CN114700114A - Water-phase bifunctional catalyst and method for preparing dihydric alcohol by using same in external loop reaction process - Google Patents
Water-phase bifunctional catalyst and method for preparing dihydric alcohol by using same in external loop reaction process Download PDFInfo
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- CN114700114A CN114700114A CN202210261967.XA CN202210261967A CN114700114A CN 114700114 A CN114700114 A CN 114700114A CN 202210261967 A CN202210261967 A CN 202210261967A CN 114700114 A CN114700114 A CN 114700114A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 49
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 44
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008346 aqueous phase Substances 0.000 claims abstract description 23
- 239000012071 phase Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000005580 one pot reaction Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 48
- 239000004593 Epoxy Substances 0.000 description 39
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
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- 150000005676 cyclic carbonates Chemical class 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
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- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a water-phase bifunctional catalyst and a method for preparing dihydric alcohol by using the same in an external loop reaction process, belonging to the technical field of preparation of the dihydric alcohol. The method for preparing the dihydric alcohol by the aqueous phase bifunctional catalyst in the outer loop reaction process adopts an outer loop reactor, and the aqueous phase bifunctional catalyst is used for preparing the dihydric alcohol by reacting carbon dioxide, alkylene oxide and water as raw materials under the reaction pressure of 0.3-3.0 MPa and the reaction temperature of 50-150 ℃. The external loop reaction process can effectively strengthen gas-liquid mass transfer and improve reaction efficiency. The water-phase heteronuclear bimetallic catalyst has better water solubility, higher efficiency of catalyzing the hydration reaction of the alkylene oxide, and can realize high-efficiency reaction under low concentration of the alkylene oxide. The reaction can be carried out at a mild reaction temperature under a relatively low carbon dioxide pressure. Solves the problems of insufficient reaction activity and poor selectivity in the prior art, and has good industrial application value.
Description
Technical Field
The invention belongs to the technical field of carbonate preparation, and relates to a method for preparing dihydric alcohol by combining a water-phase heteronuclear bimetallic complex bifunctional catalyst with an external loop process, in particular to a method for preparing the dihydric alcohol by reacting alkylene oxide, carbon dioxide and water.
Background
Ethylene Glycol (EG), 1, 2-Propanediol (PG), and other mono-diols are a widely used class of basic chemical raw materials. EG is used mainly for the production of polyester fibers, polyethylene terephthalate plastics and resins, and as a raw material for chemical products such as surfactants, plasticizers, glycol ethers, glyoxal, oxalic acid, etc. In addition, it is used as a polar solvent with a high boiling point, an antifreeze for automobile radiator, a refrigerant for engine, etc.
At present, most of the industrial production of dihydric alcohol still mainly adopts the traditional Ethylene Oxide (EO) hydration process, but the technical route has high reaction temperature (180-200 ℃) and large water ratio (H)2O/EO is 20-25: 1), and EG selectivity is poor (88% -91%), so that subsequent separation and purification steps are complicated, the process is long, the energy consumption is high, and the production cost is high.
The alkylene oxide and the carbon dioxide can be synthesized into corresponding cyclic carbonate with high selectivity under the action of a proper catalyst, and the formed cyclic carbonate can be easily hydrolyzed with high selectivity to obtain the dihydric alcohol, so the technical route of synthesizing the dihydric alcohol by hydrolyzing the alkylene oxide and the carbon dioxide through the cyclic carbonate attracts attention. EP776890, JP 5690029, JP 57106631, GB 2098895A, GB 2107712, US 4400559, US 4508927, CN 1955152A, CN 1850755A, CN 101121641A, CN 101238087, CN 102060657A and the like disclose an indirect homogeneous catalytic hydration method, wherein ethylene oxide and carbon dioxide are used as raw materials, ethylene carbonate is generated through cycloaddition reaction, then the ethylene carbonate and water are subjected to hydrolysis reaction to prepare ethylene glycol, the molar ratio of the water to the ethylene oxide can be reduced to be less than 5:1, and the selectivity of the ethylene glycol can reach 98%. For example, EP776890 supplies the gas from the ethylene oxide reactor to an absorber in which the absorption liquid contains mainly ethylene carbonate and ethylene glycol. The ethylene oxide in the absorption solution is supplied to a reactor and converted into ethylene carbonate under the action of a catalyst. The ethylene carbonate in the absorption solution is then supplied to the hydrolysis reactor together with added water and finally converted to ethylene glycol. CN 101238087 discloses the use of a combined catalyst of a halide, a molybdate and a macrocyclic crown ether for the hydrolysis of alkylene oxides to produce alkylene glycols with a mono-diol selectivity of up to 98% at a water/alkylene oxide molar ratio of 4 in the presence of carbon dioxide. CN 102060657A describes the preparation of cyclic carbonate by the cycloaddition reaction of carbon dioxide and epoxy compound catalyzed by a catalytic system consisting of metal salt, ionic liquid and quaternary ammonium salt. The cyclic carbonate after the catalyst is separated is hydrolyzed into corresponding dihydric alcohol by using a supported alkaline ionic liquid catalyst, and the selectivity is more than or equal to 98 percent.
