CN112316939A - Preparation method of high-trans-proportion hydrogenated bisphenol A - Google Patents
Preparation method of high-trans-proportion hydrogenated bisphenol A Download PDFInfo
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- -1 alicyclic diol Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to a preparation method of hydrogenated bisphenol A with a high trans ratio, which adopts a catalytic hydrogenation technology, uses bisphenol A as a raw material to prepare hydrogenated bisphenol A with a high trans ratio by one-step hydrogenation, uses modified alumina as a carrier, adopts a template agent to treat the carrier, loads Rh and Ru on the carrier, and then places the carrier in a hydrogen atmosphere to perform reduction activation to obtain a noble metal loaded catalyst with the Rh content of 2-3% and the Ru content of 1-2%. According to the invention, a fixed bed hydrogenation reactor is adopted for bisphenol A reaction, and hydrogenated bisphenol A with a high trans-form ratio is obtained through one-step hydrogenation, wherein the trans-form isomer ratio can reach more than 70% at most.
Description
Technical Field
The invention relates to a method for preparing high trans-proportion hydrogenated bisphenol A by hydrogenating bisphenol A. The catalyst has the characteristics of high activity and high selectivity, and can obviously improve the content of the trans-isomer in the product.
Background
Hydrogenated bisphenol A (HBPA) is hydrogenated by bisphenol A (BPA) to obtain alicyclic diol, and because the alicyclic diol does not contain a double-bond unsaturated structure, the alicyclic diol has the advantages of thermal stability, chemical stability, weather resistance and the like, is more suitable for outdoor engineering, does not cause adverse effects on human health, and makes up the defects of bisphenol A as a product in the food and medicine industries. The method is mainly used for manufacturing polycarbonate, epoxy resin, polyacrylic resin and the like, and can also be used in food and medical industries.
The preparation of hydrogenated bisphenol A is carried out by taking bisphenol A as raw material and carrying out hydrogenation reaction in solution state under the action of catalyst, and the technical key lies in the selection of active components and carrier of hydrogenation catalyst. After decades of development, bisphenol a hydrogenation mainly comprises the following three catalysts, namely a metal framework type catalyst, a noble metal supported catalyst and a homogeneous catalyst, the general reaction conditions are 50-250 ℃ and the hydrogen pressure is 1-30 MPa, an intermittent or continuous hydrogenation process flow can be adopted, and the reaction product is separated and purified by a vacuum rectification or recrystallization process.
Chinese patent CN 1375484 discloses a method for preparing hydrogenated bisphenol a, which uses silica as a carrier and supported metal ruthenium as an active component, and adopts a fixed bed reactor to perform a hydrogenation reaction of bisphenol a, but the carrier of the method has high acidity, which can cause dehydroxylation of the product and affect the selectivity of the product. The US patent US 4192960 uses transition organometallic homogeneous catalysts and the reaction process is a catalytic hydrogenation reaction in the presence of water and ethanol to produce hydrogenated bisphenol a, which requires a catalyst separation step after the reaction. U.S. Pat. No. 6,989,530 discloses an active Pd, Ni colloidal catalyst which permits the batchwise preparation of hydrogenated bisphenol A in an autoclave, although the reaction mixture is easily separated off, but the catalyst preparation is complicated and is not industrially convenient. Hydrogenated bisphenol A has three isomers, of which the trans isomer is more valuable in applications, which can produce synergistic effects in the polymer and better mechanical properties, such as increasing the softening point of the polymer. In the current production technology, the proportion of trans-isomers is usually 30-45%, and in order to obtain higher proportion of trans-isomers, subsequent treatment is generally required. Recrystallization using chlorinated organic compounds as solvents, as in US4487979, can lead to products with high trans-isomer ratios.
Different from the technology, the invention improves the activity and selectivity of the catalyst by the modes of catalyst carrier modification and treatment, double-active component loading and the like, and can obtain a hydrogenated bisphenol A mixture with high trans-isomer ratio through one-time hydrogenation reaction under high catalyst load.
Disclosure of Invention
The invention provides a preparation method of high trans-form proportion hydrogenated bisphenol A, which adopts modified alumina treated by a template agent as a carrier to carry out bi-component noble metal loading and uses a fixed bed reactor to carry out continuous hydrogenation reaction of bisphenol A. The catalyst used in the invention has high activity and selectivity, the conversion rate and the selectivity of the reaction are close to 100%, and the proportion of the trans-isomer in the hydrogenated product is up to more than 70%.
The modified alumina carrier consists of 85-95 parts by weight of pseudo-boehmite and 5-15 parts by weight of magnesium oxide.
The modified alumina carrier needs to be treated by a template agent, the template agent is one of ethylenediamine and n-butylamine, and the weight ratio of the template agent to the carrier is (1-5): 100, preferably 2-4.5: 100.
the catalyst carrier is characterized by having a pore volume of 0.4-0.6 cm3(ii)/g; the specific surface area is 100-150 m2Preferably 105 to 150 m/g2(iv)/g, more preferably 115 to 150m2/g。
Preferably, the weight content of the catalyst active component Rh relative to the carrier is 2.2-2.6%.
