CN111215077A - Catalyst for synthesizing isopropanol and preparation method and application thereof - Google Patents
Catalyst for synthesizing isopropanol and preparation method and application thereof Download PDFInfo
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- CN111215077A CN111215077A CN202010101864.8A CN202010101864A CN111215077A CN 111215077 A CN111215077 A CN 111215077A CN 202010101864 A CN202010101864 A CN 202010101864A CN 111215077 A CN111215077 A CN 111215077A
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- isopropanol
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- active component
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 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 25
- 238000000034 method Methods 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 229960004592 isopropanol Drugs 0.000 description 53
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000005470 impregnation Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- -1 firstly Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YIBPLYRWHCQZEB-UHFFFAOYSA-N formaldehyde;propan-2-one Chemical compound O=C.CC(C)=O YIBPLYRWHCQZEB-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009475 tablet pressing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for synthesizing isopropanol and a preparation method and application thereof, wherein the catalyst comprises an active component and a composite carrier; the active component is NiO; the composite carrier is a modified alumina carrier; the modifying component in the modified alumina carrier is TiO2And/or SiO2(ii) a The mass percentage of the active component in the catalyst is 12-33%, and the mass percentage of the carrier is 88-67%. Compared with the prior art, the catalyst provided by the invention takes NiO as an active component, and is combined with a composite carrier with a specific content of components to realize better interaction, so that the catalyst has higher conversion rate and selectivity in the process of synthesizing isopropanol by hydrogenating acetone; moreover, the catalyst mainly adopts non-noble metal components, thereby greatly reducing the cost,The preparation process is simplified, thereby meeting the requirements of industrial practical application.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a catalyst for synthesizing isopropanol and a preparation method and application thereof.
Background
With the continuous improvement of the current industrial technology, the acetone production capacity is continuously increased to generate surplus situations. In recent years, the application of acetone in solvents is gradually reduced, and the application range of acetone is becoming narrower and narrower. Thus, the greatest disadvantage of the synthesis of isopropanol by acetone hydrogenation is not present, and therefore, it is of great practical significance to develop a technique for synthesizing isopropanol by acetone hydrogenation. In japan, the mitsui chemical company announced in 2011, 8 months and 30 days, plans to modify a device for preparing isopropyl alcohol (IPA) by utilizing a propylene direct hydration method in an osaka factory, adopts an acetone hydrogenation method in a new device, and has an annual capacity of 2.8 ten thousand tons in an original device and an annual capacity of 6 ten thousand tons in a modified device. The key point of the technology for synthesizing isopropanol by the acetone hydrogenation method is to research a high-performance catalyst.
At present, the catalyst for preparing isopropanol by hydrogenating acetone mainly takes metal nickel and copper or noble metals such as platinum, rhodium, ruthenium and the like as active components. For example, chinese patent publication No. CN1255482A discloses a process for preparing isopropanol by hydrogenating acetone, which uses a CuO-ZnO oxide mixture catalyst formed by tablet pressing, and the reaction is carried out at a use temperature of 150-250 ℃, a pressure of 1.0-5.0 MPa, a hydrogen-to-ketone ratio of 1.5: 1-4.5: 1. the hourly space velocity of the acetone solution is 0.5h-1～4.0h-1Under the condition, the conversion rate of the acetone is up to 99.9 percent, and the selectivity of the isopropanol is up to 99.9 percent; chinese patent publication No. 101927168A discloses a nickel-based catalyst for synthesizing isopropanol by acetone hydrogenation and application thereof, wherein a small amount of metal Mo and Zn is added into the nickel-based catalyst, so that the yield of isopropanol produced by acetone hydrogenation of the catalyst can be remarkably improved, and the yield of isopropanol can reach 99.4%; chinese patent publication No. CN102746113A discloses a method for synthesizing isopropanol, in which Ba, La, Mg, etc. are added to a nickel-based catalyst to perform catalyst modification. Further, Mooksuwan W employs NThe i-Cu alloy catalyst is used for researching the endothermic reaction of acetone gas phase hydrogenation, and the maximum conversion rate of acetone can reach 25% by improving the bed temperature of the catalyst and the inlet temperature of reactants. Although the alloy catalyst has high catalytic performance, the requirement on a reducing agent is high, the operation is complex, and industrial amplification is difficult. Meanwhile, the prior art discloses that a Raney nickel catalyst is adopted, liquid-phase acetone, gas-phase hydrogen and the catalyst are subjected to contact reaction in a trickle bed reactor, the reaction temperature is 100 ℃, and the conversion rate of acetone and the selectivity of isopropanol are high. Although the raney nickel catalyst has good catalytic performance for the acetone hydrogenation reaction, the raney nickel catalyst is expensive, the production flow is complex and the operation is not easy.
