CN112138669B - Method for continuously preparing copper-zinc-aluminum catalyst - Google Patents
Method for continuously preparing copper-zinc-aluminum catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- -1 copper-zinc-aluminum Chemical compound 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 50
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 31
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 24
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 9
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017518 Cu Zn Inorganic materials 0.000 claims 1
- 229910017752 Cu-Zn Inorganic materials 0.000 claims 1
- 229910017943 Cu—Zn Inorganic materials 0.000 claims 1
- 229910007570 Zn-Al Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 53
- 239000010949 copper Substances 0.000 description 18
- 239000011701 zinc Substances 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- B01J35/613—
-
- 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
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/633—
-
- 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
- C07C29/175—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 with simultaneous reduction of an oxo group
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for continuously preparing a copper-zinc-aluminum catalyst. After zinc-aluminum solution and copper-zinc solution are prepared from zinc nitrate solution, aluminum nitrate solution and copper nitrate solution, the zinc-aluminum solution and sodium carbonate solution are injected into a reaction cavity of a tubular reactor from one end of the tubular reactor to react to obtain precursor slurry containing zinc-aluminum precipitated particles, the zinc-aluminum solution and the sodium carbonate solution move forward towards the other end of the tubular reactor while being mixed and reacted, the copper-zinc solution and the sodium carbonate solution are injected into the reaction cavity from the middle part of the tubular reactor, are continuously mixed and reacted with the precursor slurry containing the zinc-aluminum precipitated particles in the reaction cavity and move forward to the other end of the tubular reactor to be discharged, and the discharged materials are subjected to suction filtration, washing and drying, then are roasted and molded to obtain the copper-zinc-aluminum catalyst. The method eliminates local back mixing in the preparation process, improves the activity of the catalyst, effectively avoids the blockage of a reaction channel by adopting the reactor, and realizes continuous large-scale production.
Description
Technical Field
The invention relates to the field of biological medicine, in particular to a method for continuously preparing a copper-zinc-aluminum catalyst.
Background
The copper-zinc-aluminum catalyst has the advantages of low price, low toxicity, good catalytic activity and the like, and is widely applied to organic catalytic reaction. The copper-zinc-aluminum catalyst has low reaction activity on the hydrogenolysis of C-C bonds, but has good reaction activity on the hydrogenolysis of C-O bonds, and copper can play a good role in selective catalysis in a plurality of reactions, including a methanol synthesis catalyst, a CO low-temperature transformation catalyst, a carbonyl aldehyde hydrogenation catalyst, a fatty acid ester hydrogenation catalyst, a glycerol hydrogenolysis catalyst, a nitrobenzene to aniline catalyst, a cyclohexanol dehydrogenation to cyclohexanone catalyst and the like.
Researches show that the synergistic effect between copper, zinc and aluminum and the specific surface area of Cu play an important role in the development of high-activity catalysts, and the smaller the grain size of the copper serving as an active component is, the higher the mutual dispersion degree of the copper, the zinc and the aluminum is, the higher the activity of the catalyst is. Therefore, the most important thing in the preparation of the copper-zinc-aluminum catalyst is the uniform mixing of copper, zinc and aluminum and the good mutual dispersion of metal elements.
At present, the copper-zinc-aluminum catalyst is industrially prepared by a coprecipitation method. However, due to the limitation of the equipment structure, the traditional coprecipitation method is difficult to mix uniformly, local reaction conditions are not uniform, mutual dispersion of copper, zinc and aluminum components is not facilitated, and precipitates and reaction raw material liquid generated at different moments are greatly back-mixed and agglomerated, so that the particle size and distribution of particles are difficult to control. On the other hand, the structure of the precursor often determines the structure and activity of the finally obtained catalyst, but the formation of the precursor is very sensitive to preparation conditions, and the structure of the existing preparation method is difficult to accurately control.
Chinese patent "a method for preparing a copper-zinc catalyst using a microchannel reactor" (publication No. CN104841437A, published japanese 2015.08.19) discloses a method for preparing a copper-zinc-aluminum catalyst using a microchannel reactor, wherein the process for preparing the catalyst is performed in the microchannel reactor, so that the problem that crystal nuclei are easily agglomerated during preparation by a coprecipitation method is solved, and catalyst grains with a large specific surface area and a small particle size are easily obtained. Because of the small scale of the micro-reactor, the diffusion distance between different materials, Cu can be well compressed 2+ And Zn 2+ With a precipitating agent CO 3 2- Can quickly achieve uniform mixing to ensure that Cu 2+ 、Zn 2+ The precipitation zones are as close as possible, the interaction between Cu and Zn is enhanced, and the mutual dispersion of copper and zinc components is increased.
