WO2010085018A1 - Method of regenerating heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol and chlorinating agent, method of preparing dichloropropanol comprising the method of regenerating heteropolyacid catalyst and method of preparing epichlorohydrin comprising the method of preparing dichloropropanol - Google Patents
Method of regenerating heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol and chlorinating agent, method of preparing dichloropropanol comprising the method of regenerating heteropolyacid catalyst and method of preparing epichlorohydrin comprising the method of preparing dichloropropanol Download PDFInfo
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- WO2010085018A1 WO2010085018A1 PCT/KR2009/000772 KR2009000772W WO2010085018A1 WO 2010085018 A1 WO2010085018 A1 WO 2010085018A1 KR 2009000772 W KR2009000772 W KR 2009000772W WO 2010085018 A1 WO2010085018 A1 WO 2010085018A1
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- heteropolyacid catalyst
- catalyst
- dichloropropanol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 99
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical compound CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 28
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims description 131
- 239000012320 chlorinating reagent Substances 0.000 title claims description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 35
- 230000008020 evaporation Effects 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000001953 recrystallisation Methods 0.000 claims abstract description 20
- 239000011541 reaction mixture Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 6
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 claims description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005660 chlorination reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 description 40
- 239000003377 acid catalyst Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 32
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 15
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 2
- HUXDTFZDCPYTCF-UHFFFAOYSA-N 1-chloropropane-1,1-diol Chemical compound CCC(O)(O)Cl HUXDTFZDCPYTCF-UHFFFAOYSA-N 0.000 description 2
- ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 2,3-dichloropropan-1-ol Chemical compound OCC(Cl)CCl ZXCYIJGIGSDJQQ-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 239000008235 industrial water Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
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Images
Classifications
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
-
- 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
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- An embodiment of the present invention relates to a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent , a method of preparing dichloropropanol including the method of regenerating the heteropolyacid catalyst, and a method of preparing epichlorohydrin including the method of preparing dichloropropanol, and more particularly, to a method of regenerating a heteropolyacid catalyst including a simple evaporation stage and a calcination stage, and selectively including a recrystallization stage.
- bio-diesels have been competitively developed and produced worldwide, and also domestically manufactured and brought to markets as an additive to petro-diesel.
- glycerol a large amount of glycerol, corresponding to about 10% of the amount of the produced bio-diesel, is generated as a by-product.
- supply of glycerol is greater than demand therefor and oversupply of glycerol decreases its value.
- dichloropropanol is a raw material used to produce epichlorohydrin which is applied to a variety of fields as a raw material for epoxy resins, synthesized glycerin, ion exchange resins, flame retardants, solvents, medicines, dyes, and the like.
- Most of the dichloropropanol which is currently supplied to markets is manufactured from propylene.
- a method of preparing dichloropropanol includes a two-stage process of preparing allyl chloride through chlorination reaction of propylene at a high temperature and preparing dichloropropanol by reacting the allyl chloride with hydrochloric acid using an excess amount of industrial water (US Patent Nos.
- a single-stage process of directly preparing dichloropropanol by reacting glycerol with hydrochloric acid is more economical.
- the single-stage process using glycerol is advantageous in that costs of raw materials can be reduced by using inexpensive glycerol as a reactant, the amount of waster water and other waste can be dramatically reduced since industrial water is not required for the process, thereby being environmentally friendly and initial investment costs related to the process and environment can be reduced.
- the method of preparing dichloropropanol from glycerol using a single-stage process is environmentally friendly since dichloropropanol is directly prepared from glycerol which is a by-product generated in the preparation of bio-diesels, which is different from the conventional method of preparing dichloropropanol through the two-stage manufacturing process.
- glycerol which is inexpensive and a by-product generated in the preparation of bio-diesel, instead of propylene as a reactant and by developing an efficient catalyst by which a single-stage process is used instead of using a two-stage manufacturing process of preparing dichloropropanol.
- Chinese Patent Publication No. CN 101007751A discloses a method of preparing dichloropropanol in which consumption of hydrogen chloride gas is decreased by performing a first reaction in a plug flow reactor using a nitrile-based catalyst and continuously removing water from a second reaction performed using a bubble cap tray.
- the present invention provides a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent, the method including a simple evaporation stage and a calcination stage, and selectively including a recrystallization stage.
- the present invention also provides a method of directly preparing dichloropropanol, the method including the method of regenerating a heteropolyacid catalyst, wherein the regenerated heteropolyacid catalyst is re-used.
- the present invention also provides a method of preparing epichlorohydrin, the method including the method of preparing dichloropropanol.
- a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent including:
- the method may further include recrystallizing the calcined heteropolyacid catalyst in a recrystallization stage.
- the recrystallization stage may include: preparing a catalyst solution by dissolving the calcined heteropolyacid catalyst in water; removing impurities from the catalyst solution by filtering the catalyst solution; and heating the filtered catalyst solution to a temperature in the range of about 50 to about 100 °C for about 1 to about 20 hours.
- the method of claim 3 may further include drying the recrystallized heteropolyacid catalyst at a temperature in the range of about 50 to about 100 °C for about 1 to about 48 hours (drying stage) after the recrystallization.
- the simple evaporation stage may include heating the reaction mixture to a temperature in the range of about 100 to about 400 °C for about 10 minutes to about 5 hours.
- the calcination stage may further include heating the separated solid heteropolyacid catalyst in the presence of oxygen to a temperature in the range of about 200 to about 400 °C for about 1 to about 40 hours.
- the heteropolyacid catalyst may include a Keggin-type heteropolyacid catalyst in which the ratio of the number of central atoms to the number of coordinated atoms is 1:12.
- the Keggin-type heteropolyacid catalyst may include 12-tungstophosphoric acid (H 3 PW 12 O 40 ).
- a method of directly preparing dichloropropanol by reacting glycerol with a chlorinating agent, constituting a chlorination reaction, using a heteropolyacid catalyst the method including the method of regenerating a heteropolyacid catalyst, wherein the regenerated heteropolyacid catalyst is re-used.
- the chlorinating agent may include hydrogen chloride gas or hydrochloric acid.
- the chlorination reaction may be performed at a temperature in the range of about 50 to about 300 °C at a pressure in the range of about 0.1 to about 30 bar for about 10 minutes to about 50 hours.
- the chlorination reaction may be performed in at least one reactor selected from a group consisting of a batch reactor, a semi-batch reactor, a constant stirred tank reactor (CSTR), and a plug flow reactor.