In recent years, different bifunctional catalysts and heterogeneous catalysts are also adopted to synthesize glycol (CN 102936181, CN 103100422 and CN 102921468) by high-selectivity hydrolysis of alkylene oxide with participation of carbon dioxide, and the defects of high molar ratio of water to alkylene oxide, high energy consumption and more byproducts in the prior art are mainly overcome. However, similar to other methods, there is a problem that the reaction is efficiently carried out by adding alkylene oxide at one time, and since epoxy is a high-molecular internal energy substance and the reaction is violent in heat release, the method cannot be applied to actual production, and the reaction process depends on high CO2Pressure or high CO2The dosage improves the reaction activity and the diol product selectivity, and has defects.
Disclosure of Invention
The invention mainly aims to provide a water-phase high-activity heteronuclear bimetallic complex bifunctional catalyst, and a method for enhancing gas-liquid mass transfer and efficiently synthesizing dihydric alcohol by hydration of alkylene oxide by applying the catalyst and combining an external loop reaction process.
The technical scheme of the invention is as follows:
the water phase bifunctional catalyst is a heteronuclear bimetallic complex and has the structure as follows:
in the formula: x-Is OH-1、HCO3 -Or OCH3 -Negative ions, preferably X is OH-1。
The method for preparing the dihydric alcohol by the aqueous phase bifunctional catalyst in the outer loop reaction process adopts an outer loop reactor, utilizes the aqueous phase bifunctional catalyst, and takes carbon dioxide, alkylene oxide and water as raw materials to carry out reaction preparation under the reaction pressure of 0.3-3.0 MPa and the reaction temperature of 50-150 ℃, and the reaction equation is as follows:
the reaction process can be divided into a one-pot method and a two-step method.
The one-pot reaction process comprises the following steps: adding an aqueous solution containing a water-phase bifunctional catalyst into the outer loop reactor; heating the initial material to the reaction temperature through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is the reaction pressure to complete the preparation stage; then introducing alkylene oxide into the outer loop reactor for reaction; and after the alkylene oxide feeding is finished, continuously reacting until the alkylene oxide is completely consumed, keeping the pressure unchanged, then cooling and discharging the pressure to transfer the material to a flash tank, removing carbon dioxide, and separating the water-phase bifunctional catalyst by distillation to obtain a dihydric alcohol product.
The two-step reaction process comprises the following steps: adding an aqueous solution containing a water-phase bifunctional catalyst into the outer loop reactor; heating the initial material to the reaction temperature through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is the reaction pressure to complete the preparation stage; in the first stage of reaction, introducing alkylene oxide into an outer loop reactor for reaction, and supplementing carbon dioxide to maintain the reaction pressure constant until the alkylene oxide feeding is finished; the second stage continues the reaction and discharges CO2The pressure was maintained constant until the pressure no longer varied and the reaction was complete. Transferring the material to a flash tank by cooling and pressure discharge, removing carbon dioxide, and separating by distillationThe dihydric alcohol product can be obtained by the water and water phase double-function catalyst.
The method for preparing the dihydric alcohol by the aqueous phase bifunctional catalyst in the outer loop reaction process has the preferable reaction pressure of 0.6-1.2 MPa and the preferable reaction temperature of 80-120 ℃.
The method for preparing the dihydric alcohol by using the aqueous phase bifunctional catalyst in the outer loop reaction process has the mol ratio of the alkylene oxide to the aqueous phase bifunctional catalyst of 500-50000: 1.
