CN115069299A - Super-hydrophobic Ni-Cu catalyst and preparation method, application and use method thereof - Google Patents
Super-hydrophobic Ni-Cu catalyst and preparation method, application and use method thereof Download PDFInfo
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- CN115069299A CN115069299A CN202210639476.4A CN202210639476A CN115069299A CN 115069299 A CN115069299 A CN 115069299A CN 202210639476 A CN202210639476 A CN 202210639476A CN 115069299 A CN115069299 A CN 115069299A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 229910018054 Ni-Cu Inorganic materials 0.000 title claims abstract description 34
- 229910018481 Ni—Cu Inorganic materials 0.000 title claims abstract description 34
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 60
- 150000002815 nickel Chemical class 0.000 claims abstract description 25
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001879 copper Chemical class 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 24
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 12
- 229940014800 succinic anhydride Drugs 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006004 Quartz sand Substances 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- -1 hydrogen anhydride Chemical class 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 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 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 208000010444 Acidosis Diseases 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000007950 acidosis Effects 0.000 description 3
- 208000026545 acidosis disease Diseases 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical class [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0228—Sulfur-containing compounds with a metal-sulfur link, e.g. mercaptides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
Abstract
The invention discloses a super-hydrophobic Ni-Cu catalyst and a preparation method, application and a using method thereof. The super-hydrophobic Ni-Cu hydrogenation catalyst is prepared from the following raw materials: the composite template comprises nickel salt, copper salt, urea, a hydrophobic template and water, wherein the molar ratio of the nickel salt to the copper salt to the urea is 1:0.1-2:0.1-4, and the molar mass of the hydrophobic template is 0.01-0.5% of the total molar mass of the nickel salt to the copper salt to the urea.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, and in particular relates to a super-hydrophobic Ni-Cu catalyst and a preparation method and application thereof.
Background
The hydrogenation catalytic reaction has wide application in the field of catalysis, and typical examples thereof include hydrogenation of various unsaturated hydrocarbons, such as hydrogenation saturation catalytic reaction of olefin or alkyne, selective hydrogenation catalytic reaction of diene, direct hydrogenation reaction of maleic anhydride, and the like. The addition of a hydrogenation catalyst is generally required during the hydrogenation catalytic reaction. The hydrogenation catalyst is generally a catalyst used in the addition of a compound to hydrogen, and is usually a metal catalyst containing a group VIII transition metal element, a metal oxide or sulfide catalyst, a complex catalyst, or the like. Another hydrogenation catalyst which is relatively common in the industry is usually in the form of an active metal component supported on a carrier.
Maleic anhydride, also known as anhydromalic anhydride, maleic anhydride is anhydride of maleic acid, which is a white crystal with strong pungent odor at room temperature and has chemical formula C 4 H 2 O 3 . In a common maleic anhydride hydrogenation reaction, a number of different reactions occur at different stages of the reaction.
Maleic anhydride is hydrogenated under the action of a nickel catalyst to prepare succinic anhydride, which is shown in the following formula (1):
the maleic anhydride is hydrogenated under the action of a copper catalyst to prepare the gamma-butyrolactone which is shown as the following formula (2):
the gamma-butyrolactone can also be prepared by hydrogenation reaction of succinic anhydride under the action of a copper catalyst, and is shown in the following formula (3):
in addition, in the presence of water, the maleic anhydride and succinic anhydride respectively react as follows:
in conclusion, water is generated in the maleic anhydride hydrogenation catalytic reaction, the adopted raw materials inevitably contain part of water, the water can cause the content of water in the hydrogenation reaction to fluctuate, the reaction process is further influenced, and some water can even influence the stable operation of the device, and unpredictable influence can be brought. For example, the above reaction may generate acids such as maleic acid and 1, 4-succinic acid, the metal catalyst may cause loss of active metal due to acidosis, and further, the life and performance of the catalyst may be adversely affected, and the acids may corrode equipment, and further, the requirement for acid corrosion prevention of the equipment may be increased. Therefore, it is urgently needed to provide a hydrogenation catalyst which is not affected by-product acid and can ensure the catalytic efficiency.
Disclosure of Invention
The invention discloses a super-hydrophobic Ni-Cu catalyst, and a preparation method, application and a use method thereof. The catalyst of the invention can well solve the adverse effect caused by the by-product dibasic acid in the hydrogenation catalysis process of maleic anhydride, avoid the loss of active metal caused by acidosis and ensure the service life of the catalyst. The catalyst has uniform particles, rich mesoporous structure and good catalytic activity, succinic anhydride and gamma-butyrolactone can be adjusted in any proportion according to reaction conditions, a two-stage hydrogenation process is omitted, the equipment investment cost is obviously reduced, and the catalyst is easy for industrial production.