- a batch reactor a semi-batch reactor
- CSTR constant stirred tank reactor
- a method of preparing epichlorohydrin (ECH) after directly preparing dichloropropanol by reacting glycerol with a chlorinating agent using a heteropolyacid catalyst the method including the method of preparing dichloropropanol.
- FIG. 1 is a graph illustrating infrared (IR) analysis results of regenerated heteropolyacid catalysts according to embodiments of the present invention and a pure heteropolyacid catalyst.
- a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent includes a simple evaporation stage and a calcination stage.
- the simple evaporation stage is a stage by which a solid heteropolyacid catalyst is separated from a reaction mixture including reactants, products, heteropolyacid catalyst and/or water by simply evaporating components having a boiling point lower than that of the heteropolyacid catalyst from the reaction mixture.
- the calcination stage is a stage by which impurities contained in the separated solid heteropolyacid catalyst are removed by being burned.
- the simple evaporation stage may include heating the reaction mixture to a temperature in the range of about 100 to about 400°C for about 10 minutes to about 5 hours. If the simple evaporation stage is performed at a temperature higher than 100°C or for longer than 10 minutes, the reaction mixture except for the heteropolyacid catalyst is smoothly evaporated. On the other hand, if the simple evaporation stage is performed at a temperature lower than 400°C or for shorter than 5 hours, pyrolysis of the heteropolyacid catalyst may be inhibited, thereby preventing the chemical structure of the heteropolyacid catalyst from being broken.
- the calcination stage may include heating the separated solid heteropolyacid catalyst in the presence of oxygen to a temperature in the range of about 200 to about 400°C for about 1 to about 40 hours. If the calcination stage is performed at a temperature higher than 200°C or for longer than 1 hour, contact time with oxygen is long enough, and thus impurities such as carbon attached to the heteropolyacid catalyst are sufficiently burned. On the other hand, if the calcination stage is performed at a temperature lower than 400°C or for shorter than 40 hours, pyrolysis of the heteropolyacid catalyst may be inhibited, thereby preventing the chemical structure of the heteropolyacid catalyst from being broken.
- the calcination stage may be performed under an air atmosphere. Impurities (reactants and/or products) are attached to the solid heteropolyacid catalyst obtained through the simple evaporation stage, and most of the impurities are burned and removed during the calcination stage.
- the method of regenerating a heteropolyacid catalyst according to the present embodiment may further include recrystallizing the calcined heteropolyacid catalyst (recrystallization stage). As a result of the recrystallization stage, impurities remaining in the heteropolyacid catalyst are further removed, and the amount of water of crystallization contained in the heteropolyacid catalyst is controlled. Accordingly, the crystal structure of the heteropolyacid catalyst is changed.
- the recrystallization stage may include: preparing a catalyst solution by dissolving the calcined heteropolyacid catalyst in water; removing impurities from the catalyst solution by filtering the catalyst solution using filter paper; and heating the filtered catalyst solution to a temperature in the range of about 50 to about 100°C for about 1 to about 20 hours. If the recrystallization stage is performed at a temperature higher than 50°C or for longer than 1 hour, water constituting water of crystallization is easily evaporated during the recrystallization of the heteropolyacid catalyst so that the amount of the water of crystallization is not changed, thereby preventing the chemical structure of the heteropolyacid catalyst from being changed.
- the recrystallization stage is performed at a temperature lower than 100°C or for shorter than 20 hours, all water constituting water of crystallization, may not be evaporated during the recrystallization of the heteropolyacid catalyst, thereby preventing the heteropolyacid catalyst from being burned.
- the method of regenerating a heteropolyacid catalyst according to the present embodiment may further include drying the recrystallized heteropolyacid catalyst at a temperature in the range of about 50 to about 100°C for about 1 to about 48 hours (drying stage) after the recrystallization stage.
- the drying is performed in order to remove water still remaining in the recrystallized heteropolyacid catalyst. If the drying is performed at a temperature higher than 50°C or for longer than 1 hour, the remained water other than water constituting water of crystallization is sufficiently removed. On the other hand, if the drying is performed at a temperature lower than 100°C or for shorter than 48 hours, energy and time consumed during the drying stage may be reduced.
- the heteropolyacid catalyst may include a Keggin-type heteropolyacid catalyst in which the ratio of the number of central atoms to the number of coordinated atoms is 1:12.
- the Keggin-type heteropolyacid catalyst may include 12-tungstophosphoric acid (H 3 PW 12 O 40 ).
- the present invention also provides a method of directly preparing dichloropropanol by reacting glycerol with a chlorinating agent using a heteropolyacid catalyst.
- the method of directly preparing dichloropropanol includes the method of regenerating a heteropolyacid catalyst according to the embodiment described above, and re-using the regenerated heteropolyacid catalyst.
- the chlorinating agent used in the chlorination reaction may include hydrogen chloride gas or hydrochloric acid.
- the chlorination reaction may be performed at a temperature in the range of about 50 to about 300°C, for example, about 100 to about 200°C. If the chlorination reaction is performed at a temperature higher than 50°C, the reaction rate may be sufficiently high. On the other hand, if the chlorination reaction is performed at a temperature lower than 300°C, energy loss may be minimized.
- the chlorination reaction may be performed at a pressure in the range of about 0.1 to about 30 bar, for example, about 1 to about 15 bar. Even though higher activity may be observed at a higher reaction pressure, when the pressure is higher than a predetermined level (30 bar), the reaction activity is not increased any longer.
- the reaction pressure is regulated by the pressure of the chlorinating agent.
- the reaction may be performed for about 10 minutes to about 50 hours, and preferably for about 1 to about 20 hours. If the reaction is performed for longer than 10 minutes, the glycerol-conversion rate is high. On the other hand, if the reaction is performed for longer than 50 hours, the reaction is nearly terminated, and thus the conversion rate or selectivity is not increased any longer.
- the 'dichloropropanol' indicates a mixture of isomers including 1,3-dichloropropane-2-ol and 1,2-dichloropropane-3-ol.
- 1,3-dichloropropane-2-ol which is a suitable reactant for the preparation of epichlorohydrin, is mainly produced.
- the chlorination reaction may be performed in at least one reactor selected from a group consisting of a batch reactor, a semi-batch reactor, a constant stirred tank reactor (CSTR), and a plug flow reactor.
- the reactor may be formed of a material which has resistance to a chlorinating agent or may include interior structures coated with such material.
- the material having resistance to the chlorinating agent may be Hastelloy C, Teflon, or the like.