Chinese patent 'a method for preparing a methanol synthesis catalyst by using a microchannel reactor' (publication No. CN105727959A, published Japanese 2014.12.11) discloses a method for preparing a methanol synthesis catalyst by using a microchannel reactor, which comprises mixing a mixed salt solution of Cu, Zn and Al with a salt solutionRespectively pumping the alkali solution into a micro mixer for mixing, then introducing the mixed materials into a micro-channel reaction tube to obtain a Cu, Zn and Al ternary precipitate, washing, filtering, drying, calcining and tabletting to obtain the CuO/ZnO/Al ternary precipitate 2 O 3 A methanol synthesis catalyst. The method realizes the continuous preparation of the high-dispersity Cu, Zn and Al ternary precipitate, and has the advantages of low device cost, continuous and controllable process, large specific surface area of the prepared catalyst, high activity and the like.
Although the two disclosed methods realize continuous preparation of the copper-zinc-aluminum catalyst, the micro-channel reactor has thin channels and small flux, so that the formed precipitation slurry is easy to block the channels, thereby limiting large-scale production application.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art, and provides a method for continuously preparing a copper-zinc-aluminum catalyst, which eliminates local back mixing in the preparation process, shortens the retention time of fluid in a reactor, and fully and quickly mixes and contacts materials in a section, so that the obtained catalyst has large crystal grain surface area, smaller grain diameter, good dispersion of metal elements, improved catalyst activity and larger reactor flux, can effectively avoid the blockage of the reactor, and realizes continuous large-scale production.
The technical scheme adopted by the invention is that,
a method for continuously preparing a copper-zinc-aluminum catalyst comprises the following steps:
s1, uniformly mixing the zinc nitrate solution and the aluminum nitrate solution to obtain a zinc-aluminum solution, and uniformly mixing the copper nitrate solution and the zinc nitrate solution to obtain a copper-zinc solution;
s2, injecting the zinc-aluminum solution and the sodium carbonate solution prepared in the step S1 into a reaction cavity of a horizontally arranged tubular reactor from one end of the tubular reactor, reacting under the stirring of an axial stirring column of the vertical tubular reactor to obtain precursor slurry containing zinc-aluminum precipitate particles, injecting the zinc-aluminum solution and the sodium carbonate solution to push the zinc-aluminum solution and the sodium carbonate solution in the reaction cavity to advance towards the other end of the tubular reactor while carrying out mixed reaction, injecting the copper-zinc solution and the sodium carbonate solution prepared in the step S1 into the reaction cavity from the middle of the tubular reactor, continuously carrying out mixed reaction with the precursor slurry containing the zinc-aluminum precipitate particles in the reaction cavity, and advancing to the other end of the tubular reactor to be discharged;
s3, collecting the material discharged in the step S2, carrying out suction filtration, washing and drying on the obtained material, roasting, and carrying out forming treatment to obtain the copper-zinc-aluminum catalyst.
In the technical scheme, the reaction materials flowing in the reaction cavity are stirred by the stirring column, and the baffle is replaced to isolate the materials before and after the reaction, so that the isolation is realized, a larger specific surface area is provided to facilitate mass transfer, the contradiction problem between the isolation and the mass transfer is solved, the full and rapid mixing and contact of the materials in the section are ensured, and the Cu is facilitated 2+ 、Zn 2+ And Al 3+ With a precipitating agent CO 3 2- Fully and uniformly mixing to obtain Cu 2+ 、Zn 2+ And Al 3+ The precipitation zones are closer, so that the interaction among Cu, Zn and Al is strengthened, the mutual dispersion of the Cu-Zn-Al components is increased, and the aging of crystal grains is facilitated; the stirring column is vertical to the rotating shaft, and is used for stirring the materials in the tangential direction, so that the materials cannot generate forward or backward driving force, the back-mixing phenomenon of the materials is effectively avoided, and the crystal nucleus agglomeration is avoided, so that the catalyst crystal grains with large specific surface area and small grain diameter are obtained; secondly, the materials are stirred through the stirring column, so that the formed precipitation slurry is effectively prevented from blocking a reaction channel; through injecting zinc-aluminum solution and copper-zinc solution into a plurality of points, dispersing and feeding in batches, promoting mixed mass transfer effect, optimizing material ratio, and simultaneously reducing internal pressure of the reactor, the adopted tubular reactor has a relatively large space structure, has larger flux, can realize industrial production, and prepares the copper-zinc-aluminum catalyst with good performance on a large scale with large flux.
