CN111039756B - Method and system for preparing 1, 3-propanediol - Google Patents
Method and system for preparing 1, 3-propanediol Download PDFInfo
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- CN111039756B CN111039756B CN201811195661.9A CN201811195661A CN111039756B CN 111039756 B CN111039756 B CN 111039756B CN 201811195661 A CN201811195661 A CN 201811195661A CN 111039756 B CN111039756 B CN 111039756B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides a method for preparing 1, 3-propanediol from glycerol, comprising: s1, introducing a glycerol aqueous solution into a hydrogenation unit, and enabling the glycerol aqueous solution to contact with hydrogen in the presence of a hydrogenation catalyst to react to generate a hydrogenation mixed product containing 1, 3-propylene glycol; s2, introducing the hydrogenation mixed product into a product separation unit, separating out 1, 3-propylene glycol, byproducts and unreacted glycerol, wherein the unreacted glycerol is returned to the hydrogenation unit. A system for preparing 1, 3-propanediol from glycerol is also provided. Compared with the prior art, the method provided by the invention integrates a high-efficiency catalyst, a reactor and a separation system, and improves the reactivity, selectivity and stability of glycerin hydrogenolysis.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method and a system for preparing 1, 3-propanediol.
Background
1, 3-propanediol (1, 3-PDO) is an important organic chemical raw material, and the most main application of the 1, 3-Propanediol (PTT) is the raw material of novel polyester material, namely, poly (1, 3-propanediol terephthalate). The PTT fiber is widely considered to gradually replace polyester and nylon to become a large-scale fiber in the 21 st century, and has wide application prospect. In addition, the glycerol which is a byproduct in the biodiesel production process is seriously excessive, and the research on the deep processing technology of the glycerol has important significance. Therefore, the preparation of 1, 3-propanediol from glycerol is widely regarded as a transformation approach with important application prospect. At present, main methods for producing 1, 3-propylene glycol from glycerol include a biological fermentation method, an ethylene oxide oxo synthesis method, an acrolein hydration hydrogenation method, a one-step hydrogenation method and the like. The one-step hydrogenolysis method has the advantages of wide raw material adaptability, short process flow, low hydrogen consumption, less environmental pollution, low toxicity and the like, and has important application prospect.
Literature (Green Chemistry,2011, 13:2004) uses Pt-supported/ZrO 2 The catalyst takes DMI as a solvent, and the conversion rate and the selectivity of glycerin are high (83.5 wt%) at 170 ℃ and 7.3MPa, but the reaction pressure is high, and the organic solvent has the problems of environmental pollution and the like. Patent CN101723801A discloses a method for preparing 1, 3-propanediol by directly hydrogenating glycerol, wherein two or more solvents are adopted to dissolve the glycerol for reaction, and the catalyst carrier is ZrO 2 、SiO 2 -Al 2 O 3 Or Al 2 O 3 The active component is one or more of Ru, pt, pd, rh, and the auxiliary component is WO 3 、ZnO、La 2 O 3 One or more of them. However, the selectivity of the catalyst 1, 3-propanediol is low, and the stability of the catalyst is not illustrated. Patent CN104582839A discloses a Pt-WO with boehmite as a carrier x The catalyst, however, has low overall activity. The glycerol one-step hydrogenolysis method reported in the literature and the patent generally has the problems of low catalyst activity, low 1,3 propylene glycol selectivity, low space-time yield, high catalyst cost, poor stability and the like. Therefore, how to improve the utilization rate, selectivity, stability and reduce the cost of the active metals (such as Pt, ir, etc.) has been a difficulty and direction of developing glycerol hydrogenolysis catalysts.
Disclosure of Invention
To overcome the above disadvantages, the present invention provides a method and system for preparing 1, 3-propanediol from glycerol.
In one aspect, the present invention provides a process for preparing 1, 3-propanediol from glycerol comprising: s1, introducing a glycerol aqueous solution into a hydrogenation unit, and enabling the glycerol aqueous solution to contact with hydrogen in the presence of a hydrogenation catalyst to react to generate a hydrogenation mixed product containing 1, 3-propylene glycol; s2, introducing the hydrogenation mixed product into a product separation unit, separating out 1, 3-propylene glycol, byproducts and unreacted glycerol, wherein the unreacted glycerol is returned to the hydrogenation unit.
According to an embodiment of the invention, the aqueous glycerol solution has a concentration of 5% to 90% by weight, preferably 7% to 70% by weight, more preferably 8% to 60% by weight.