- the heteropolyacid catalyst is regenerated after the chlorination reaction and re-used. That is, the regenerated heteropolyacid catalyst according to the present invention may be added to the reactor and re-used. Since the heteropolyacid catalyst and the reaction mixture except for the heteropolyacid catalyst do not form an azeotrope after the reaction, the heteropolyacid catalyst may be regenerated and re-used. As in the case of using a conventional carboxylic acid-based catalyst, if a reaction mixture except for the catalyst and the catalyst form an azeotrope, equilibrium is established between liquid and gas phases. Thus, the catalyst may not be simply separated from the reaction mixture since the ratio of components between the liquid and gas phases is constantly maintained and the boiling point of each component is not changed.
- the addition of the catalyst may be performed in a continuous or discontinuous way in the reactor.
- Glycerol-conversion rate (%) (the number of moles of reacted glycerol/the number of moles of supplied glycerol) ⁇ 100
- the selectivity for dichloropropanol is calculated based on the mixture of isomers of 1,3-dichloropropane-2-ol and 1,2-dichloropropane-3-ol.
- the present invention also provides a method of preparing epichlorohydrin including the method of preparing the dichloropropanol.
- a method of preparing epichlorohydrin from glycerol using a heteropolyacid catalyst is shown in Reaction Scheme 1 below.
- Dichloropropanol was directly prepared from glycerol and hydrogen chloride gas using a heteropolyacid catalyst.
- the reaction was performed in a liquid phase in a 200 ml batch reactor from which water was completely removed.
- the interior structures of the batch reactor were formed of Hastelloy C and Teflon which has resistance to a chlorinating agent.
- 100 g of glycerol and 3 g of 12-tungstophosphoric acid, as a pure Keggin-type heteropolyacid catalyst were added to the batch reactor.
- the term 'pure catalyst' used herein indicates 'unused catalyst with high purity'.
- reaction temperature was fixed at 130°C, and the reaction was performed by continuously supplying 99.7 wt% of hydrogen chloride gas, as a chlorinating agent, at a constant pressure of 3 bar to the batch reactor for 3 hours while stirring at 900 rpm to directly prepare dichloropropanol.
- the heteropolyacid catalyst was collected by heating the batch reactor at 300°C for 2 hours so that components having a boiling point lower than that of the heteropolyacid catalyst were removed. As a result, a solid 12-tungstophosphoric acid catalyst was obtained.
- Example 1-1 Method of regenerating heteropolyacid catalyst including simple evaporation and calcination
- the 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 was added to an electric furnace and calcined at 350°C for 20 hours under an air atmosphere to regenerate the 12-tungstophosphoric acid catalyst.
- Example 1-2 Method of regenerating heteropolyacid catalyst including simple evaporation, calcination, recrystallization, and drying
- the 12-tungstophosphoric acid regenerated according to Example 1-1 was dissolved in water to prepare a catalyst solution.
- the catalyst solution was filtered using filter paper to remove impurities. Then, the catalyst of the catalyst solution was recrystallized by heating the catalyst solution at 80°C for 5 hours. And then the catalyst solution was dried in a drying device at 80°C for 24 hours.
- Dichloropropanol was prepared from glycerol using a pure 12-tungstophosphoric acid catalyst, and the 12-tungstophosphoric acid catalysts regenerated according to Experimental Example 1, Example 1-1, and Example 1-2, respectively. Then, glycerol-conversion rates, selectivities for dichloropropanol, and yields of dichloropropanol were calculated by analyzing the reaction mixtures after the reactions were terminated.
- Experimental Example 2-1 (Comparative Example 2-1): Direct preparation of dichloropropanol from glycerol using pure Keggin-type heteropolyacid catalyst, 12-tungstophosphoric acid (H 3 PW 12 O 40 )
- Dichloropropanol was directly prepared by reacting glycerol with hydrogen chloride gas in the same manner as in Experimental Example 1, except that a catalyst was not used, or 12-tungstophosphoric acid (H 3 PW 12 O 40 ) was used as a pure Keggin-type heteropolyacid catalyst by the amounts described in Table 1 below . After each of the reactions was terminated, the reactor was cooled to room temperature. Then, the reaction mixtures were analyzed using gas chromatography. In addition, glycerol-conversion rates, selectivities for dichloropropanol, and yields of dichloropropanol were calculated using Equations 1 to 3, and the results are shown in Table 1 below.
- 'MCPD' and 'DCP' of Table 1 respectively indicate monochloropropandiol and dichloropropanol.
- Products of the reaction mainly include monochloropropandiol and dichloropropanol.
- the products may further include a small amount (less than 3 wt%) of by-products such as epichlorohydrin and trichloropropane (TCP).
- dichloropropanol increases as the amount of the 12-tungstophosphoric acid catalyst increases.
- dichloropropanol may be more efficiently prepared when a large amount of the catalyst is used.
- Experimental Example 2-2 (Comparative Example 2-2): Direct preparation of dichloropropanol from glycerol using 12-tungstophosphoric acid (H 3 PW 12 O 40 ) regenerated according to Experimental Example 1 (simple evaporation)
- Example 2-1 Direct preparation of dichloropropanol from glycerol using 12-tungstophosphoric acid (H 3 PW 12 O 40 ) catalyst regenerated according to Example 1-1
- Example 2-2 Direct preparation of dichloropropanol from glycerol using 12-tungstophosphoric acid (H 3 PW 12 O 40 ) catalyst regenerated according to Example 1-2
- the yield of dichloropropanol is not much changed even if the number of times the catalyst is regenerated increases when dichloropropanol is directly prepared using the 12-tungstophosphoric acid catalyst regenerated according to Example 1-2. Furthermore, there is no big difference between the yield of dichloropropanol using the 12-tungstophosphoric acid catalyst regenerated according to Example 1-2 and the yield of dichloropropanol using the pure 12-tungstophosphoric acid catalyst (the yield of DCP in case of using the pure 12-tungstophosphoric acid catalyst: 81.0%, and the yield of DCP in case of using the 12-tungstophosphoric acid catalyst regenerated three times: 79.0%).
- Evaluation Example 1 IR analysis results of pure 12-tungstophosphoric acid (H 3 PW 12 O 40 ) catalyst; and 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 (simple evaporation), Example 1-1, and Example 1-2
- the 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 does not exhibit IR peaks indicating intrinsic properties of the pure 12-tungstophosphoric acid catalyst.
- the 12-tungstophosphoric acid catalysts regenerated according to Example 1-1 (simple evaporation+calcination) and Example 1-2 (simple evaporation+calcination+recrystallization+drying) exhibit IR peaks indicating intrinsic properties of the pure 12-tungstophosphoric acid catalyst.