Therefore, with the increasing demand for the catalytic performance of the catalyst for synthesizing isopropanol and the need for industrial scale-up, the need to provide a catalyst with higher conversion rate and selectivity and to realize industrial practical application has become a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst for synthesizing isopropanol, and a preparation method and an application thereof, and the catalyst provided by the present invention has higher conversion rate and selectivity in the process of synthesizing isopropanol by hydrogenating acetone, and can meet the requirements of industrial practical application.
The invention provides a catalyst for synthesizing isopropanol, which comprises an active component and a composite carrier;
the active component is NiO;
the composite carrier is a modified alumina carrier; the modifying component in the modified alumina carrier is TiO2And/or SiO2；
The mass percentage of the active component in the catalyst is 12-33%, and the mass percentage of the carrier is 88-67%.
Preferably, Al in the modified alumina carrier2O3The mass of the catalyst accounts for 59-71 percent of the mass of the catalyst, and TiO2The mass of the catalyst accounts for 8 to 15 percent of the mass of the catalyst, and SiO2The mass of the catalyst accounts for 0 to 2 percent of the mass of the catalyst.
Preferably, the specific surface area of the catalyst is 140m2/g～200m2The pore volume is 0.42mL/g to 0.48 mL/g.
The invention also provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:
a) uniformly mixing an aluminum source, a titanium source, a silicon source, an auxiliary agent and an acid solution, forming, and drying and roasting in sequence to obtain a composite carrier;
b) fixing a Ni source on the composite carrier obtained in the step a), and performing high-temperature treatment to obtain the catalyst for synthesizing isopropanol.
Preferably, the drying process in step a) is specifically as follows:
drying for 2-4 h at 70-90 ℃, and then drying for 2-4 h at 110-130 ℃.
Preferably, the roasting process in the step a) is specifically as follows:
heating to 450-600 ℃ at the heating rate of 4-6 ℃/min and preserving the heat for 1-6 h.
Preferably, the high-temperature treatment process in the step b) specifically comprises the following steps:
after the catalyst is dried, the temperature is raised to 400-550 ℃ at the heating rate of 4-6 ℃/min, and the temperature is preserved for 1-6 h.
The invention also provides a synthesis method of isopropanol, which comprises the following steps:
under the condition of hydrogen, firstly, carrying out catalyst reduction activation, and then introducing acetone for catalytic reaction to obtain isopropanol; the catalyst is the catalyst in the technical scheme.
Preferably, the partial pressure of hydrogen for reduction activation of the catalyst is less than or equal to 0.7MPa, and the gas-agent ratio is (500-2000): 1, the reduction temperature is less than or equal to 200 ℃, and the reduction time is more than or equal to 48 hours.
Preferably, the liquid volume space velocity of the acetone for the catalytic reaction is 0.5h-1～1.5h-1The molar ratio of hydrogen to ketone is (7-10): 1, reaction pressureThe force is 1MPa to 2.5MPa, and the reaction temperature is 135 ℃ to 160 ℃.