According to another embodiment of the present invention, the glycerol hydrogenation reaction conditions in the hydrogenation unit include: the reaction temperature is 100-300 ℃, the pressure is 0.1-8 MPa, the molar ratio of hydrogen to glycerol is 1-200, the flow rate of hydrogen is 5-25L/h, the flow rate of glycerol aqueous solution is 2-20ml/h, and the contact time of glycerol and the hydrogenation catalyst is less than 10 hours; preferably, the reaction temperature is 150-220 ℃, the pressure is 1-5 MPa, the flow rate of the glycerol aqueous solution is 5-15ml/h, and the contact time of the glycerol and the hydrogenation catalyst is less than 6 hours.
According to another embodiment of the present invention, the separating the hydrogenation mixed product in the step S2 comprises: s21, introducing the hydrogenation product mixture into a first separation unit, and separating unreacted glycerin bottom stream and a first tower top hot steam stream through distillation; s22 introducing the first overhead hot vapor stream into a second separation unit, separating by distillation a second bottoms stream comprising 1, 3-propanediol in a concentration greater than the concentration of 1, 3-propanediol in the first overhead hot vapor stream and a second overhead hot vapor stream comprising a light fraction; s23, introducing the second bottom stream into a 1, 3-propylene glycol separator, and separating and purifying to obtain a 1, 3-propylene glycol bottom stream with the concentration far greater than that of the 1, 3-propylene glycol in the second bottom stream; the second overhead hot vapor stream is introduced into a light ends separator to yield n-propanol, water and 1, 2-propanediol.
According to another embodiment of the present invention, in the step S21, the conditions of the distillation include: the pressure is 0.1-80Kpa, and the distillation temperature is 100-190 ℃.
According to another embodiment of the present invention, in the step S22, the conditions of the distillation include: the pressure is 0.1-80Kpa, and the distillation temperature is 110-180 ℃.
According to another embodiment of the present invention, in the step S23, the conditions for separation and purification include: the pressure is 0.1-80Kpa, and the distillation temperature is 110-180 ℃; the separation conditions of the light fraction separator include: the pressure is 0.1-80Kpa, and the distillation temperature is 120-170 ℃.
According to another embodiment of the invention, the hydrogenation catalyst comprises a Si-modified alumina support, a first component M1 and a second component M2; the first component M1 is selected from one or more of Pt, ir, rh, pd; the second component M2 is selected from one or more of Zr, ta, mn, W, re; based on the total weight of the catalyst, the content of Si is 0.01-20.0 wt%, the content of the first component M1 is 0.01-10.0 wt%, and the content of the second component M2 is 0.1-20.0 wt%; (Si/Al) XPS /(Si/Al) XRF >2.0; the molar ratio of Si to the second component M2 is 0.1-16; wherein, (Si/Al) XPS The weight ratio of Si to Al in the catalyst characterized by X-ray photoelectron spectroscopy (Si/Al) XRF Is the weight ratio of Si to Al of the catalyst characterized by X-ray fluorescence spectrum.
According to another embodiment of the invention, the reductive activation is carried out in the presence of hydrogen prior to the glycerol hydrogenolysis reaction, said reductive activation being: carrying out the reduction activation under hydrogen-containing atmosphere at a reduction temperature of 100 ℃ to 800 ℃ and a reduction time of 0.5-72 hours; the hydrogen-containing atmosphere comprises pure hydrogen or mixed gas of hydrogen and inert gas, and the hydrogen pressure is 0.1-4MPa; preferably, the reduction temperature is 120-600 ℃, the reduction time is 1-24 hours, and the hydrogen pressure is 0.1-2MPa; more preferably, the reduction temperature is 150 ℃ to 400 ℃ and the reduction time is 2 to 8 hours.
In another aspect, the present invention provides a system for preparing 1, 3-propanediol from glycerol, comprising: a mixing unit for mixing glycerol and water; a hydrogenation unit for hydrogenation reaction of glycerin; a separation unit for separating the product produced by the hydrogenation unit; and a recovery unit for recovering the product separated by the product separation unit.
According to an embodiment of the invention, the hydrogenation unit comprises a catalyst comprising a Si modified alumina support, a first component M1 and a second component M2; the first component M1 is selected from one or more of Pt, ir, rh, pd; the second component M2 is selected from one or more of Zr, ta, mn, W, re; based on the total weight of the catalyst, the content of Si is 0.01-20.0 wt%, the content of the first component M1 is 0.01-10.0 wt%, and the content of the second component M2 is 0.1-20.0 wt%; (Si/Al) XPS /(Si/Al) XRF >2.0; the molar ratio of Si to the second component M2 is 0.1-16; wherein, (Si/Al) XPS The weight ratio of Si to Al in the catalyst characterized by X-ray photoelectron spectroscopy (Si/Al) XRF Is the weight ratio of Si to Al of the catalyst characterized by X-ray fluorescence spectrum.