The molar ratio of the water to the alkylene oxide is 1: 1-5: 1.
The alkylene oxide is propylene oxide, ethylene oxide, epichlorohydrin, styrene oxide, phenyl glycidyl ether or cyclohexene oxide.
The external loop reactor comprises a spraying reactor and a spraying reactor.
The invention has the beneficial effects that:
(1) the external loop reaction process can effectively strengthen gas-liquid mass transfer and improve reaction efficiency.
(2) The water-phase heteronuclear bimetallic catalyst has better water solubility, higher efficiency of catalyzing the alkoxy alkane hydration reaction, and can realize high-efficiency reaction under low concentration of the epoxy alkane.
(3) The reaction can be carried out at a mild reaction temperature under a relatively low carbon dioxide pressure.
(4) Solves the problems of insufficient reaction activity and poor selectivity in the prior art, and has good industrial application value.
Drawings
FIG. 1 is a schematic view of an external loop reaction process system according to the present invention.
Detailed Description
The technical solution of the present invention is further described below by way of examples.
Example 1: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.05mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the starting material to 100 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.8 MPa. Then to the outer ringAnd introducing ethylene oxide into the reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 0.5MPa, consuming 4.4kg of ethylene oxide within 5 hours, and continuing to react for 1.5 hours after the addition of the epoxy is stopped to ensure that the pressure is not changed any more. After the carbon dioxide and the epoxy are removed by temperature reduction and pressure discharge, a sample is taken for gas chromatographic column detection, the selectivity of the ethylene glycol is 98 percent, the content of the ethylene carbonate is 1 percent, the weight of the material is about 6.2kg, and the conversion rate of the epoxy is more than 99.5 percent.
Example 2: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.05mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the starting material to 100 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.8 MPa. 4.4kg of ethylene oxide were then fed in at a rate of 0.88kg/h for the reaction, and CO was added2The reaction pressure was maintained at not less than 0.8MPa until the end of the ethylene oxide feed. Stopping CO after the feeding is finished2Feeding, wherein the ethylene carbonate hydrolysis reaction is carried out in the system, and CO is continuously discharged to the outside2The pressure is kept constant at 0.8MPa, and the pressure is not changed after the reaction is continued for 45 min. After the carbon dioxide and the epoxy are removed by temperature reduction and pressure discharge, sampling and carrying out gas chromatography column detection, wherein the selectivity of ethylene glycol is 99%, the content of ethylene carbonate is less than 0.5%, the weight of the material is about 6.2kg, and the conversion rate of the epoxy is more than 99.5%.
Example 3: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.05mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the initial material to 100 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.2 MPa. 4.4kg of ethylene oxide were then fed in at a rate of 0.88kg/h for the reaction, and CO was added2The reaction pressure is maintained at not less than 1.2MPa until the end of the ethylene oxide feed. Stopping CO after the feeding is finished2Feeding, wherein the ethylene carbonate hydrolysis reaction is carried out in the system, and CO is continuously discharged to the outside2The pressure is kept unchanged at 1.2MPa, and the pressure is not changed after the reaction is continued for 30 min. Cooling, discharging pressure, removing carbon dioxide and epoxy, sampling, gas chromatographic column detecting, and adding ethylene glycolThe selectivity is more than 99.5 percent, the content of ethylene carbonate is less than 0.5 percent, the weight of the material is about 6.2kg, and the conversion rate of epoxy is more than 99.5 percent.
Example 4: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.05mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the starting material to 100 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 3.0 MPa. Then 4.4kg of ethylene oxide was fed in at a rate of 0.88kg/h to effect reaction, and CO was supplied2The reaction pressure is maintained at not less than 3.0MPa until the end of the ethylene oxide feed. Stopping CO after the feeding is finished2Feeding, wherein the ethylene carbonate hydrolysis reaction is carried out in the system, and CO is continuously discharged to the outside2The pressure is kept unchanged at 3.0MPa, and the pressure is not changed after the reaction is continued for 30 min. After the carbon dioxide and the epoxy are removed by temperature reduction and pressure discharge, sampling and carrying out gas chromatography column detection, wherein the selectivity of ethylene glycol is more than 99.5 percent, the content of ethylene carbonate is less than 0.5 percent, the weight of the material is about 6.2kg, and the conversion rate of the epoxy is more than 99.5 percent.