Preferably, the weight content of the catalyst active component Ru relative to the carrier is 1.2-1.8%.
Further, the present invention also provides a use of the catalyst for producing hydrogenated bisphenol a having a high trans ratio, which may be 95% or more, preferably 98% or more, and more preferably 99% or more in some specific embodiments.
The invention prepares the modified alumina carrier through a large amount of experimental researches, improves the activity and the selectivity of the catalyst through modifying the carrier, simultaneously the catalyst has higher load, and the hydrogenated bisphenol A mixture with high trans-form ratio can be obtained by using the catalyst. The technical method of the invention is as follows:
preparation of modified carrier: mixing commercially available pseudo-boehmite and magnesium oxide powder according to a certain proportion to obtain uniform powder, quantitatively weighing a dilute nitric acid aqueous solution, uniformly spraying the dilute nitric acid aqueous solution into the powder in a kneader, kneading and aging for a certain time, extruding and molding on a double-screw extruder, drying, and roasting under a preset program temperature control to obtain the modified carrier.
Treating the modified carrier: weighing a certain amount of modified carrier, grinding into powder, weighing a certain amount of template agent, fully mixing with carrier powder, tabletting and forming on a tabletting machine, drying, roasting under the temperature control of a preset program, removing the template agent, and crushing and sieving to obtain 10-20-mesh particles as a catalyst carrier.
Loading of active components: the impregnation method is adopted to carry out impregnation loading on the active components, the catalyst carrier is placed in a mixed water solution of chlorides of rhodium and ruthenium with a certain concentration for impregnation, clear liquid is filtered out after the impregnation liquid is clarified, roasting is carried out under the control of temperature programming after drying, and reduction activation is carried out in a reactor under the hydrogen atmosphere before hydrogenation reaction.
Evaluation of catalyst: and (3) loading a catalyst into the fixed bed reactor, and carrying out reduction activation for 4 hours at the programmed temperature of 280 ℃ in a hydrogen atmosphere to obtain the catalyst. Dissolving bisphenol A in isopropanol to form a raw material solution with the concentration of 20 percent (wt), pumping the raw material solution into a reactor through a metering pump to contact with hydrogen for hydrogenation reaction, wherein the reaction conditions are as follows: the pressure is 7.8MPa, the bed temperature is 165 ℃, and the liquid space velocity is 6.6h-1(V), hydrogen space velocity of 450h-1And (V) cooling the hydrogenated mixed product, and separating hydrogen in a gas-liquid separation tank to obtain a mixed product of hydrogenated bisphenol A containing the solvent.
The invention adopts the catalyst prepared by the method to carry out bisphenol A hydrogenation reaction to obtain a hydrogenated bisphenol A product with high trans-isomer ratio, and solves the problem of low trans-isomer ratio in the conventional bisphenol A hydrogenation product.
The specific implementation mode is as follows:
the present invention is described in further detail below by way of specific examples, which illustrate details of the invention, but the procedures and data set forth are not intended to limit the scope of the invention.
Examples 1 to 3 are experiments for preparing modified alumina.
Examples 4-14 are catalyst support preparation and characterization analysis experiments.
Examples 15 to 33 are active ingredient impregnation and catalyst preparation experiments.
Examples 34 to 52 are catalyst evaluation experiments.
Example 1
170g of pseudo-boehmite and 30g of magnesium oxide powder are weighed and uniformly mixed, 80g of 3 percent dilute nitric acid (wt%) aqueous solution is weighed, the dilute nitric acid aqueous solution is uniformly sprayed in the powder in a kneader, kneaded and aged for 20min, then extruded and molded on a double-screw extruder, dried at 120 ℃ for 12 hours, and roasted at 650 ℃ for 6 hours to obtain the modified aluminum oxide L-1.
Example 2
Weighing 180g of pseudo-boehmite and 20g of magnesium oxide powder, uniformly mixing, weighing 80g of 3% dilute nitric acid (wt%) aqueous solution, uniformly spraying the dilute nitric acid aqueous solution in a kneading machine into powder, kneading and aging for 20min, then extruding and molding on a double-screw extruder, drying at 120 ℃ for 12 hours, and roasting at 650 ℃ for 6 hours to obtain the modified aluminum oxide L-2.
Example 3
Weighing 190g of pseudo-boehmite and 10g of magnesium oxide powder, uniformly mixing, weighing 80g of 3% dilute nitric acid (wt%) aqueous solution, uniformly spraying the dilute nitric acid aqueous solution in a kneading machine into powder, kneading and aging for 20min, then extruding and molding on a double-screw extruder, drying at 120 ℃ for 12 hours, and roasting at 650 ℃ for 6 hours to obtain the modified aluminum oxide L-3.