- Evaluation Example 2 CHNS analysis results of 12-tungstophosphoric acid catalysts regenerated according to Experimental Example 1 (simple evaporation), Example 1-1, and Example 1-2
- the 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 (simple evaporation) has a larger amount of carbon than the 12-tungstophosphoric acid catalysts regenerated according to Example 1-1 and Example 1-2.
- carbon deposits are not completely evaporated during the evaporation but remain on the surface of the 12-tungstophosphoric acid catalyst regenerated by the simple evaporation of Experimental Example 1.
- a large amount of carbon attached to the 12-tungstophosphoric acid catalysts is removed during the calcination stage under an air atmosphere, and thus only a small amount of carbon remains.
Abstract
Provided are a method of regenerating a heteropolyacid catalyst, a method of preparing dichloropropanol including the method of regenerating a heteropolyacid catalyst, and a method of preparing epichlorohydrin including the method of preparing dichloropropanol. The method of regenerating a heteropolyacid catalyst includes: separating a solid heteropolyacid catalyst from a reaction mixture after preparing dichloropropanol by simply evaporating components having a boiling point lower than that of the heteropolyacid catalyst (simple evaporation); and calcining the separated solid heteropolyacid catalyst (calcination). The method of regenerating the heteropolyacid catalyst may further include recrystallizing the calcined heteropolyacid catalyst (recrystallization).
Description
An embodiment of the present invention relates to a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent , a method of preparing dichloropropanol including the method of regenerating the heteropolyacid catalyst, and a method of preparing epichlorohydrin including the method of preparing dichloropropanol, and more particularly, to a method of regenerating a heteropolyacid catalyst including a simple evaporation stage and a calcination stage, and selectively including a recrystallization stage.
Recently, bio-diesels have been competitively developed and produced worldwide, and also domestically manufactured and brought to markets as an additive to petro-diesel.
During the production of bio-diesel, a large amount of glycerol, corresponding to about 10% of the amount of the produced bio-diesel, is generated as a by-product. However, supply of glycerol is greater than demand therefor and oversupply of glycerol decreases its value. Thus, it is economically advantageous to convert glycerol into dichloropropanol which is a higher-value added product compared to glycerol.
Meanwhile, dichloropropanol is a raw material used to produce epichlorohydrin which is applied to a variety of fields as a raw material for epoxy resins, synthesized glycerin, ion exchange resins, flame retardants, solvents, medicines, dyes, and the like. Most of the dichloropropanol which is currently supplied to markets is manufactured from propylene. More particularly, a method of preparing dichloropropanol includes a two-stage process of preparing allyl chloride through chlorination reaction of propylene at a high temperature and preparing dichloropropanol by reacting the allyl chloride with hydrochloric acid using an excess amount of industrial water (US Patent Nos. 4,479,020, 6,051,742, and 6,333,420). However, the method of preparing dichloropropanol using propylene has problems in terms of instability of propylene supply and demand caused by increased price of propylene, generation of a large amount of waste water and other waste, excessive initial investment costs due to the two-stage manufacturing process and difficulty of modifying the process.
Accordingly, a single-stage process of directly preparing dichloropropanol by reacting glycerol with hydrochloric acid is more economical. The single-stage process using glycerol is advantageous in that costs of raw materials can be reduced by using inexpensive glycerol as a reactant, the amount of waster water and other waste can be dramatically reduced since industrial water is not required for the process, thereby being environmentally friendly and initial investment costs related to the process and environment can be reduced. In addition, the method of preparing dichloropropanol from glycerol using a single-stage process is environmentally friendly since dichloropropanol is directly prepared from glycerol which is a by-product generated in the preparation of bio-diesels, which is different from the conventional method of preparing dichloropropanol through the two-stage manufacturing process.
In addition, manufacturing costs for dichloropropanol and energy consumption can be reduced by using glycerol, which is inexpensive and a by-product generated in the preparation of bio-diesel, instead of propylene as a reactant and by developing an efficient catalyst by which a single-stage process is used instead of using a two-stage manufacturing process of preparing dichloropropanol. Thus, when an excellent catalyst process by which dichloropropanol can be directly prepared using glycerol is developed, technological competitiveness in the preparation of dichloropropanol can be gained with regard to environmental, economical, and investment cost factors.
Dow Chemical Company, U.S.A. and Solvay, S.A., Germany are major companies currently manufacturing epichlorohydrin from glycerol. These companies manufacture dichloropropanol from glycerol by using a continuous process using a carboxylic acid-based homogeneous catalyst and hydrogen chloride gas as a chlorinating agent (International Publication Nos. WO2006/020234, WO2005/054167 and WO2005/021476).
In addition, Chinese Patent Publication No. CN 101007751A discloses a method of preparing dichloropropanol in which consumption of hydrogen chloride gas is decreased by performing a first reaction in a plug flow reactor using a nitrile-based catalyst and continuously removing water from a second reaction performed using a bubble cap tray.
In addition, a method of preparing dichloropropanol by diluting glycerol in a solvent and passing the diluted glycerol and hydrogen chloride gas through a packed bed packed with glass beads without using a catalyst is reported by Isu Chemical Company, Korea (Korean Patent Publication No. 2008-0038284).
However, apart from the above publications, inventions related to a method of directly preparing dichloropropanol from glycerol have not been disclosed.
The present invention provides a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent, the method including a simple evaporation stage and a calcination stage, and selectively including a recrystallization stage.
The present invention also provides a method of directly preparing dichloropropanol, the method including the method of regenerating a heteropolyacid catalyst, wherein the regenerated heteropolyacid catalyst is re-used.
The present invention also provides a method of preparing epichlorohydrin, the method including the method of preparing dichloropropanol.
According to an aspect of the present invention, there is provided a method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent, the method including:
separating a solid heteropolyacid catalyst from a reaction mixture by simply evaporating components having a boiling point lower than that of the heteropolyacid catalyst in a simple evaporation stage; and
calcining the separated solid heteropolyacid catalyst in a calcination stage.
The method may further include recrystallizing the calcined heteropolyacid catalyst in a recrystallization stage.
The recrystallization stage may include: preparing a catalyst solution by dissolving the calcined heteropolyacid catalyst in water; removing impurities from the catalyst solution by filtering the catalyst solution; and heating the filtered catalyst solution to a temperature in the range of about 50 to about 100 ℃ for about 1 to about 20 hours.
The method of claim 3 may further include drying the recrystallized heteropolyacid catalyst at a temperature in the range of about 50 to about 100 ℃ for about 1 to about 48 hours (drying stage) after the recrystallization.