Example 5: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.05mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the initial material to 100 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 0.3 MPa. Then 4.4kg of ethylene oxide was fed at a rate of 0.5kg/h to carry out the reaction and make up CO2The reaction pressure is maintained at not less than 0.3MPa until the end of the ethylene oxide feed. Stopping CO after the feeding is finished2Feeding, wherein the ethylene carbonate hydrolysis reaction is carried out in the system, and CO is continuously discharged to the outside2The pressure is kept constant at 0.3MPa, and the pressure is not changed after the reaction is continued for 3 hours. After the carbon dioxide and the epoxy are removed by cooling and pressure discharge, a sample is taken for gas chromatographic column detection, the selectivity of the ethylene glycol is 96 percent, the content of the ethylene carbonate is 2 percent, the weight of the material is about 6.2kg, and the conversion rate of the epoxy is more than 99.5 percent.
Example 6: an external loop injection reactor of 10L effective volume is charged with a bifunctional catalyst (X) containing 0.002mol of aqueous phase-Is OH-1) 1.8kg ofDeionized water; starting the reaction device, heating the initial material to 150 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.5 MPa. And introducing ethylene oxide into the outer loop reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 1.2MPa, consuming 4.4kg of ethylene oxide within 8 hours, and continuing to react for 2 hours after the addition of the epoxy is stopped, wherein the pressure is not changed any more. After the carbon dioxide and the epoxy are removed by cooling and pressure discharge, a sample is taken for gas chromatographic column detection, the selectivity of the ethylene glycol is 90 percent, the content of the ethylene carbonate is 5 percent, the weight of the material is about 6.26kg, and the conversion rate of the epoxy is about 99 percent.
Example 7: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.2mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the starting material to 50 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.5 MPa. And introducing ethylene oxide into the outer loop reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 1.2MPa, consuming 4.4kg of ethylene oxide within 10 hours, and continuing to react for 1.5 hours after the epoxy addition is stopped, wherein the pressure is not changed any more. After the carbon dioxide and the epoxy are removed by temperature reduction and pressure discharge, sampling and carrying out gas chromatography column detection, wherein the selectivity of ethylene glycol is 99%, the content of ethylene carbonate is less than 0.5%, the weight of the material is about 6.2kg, and the conversion rate of the epoxy is more than 99.5%.
Example 8: an external loop injection reactor of effective volume 10L is charged with a catalyst containing 0.05mol of aqueous phase bifunctional catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the initial material to 100 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.2 MPa. And introducing ethylene oxide into the outer loop reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 0.8MPa, consuming 2.2kg of ethylene oxide within 2 hours, stopping adding epoxy, continuing to react for 30min, and ensuring that the pressure is not changed. After the carbon dioxide and the epoxy are removed by temperature reduction and pressure discharge, a sample is taken for gas chromatographic column detection, the selectivity of the ethylene glycol is more than 99.5 percent, the content of the ethylene carbonate is less than 0.5 percent, the weight of the material is 4.0kg, and the conversion rate of the epoxy is more than 99.5 percent.
Example 9: an external loop spray reactor of effective volume 10L was charged with a solution containing 0.05mol of aqueous phase dual-function catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the starting material to 120 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.2 MPa. And introducing propylene oxide into the outer loop reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 0.8MPa, consuming 5.8kg of propylene oxide within 6.5 hours, and continuously reacting for 1.5 hours after the epoxy addition is stopped until the pressure is not changed. After the carbon dioxide and the epoxy are removed by cooling and pressure discharge, sampling and carrying out gas chromatography column detection, wherein the propylene glycol selectivity is 99%, the propylene carbonate content is less than 0.5%, the material weight is 7.6kg, and the epoxy conversion rate is more than 99.5%.
Example 10: an external loop spray reactor of effective volume 10L was charged with a solution containing 0.05mol of aqueous phase dual-function catalyst (X)-Is OH-1) 1.8kg of deionized water; starting the reaction device, heating the starting material to 120 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.5 MPa. And introducing propylene oxide into the outer loop reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 1.2MPa, consuming 2.9kg of propylene oxide within 3 hours, and continuing to react for 45min after the addition of the epoxy is stopped, wherein the pressure is not changed any more. After the carbon dioxide and the epoxy are removed by cooling and pressure discharge, sampling and carrying out gas chromatography column detection, wherein the selectivity of the propylene glycol is more than 99.5 percent, the content of the propylene carbonate is less than 0.5 percent, the weight of the material is 4.7kg, and the conversion rate of the epoxy is more than 99.5 percent.