Preferably, in the zinc-aluminum solution, the concentration of zinc nitrate is 5.0-6.2 g/100ml in terms of zinc oxide; the concentration of aluminum nitrate is 2.5 to 3.5g/100ml in terms of alumina.
More preferably, in the zinc-aluminum solution, the concentration of zinc nitrate is 6.0g/100ml in terms of zinc oxide; the concentration of aluminum nitrate was 3.0g/100ml in terms of alumina.
Preferably, in the copper-zinc solution, the concentration of copper nitrate is 3.1-3.9 g/100ml calculated by copper oxide; the concentration of zinc nitrate is 6.1-6.8 g/100ml in terms of zinc oxide.
More preferably, in the copper-zinc solution, the concentration of copper nitrate is 3.6g/100ml in terms of copper oxide; the concentration of zinc nitrate was 6.3g/100ml based on zinc oxide.
Preferably, the concentration of the sodium carbonate solution is 6.5-7.3 g/100ml in terms of sodium oxide.
More preferably, the sodium carbonate solution has a concentration of 7.0g/100ml in terms of sodium oxide.
Preferably, in step S2, the reaction temperature is 50-95 ℃.
More preferably, in step S2, the reaction temperature is 75-85 ℃.
Preferably, the reaction temperature is controlled by a heat exchange fluid surrounding the reaction chamber.
In the reaction process, if heat exchange efficiency is too low, the temperature in the reactor is uneven, and the reaction speed of each part in the reactor cannot be effectively controlled, so that the yield and the performance of the prepared catalyst are reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the stirring column vertical to the rotating shaft stirs the materials in the tangential direction, so that the back mixing phenomenon of the materials is avoided, the obtained catalyst crystal grains have large surface area and small grain diameter, the metal components are well dispersed, and the activity of the catalyst is improved;
(2) materials in the reaction section are fully and quickly mixed and contacted, so that the mixing is more uniform, and the curing of crystal grains is facilitated;
(3) the reactor has large flux, and the stirring column vertical to the rotating shaft can stir the materials in the tangential direction, thereby effectively avoiding the formed precipitation slurry from blocking a reaction channel and realizing continuous large-scale production;
drawings
FIG. 1 is an axial sectional view of a tubular reactor used in a continuous preparation method of a copper-zinc-aluminum catalyst of the present invention.
FIG. 2 is a partially enlarged axial sectional view of a tubular reactor used in a method for continuously preparing a Cu-Zn-Al catalyst according to the present invention.
In the drawings are labeled: 1-a rotary power assembly; 2-a heat exchange fluid inlet; 3-a raw material feeding port; 4-heat exchange jacket; 5-a heat exchange fluid outlet; 6-a discharge port for reaction products; 12-a stirring column; 13-a hollow rotating shaft; 14-a reaction chamber; 15-reactor shell.
Detailed Description
The drawings are only for purposes of illustration and are not to be construed as limiting the invention. For a better understanding of the following embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
As shown in fig. 1 and fig. 2, the tubular reactor used in the method for continuously preparing the cu-zn-al catalyst of the present invention is horizontally arranged, and includes a reactor shell 15, a hollow rotating shaft 13 disposed in the reactor shell, a rotating power assembly 1 for connecting the hollow rotating shaft 13 and the reactor shell 15, and a material inlet and material outlet assembly disposed on the outer wall surface of the reactor shell, wherein a heat exchange component is further disposed outside the reactor shell 15; a plurality of stirring columns 12 are vertically arranged on the outer wall surface of the hollow rotating shaft 13; a reaction cavity 14 is formed between the inner wall surface of the reactor shell 15 and the outer wall surface of the hollow rotating shaft 13.