The simple evaporation stage may include heating the reaction mixture to a temperature in the range of about 100 to about 400 ℃ for about 10 minutes to about 5 hours.
The calcination stage may further include heating the separated solid heteropolyacid catalyst in the presence of oxygen to a temperature in the range of about 200 to about 400 ℃ for about 1 to about 40 hours.
The heteropolyacid catalyst may include a Keggin-type heteropolyacid catalyst in which the ratio of the number of central atoms to the number of coordinated atoms is 1:12.
The Keggin-type heteropolyacid catalyst may include 12-tungstophosphoric acid (H3PW12O40).
According to another aspect of the present invention, there is provided a method of directly preparing dichloropropanol by reacting glycerol with a chlorinating agent, constituting a chlorination reaction, using a heteropolyacid catalyst, the method including the method of regenerating a heteropolyacid catalyst, wherein the regenerated heteropolyacid catalyst is re-used.
The chlorinating agent may include hydrogen chloride gas or hydrochloric acid.
The chlorination reaction may be performed at a temperature in the range of about 50 to about 300 ℃ at a pressure in the range of about 0.1 to about 30 bar for about 10 minutes to about 50 hours.
The chlorination reaction may be performed in at least one reactor selected from a group consisting of a batch reactor, a semi-batch reactor, a constant stirred tank reactor (CSTR), and a plug flow reactor.
According to another aspect of the present invention, there is provided a method of preparing epichlorohydrin (ECH) after directly preparing dichloropropanol by reacting glycerol with a chlorinating agent using a heteropolyacid catalyst, the method including the method of preparing dichloropropanol.
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:
FIG. 1 is a graph illustrating infrared (IR) analysis results of regenerated heteropolyacid catalysts according to embodiments of the present invention and a pure heteropolyacid catalyst.
Hereinafter, a method of regenerating a heteropolyacid catalyst according to an embodiment of the present invention will be described.
A method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent according to an embodiment of the present invention includes a simple evaporation stage and a calcination stage.
The simple evaporation stage is a stage by which a solid heteropolyacid catalyst is separated from a reaction mixture including reactants, products, heteropolyacid catalyst and/or water by simply evaporating components having a boiling point lower than that of the heteropolyacid catalyst from the reaction mixture. The calcination stage is a stage by which impurities contained in the separated solid heteropolyacid catalyst are removed by being burned.
The simple evaporation stage may include heating the reaction mixture to a temperature in the range of about 100 to about 400℃ for about 10 minutes to about 5 hours. If the simple evaporation stage is performed at a temperature higher than 100℃ or for longer than 10 minutes, the reaction mixture except for the heteropolyacid catalyst is smoothly evaporated. On the other hand, if the simple evaporation stage is performed at a temperature lower than 400℃ or for shorter than 5 hours, pyrolysis of the heteropolyacid catalyst may be inhibited, thereby preventing the chemical structure of the heteropolyacid catalyst from being broken.
The calcination stage may include heating the separated solid heteropolyacid catalyst in the presence of oxygen to a temperature in the range of about 200 to about 400℃ for about 1 to about 40 hours. If the calcination stage is performed at a temperature higher than 200℃ or for longer than 1 hour, contact time with oxygen is long enough, and thus impurities such as carbon attached to the heteropolyacid catalyst are sufficiently burned. On the other hand, if the calcination stage is performed at a temperature lower than 400℃ or for shorter than 40 hours, pyrolysis of the heteropolyacid catalyst may be inhibited, thereby preventing the chemical structure of the heteropolyacid catalyst from being broken.
For example, the calcination stage may be performed under an air atmosphere. Impurities (reactants and/or products) are attached to the solid heteropolyacid catalyst obtained through the simple evaporation stage, and most of the impurities are burned and removed during the calcination stage.
The method of regenerating a heteropolyacid catalyst according to the present embodiment may further include recrystallizing the calcined heteropolyacid catalyst (recrystallization stage). As a result of the recrystallization stage, impurities remaining in the heteropolyacid catalyst are further removed, and the amount of water of crystallization contained in the heteropolyacid catalyst is controlled. Accordingly, the crystal structure of the heteropolyacid catalyst is changed.
The recrystallization stage may include: preparing a catalyst solution by dissolving the calcined heteropolyacid catalyst in water; removing impurities from the catalyst solution by filtering the catalyst solution using filter paper; and heating the filtered catalyst solution to a temperature in the range of about 50 to about 100℃ for about 1 to about 20 hours. If the recrystallization stage is performed at a temperature higher than 50℃ or for longer than 1 hour, water constituting water of crystallization is easily evaporated during the recrystallization of the heteropolyacid catalyst so that the amount of the water of crystallization is not changed, thereby preventing the chemical structure of the heteropolyacid catalyst from being changed. On the other hand, if the recrystallization stage is performed at a temperature lower than 100℃ or for shorter than 20 hours, all water constituting water of crystallization, may not be evaporated during the recrystallization of the heteropolyacid catalyst, thereby preventing the heteropolyacid catalyst from being burned.
The method of regenerating a heteropolyacid catalyst according to the present embodiment may further include drying the recrystallized heteropolyacid catalyst at a temperature in the range of about 50 to about 100℃ for about 1 to about 48 hours (drying stage) after the recrystallization stage. The drying is performed in order to remove water still remaining in the recrystallized heteropolyacid catalyst. If the drying is performed at a temperature higher than 50℃ or for longer than 1 hour, the remained water other than water constituting water of crystallization is sufficiently removed. On the other hand, if the drying is performed at a temperature lower than 100℃ or for shorter than 48 hours, energy and time consumed during the drying stage may be reduced.
The heteropolyacid catalyst may include a Keggin-type heteropolyacid catalyst in which the ratio of the number of central atoms to the number of coordinated atoms is 1:12. For example, the Keggin-type heteropolyacid catalyst may include 12-tungstophosphoric acid (H3PW12O40).
The present invention also provides a method of directly preparing dichloropropanol by reacting glycerol with a chlorinating agent using a heteropolyacid catalyst. The method of directly preparing dichloropropanol includes the method of regenerating a heteropolyacid catalyst according to the embodiment described above, and re-using the regenerated heteropolyacid catalyst.
The chlorinating agent used in the chlorination reaction may include hydrogen chloride gas or hydrochloric acid.
The chlorination reaction may be performed at a temperature in the range of about 50 to about 300℃, for example, about 100 to about 200℃. If the chlorination reaction is performed at a temperature higher than 50℃, the reaction rate may be sufficiently high. On the other hand, if the chlorination reaction is performed at a temperature lower than 300℃, energy loss may be minimized.