According to another embodiment of the present invention, the Si content in the catalyst is preferably 0.1 to 15.0wt%, more preferably 0.5 to 10.0wt%.
According to another embodiment of the invention, the alumina support in the catalyst is selected from one or more of alumina, alumina-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia.
According to another embodiment of the present invention, the specific surface area of the alumina carrier is 5 to 600m 2 Preferably 5 to 500m 2 Preferably 10 to 500m 2 /g; the pore volume is 0.05-3.00 mL/g, and the pore diameter is generally 0.3-50.0 nm.
According to another embodiment of the present invention, the alumina carrier is in the form of particles, spheres, columns, flakes, strips, rings, honeycombs or clover; the alumina carrier has an average particle diameter of 50-500 μm.
According to another embodiment of the invention, the content of the first component M1 in the catalyst is preferably 0.1 to 8.0wt%, more preferably 0.3 to 6.0wt%.
According to another embodiment of the invention, the content of the second component M2 in the catalyst is preferably 0.5 to 15wt%, more preferably 1.0 to 12wt%.
According to another embodiment of the invention, the (Si/Al) of the catalyst XPS /(Si/Al) XRF Preferably greater than 3.0, more preferably greater than 4.0.
According to another embodiment of the invention, the molar ratio of Si to the second component M2 in the catalyst is preferably greater than 0.2, more preferably greater than 0.3.
According to another embodiment of the present invention, the hydrogenation unit comprises a three-dimensional channel structured reactor, the reactor comprises a fluid distributor, a reaction channel, a fluid inlet distribution cavity and a fluid outlet collection cavity, the reaction channel is a linear channel, the fluid channel is a nonlinear channel, n parallel reaction channels form a single reaction channel layer, m parallel fluid channels form a single fluid channel layer, x reaction channel layers and y fluid channel layers form a staggered three-dimensional channel structure, wherein n is 5-10000, m is 5-10000, x is 1-10000, y is 2-10000, the inlet of the fluid channel is connected with the fluid inlet distribution cavity, and the outlet of the fluid channel is connected with the fluid outlet collection cavity.
According to another embodiment of the invention, the separation unit comprises: the first separator is connected with the hydrogenation unit and is used for separating products of the hydrogenation unit to obtain a first tower top hot steam stream and a first tower bottom stream, and the tower bottom stream returns to the hydrogenation unit; a second separator connected to the first separator for separating the first overhead hot vapor stream to obtain a second overhead hot vapor stream and a second bottoms stream; a light fraction separator connected to the second separator for separating the second overhead hot vapor to obtain n-propanol, water and 1, 2-propanediol; and a 1, 3-propanediol separator, connected to the second separator, for separating the second bottom stream to obtain 1, 3-propanediol G.
When the catalyst is used in the glycerin hydrogenation reaction in a selected system, compared with the prior art, the activity and the product selectivity of the catalyst are improved, the conversion rate and the 1, 3-propanediol selectivity are high, the reaction condition is mild, the energy consumption is low, the reaction can be carried out at a high airspeed, and the method is favorable for industrialized popularization.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.
FIG. 1 is a flow chart of a method of preparing an embodiment of the present invention.
FIG. 2 is a flow chart of a preparation method according to another embodiment of the present invention.
FIG. 3 is a system for preparing 1, 3-propanediol of the present invention.
Wherein reference numerals are as follows:
s1, S2, S21, S22, S23: step I, raw material mixing unit II, hydrogenation unit III, product separation unit IV, finished product recovery unit A, glycerin aqueous solution B, reaction product mixture C, unreacted glycerin bottom stream D, first overhead hot steam stream E, second overhead hot steam stream F, second bottom stream G, 1, 3-propanediol H, 1, 2-propanediol V, n-propanol K, water J, unreacted H 2 L is fresh H 2 M: raw material tank N: reactor O: first separator P: second separator Q: light fraction separator R n-propanol product tank S1, 2-propanediol product tank T:1, 3-propanediol separator U1, 3-propanediol product tank
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
As shown in fig. 1, a method for preparing 1, 3-propanediol from glycerol according to an embodiment of the present invention includes: s1, introducing a glycerol aqueous solution into a hydrogenation unit, enabling the glycerol aqueous solution to contact hydrogen in the presence of a hydrogenation catalyst, and reacting to generate a hydrogenation mixed product containing 1, 3-propylene glycol; s2, introducing the hydrogenation mixed product into a product separation unit, separating out 1, 3-propylene glycol, byproducts and unreacted glycerin, and returning the unreacted glycerin to the hydrogenation unit.