The inlet and outlet assembly comprises a plurality of raw material inlets 3 and a reaction product outlet 6, and the plurality of inlets can realize multi-site feeding and batch dispersed feeding, and are used for promoting the mixed mass transfer effect, optimizing the material ratio and relieving the internal pressure; the hollow rotating shaft 13 is used for internal heat exchange, the heat exchange part comprises a heat exchange jacket 4, a heat exchange fluid inlet 2 and a heat exchange fluid outlet 5, the heat exchange fluid inlet 2 is arranged at the left end of the lower side of the heat exchange jacket 4, the heat exchange fluid outlet 5 is arranged at the right end of the upper side of the heat exchange jacket 4, when in use, the heat exchange fluid is injected from the heat exchange fluid inlet 2 and discharged from the heat exchange fluid outlet, so that the heat exchange fluid wraps the reaction cavity to perform external heat exchange, the flow direction of the heat exchange fluid is from the first raw material inlet 2 to the reaction product outlet 6, the flow direction adapts to the heat release rule of continuous reaction, and is more favorable for reaction heat exchange, therefore, the reaction temperature is better controlled, the heat exchange is carried out on the inner surface and the outer surface of the reaction space, the temperature gradient of each part in the reaction cavity is smaller, the heat transfer efficiency is very high, the local reaction overheating is prevented, and the control of the reaction speed is facilitated; the rotary power component 1 fixes the hollow rotary shaft 13 and provides rotary power for the hollow rotary shaft 13, the hollow rotary shaft 13 is used for driving the stirring column 12, the stirring column 12 is vertically arranged on the outer wall surface of the hollow rotary shaft 13, materials can be stirred in the tangential direction along with the rotation of the hollow rotary shaft 13, so that the materials are mixed more uniformly, the mutual dispersion of copper, zinc and aluminum components is increased, the stirring column 12 is vertical to the outer wall surface of the hollow rotary shaft 13, the materials are stirred in the tangential direction, forward or backward driving force cannot be generated by the materials, the materials are mainly driven by the driving force generated by continuously injecting new materials, so that the back mixing phenomenon of the materials is eliminated, the traditional isolation baffle which is not beneficial to mass transfer can be replaced by the stirring of the stirring column 12, the mass transfer is facilitated while the isolation of reaction materials is realized, and the yield of products is further improved; meanwhile, the materials are stirred by the stirring column 12, so that the formed precipitation slurry is effectively prevented from blocking a reaction channel.
The invention provides a method for continuously preparing a copper-zinc-aluminum catalyst, which comprises the following steps:
s1, uniformly mixing the zinc nitrate solution and the aluminum nitrate solution to obtain a zinc-aluminum solution, and uniformly mixing the copper nitrate solution and the zinc nitrate solution to obtain a copper-zinc solution;
preheating the S2 reactor in advance, controlling the reaction temperature at 50-95 ℃, injecting the zinc-aluminum solution and the sodium carbonate solution prepared in the step S1 into the reaction cavity 14 of the flat tubular reactor from the first raw material inlet 3 by using a metering pump, reacting under the stirring of a stirring column 12 in the axial direction of the vertical tubular reactor to obtain precursor slurry containing zinc-aluminum precipitate particles, injecting a zinc-aluminum solution and a sodium carbonate solution to push the zinc-aluminum solution and the sodium carbonate solution in the reaction chamber 14 to advance towards a reaction product discharge port 6 of the tubular reactor while carrying out mixed reaction, injecting the copper-zinc solution and the sodium carbonate solution prepared in the step S1 into the reaction chamber 14 from a second raw material feed port 3 of the tubular reactor by using another metering pump, continuously mixes and reacts with the precursor slurry containing the zinc-aluminum precipitated particles in the reaction chamber 14 and advances, staying in the reactor for 10-20 min, and discharging to a discharge port 6 of a reaction product of the tubular reactor;
s3, collecting the material discharged in the step S2, carrying out suction filtration, washing and drying on the obtained material, roasting, and carrying out forming treatment to obtain the copper-zinc-aluminum catalyst.
The prepared copper-zinc-aluminum catalyst is tested for specific surface area and pore volume by a specific surface area and pore volume and pore diameter tester.
The hydrogenation activity evaluation of the copper-zinc-aluminum catalyst is carried out on a small fixed bed hydrogenation experimental device: the catalyst is dried and dehydrated before use, and is filled into a fixed bed reactor, and hydrogen with the purity of more than 98.6 percent and octenal with the purity of more than 97.7 percent are pumped into the fixed bed reactor according to the hydrogen-oil ratio (mol) of 28:1 for reaction. The activity evaluation conditions were: hydrogen is used as reducing gas, the reaction temperature is 170-210 ℃, the reaction pressure is 0.45MPa, and the space velocity is 2.5h -1 . The raw materials and products were analyzed by a gas chromatograph.