The invention provides a catalyst for synthesizing isopropanol and a preparation method and application thereof, wherein the catalyst comprises an active component and a composite carrier; the active component is NiO; the composite carrier is a modified alumina carrier; the modifying component in the modified alumina carrier is TiO2And/or SiO2(ii) a The mass percentage of the active component in the catalyst is 12-33%, and the mass percentage of the carrier is 88-67%. Compared with the prior art, the catalyst provided by the invention takes NiO as an active component, and is combined with a composite carrier with a specific content of components to realize better interaction, so that the catalyst has higher conversion rate and selectivity in the process of synthesizing isopropanol by hydrogenating acetone; in addition, the catalyst mainly adopts non-noble metal components, so that the cost is greatly reduced, the preparation flow is simplified, and the requirement of industrial practical application can be met. Experimental results show that the catalyst provided by the invention is used for synthesizing isopropanol by hydrogenating acetone, the acetone conversion rate can reach more than 99.5%, and the isopropanol selectivity can reach more than 99.5%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a catalyst for synthesizing isopropanol, which comprises an active component and a composite carrier;
the active component is NiO;
the composite carrier is a modified alumina carrier; the modifying component in the modified alumina carrier is TiO2And/or SiO2；
The mass percentage of the active component in the catalyst is 12-33%, and the mass percentage of the carrier is 88-67%.
In the invention, the catalyst comprises an active component and a composite carrier, and preferably consists of the active component and the composite carrier. In the invention, the active component is NiO; the mass percentage of the active component in the catalyst is 12-33%, preferably 15-26%, and more preferably 22-26%.
In the invention, the composite carrier is a modified alumina carrier; the mass percentage content of the carrier in the catalyst is 88-67%, preferably 85-74%.
In the invention, the modifying component in the modified alumina carrier is TiO2And/or SiO2(ii) a Al in the modified alumina carrier2O3The percentage content of (b) by mass to the mass of the catalyst is preferably 59% to 71%, more preferably 59% to 68%; TiO in the modified alumina carrier2The mass percentage of the catalyst is preferably 8 to 15 percent; SiO in the modified alumina carrier2The mass percentage of (B) in the catalyst mass is preferably 0-2%.
In the present invention, the specific surface area of the catalyst is preferably 140m2/g～200m2(ii)/g; the pore volume of the catalyst is preferably 0.42mL/g to 0.48 mL/g.
The catalyst provided by the invention takes NiO as an active component and is combined with a composite carrier with a specific content of components to realize better interaction, so that the catalyst has higher conversion rate and selectivity in the process of synthesizing isopropanol by hydrogenating acetone; in addition, the catalyst provided by the invention also has the characteristics of stable property, long service life and the like.
The invention also provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:
a) uniformly mixing an aluminum source, a titanium source, a silicon source, an auxiliary agent and an acid solution, forming, and drying and roasting in sequence to obtain a composite carrier;
b) fixing a Ni source on the composite carrier obtained in the step a), and performing high-temperature treatment to obtain the catalyst for synthesizing isopropanol.
The preparation method comprises the steps of firstly, uniformly mixing an aluminum source, a titanium source, a silicon source, an auxiliary agent and an acid solution, then forming, and drying and roasting in sequence to obtain the composite carrier. In the present invention, the aluminium source is preferably selected from pseudo-boehmite and/or dry glue; the source of the aluminum source is not particularly limited in the present invention, and commercially available products of the above pseudoboehmite and dry gum well known to those skilled in the art may be used.
In the present invention, the titanium source is preferably selected from metatitanic acid and/or TiO2(ii) a The source of the titanium source is not particularly limited in the present invention, and the above-mentioned metatitanic acid and TiO known to those skilled in the art are used2The product of (4) is a commercially available product.
In the present invention, the silicon source is preferably selected from silica sol and/or molecular sieves; the source of the silicon source is not particularly limited in the present invention, and commercially available products of the above silica sol and/or molecular sieve known to those skilled in the art may be used.
In the present invention, the addition amounts of the aluminum source, the titanium source and the silicon source are preferably selected in accordance with Al in the modified alumina support2O3、TiO2、SiO2Calculated as a percentage of the mass of the catalyst.