Example 11: an external loop spray reactor of effective volume 10 liters was charged with a solution containing 0.05mol of aqueous phase dual-function catalyst (X)-Is OCH3 -) 1.8kg of deionized water; starting the reaction device, heating the starting material to 120 ℃ through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is 1.5 MPa. Then introducing epoxy chloropropane into the outer loop reactor for reaction, controlling the epoxy feeding speed in the reaction process to ensure that the reaction pressure is not lower than 1.2MPa, consuming 4.6kg of epoxy propane within 5 hours, stopping adding epoxy, continuing to react for 1 hour, and ensuring that the pressure does not change any more. After the carbon dioxide and the epoxy are removed by cooling and pressure discharge, sampling and carrying out gas chromatography column detection, wherein the selectivity of the diol is more than 99.5 percent, the content of the cyclic carbonate is less than 0.5 percent, the weight of the material is 6.4kg, and the conversion rate of the epoxy is more than 99.5 percent.
Claims (6)
1. The water-phase bifunctional catalyst is characterized by being a heteronuclear bimetallic complex and having the structure as follows:
in the formula: x-Is OH-1、HCO3 -Or OCH3 -And (4) negative ions.
2. The method for preparing dihydric alcohol by using the aqueous phase bifunctional catalyst in the external loop reaction process as claimed in claim 1, wherein the external loop reactor is adopted, the aqueous phase bifunctional catalyst is used, carbon dioxide, alkylene oxide and water are used as raw materials to carry out reaction preparation under the reaction pressure of 0.3-3.0 MPa and the reaction temperature of 50-150 ℃, and the reaction equation is as follows:
3. the method for preparing dihydric alcohol by using the aqueous phase bifunctional catalyst in the external loop reaction process as claimed in claim 2, wherein the method can be divided into a one-pot method and a two-step method;
the one-pot reaction process comprises the following steps:
adding an aqueous solution containing a water-phase bifunctional catalyst into the outer loop reactor; heating the initial material to the reaction temperature through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is the reaction pressure to complete the preparation stage; then introducing alkylene oxide into the outer loop reactor for reaction; after the alkylene oxide feeding is finished, continuously reacting until the alkylene oxide is completely consumed, the pressure is not changed, then cooling and discharging pressure to transfer the material to a flash tank, removing carbon dioxide, and separating the water-phase dual-function catalyst by distillation to obtain a dihydric alcohol product;
the two-step reaction process comprises the following steps:
adding an aqueous solution containing a water-phase bifunctional catalyst into an outer loop reactor; heating the initial material to the reaction temperature through a heat exchanger, and introducing carbon dioxide until the pressure of the reaction system is the reaction pressure to complete the preparation stage; in the first stage of reaction, introducing alkylene oxide into an outer loop reactor for reaction, and supplementing carbon dioxide to maintain the reaction pressure constant until the alkylene oxide feeding is finished; the second stage continues the reaction and discharges CO2Maintaining the pressure constant until the pressure is not changed any more, and finishing the reaction; and then cooling and discharging pressure to transfer the material to a flash tank, removing carbon dioxide, and separating the water-water phase dual-function catalyst by distillation to obtain a dihydric alcohol product.
4. The method for preparing the dihydric alcohol by using the water-phase bifunctional catalyst in the outer loop reaction process according to the claims 2 and 3, wherein the reaction pressure is 0.6-1.2 MPa, and the reaction temperature is 80-120 ℃.
5. The method for preparing the dihydric alcohol by using the aqueous phase bifunctional catalyst in the outer loop reaction process as claimed in claims 2 and 3, wherein the molar ratio of the alkylene oxide to the aqueous phase bifunctional catalyst is 500-50000: 1; the molar ratio of the water to the alkylene oxide is 1: 1-5: 1.
6. The method for preparing dihydric alcohol by using the aqueous phase bifunctional catalyst in the outer loop reaction process according to the claims 2 and 3, wherein the alkylene oxide is propylene oxide, ethylene oxide, epichlorohydrin, styrene oxide, phenyl glycidyl ether or cyclohexene oxide; the external loop reactor comprises a spraying reactor and a spraying reactor.
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