Specifically, as shown in fig. 2, separating the hydrogenation mixed product in step S2 includes: s21, introducing the hydrogenation product mixture into a first separation unit, and separating unreacted glycerin bottom stream and a first tower top hot steam stream through distillation; s22, introducing the first tower top hot steam stream into a second separation unit, and separating a second tower bottom stream and a second tower top hot steam stream by distillation, wherein the second tower bottom stream comprises 1, 3-propanediol with a concentration greater than that of the 1, 3-propanediol in the first tower top hot steam stream, and the second tower top hot steam stream comprises light fraction; s23, introducing the second bottom stream into a 1, 3-propylene glycol separator, and separating and purifying to obtain a 1, 3-propylene glycol bottom stream with the concentration far greater than that of the 1, 3-propylene glycol in the second bottom stream; the second overhead hot vapor stream is introduced into a light ends separator to yield n-propanol, water and 1, 2-propanediol.
The process for preparing 1, 3-propanediol from glycerol according to the present invention is explained in detail in connection with the system shown in fig. 3. The system comprises a raw material mixing unit I, a hydrogenation unit II, a product separation unit III and a finished product recovery unit IV. The mixing unit I is for mixing glycerol and water, including the feed tank M. The hydrogenation unit II is used for the hydrogenation reaction of glycerin and comprises a reactor N. The separation unit III is used for separating a mixture generated after the reaction and comprises a first separator O, a second separator P, a light fraction separator Q and a 1, 3-propylene glycol separator T. The finished product recovery unit IV is used for recovering finished products formed after separation and comprises an n-propanol product tank R, a 1, 2-propylene glycol product tank and a 1, 3-propylene glycol product tank U.
First, glycerin is dissolved in water in a feed tank M of a mixing unit I to form a glycerin aqueous solution a having a predetermined concentration. The concentration of the glycerol aqueous solution is 5-90 wt%, if the concentration of the glycerol is lower than 5%, the conversion rate is too high under the reaction condition, so that the target product 1,3-PDO is further hydrogenated to generate byproducts; if the glycerol concentration is higher than 90%, the conversion rate is too low under the reaction condition, and the yield of the target product is affected. Preferably, the glycerol concentration is from 7wt% to 70wt%, more preferably from 8wt% to 60wt%.
Then, the aqueous glycerol solution a is introduced into a reactor N of a hydrogenation unit II, and the aqueous glycerol solution a is contacted with hydrogen L in the presence of a hydrogenation catalyst to prepare a hydrogenation mixed product B containing 1, 3-propanediol. Unreacted H 2 Flow out from the upper part of the reactor N and fresh H 2 L is used for hydrogenation reaction after being mixed. The glycerol hydrogenation reaction conditions in the hydrogenation unit may be: the reaction temperature is 100-300 ℃, the pressure is 0.1-8 MPa, the molar ratio of hydrogen to glycerol is 1-200, the flow rate of hydrogen is 5-25L/h, the flow rate of glycerol aqueous solution is 2-20ml/h, and the contact time of glycerol and hydrogenation catalyst is less than 10 hours; preferably, the reaction temperature is 150-220 ℃, the pressure is 1-5 MPa, the flow rate of the glycerol aqueous solution is 5-15ml/h, and the contact time of the glycerol and the hydrogenation catalyst is less than 6 hours.
The hydrogenation catalyst in reactor N comprises a Si-modified alumina support, a first component M1 and a second component M2. The first component M1 is selected from one or more of Pt, ir, rh, pd. The second component M2 is selected from one or more of Zr, ta, mn, W, re. Based on the total weight of the catalyst, the content of Si is 0.01-20.0wt%, the content of the first component M1 is 0.01-10.0wt%, and the content of the second component M2 is 0.1-20.0wt%. (Si/Al) XPS /(Si/Al) XRF >2.0. The molar ratio of Si to the second component M2 is 0.1 to 16. Wherein, (Si/Al) XPS The weight ratio of Si to Al in the catalyst characterized by X-ray photoelectron spectroscopy (Si/Al) XRF Is the weight ratio of Si to Al of the catalyst characterized by X-ray fluorescence spectrum. The Si content is preferably 0.1 to 15.0wt%, more preferably 0.5 to 10.0wt%. The alumina carrier is one or more selected from alumina, alumina-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia. The specific surface area of the alumina carrier is 5-600 m 2 Preferably 5 to 500m 2 Preferably 10 to 500m 2/ g; the pore volume is 0.05-3.00 mL/g, and the pore diameter is generally 0.3-50.0 nm. The alumina carrier is in the shape of particles, spheres and columnsA sheet, strip, ring, honeycomb or clover. The alumina carrier has an average particle size of 50-500 μm. The content of the first component M1 is preferably 0.1 to 8.0% by weight, more preferably 0.3 to 6.0% by weight. The content of the second component M2 is preferably 0.5 to 15% by weight, more preferably 1.0 to 12% by weight. (Si/Al) XPS /(Si/Al) XRF Preferably greater than 3.0, more preferably greater than 4.0. The molar ratio of Si to the second component M2 is preferably 0.2 to 15, more preferably 0.3 to 14.