In the invention, the auxiliary agent is preferably sesbania powder; the source of the adjuvant in the present invention is not particularly limited, and commercially available products of the above-mentioned sesbania powder known to those skilled in the art may be used. In the invention, the addition amount of the auxiliary agent is preferably 1-3% of the total mass of the aluminum source, the titanium source and the silicon source.
In the present invention, the acid solution is preferably a mixed solution of nitric acid and citric acid; the concentration of the nitric acid is preferably 65-68%, and commercial products well known to those skilled in the art can be adopted; the source of the citric acid is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the addition amount of the nitric acid is preferably 0.1-4% of the total mass of the aluminum source, the titanium source and the silicon source; the addition amount of the citric acid is preferably 0.1-3% of the total mass of the aluminum source, the titanium source and the silicon source.
In the present invention, the preferable process for uniformly mixing the aluminum source, the titanium source, the silicon source, the auxiliary agent and the acid solution is as follows:
after an aluminum source, a titanium source, a silicon source and an auxiliary agent are mixed, an acid solution is added and mixed evenly. The device for forming is not particularly limited in the present invention, and a plodder well known to those skilled in the art may be used.
In the present invention, the drying process preferably includes:
drying for 2-4 h at 70-90 ℃, and then drying for 2-4 h at 110-130 ℃;
more preferably:
drying at 80 deg.C for 3 hr, and drying at 120 deg.C for 3 hr.
The apparatus for the calcination according to the present invention is not particularly limited, and a muffle furnace known to those skilled in the art may be used. In the present invention, the roasting process is preferably as follows:
heating to 450-600 ℃ at the heating rate of 4-6 ℃/min and preserving the heat for 1-6 h;
more preferably:
heating to 550 ℃ at the heating rate of 5 ℃/min and preserving the heat for 4 h.
After the composite carrier is obtained, the Ni source is fixed on the obtained composite carrier, and the catalyst for synthesizing the isopropanol is obtained after high-temperature treatment. In the present invention, the Ni source is preferably selected from one or more of nickel nitrate, nickel acetate, and basic nickel carbonate; the source of the Ni source is not particularly limited in the present invention, and commercially available products of the above nickel nitrate, nickel acetate and basic nickel carbonate, which are well known to those skilled in the art, may be used.
In the present invention, the fixing manner is preferably drying after impregnation; on this basis, the Ni source takes the form of a solution. In the present invention, the drying process is preferably performed in an oven; the drying temperature is preferably 80-150 ℃, and more preferably 105 ℃; the drying time is preferably 1 to 6 hours, more preferably 4 hours.
In the present invention, the drying process after the impregnation is preferably performed twice, and each time the high temperature treatment is performed.
In the present invention, the high temperature treatment process preferably includes:
heating to 400-550 ℃ at the heating rate of 4-6 ℃/min, and keeping the temperature for 1-6 h;
more preferably:
heating to 500-540 ℃ at the heating rate of 4-6 ℃/min and preserving the heat for 3 h.
In a preferred embodiment of the present invention, the process of fixing the Ni source on the obtained composite carrier and obtaining the catalyst for synthesizing isopropanol after the high temperature treatment is preferably specifically as follows:
soaking the obtained composite carrier twice by using a solution prepared from a Ni source; after the first impregnation is finished, drying for 4 hours in a drying oven at 105 ℃, and then roasting for 3 hours in a muffle furnace at 540 ℃; and then carrying out second impregnation, drying for 4h in an oven at 105 ℃, and roasting for 3h in a muffle furnace at 520 ℃ to obtain the catalyst for synthesizing isopropanol.
The preparation method provided by the invention has the advantages that the catalyst mainly adopts non-noble metal components, the corresponding raw material cost is greatly reduced, and the preparation process is simpler than other catalysts for synthesizing the isopropanol by hydrogenating the acetone in the prior art, and is suitable for industrial amplification.
The invention also provides a synthesis method of isopropanol, which comprises the following steps:
under the condition of hydrogen, firstly, catalyst reduction activation is carried out, and then acetone is introduced for catalytic reaction to obtain isopropanol.