In addition, generally, the chlorination reaction may be performed at a pressure in the range of about 0.1 to about 30 bar, for example, about 1 to about 15 bar. Even though higher activity may be observed at a higher reaction pressure, when the pressure is higher than a predetermined level (30 bar), the reaction activity is not increased any longer. The reaction pressure is regulated by the pressure of the chlorinating agent. The reaction may be performed for about 10 minutes to about 50 hours, and preferably for about 1 to about 20 hours. If the reaction is performed for longer than 10 minutes, the glycerol-conversion rate is high. On the other hand, if the reaction is performed for longer than 50 hours, the reaction is nearly terminated, and thus the conversion rate or selectivity is not increased any longer.
Here, the 'dichloropropanol' indicates a mixture of isomers including 1,3-dichloropropane-2-ol and 1,2-dichloropropane-3-ol. In the method of preparing dichloropropanol, 1,3-dichloropropane-2-ol, which is a suitable reactant for the preparation of epichlorohydrin, is mainly produced.
The chlorination reaction may be performed in at least one reactor selected from a group consisting of a batch reactor, a semi-batch reactor, a constant stirred tank reactor (CSTR), and a plug flow reactor. The reactor may be formed of a material which has resistance to a chlorinating agent or may include interior structures coated with such material. The material having resistance to the chlorinating agent may be Hastelloy C, Teflon, or the like.
In addition, the heteropolyacid catalyst is regenerated after the chlorination reaction and re-used. That is, the regenerated heteropolyacid catalyst according to the present invention may be added to the reactor and re-used. Since the heteropolyacid catalyst and the reaction mixture except for the heteropolyacid catalyst do not form an azeotrope after the reaction, the heteropolyacid catalyst may be regenerated and re-used. As in the case of using a conventional carboxylic acid-based catalyst, if a reaction mixture except for the catalyst and the catalyst form an azeotrope, equilibrium is established between liquid and gas phases. Thus, the catalyst may not be simply separated from the reaction mixture since the ratio of components between the liquid and gas phases is constantly maintained and the boiling point of each component is not changed.
The addition of the catalyst may be performed in a continuous or discontinuous way in the reactor.
In the direct preparation of dichloropropanol from glycerol using the heteropolyacid catalyst, the glycerol-conversion rate, the selectivity for dichloropropanol, and the yield of dichloropropanol are respectively calculated using Equations 1 to 3 below.
Equation 1
Glycerol-conversion rate (%) = (the number of moles of reacted glycerol/the number of moles of supplied glycerol)×100
Equation 2
Selectivity for dichloropropanol (%) = (the number of moles of produced dichloropropanol/the number of moles of reacted glycerol)×100
The selectivity for dichloropropanol is calculated based on the mixture of isomers of 1,3-dichloropropane-2-ol and 1,2-dichloropropane-3-ol.
Equation 3
Yield of dichloropropanol (%) = (the number of moles produced dichloropropanol/the number of moles of supplied glycerol)×100
Meanwhile, the present invention also provides a method of preparing epichlorohydrin including the method of preparing the dichloropropanol. In particular, a method of preparing epichlorohydrin from glycerol using a heteropolyacid catalyst is shown in Reaction Scheme 1 below.
Reaction Scheme 1
Hereinafter, the present invention will be described in greater detail with reference to the following examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Examples
Experimental Example 1 (Comparative Example 1-1): Method of regenerating heteropolyacid catalyst including simple evaporation
Dichloropropanol was directly prepared from glycerol and hydrogen chloride gas using a heteropolyacid catalyst. The reaction was performed in a liquid phase in a 200 ml batch reactor from which water was completely removed. The interior structures of the batch reactor were formed of Hastelloy C and Teflon which has resistance to a chlorinating agent. First, 100 g of glycerol and 3 g of 12-tungstophosphoric acid, as a pure Keggin-type heteropolyacid catalyst were added to the batch reactor. The term 'pure catalyst' used herein indicates 'unused catalyst with high purity'. Then, the reaction temperature was fixed at 130℃, and the reaction was performed by continuously supplying 99.7 wt% of hydrogen chloride gas, as a chlorinating agent, at a constant pressure of 3 bar to the batch reactor for 3 hours while stirring at 900 rpm to directly prepare dichloropropanol.
After the reaction was terminated, the heteropolyacid catalyst was collected by heating the batch reactor at 300℃ for 2 hours so that components having a boiling point lower than that of the heteropolyacid catalyst were removed. As a result, a solid 12-tungstophosphoric acid catalyst was obtained.
Example 1-1: Method of regenerating heteropolyacid catalyst including simple evaporation and calcination
The 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 was added to an electric furnace and calcined at 350℃ for 20 hours under an air atmosphere to regenerate the 12-tungstophosphoric acid catalyst.
Example 1-2: Method of regenerating heteropolyacid catalyst including simple evaporation, calcination, recrystallization, and drying
The 12-tungstophosphoric acid regenerated according to Example 1-1 was dissolved in water to prepare a catalyst solution. The catalyst solution was filtered using filter paper to remove impurities. Then, the catalyst of the catalyst solution was recrystallized by heating the catalyst solution at 80℃ for 5 hours. And then the catalyst solution was dried in a drying device at 80℃ for 24 hours.
Dichloropropanol was prepared from glycerol using a pure 12-tungstophosphoric acid catalyst, and the 12-tungstophosphoric acid catalysts regenerated according to Experimental Example 1, Example 1-1, and Example 1-2, respectively. Then, glycerol-conversion rates, selectivities for dichloropropanol, and yields of dichloropropanol were calculated by analyzing the reaction mixtures after the reactions were terminated.
Experimental Example 2-1 (Comparative Example 2-1): Direct preparation of dichloropropanol from glycerol using pure Keggin-type heteropolyacid catalyst, 12-tungstophosphoric acid (H
3
PW
12
O
40
)
Dichloropropanol was directly prepared by reacting glycerol with hydrogen chloride gas in the same manner as in Experimental Example 1, except that a catalyst was not used, or 12-tungstophosphoric acid (H3PW12O40) was used as a pure Keggin-type heteropolyacid catalyst by the amounts described in Table 1 below . After each of the reactions was terminated, the reactor was cooled to room temperature. Then, the reaction mixtures were analyzed using gas chromatography. In addition, glycerol-conversion rates, selectivities for dichloropropanol, and yields of dichloropropanol were calculated using Equations 1 to 3, and the results are shown in Table 1 below. 'MCPD' and 'DCP' of Table 1 respectively indicate monochloropropandiol and dichloropropanol. Products of the reaction mainly include monochloropropandiol and dichloropropanol. The products may further include a small amount (less than 3 wt%) of by-products such as epichlorohydrin and trichloropropane (TCP).