The hydrogenation reaction is carried out in a conventional fixed bed reactor or a microchannel reactor. If a microchannel reactor is selected, the reactor can comprise a fluid distributor, a reaction channel, a fluid inlet distribution cavity and a fluid outlet collection cavity, wherein the reaction channel is a linear channel, the fluid channel is a nonlinear channel, n parallel reaction channels form a single reaction channel layer, m parallel fluid channels form a single fluid channel layer, x reaction channel layers and y fluid channel layers form a staggered three-dimensional channel structure, wherein n is 5-10000, m is 5-10000, x is 1-10000, y is 2-10000, the inlet of the fluid channel is connected with the fluid inlet distribution cavity, and the outlet of the fluid channel is connected with the fluid outlet collection cavity.
The hydrogenation mixed product B discharged from the hydrogenation unit II enters a product separation unit III. First into a first separator O, heating is performed to produce an unreacted glycerin bottom stream C (including glycerin) and a first overhead hot vapor stream D (including water, n-propanol, 1,2-PDO and 1, 3-PDO) by distillation. The distillation conditions may be 0.1-80Kpa, and the distillation temperature is 100-190 ℃. Unreacted glycerin bottom stream C enters a hydrogenation unit II again to participate in hydrogenation reaction.
The first overhead hot vapor is introduced into a second thermal separator P to produce a second overhead hot vapor stream E and a second bottoms stream F at the bottom of the column. The second bottoms stream F contains 1, 3-propanediol in a concentration greater than the concentration of 1, 3-propanediol in the first overhead hot vapor, and the second overhead hot vapor stream E contains light ends (overhead light ends comprising n-propanol, 1,2-PDO, and water). The distillation conditions may be a pressure of 0.1-80Kpa and a distillation temperature of 110-180deg.C.
The second bottom stream F is introduced into a 1, 3-propanediol separator T to produce a 1, 3-propanediol bottom stream having a concentration substantially greater than the concentration of 1, 3-propanediol in the second bottom stream F, the bottom stream being high purity 1, 3-propanediol G. The 1, 3-propanediol G flows into the 1, 3-propanediol product tank U. The second overhead hot vapor stream E is introduced into a light ends separator Q to yield n-propanol V, water K and 1, 2-propanediol H, which are fed to n-propanol product tank R, feed tank M and 1, 2-propanediol product tank S, respectively. The conditions for separation and purification can be 0.1-80Kpa, and the distillation temperature is 110-180 ℃; the separation conditions of the light fraction separator may be a pressure of 0.1 to 80Kpa and a distillation temperature of 120 to 170 ℃.
In order to improve the reaction efficiency, the reduction activation can be carried out in the presence of hydrogen before the glycerol hydrogenolysis reaction, and the reduction activation is as follows: performing reduction activation under hydrogen-containing atmosphere at a reduction temperature of 100-800 ℃ for a reduction time of 0.5-72 hours; the hydrogen-containing atmosphere comprises pure hydrogen or mixed gas of hydrogen and inert gas, and the hydrogen pressure is 0.1-4MPa; preferably, the reduction temperature is 120-600 ℃, the reduction time is 1-24 hours, and the hydrogen pressure is 0.1-2MPa; more preferably, the reduction temperature is 150 ℃ to 400 ℃ and the reduction time is 2 to 8 hours.
Preparation example 1
(1) Modified carrier and preparation thereof
3.417g of ethyl orthosilicate was dissolved in 50mL of cyclohexane to obtain an impregnation solution. 16.723g of alumina micro (kaolin catalyst product, specific surface area 260m 2 And/g) dispersing the mixture in the impregnating solution, stirring the mixture at 60 ℃ for 2 hours, and performing rotary evaporation to obtain a dried sample, drying the sample at 120 ℃ for 2 hours, and roasting the sample at 650 ℃ for 2 hours.