In the present invention, the synthesis process is preferably carried out in a fixed bed reactor; the present invention is not particularly limited with respect to the sources of the hydrogen and acetone. In the invention, the catalyst is the catalyst in the technical scheme.
In the present invention, the partial pressure of hydrogen for reductive activation of the catalyst is preferably 0.7MPa or less; the ratio of the gas (hydrogen) agent (catalyst) reduced by the catalyst is preferably (500-2000): 1; the reduction temperature of the catalyst is preferably less than or equal to 200 ℃; the reduction time of the catalyst is preferably more than or equal to 48 hours.
In the present invention, the liquid volume space velocity of acetone for the catalytic reaction is preferably 0.5h-1～1.5h-1More preferably 1.0h-1(ii) a The hydrogen (hydrogen) ketone (acetone) mole ratio of the catalytic reaction is preferably (7-10): 1; the reaction pressure of the catalytic reaction is preferably 1MPa to 2.5MPa, and more preferably 1.5MPa to 2.0 MPa; the reaction temperature of the catalytic reaction is preferably 135 ℃ to 160 ℃.
The catalyst adopting the technical scheme can meet the requirements of industrial practical application of synthesizing the isopropanol by hydrogenating the acetone under specific synthesis steps, conditions of the steps and parameters of the conditions.
The invention provides a catalyst for synthesizing isopropanol and a preparation method and application thereof, wherein the catalyst comprises an active component and a composite carrier; the active component is NiO; the composite carrier is a modified alumina carrier; the modifying component in the modified alumina carrier is TiO2And/or SiO2(ii) a The mass percentage of the active component in the catalyst is 12-33%, and the mass percentage of the carrier is 88-67%. Compared with the prior art, the catalyst provided by the invention takes NiO as an active component, and is combined with a composite carrier with a specific content of components to realize better interaction, so that the catalyst has higher conversion rate and selectivity in the process of synthesizing isopropanol by hydrogenating acetone; in addition, the catalyst mainly adopts non-noble metal components, so that the cost is greatly reduced, the preparation flow is simplified, and the requirement of industrial practical application can be met. Experimental results show that the catalyst provided by the invention is used for synthesizing isopropanol by hydrogenating acetone, the acetone conversion rate can reach more than 99.5%, and the isopropanol selectivity can reach more than 99.5%.
To further illustrate the present invention, the following examples are provided for illustration. The starting materials used in the following examples of the present invention are all commercially available products.
Example 1
(1) 81.33g of pseudo-boehmite (dry basis 75%), 17.41g of metatitanic acid (dry basis 80.36%) and 2.96g of sesbania powder were mixed, and 55mL of a mixture containing 2.47g of citric acid and 3.80g of HNO was added3(65%) mixed acid solution, mixing well, forming on a bar extruder, drying at 80 deg.C for 3h, drying at 120 deg.C for 3h, and then drying in a muffle furnaceHeating to 550 ℃ at the heating rate of 5 ℃/min and roasting for 4h to obtain the composite carrier.
(2) 98.91gNi (NO) was weighed out3)2·6H2Preparing 46.37mL of aqueous solution from O, and soaking the composite carrier obtained in the step (1) twice; after the first impregnation is finished, drying for 4 hours in a drying oven at 105 ℃, and then roasting for 3 hours in a muffle furnace at 540 ℃; then carrying out secondary impregnation, drying for 4h in a drying oven at 105 ℃, and then roasting for 3h in a muffle furnace at 500 ℃ to obtain a catalyst for synthesizing isopropanol; the specific surface area is 160m2The pore volume is 0.42mL/g, and the contents of the components are as follows: NiO content 25 wt%, Al2O361 wt% of TiO2The content was 14 wt%.