Example 1
In this example, the continuous preparation of the copper-zinc-aluminum catalyst was performed according to the above-described steps of the preparation method, and the concentration of zinc nitrate in the prepared zinc-aluminum solution was 5.0g/100ml in terms of zinc oxide, and the concentration of aluminum nitrate was 3.0g/100ml in terms of aluminum oxide; in the prepared copper-zinc solution, the concentration of copper nitrate is 3.6g/100ml calculated by copper oxide; the concentration of zinc nitrate is 6.1g/100ml calculated by zinc oxide; the concentration of the selected sodium carbonate solution is 7.0g/100ml calculated by sodium oxide, in step S2, the reaction temperature is controlled at 50 ℃, and the reaction materials stay in the reactor for 20 min.
The specific surface area of the obtained copper-zinc-aluminum catalyst is 65.2m 2 The copper-zinc-aluminum catalyst is tested by the activity test method, and the conversion rate of octenal is 99.89% and the selectivity of octanol is 99.68%.
Example 2
In this example, the continuous preparation of the copper-zinc-aluminum catalyst was performed according to the above-described steps of the preparation method, and the concentration of zinc nitrate in the prepared zinc-aluminum solution was 6.0g/100ml in terms of zinc oxide, and the concentration of aluminum nitrate was 2.5g/100ml in terms of aluminum oxide; in the prepared copper-zinc solution, the concentration of copper nitrate is 3.4g/100ml calculated by copper oxide; the concentration of zinc nitrate is 6.3g/100ml based on zinc oxide; the concentration of the selected sodium carbonate solution is 6.5g/100ml calculated by sodium oxide, in step S2, the reaction temperature is controlled to be 75 ℃, and the reaction materials stay in the reactor for 17 min.
The specific surface area of the obtained copper-zinc-aluminum catalyst is 66.3m 2 The copper-zinc-aluminum catalyst is tested by the activity test method, and the conversion rate of octenal and the selectivity of octanol are 99.86 percent and 99.58 percent respectively.
Example 3
In this example, the continuous preparation of the copper-zinc-aluminum catalyst was performed according to the above-described steps of the preparation method, and the concentration of zinc nitrate in the prepared zinc-aluminum solution was 6.2g/100ml in terms of zinc oxide, and the concentration of aluminum nitrate was 3.5g/100ml in terms of aluminum oxide; in the prepared copper-zinc solution, the concentration of copper nitrate is 3.1g/100ml calculated by copper oxide; the concentration of zinc nitrate is 6.8g/100ml based on zinc oxide; the concentration of the selected sodium carbonate solution is 7.3g/100ml calculated by sodium oxide, in step S2, the reaction temperature is controlled at 85 ℃, and the reaction materials stay in the reactor for 13 min.
The specific surface area of the obtained copper-zinc-aluminum catalyst is 68.5m 2 The copper-zinc-aluminum catalyst is tested by the activity test method, and the conversion rate of octenal is 99.92% and the selectivity of octanol is 99.76%.
Example 4
In this example, the continuous preparation of the cu-zn-al catalyst was performed according to the above-described steps of the preparation method, and in the prepared zn-al solution, the concentration of zinc nitrate was 5.7g/100ml in terms of zinc oxide, and the concentration of aluminum nitrate was 3.3g/100ml in terms of aluminum oxide; in the prepared copper-zinc solution, the concentration of copper nitrate is 3.8g/100ml calculated by copper oxide; the concentration of zinc nitrate is 6.7g/100ml calculated by zinc oxide; the concentration of the selected sodium carbonate solution is 7.0g/100ml calculated by sodium oxide, in step S2, the reaction temperature is controlled at 80 ℃, and the reaction materials stay in the reactor for 15 min.
The specific surface area of the obtained copper-zinc-aluminum catalyst is 67.4m 2 The obtained copper-zinc-aluminum catalyst is tested by the activity test method, and the conversion rate of the octenal is 99.95 percent and the selectivity of the octanol is 99.74 percent after analysis.