Table 1
Referring to Table 1, the yield of dichloropropanol increases as the amount of the 12-tungstophosphoric acid catalyst increases. Thus, dichloropropanol may be more efficiently prepared when a large amount of the catalyst is used.
Experimental Example 2-2 (Comparative Example 2-2): Direct preparation of dichloropropanol from glycerol using 12-tungstophosphoric acid (H
3
PW
12
O
40
)
regenerated according to Experimental Example 1 (simple evaporation)
3 g of the 12-tungstophosphoric acid catalyst used in Experimental Example 2-1 was regenerated using the simple evaporation stage according to Experimental Example 1, and dichloropropanol was prepared in the same manner as in Experimental Example 2-1 using the regenerated 12-tungstophosphoric acid catalyst. Then, this process of regenerating the12-tungstophosphoric acid catalyst used in the preparation of dichloropropanol and preparing dichloropropanol using the regenerated the12-tungstophosphoric acid catalyst was repeated (the 12-tungstophosphoric acid catalyst was regenerated three times and dichloropropanol was prepared three times using the each regenerated 12-tungstophosphoric acid catalyst). After each of the reactions was terminated, the reaction mixtures were analyzed in the same manner as in Experimental Example 2-1. Glycerol-conversion rates, selectivities for dichloropropanol, and yields of dichloropropanol were calculated, and the results are shown in Table 2 below. The result of the analysis using 3 g of the catalyst which is shown in Table 1 is also shown in Table 2.
Table 2
Referring to Table 2, the yield of dichloropropanol decreases as the number of times the catalyst is regenerated increases when dichloropropanol is directly prepared using the 12-tungstophosphoric acid catalyst regenerated using the simple evaporation process according to Experimental Example 1.
Example 2-1: Direct preparation of dichloropropanol from glycerol using 12-tungstophosphoric acid (H
3
PW
12
O
40
)
catalyst regenerated according to Example 1-1
A process of regenerating a 12-tungstophosphoric acid catalyst and preparing dichloropropanol was repeated in the same manner as in Experimental Example 2-2, except that 3 g of the 12-tungstophosphoric acid catalyst like the catalyst used in Experimental Example 2-1 was regenerated according to Example 1-1 and used to prepare dichloropropanol. After each of the reactions was terminated, the reaction mixture was analyzed in the same manner as in Experimental Example 2-1. Glycerol-conversion rates, selectivity for dichloropropanol, and yields of dichloropropanol were calculated, and the results are shown in Table 3 below. The result of the analysis using 3 g of the catalyst which is shown in Table 1 is also shown in Table 3.
Table 3
Referring to Table 3, the yield of dichloropropanol is not much changed even if the number of times the catalyst is regenerated increases when dichloropropanol is directly prepared using the 12-tungstophosphoric acid catalyst regenerated according to Example 1-1.
Example 2-2: Direct preparation of dichloropropanol from glycerol using 12-tungstophosphoric acid (H
3
PW
12
O
40
)
catalyst regenerated according to Example 1-2
A process of regenerating a 12-tungstophosphoric acid catalyst and preparing dichloropropanol was repeated in the same manner as in Experimental Example 2-2, except that 3 g of the 12-tungstophosphoric acid catalyst like the catalyst used in Experimental Example 2-1 was regenerated according to Example 1-2 and used to prepare dichloropropanol. After each of the reactions was terminated, the reaction mixture was analyzed in the same manner as in Experimental Example 2-1. Glycerol-conversion rates, selectivity for dichloropropanol, and yields of dichloropropanol were calculated, and the results are shown in Table 4 below. The result of the analysis using 3 g of the catalyst which is shown in Table 1 is also shown in Table 4.
Table 4
Referring to Table 4, the yield of dichloropropanol is not much changed even if the number of times the catalyst is regenerated increases when dichloropropanol is directly prepared using the 12-tungstophosphoric acid catalyst regenerated according to Example 1-2. Furthermore, there is no big difference between the yield of dichloropropanol using the 12-tungstophosphoric acid catalyst regenerated according to Example 1-2 and the yield of dichloropropanol using the pure 12-tungstophosphoric acid catalyst (the yield of DCP in case of using the pure 12-tungstophosphoric acid catalyst: 81.0%, and the yield of DCP in case of using the 12-tungstophosphoric acid catalyst regenerated three times: 79.0%).
Evaluation Examples
Evaluation Example 1: IR analysis results of pure 12-tungstophosphoric acid (H
3
PW
12
O
40
) catalyst; and 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 (simple evaporation), Example 1-1, and Example 1-2
IR analysis results of a pure 12-tungstophosphoric acid (H3PW12O40) catalyst, and 12-tungstophosphoric acid catalysts regenerated according to Experimental Example 1 (simple evaporation), Example 1-1, and Example 1-2 are shown in FIG. 1.
Referring to FIG. 1, the 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 (Comparative Example 1-1, simple evaporation) does not exhibit IR peaks indicating intrinsic properties of the pure 12-tungstophosphoric acid catalyst. However, the 12-tungstophosphoric acid catalysts regenerated according to Example 1-1 (simple evaporation+calcination) and Example 1-2 (simple evaporation+calcination+recrystallization+drying) exhibit IR peaks indicating intrinsic properties of the pure 12-tungstophosphoric acid catalyst.
Evaluation Example 2: CHNS analysis results of 12-tungstophosphoric acid catalysts regenerated according to Experimental Example 1 (simple evaporation), Example 1-1, and Example 1-2
CHNS analysis results of a pure 12-tungstophosphoric acid (H3PW12O40) catalyst, and 12-tungstophosphoric acid catalysts regenerated according to Experimental Example 1 (simple evaporation), Example 1-1 (simple evaporation+calcination), and Example 1-2 (simple evaporation+calcination+recrystallization+drying) are shown in Table 5.
Table 5
Referring to Table 5, the 12-tungstophosphoric acid catalyst regenerated according to Experimental Example 1 (simple evaporation) has a larger amount of carbon than the 12-tungstophosphoric acid catalysts regenerated according to Example 1-1 and Example 1-2. Thus, it can be seen that carbon deposits are not completely evaporated during the evaporation but remain on the surface of the 12-tungstophosphoric acid catalyst regenerated by the simple evaporation of Experimental Example 1. However, in the 12-tungstophosphoric acid catalysts regenerated according to Example 1-1 and Example 1-2, a large amount of carbon attached to the 12-tungstophosphoric acid catalysts is removed during the calcination stage under an air atmosphere, and thus only a small amount of carbon remains.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (13)
1. A method of regenerating a heteropolyacid catalyst used in the direct process of preparing dichloropropanol by reacting glycerol with a chlorinating agent, the method comprising:
separating a solid heteropolyacid catalyst from a reaction mixture by simply evaporating components having a boiling point lower than that of the heteropolyacid catalyst in a simple evaporation stage; and
calcining the separated solid heteropolyacid catalyst in a calcination stage.
