized in that: in the step (2), the mass feeding space velocity of the gas-phase methanol is 0.2-1.5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The feeding airspeed of all materials after the methyl esterification pre-reaction in the step (1) is 0.5-2.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst B is a solid acid catalyst; the catalytic distillation tower, the top of which is: pressure: -1.0-0.0Mpa and 30-100 ℃; and (3) tower kettle: the pressure is 0.01-1.5Mpa and the temperature is 50-200 ℃.
4. The method according to claim 1, characterized in that: in the step (3), the vacuum degree of the jet pump is-1.0-0 MPa; the methanol recovery tower is characterized in that the top of the tower is provided with: the pressure is 0.05-0.35Mpa and the temperature is 30-80 ℃; and (3) tower kettle: the pressure is 0.1-0.55Mpa and the temperature is 80-200 ℃; the condenser (6) is used for condensing the water at the temperature of cooling water: 20-40 ℃; when the materials in the receiving tank (5) are refluxed into the catalytic distillation tower, the reflux ratio is 0.2-2.0; when the material in the condensing tank (7) flows back to the methanol recovery tower, the reflux ratio is 0.5-2.0.
5. The utility model provides an utilize device of catalytic distillation technique production fatty acid methyl ester, includes fixed bed reactor (1), catalytic distillation tower (2), methyl alcohol recovery tower (3) that connect gradually, and fatty acid and methyl alcohol in the deodorization oil carry out methyl esterification pre-reaction in fixed bed reactor, then pass into catalytic distillation tower and continue to carry out methyl esterification reaction and collect the product, and excessive methyl alcohol is retrieved in entering methyl alcohol recovery tower, its characterized in that:
the fixed bed reactor is provided with a feed inlet (1A) and a discharge outlet (1B); the feed inlet is connected with a device for providing deodorization oil and methanol;
the catalytic distillation tower, the top of the tower is equipped with water and methyl alcohol export (2A), tower wall top one side is equipped with backward flow mouth (2B), the opposite side is equipped with material import (2C), tower wall below is equipped with gaseous phase methyl alcohol make-up mouth (2D), the tower bottom is equipped with fatty acid methyl ester export (2E), wherein: the material inlet (2C) is connected with the discharge port (1B), the gas-phase methanol supplementing port (2D) is connected with a device capable of providing gas-phase methanol, and the fatty acid methyl ester outlet (2E) is connected with a device for collecting fatty acid methyl ester; the water and methanol outlet (2A) is connected with a jet pump (4), the jet pump outlet of the jet pump is connected with a receiving tank (5), the outlet of the receiving tank is divided into two paths, one path is connected with a reflux port (2B) through a chemical pump I (I), and the other path is connected with a methanol recovery tower through a chemical pump II (II); realizing alcohol-water separation in a methanol recovery tower to recover methanol;
the methanol recovery tower (3), the top of the tower is equipped with high concentration methanol outlet (3A), the bottom of the tower is equipped with waste water outlet (3B), tower wall central authorities are equipped with water and methanol inlet (3D), tower wall top is equipped with methyl alcohol reflux mouth (3C), wherein: the water and methanol inlet (3D) is connected with the pump outlet of the chemical pump II, the wastewater outlet (3B) is connected with the wastewater treatment system, the high-concentration methanol outlet (3A) is sequentially connected with the condenser (6), the condensing tank (7) and the chemical pump III (III), the pump outlet of the chemical pump III is divided into two paths, one path is connected with the methanol reflux port (3C), and the other path is connected with the gas-phase methanol supplementing port (2D) through the heater (8);
the jet pump (4) is provided with a jet pump inlet (L), a jet pump outlet (F) and a jet stream inlet (G), wherein: the jet pump inlet (L) is connected with the water and methanol outlet (2A) of the catalytic distillation tower;
the receiving tank (5) is provided with an inlet and an outlet, wherein: the inlet is connected with a jet pump outlet (F) of the jet pump, the outlet is divided into two paths, one path is connected with a pump inlet of a chemical pump I, the pump outlet of the chemical pump I is connected with a reflux port (2B) of the catalytic distillation tower, and the other path is connected with a pump inlet of a chemical pump II;
the pump outlet of the chemical pump II is divided into two paths, one path is connected with the water of the methanol recovery tower (3) and the methanol inlet (3D) so as to lead the material into the methanol recovery tower (3) for alcohol-water separation, and the other path is connected with the jet material flow inlet (G) of the jet pump (4) so as to lead the jet material flow into the jet pump for providing vacuumizing power for the jet pump.
6. The apparatus according to claim 5, wherein: the feeding mode of the fixed bed reactor is forward flow or reverse flow, wherein: concurrent flow means that the feed inlet is positioned at the top end of the fixed bed reactor, and the discharge outlet is positioned at the bottom end of the fixed bed reactor; countercurrent means that the feed inlet is positioned at the bottom end of the fixed bed reactor and the discharge outlet is positioned at the top end of the fixed bed reactor; the fixed bed reactors are one or more, and when the number of the fixed bed reactors is more than one, the fixed bed reactors can be connected in series or in parallel; the fixed bed reactor is filled with a catalyst A, and the catalyst A is a solid acid catalyst.
7. The apparatus according to claim 5, wherein: the catalytic distillation tower is designed according to three sections, wherein the upper section in the tower is a rectifying section, the lower section is a stripping section, and the middle is a catalytic section, wherein: the rectifying section and the stripping section are filled with internal parts, and the internal parts are sieve plates or structured packing; the catalyst section is filled with a catalyst B, the catalyst B is a solid acid catalyst, and the solid acid catalyst is in bulk or is designed into a module catalyst form; when catalyst B is designed as a modular catalyst, it comprises an active catalyst, wire mesh and wire corrugated plate: the module catalyst is formed by arranging the wire mesh and the wire mesh corrugated plates in parallel at intervals, wherein the two wire mesh plates are filled with the catalyst particles to form an active catalyst layer, and the active catalyst particles in the catalyst layer are separated by the wire mesh corrugated plates; the active catalyst layers in the module catalyst are arranged at intervals; the methanol recovery tower is filled with internal parts, and the internal parts are sieve plates or structured packing.
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