(2) Catalyst and preparation thereof
Dispersing the modified carrier into 2.078g of ammonium metatungstate (72.17 wt% of W mass fraction) and dissolving in 40mL of deionized impregnation liquid, stirring at room temperature for 10min, performing rotary evaporation to obtain a dried sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h; the resulting sample was dispersed into 14.035g of an impregnating solution comprising a Pt 2.85wt% chloroplatinic acid solution mixed with 10mL deionized water; stirring at room temperature for 10min, rotary evaporating to obtain dried sample, drying at 150deg.C for 2 hr, and calcining at 300deg.C for 2 hr to obtain catalyst C-1 with Pt content of 2.0wt%, W content of 7.5wt% and Si content of 2.3wt% based on element.
Preparation example 2
(1) Modified carrier and preparation thereof
3.417g of ethyl orthosilicate was dissolved in 50mL of cyclohexane to obtain an impregnation solution. Crushing 16.723g of alumina butterfly-shaped strip carrier (kaolin catalyst product, specific surface area 260 m) 2 And/g, crushing to 100-200 meshes), dispersing in the impregnating solution, stirring at 60 ℃ for 2 hours, performing rotary evaporation to obtain a dried sample, drying at 120 ℃ for 2 hours, and roasting at 650 ℃ for 2 hours.
(2) Catalyst and preparation thereof
Dispersing the modified carrier into 2.078g of ammonium metatungstate (72.17 wt% of W mass fraction) and dissolving in 40mL of deionized impregnation liquid, stirring at room temperature for 10min, performing rotary evaporation to obtain a dried sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h; the resulting sample was dispersed into 14.035g of an impregnating solution comprising a Pt 2.85wt% chloroplatinic acid solution mixed with 10mL deionized water; stirring at room temperature for 10min, rotary evaporating to obtain dried sample, drying at 150deg.C for 2 hr, and roasting at 300deg.C for 2 hr to obtain catalyst C-2, wherein Pt is 2.0wt% based on element, W is 7.5wt% and Si is 2.3wt%.
Preparation of comparative example 1
(1) Modified support
Unmodified alumina from example 1 was used as support.
(2) Catalyst and preparation thereof
17.709g of alumina microspheres (kaolin catalyst product, specific surface area 260m 2 Dispersing 2.078g of ammonium metatungstate (weight fraction of W is 72.17 wt%) in 40mL of deionized impregnating solution, stirring at room temperature for 10min, rotary evaporating to obtain dried sample, drying at 150deg.C for 2h, and roasting at 600deg.C for 2h; the resulting sample was dispersed into 14.035g of an impregnating solution comprising a Pt 2.85wt% chloroplatinic acid solution mixed with 10mL deionized water; stirring at room temperature for 10min, rotary evaporating to obtain a dried sample, drying at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain the catalyst BC-1, wherein the Pt in terms of elements in the BC-1 is 2.0wt% and the W is 7.5wt%.
Preparation of comparative example 2
(1) Modified carrier and preparation thereof
Unmodified alumina from example 2 was used as support.
(2) Catalyst and preparation thereof
Dispersing the modified carrier into 2.078g of ammonium metatungstate (72.17 wt% of W mass fraction) and dissolving in 40mL of deionized impregnation liquid, stirring at room temperature for 10min, performing rotary evaporation to obtain a dried sample, drying the sample at 150 ℃ for 2h, and roasting at 600 ℃ for 2h; the resulting sample was dispersed into 14.035g of an impregnating solution comprising a Pt 2.85wt% chloroplatinic acid solution mixed with 10mL deionized water; stirring at room temperature for 10min, rotary evaporating to obtain a dried sample, drying at 150 ℃ for 2h, and roasting at 300 ℃ for 2h to obtain the catalyst BC-2, wherein the Pt in terms of elements in the BC-2 is 2.0wt% and the W is 7.5wt%.
Examples 1-2 are provided to illustrate the process of the present invention for 1, 3-propanediol.
Example 1
The system of the 1, 3-propylene glycol shown in fig. 3 is adopted in the embodiment, and comprises a raw material mixing unit I, a hydrogenation unit II, a product separation unit III and a finished product recovery unit IV. The specific method flow is as follows.