On a fixed bed reactor, the catalyst for synthesizing isopropanol provided in example 1 is first subjected to reductive activation under hydrogen conditions: hydrogen partial pressure is 0.5MPa, gas-agent ratio is 1000: 1, the reduction temperature is 180 ℃, and the reduction time is 48 hours; then carrying out catalytic reaction: the space velocity of the volume of the acetone liquid is 1.0h-1The molar ratio of hydrogen to ketone is 8: 1, synthesizing isopropanol under the conditions that the reaction pressure is 2.0MPa and the reaction temperature is 140 ℃; the detection proves that the acetone conversion rate can reach 99.9 percent, and the isopropanol selectivity can reach 99.9 percent.
Example 2
(1) 94.67g of pseudo-boehmite, 17.41g of metatitanic acid and 3.36g of sesbania powder were mixed, and 62mL of a mixture containing 2.80g of citric acid and 4.31g of HNO was added3(65%) mixed acid solution, evenly mixing, forming on a strip extruding machine, drying for 3h at 80 ℃, then drying for 3h at 120 ℃, and then heating to 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min and roasting for 4h to prepare the composite carrier.
(2) Weighing 51.30g of nickel acetate to prepare 55.25mL of solution, and soaking the composite carrier obtained in the step (1) twice; after the first impregnation is finished, drying for 4 hours in a drying oven at 110 ℃, and then roasting for 3 hours in a muffle furnace at 540 ℃; then carrying out secondary impregnation, drying for 4h in a drying oven at 105 ℃, and then roasting for 3h in a muffle furnace at 500 ℃ to obtain a catalyst for synthesizing isopropanol; the specific surface area of the powder is 186m2The pore volume is 0.44mL/g, and each component containsThe amount is: NiO content 15 wt%, Al2O371 wt% of TiO2The content was 14 wt%.
On a fixed bed reactor, the catalyst for synthesizing isopropanol provided in example 2 is firstly subjected to reduction activation under hydrogen conditions: hydrogen partial pressure is 0.5MPa, gas-agent ratio is 1000: 1, the reduction temperature is 180 ℃, and the reduction time is 48 hours; then carrying out catalytic reaction: the space velocity of the volume of the acetone liquid is 1.0h-1The molar ratio of hydrogen to ketone is 8: 1, synthesizing isopropanol under the conditions that the reaction pressure is 2.0MPa and the reaction temperature is 160 ℃; the detection shows that the acetone conversion rate can reach 99.5 percent, and the isopropanol selectivity can reach 99.8 percent.
Example 3
(1) After 90.67g of pseudo-boehmite, 9.96g of metatitanic acid and 3.02g of sesbania powder were mixed, 6.67g of silica Sol (SiO)2Content 30 wt%), then 46.80mL of citric acid containing 2.52g and HNO containing 3.10g were added3(65%) mixed acid solution, evenly mixing, forming on a strip extruding machine, drying for 3h at 80 ℃, then drying for 3h at 120 ℃, and then heating to 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min and roasting for 4h to prepare the composite carrier.
(2) Weighing 85.36gNi (NO)3)2·6H2Preparing 50.00mL of solution by using O, and soaking the composite carrier obtained in the step (1) in two times; after the first impregnation is finished, drying for 4 hours in a drying oven at 110 ℃, and then roasting for 3 hours in a muffle furnace at 540 ℃; then carrying out secondary impregnation, drying for 4h in a drying oven at 105 ℃, and then roasting for 3h in a muffle furnace at 500 ℃ to obtain a catalyst for synthesizing isopropanol; the specific surface area is 150m2The pore volume is 0.42mL/g, and the contents of the components are as follows: NiO content 22 wt%, Al2O368 wt% of TiO28 wt% of SiO2The content was 2 wt%.
On a fixed bed reactor, the catalyst for synthesizing isopropanol provided in example 3 is first subjected to reductive activation under hydrogen conditions: hydrogen partial pressure is 0.5MPa, gas-agent ratio is 1000: 1, the reduction temperature is 180 ℃, and the reduction time is 48 hours; then carrying out catalytic reaction: in volume of acetone liquidThe space velocity is 1.0h-1The molar ratio of hydrogen to ketone is 7: 1, synthesizing isopropanol under the conditions that the reaction pressure is 2.0MPa and the reaction temperature is 145 ℃; the detection proves that the acetone conversion rate can reach 99.9 percent, and the isopropanol selectivity can reach 99.7 percent.