Example 5
In this example, the continuous preparation of the copper-zinc-aluminum catalyst was performed according to the above-described steps of the preparation method, and the concentration of zinc nitrate in the prepared zinc-aluminum solution was 5.2g/100ml in terms of zinc oxide, and the concentration of aluminum nitrate was 2.7g/100ml in terms of aluminum oxide; in the prepared copper-zinc solution, the concentration of copper nitrate is 3.9g/100ml calculated by copper oxide; the concentration of zinc nitrate is 6.5g/100ml based on zinc oxide; the concentration of the selected sodium carbonate solution is 6.8g/100ml calculated by sodium oxide, in step S2, the reaction temperature is controlled at 95 ℃, and the reaction materials stay in the reactor for 10 min.
The specific surface area of the obtained Cu-Zn-Al catalyst is 70.5m 2 The copper-zinc-aluminum catalyst is tested by the activity test method, and the conversion rate of octenal and the selectivity of octanol are 99.78 percent after analysis.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. A method for continuously preparing a copper-zinc-aluminum catalyst is characterized by comprising the following steps:
s1, uniformly mixing the zinc nitrate solution and the aluminum nitrate solution to obtain a zinc-aluminum solution, and uniformly mixing the copper nitrate solution and the zinc nitrate solution to obtain a copper-zinc solution;
s2, injecting the zinc-aluminum solution and the sodium carbonate solution prepared in the step S1 into a reaction cavity of a horizontally arranged tubular reactor from one end of the tubular reactor, reacting under the stirring of an axial stirring column of the vertical tubular reactor to obtain precursor slurry containing zinc-aluminum precipitate particles, injecting the zinc-aluminum solution and the sodium carbonate solution to push the zinc-aluminum solution and the sodium carbonate solution in the reaction cavity to advance towards the other end of the tubular reactor while carrying out mixed reaction, injecting the copper-zinc solution and the sodium carbonate solution prepared in the step S1 into the reaction cavity from the middle of the tubular reactor, continuously carrying out mixed reaction with the precursor slurry containing the zinc-aluminum precipitate particles in the reaction cavity, and advancing to the other end of the tubular reactor to be discharged;
s3, collecting the material discharged in the step S2, carrying out suction filtration, washing and drying on the obtained material, roasting, and carrying out forming treatment to obtain the copper-zinc-aluminum catalyst;
the stirring column stirs the material in the tangential direction.
2. The continuous preparation method of the copper-zinc-aluminum catalyst according to claim 1, wherein the concentration of zinc nitrate in the zinc-aluminum solution is 5.0 to 6.2g/100ml in terms of zinc oxide; the concentration of aluminum nitrate is 2.5-3.5 g/100ml in terms of aluminum oxide.
3. The continuous preparation method of the Cu-Zn-Al catalyst according to claim 2, wherein the concentration of zinc nitrate in the Zn-Al solution is 6.0g/100ml in terms of zinc oxide; the concentration of aluminum nitrate was 3.0g/100ml in terms of alumina.
4. The continuous preparation method of the copper-zinc-aluminum catalyst according to claim 1, wherein the concentration of copper nitrate in the copper-zinc solution is 3.1-3.9 g/100ml in terms of copper oxide; the concentration of zinc nitrate is 6.1-6.8 g/100ml in terms of zinc oxide.
5. The continuous preparation method of the Cu-Zn-Al catalyst according to claim 4, wherein the concentration of the copper nitrate in the Cu-Zn solution is 3.6g/100ml in terms of copper oxide; the concentration of zinc nitrate was 6.3g/100ml in terms of zinc oxide.
6. The continuous preparation method of the copper-zinc-aluminum catalyst according to claim 1, wherein the concentration of the sodium carbonate solution is 6.5-7.3 g/100ml in terms of sodium oxide.
7. The continuous preparation method of the copper-zinc-aluminum catalyst according to claim 6, wherein the concentration of the sodium carbonate solution is 7.0g/100ml in terms of sodium oxide.
8. The continuous preparation method of the Cu-Zn-Al catalyst according to claim 1, wherein the reaction temperature in step S2 is 50-95 ℃.
9. The continuous preparation method of the Cu-Zn-Al catalyst according to claim 8, wherein the reaction temperature in step S2 is 75-85 ℃.
10. The continuous preparation method of the Cu-Zn-Al catalyst according to claim 8 or 9, wherein the reaction temperature is controlled by a heat exchange fluid surrounding the reaction chamber.
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