Glycerin and water are prepared into 30wt% glycerin aqueous solution which is stored in a raw material tank M, the glycerin aqueous solution is pumped into a hydrogenation unit II by a pump, and the glycerin aqueous solution is contacted with a microspherical catalyst C-1 in a reactor N with a three-dimensional channel structure to generate hydrogenation mixed products, and the hydrogenation mixed products enter a product separation unit III. Not involved in reaction H 2 Through the pipeline and fresh H 2 Mixing, and feeding the mixture and the glycerol aqueous solution in a raw material tank into a reactor N to continuously participate in the reaction. To the product, which is pumped into a first separator O to separate an unreacted glycerin bottom stream C and a first overhead hot vapor stream D (which includes water, n-propanol, 1,2-PDO and 1, 3-PDO). The first tower top hot steam stream D continuously enters a second separator P, the first tower top hot steam stream D is separated by a distillation method to generate a second tower top hot steam stream E and a stream F with the concentration of 1, 3-propanediol being obviously greater than D, the stream F is continuously separated and purified by the 1, 3-propanediol separator T to generate high-purity 1, 3-propanediol G with the concentration of more than 99.8wt% and the high-purity 1, 3-propanediol G is stored in a product tank U. Second towerThe overhead hot vapor stream E enters a light ends separator Q and is separated into a heavy ends 1, 2-propanediol H, water K, and n-propanol V. The water K is pumped back to the raw material tank M to continue the reaction.
Before the reaction, the microspherical reactor is filled into a reactor with a three-dimensional channel structure, and the catalyst is reduced for 2 hours at 240 ℃ under normal pressure and pure hydrogen atmosphere for activation. Cooling to 180 ℃ and controlling the pressure to be 4.0MPa, wherein the hydrogen flow is 15L/h, and the 30wt% glycerol water solution flow is 12 mL/h. The liquid after the reaction was collected periodically and analyzed for composition by gas chromatography.
Example 2
1, 3-propanediol was prepared in the same manner as in example 1, except that the catalyst was selected differently, and the catalyst of comparative example C-2 was charged in the reactor of three-dimensional channel structure to participate in the reaction.
Comparative example 1
1, 3-propanediol was prepared in the same manner as in example 1, except that the reactor type was selected differently and a conventional fixed bed reactor was used for the reaction.
Comparative example 2
1, 3-propanediol was prepared in the same manner as in example 1, except that a slurry bed was used for the reaction, with the exception of the type of reactor selected.
Comparative example 3
1, 3-propanediol was prepared in the same manner as in example 1, except that the catalyst was selected differently, and the reaction was carried out by filling the catalyst of comparative example BC-1 into the reactor having a three-dimensional channel structure.
Comparative example 4
1, 3-propanediol was prepared in the same manner as in example 1, except that the catalyst was selected differently, and the reaction was carried out by filling the catalyst of comparative example BC-2 in the reactor having a three-dimensional channel structure.
In this patent, the molar percentage of glycerol converted to 1, 3-propanediol to converted glycerol is defined as the selectivity of 1, 3-propanediol, and the mass per gram of Pt produced 1, 3-propanediol per unit time (h) (gram) is defined as the catalyst space-time yield; the percent reduction in catalyst space time yield per unit time (day) based on the space time yield of the 12h reaction is the deactivation rate and the results are shown in Table 1. Sampling and analyzing activity selectivity at the material flow B; 1,3-PDO purity was analyzed in U tank.
Table 1 table of performance parameters for the preparation methods of examples 1-2 and comparative examples 1-4
* : the purity of 1, 3-propanediol is measured based on product tank U.
The results in Table 1 show that the combination method performance of the catalyst and the reactor provided by the invention has obvious advantages: the catalyst has high space-time yield, low subsequent product separation pressure, high product purity and slow deactivation rate.