Example 4
The preparation of catalysts with different active component contents was carried out according to the preparation methods of examples 1, 2 and 3, and the data for the preparation of isopropanol by the hydrogenation of acetone are shown in table 1.
TABLE 1 catalyst test results for different active component contents
Example 5
Adopting catalyst 23% NiO-14% TiO2-63％Al2O3Different condition examinations were carried out, and the specific data are shown in the following table.
Table 2 investigation of catalyst effectiveness under different conditions
| Serial number | Space velocity/hydrogen ketone ratio/pressure/temperature | Acetone conversion rate,% of | Iso-propanol selectivity,% |
| 1 | 1.0h-1/7:1/1.0MPa/135℃ | 99.7 | 99.5 |
| 2 | 1.0h-1/8:1/2.0MPa/140℃ | 99.9 | 99.9 |
| 3 | 1.0h-1/10:1/1.5MPa/140℃ | 99.9 | 99.8 |
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A catalyst for synthesizing isopropanol comprises an active component and a composite carrier;
the active component is NiO;
the composite carrier is a modified alumina carrier; the modifying component in the modified alumina carrier is TiO2And/or SiO2；
The mass percentage of the active component in the catalyst is 12-33%, and the mass percentage of the carrier is 88-67%.
2. The catalyst of claim 1 wherein said modified alumina support comprises Al2O3The mass of the catalyst accounts for 59 to 71 percent of the mass of the catalyst, and the TiO is2The mass of the catalyst accounts for 8 to 15 percent of the mass of the catalyst, and SiO2The mass of the catalyst accounts for 0 to up to2％。
3. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 140m2/g～200m2The pore volume is 0.42mL/g to 0.48 mL/g.
4. A method for preparing the catalyst of any one of claims 1 to 3, comprising the steps of:
a) uniformly mixing an aluminum source, a titanium source, a silicon source, an auxiliary agent and an acid solution, forming, and drying and roasting in sequence to obtain a composite carrier;
b) fixing a Ni source on the composite carrier obtained in the step a), and performing high-temperature treatment to obtain the catalyst for synthesizing isopropanol.
5. The preparation method according to claim 4, wherein the drying process in step a) is specifically as follows:
drying for 2-4 h at 70-90 ℃, and then drying for 2-4 h at 110-130 ℃.
6. The preparation method according to claim 4, wherein the roasting process in the step a) is specifically as follows:
heating to 450-600 ℃ at the heating rate of 4-6 ℃/min and preserving the heat for 1-6 h.
7. The preparation method according to claim 4, wherein the high-temperature treatment in step b) is specifically performed by:
after the catalyst is dried, the temperature is raised to 400-550 ℃ at the heating rate of 4-6 ℃/min, and the temperature is preserved for 1-6 h.
8. The method for synthesizing isopropanol is characterized by comprising the following steps of:
under the condition of hydrogen, firstly, carrying out catalyst reduction activation, and then introducing acetone for catalytic reaction to obtain isopropanol; the catalyst is the catalyst according to any one of claims 1 to 3.
9. The synthesis method according to claim 8, wherein the hydrogen partial pressure of the catalyst for reduction activation is less than or equal to 0.7MPa, and the gas-to-agent ratio is (500-2000): 1, the reduction temperature is less than or equal to 200 ℃, and the reduction time is more than or equal to 48 hours.
10. The synthesis method of claim 8, wherein the catalytic reaction has an acetone liquid volume space velocity of 0.5h-1～1.5h-1The molar ratio of hydrogen to ketone is (7-10): 1, the reaction pressure is 1MPa to 2.5MPa, and the reaction temperature is 135 ℃ to 160 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115069268A (en) * | 2022-08-02 | 2022-09-20 | 山东鲁新设计工程有限公司 | Catalyst for preparing neopentyl glycol by high pressure method |
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