2. The method of claim 1, further comprising recrystallizing the calcined heteropolyacid catalyst in a recrystallization stage.
3. The method of claim 2, wherein the recrystallization stage comprises: preparing a catalyst solution by dissolving the calcined heteropolyacid catalyst in water; removing impurities from the catalyst solution by filtering the catalyst solution; and heating the filtered catalyst solution to a temperature in the range of about 50 to about 100℃ for about 1 to about 20 hours.
4. The method of claim 3, further comprising drying the recrystallized heteropolyacid catalyst at a temperature in the range of about 50 to about 100℃ for about 1 to about 48 hours (drying stage) after the recrystallization.
5. The method of claim 1, wherein the simple evaporation stage comprises heating the reaction mixture to a temperature in the range of about 100 to about 400℃ for about 10 minutes to about 5 hours.
6. The method of claim 1, wherein the calcination stage comprises heating the separated solid heteropolyacid catalyst in the presence of oxygen to a temperature in the range of about 200 to about 400℃ for about 1 to about 40 hours.
7. The method of claim 1, wherein the heteropolyacid catalyst comprises a Keggin-type heteropolyacid catalyst in which the ratio of the number of central atoms to the number of coordinated atoms is 1:12.
8. The method of claim 7, wherein the Keggin-type heteropolyacid catalyst comprises 12-tungstophosphoric acid (H3PW12O40).
9. A method of directly preparing dichloropropanol by reacting glycerol with a chlorinating agent, constituting a chlorination reaction, using a heteropolyacid catalyst, the method comprising a method of regenerating a heteropolyacid catalyst according to any one of claims 1 to 8, wherein the regenerated heteropolyacid catalyst is re-used.
10. The method of claim 9, wherein the chlorinating agent comprises hydrogen chloride gas or hydrochloric acid.
11. The method of claim 9, wherein the chlorination reaction is performed at a temperature in the range of about 50 to about 300℃ at a pressure in the range of about 0.1 to about 30 bar for about 10 minutes to about 50 hours.
12. The method of claim 9, wherein the chlorination reaction is performed in at least one reactor selected from a group consisting of a batch reactor, a semi-batch reactor, a constant stirred tank reactor (CSTR), and a plug flow reactor.
13. A method of preparing epichlorohydrin (ECH) after directly preparing dichloropropanol by reacting glycerol with a chlorinating agent using a heteropolyacid catalyst, the method comprising the method of preparing dichloropropanol according to claim 9.
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KR1020090006275A KR101102597B1 (en) | 2009-01-23 | 2009-01-23 | Method for regenerating heteropolyacid catalyst used in the direct preparation process of dichloropropanol from glycerol and chlorinating agent, methods for preparing dichloropropanol and epichlorohydrin comprising the method |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103464178A (en) * | 2013-07-09 | 2013-12-25 | 南京奥凯化工科技有限公司 | AG-01 catalyst used for synthesis of dichloropropanol by hydrochlorination of glycerin |
CN108358873A (en) * | 2018-05-10 | 2018-08-03 | 江苏安邦电化有限公司 | A method of it being used for the continuous reaction system of preparing epoxy chloropropane by using glycerol method and its is used to prepare epoxychloropropane |
CN108714436A (en) * | 2018-08-03 | 2018-10-30 | 江苏扬农化工集团有限公司 | A kind of method for activation recovering of heteropolyacid catalyst for synthesizing epoxy chloropropane |
CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
CN113230980A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Continuous production device and production method of epichlorohydrin |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4814305A (en) * | 1986-11-20 | 1989-03-21 | Mitsubishi Rayon Co., Ltd. | Method for regeneration of oxidation catalyst |
US6673733B2 (en) * | 2000-04-06 | 2004-01-06 | Nippon Shokubai Co., Ltd. | Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid |
US20070112224A1 (en) * | 2003-11-20 | 2007-05-17 | Solvay (Societe Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
-
2009
- 2009-01-23 KR KR1020090006275A patent/KR101102597B1/en not_active IP Right Cessation
- 2009-02-18 WO PCT/KR2009/000772 patent/WO2010085018A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4814305A (en) * | 1986-11-20 | 1989-03-21 | Mitsubishi Rayon Co., Ltd. | Method for regeneration of oxidation catalyst |
US6673733B2 (en) * | 2000-04-06 | 2004-01-06 | Nippon Shokubai Co., Ltd. | Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid |
US20070112224A1 (en) * | 2003-11-20 | 2007-05-17 | Solvay (Societe Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
Non-Patent Citations (1)
Title |
---|
SANG HEE LEE ET AL.: "Direct preparation of dichloropropanol (DCP) from glycerol using heteropolyacid (HPA) catalysts: A catalyst screen study", CATALYSIS COMMUNICATIONS, vol. 9, 2008, pages 1920 - 1923 * |
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CN103464178A (en) * | 2013-07-09 | 2013-12-25 | 南京奥凯化工科技有限公司 | AG-01 catalyst used for synthesis of dichloropropanol by hydrochlorination of glycerin |
CN108358873A (en) * | 2018-05-10 | 2018-08-03 | 江苏安邦电化有限公司 | A method of it being used for the continuous reaction system of preparing epoxy chloropropane by using glycerol method and its is used to prepare epoxychloropropane |
CN108358873B (en) * | 2018-05-10 | 2023-09-29 | 安道麦安邦(江苏)有限公司 | Continuous reaction system for preparing epichlorohydrin by glycerol method and method for preparing epichlorohydrin by using continuous reaction system |
CN108714436A (en) * | 2018-08-03 | 2018-10-30 | 江苏扬农化工集团有限公司 | A kind of method for activation recovering of heteropolyacid catalyst for synthesizing epoxy chloropropane |
CN108714436B (en) * | 2018-08-03 | 2021-03-30 | 江苏扬农化工集团有限公司 | Method for recovering activity of heteropoly acid catalyst for synthesizing epoxy chloropropane |
CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
CN113230980A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Continuous production device and production method of epichlorohydrin |
CN113234041B (en) * | 2021-04-07 | 2023-03-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
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KR101102597B1 (en) | 2012-01-03 |
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