When the catalyst is used in the glycerol hydrogenation reaction in the selected reactor, compared with the prior art, the catalyst has improved activity and product selectivity, high conversion rate and 1, 3-propanediol selectivity, mild reaction condition, low energy consumption and reaction at high airspeed, and is favorable for industrialized popularization.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (12)
1. A process for preparing 1, 3-propanediol from glycerol comprising:
s1, introducing a glycerol aqueous solution into a hydrogenation unit, and enabling the glycerol aqueous solution to contact with hydrogen in the presence of a hydrogenation catalyst to react to generate a hydrogenation mixed product containing 1, 3-propylene glycol;
s2, introducing the hydrogenation mixed product into a product separation unit to separate 1, 3-propylene glycol, byproducts and unreacted glycerol, wherein the unreacted glycerol returns to the hydrogenation unit;
wherein the hydrogenation catalyst comprises a Si modified alumina carrier, a first component M1 and a second component M2; the first component M1 is Pt; the second component M2 is W; the shape of the alumina carrier is spherical; based on the total weight of the catalyst, the content of Si is 0.01-20.0wt%, the content of the first component M1 is 0.01-10.0wt%, and the content of the second component M2 is 0.1-20.0wt%; (Si/Al) XPS/(Si/Al) XRF >2.0; the molar ratio of Si to the second component M2 is 0.1-16; wherein, (Si/Al) XPS is the weight ratio of Si to Al in the catalyst characterized by X-ray photoelectron spectroscopy, and (Si/Al) XRF is the weight ratio of Si to Al in the catalyst characterized by X-ray fluorescence spectroscopy;
the hydrogenation unit comprises a three-dimensional channel structure reactor, the reactor comprises a fluid distributor, a reaction channel, a fluid inlet distribution cavity and a fluid outlet collection cavity, the reaction channel is a linear channel, the fluid channel is a nonlinear channel, n parallel reaction channels form a single reaction channel layer, m parallel fluid channels form a single fluid channel layer, x reaction channel layers and y fluid channel layers form a staggered three-dimensional channel structure, wherein n is 5-10000, m is 5-10000, x is 1-10000, y is 2-10000, an inlet of the fluid channel is connected with the fluid inlet distribution cavity, and an outlet of the fluid channel is connected with the fluid outlet collection cavity;
wherein the glycerol hydrogenation reaction conditions in the hydrogenation unit comprise: the reaction temperature is 100-300 ℃, the pressure is 0.1-8 MPa, the molar ratio of hydrogen to glycerin is 1-200, the flow rate of hydrogen is 5-25L/h, the flow rate of glycerin aqueous solution is 2-20ml/h, and the contact time of glycerin and the hydrogenation catalyst is less than 10 hours.
2. The method of claim 1, wherein the aqueous glycerol solution concentration is 5wt% to 90wt%.
3. The method of claim 2, wherein the aqueous glycerol solution concentration is 7wt% to 70wt%.
4. The method of claim 2, wherein the aqueous glycerol solution concentration is 8wt% to 60wt%.
5. The process of claim 1, wherein the glycerol hydrogenation reaction conditions in the hydrogenation unit comprise: the reaction temperature is 150-220 ℃, the pressure is 1-5 MPa, the flow rate of the glycerol aqueous solution is 5-15ml/h, and the contact time of the glycerol and the hydrogenation catalyst is less than 6 hours.
6. The process of claim 1, wherein separating the hydrogenated mixture product in the S2 step comprises:
s21, introducing the hydrogenation product mixture into a first separation unit, and separating unreacted glycerin bottom stream and a first tower top hot steam stream through distillation;
s22 introducing the first overhead hot vapor stream into a second separation unit, separating by distillation a second bottoms stream comprising 1, 3-propanediol in a concentration greater than the concentration of 1, 3-propanediol in the first overhead hot vapor stream and a second overhead hot vapor stream comprising a light fraction;
s23, introducing the second bottom stream into a 1, 3-propylene glycol separator, and separating and purifying to obtain a 1, 3-propylene glycol bottom stream with the concentration being greater than that of the 1, 3-propylene glycol in the second bottom stream; the second overhead hot vapor stream is introduced into a light ends separator to yield n-propanol, water and 1, 2-propanediol.
7. The method of claim 6, wherein in the step S21, the conditions of the distillation include: the pressure is 0.1-80Kpa, and the distillation temperature is 100-190 ℃.
8. The method of claim 6, wherein in the step S22, the conditions of the distillation include: the pressure is 0.1-80Kpa, and the distillation temperature is 110-180 ℃.
9. The method according to claim 6, wherein in the step S23, the conditions for separation and purification include: the pressure is 0.1-80Kpa, and the distillation temperature is 100-190 ℃; the separation conditions of the light fraction separator include: the pressure is 0.1-80Kpa, and the distillation temperature is 120-170 ℃.
10. The process of claim 1, wherein the reductive activation is performed in the presence of hydrogen prior to the glycerol hydrogenolysis reaction, said reductive activation being: carrying out the reduction activation under hydrogen-containing atmosphere at a reduction temperature of 100 ℃ to 800 ℃ and a reduction time of 0.5-72 hours; the hydrogen-containing atmosphere comprises pure hydrogen or mixed gas of hydrogen and inert gas, and the hydrogen pressure is 0.1-4MPa.
11. The method of claim 10, wherein the reductive activation is: the reduction temperature is 120-600 ℃, the reduction time is 1-24 hours, and the hydrogen pressure is 0.1-2MPa.
12. The method of claim 10, wherein the reductive activation is: the reduction temperature is 150 ℃ to 400 ℃ and the reduction time is 2 to 8 hours.
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