Examples 4 to 14
Weighing 150g of the modified alumina obtained in the embodiment 1-3, grinding the modified alumina into powder, uniformly mixing the powder with a template agent, tabletting and forming the powder on a tabletting machine, drying the powder at 120 ℃ for 4 hours, roasting the powder at 600 ℃ for 4 hours, crushing and sieving the powder to obtain 10-20-mesh particles to obtain a catalyst carrier, and obtaining the pore volume and the specific surface area of the catalyst carrier through characterization analysis. Adopting different types and masses of template agents to obtain catalyst carriers Z-1-Z-11, wherein the specific conditions are shown in the following table 1:
[ Table 1]
Examples 15 to 33
Weighing 100g of the carrier obtained in the embodiments 4 to 14, respectively, putting the carrier into 150ml of mixed aqueous solution of ruthenium chloride and rhodium chloride with different concentrations, wherein the content of active metals Rh and Ru is 0.001 to 0.005g/ml, filtering out clear liquid after dipping for 12 hours, drying for 6 hours at 120 ℃, repeating for 3 to 4 times, and then roasting for 4 hours at 400 ℃ to obtain catalysts C-1 to C-19 with different active metal loadings, wherein the specific conditions are shown in the following table 2:
[ Table 2]
Examples 34 to 52
10mL of the catalyst obtained in examples 15 to 33 was loaded in a fixed bed reactor having an inner diameter of
The catalyst was filled up and down with an inert broken porcelain ring, and hydrogen was introduced at a flow rate of 150mL/min under normal pressure, followed by reductive activation at 280 ℃ for 4 hours. After the reduction was completed, the reaction system was slowly pressurized to 7.8MPa, followed by slowly raising the temperature to 165 ℃. After the temperature is stabilized in advance, dissolving bisphenol A in isopropanol to form a raw material solution with the concentration of 20% (wt), and pumping the raw material solution into a reactor by a metering pump for reaction, wherein the reaction conditions are as follows: the pressure is 7.8MPa, the bed temperature is 165 ℃, and the liquid space velocity is 6.6h-1(V), space velocity of hydrogen gas 450h-1(V), after cooling the hydrogenation mixed product, separating hydrogen in a gas-liquid separation tank to obtain a hydrogenation reaction product containing a solvent, and analyzing, wherein the evaluation reaction result is shown in the following table 3:
[ Table 3]
The embodiment shows that the catalyst provided by the invention has higher activity and selectivity, the highest conversion rate of the reaction can reach 100%, the highest selectivity of HBPA is close to 100%, and the proportion of trans-isomer in the hydrogenation product is higher than that in the prior art and reaches more than 70%.
Claims (10)
1. A process for preparing hydrogenated bisphenol A with high trans ratio, which comprises hydrogenating bisphenol A in the presence of a catalyst to obtain hydrogenated bisphenol A with high trans ratio,
the catalyst is prepared by taking modified alumina as a carrier, loading Rh and Ru on the carrier, and placing the carrier in a hydrogen atmosphere for reduction and activation to obtain the precious metal loaded catalyst with the Rh content of 2-3% by weight and the Ru content of 1-2% by weight.
2. The method as claimed in claim 1, wherein the modified alumina carrier is composed of 85-95 parts by weight of pseudo-boehmite and 5-15 parts by weight of magnesium oxide.
3. The method as claimed in claim 1 or 2, wherein the modified alumina carrier is treated with a template agent before loading, and the template agent is one of ethylenediamine and n-butylamine.
4. The method according to claim 1 or 2, wherein the catalyst has a carrier pore volume of 0.4 to 0.6cm3A specific surface area of 100 to 150 m/g2/g。
5. The method according to claim 1 or 2, wherein the weight content of active component Rh in the catalyst is 2.2-2.6%.
6. The method according to claim 1 or 2, wherein the weight content of the active component Ru in the catalyst is 1.2-1.8%.
7. The application of the catalyst for preparing the high trans-ratio hydrogenated bisphenol A is characterized in that the catalyst takes modified alumina as a carrier, Rh and Ru are loaded on the carrier and placed in a hydrogen atmosphere for reduction and activation, and the precious metal loaded catalyst with the Rh content of 2-3% and the Ru content of 1-2% is obtained.
8. The use as claimed in claim 7, wherein the modified alumina carrier consists of 85-95 parts by weight of pseudo-boehmite and 5-15 parts by weight of magnesium oxide.
9. The use as claimed in claim 7 or claim 8, wherein the modified alumina support is treated with a templating agent prior to loading, the templating agent being one of ethylenediamine and n-butylamine.
10. Use according to claim 7 or 8, characterized in that the catalyst has a support pore volume of 0.4 to 0.6cm3A specific surface area of 100 to 150 m/g2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011040178.0A CN112316939A (en) | 2020-09-28 | 2020-09-28 | Preparation method of high-trans-proportion hydrogenated bisphenol A |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011040178.0A CN112316939A (en) | 2020-09-28 | 2020-09-28 | Preparation method of high-trans-proportion hydrogenated bisphenol A |
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| CN112316939A true CN112316939A (en) | 2021-02-05 |
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