The invention provides a super-hydrophobic Ni-Cu hydrogenation catalyst, which is prepared from the following raw materials: the composite material comprises nickel salt, copper salt, urea, a hydrophobic template agent and water, wherein the molar ratio of the nickel salt to the copper salt to the urea is 1:0.1-2:0.1-4, and the molar mass of the hydrophobic template agent is 0.01-0.5% of the total molar mass of the nickel salt to the copper salt to the urea.
Further, in the above materials, the nickel salt is selected from one or more of nickel chloride, nickel nitrate and nickel sulfate; the copper salt is selected from one or more of copper chloride, copper nitrate and copper sulfate; the hydrophobic template agent is sodium dodecyl sulfate and derivatives thereof.
CO(NH 2 ) 2 +3H 2 O→CO 2 +2NH 4 + +2OH -
Ni 2+ +2OH - →HO-Ni＝O+H 2 O
Cu 2+ +2OH - →HO-Cu＝O+H 2 O
The OH of HO-Cu ═ O is condensed and dehydrated with the hydroxyl of dodecyl sulfonic acid, so that the surface of the catalyst has no OH group and the catalyst shows hydrophobicity
Roasting at proper temperature to crack partial organic matter and obtain residual organic functional group as hydrophobic unit
Further, the molar ratio of the nickel salt, the copper salt and the urea can be any value of 1:0.1-2:0.1-4, such as 1:0.1:0.1-4, 1:2:0.1-4, 1:0.1-2:0.1, 1:0.1-2:4, etc.
Further, the molar ratio of the nickel salt, the copper salt, and the urea is preferably 1:1: 4.
Further, the hydrophobic template has a molar mass of any value of 0.1 to 0.5% of the total molar mass of the nickel salt, the copper salt and the urea, such as 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% and 0.5%.
Further, it is preferred that the hydrophobic templating agent is sodium dodecyl sulfate, which preferably has a molar mass of 0.083% of the total molar mass of the nickel salt, the copper salt and the urea.
Furthermore, the molar mass of water may be added according to the actual requirements of the hydrothermal reaction, and the molar ratio of water to nickel salt may be any value between 1 and 100:1, such as 1:1, 2:1, 5:1, 10:1, 20:1, 30:1, 50:1, 100: 1.
Further, the molar ratio of water to nickel salt (in the case of nickel chloride) is preferably 83: 1.
The invention also provides a preparation method of the super-hydrophobic Ni-Cu hydrogenation catalyst, which adopts a hydrothermal method to directly synthesize the super-hydrophobic Ni-Cu hydrogenation catalyst by one step:
weighing nickel salt, copper salt, urea, a hydrophobic template agent and water according to the formula ratio, mixing at room temperature, stirring for 5min, filling the mixed solution into a hydrothermal kettle, performing static crystallization, repeatedly washing with deionized water for multiple times, drying, and roasting in an inert gas atmosphere to obtain the super-hydrophobic Ni-Cu hydrogenation catalyst.
Further, the temperature of the static crystallization is 100 ℃, and the time is 12 hours.
Further, the washing is repeated by using deionized water, wherein the temperature of the deionized water is 40 ℃, and the washing times are 3 times.
Further, the drying is carried out at 120 ℃ for 12 h.
Further, the roasting temperature is 200-500 ℃.
Further, the roasting temperature is 300 ℃.
Further, the roasting equipment is a muffle furnace, and the roasting time in the muffle furnace is 6-24 h.
The invention also provides a super-hydrophobic Ni-Cu hydrogenation catalyst which is prepared by any one of the preparation methods.
The invention also provides an application of the super-hydrophobic Ni-Cu hydrogenation catalyst, and the super-hydrophobic Ni-Cu hydrogenation catalyst is applied to catalyzing maleic anhydride hydrogenation to co-produce succinic anhydride and gamma-butyrolactone.
The invention also provides a use method of the super-hydrophobic Ni-Cu hydrogenation catalyst, which is characterized in that the super-hydrophobic Ni-Cu hydrogenation catalyst is added into a reaction kettle, and maleic anhydride is catalyzed and hydrogenated to co-produce succinic anhydride and gamma-butyrolactone under a proper reaction condition.
Further, tabletting and granulating the super-hydrophobic Ni-Cu hydrogenation catalyst, wherein the tabletting pressure is 30MPa, the tabletting time is 10min, the granulation size is 20-40 meshes, and the super-hydrophobic Ni-Cu hydrogenation catalyst is mixed with a proper amount of quartz sand for later use.
Further, a continuous fixed bed reaction device is adopted, 20-40 mesh catalyst and quartz sand are fully mixed, the mass ratio of the catalyst to the quartz sand is 1:1, the catalyst and the quartz sand are filled into the middle part of a reaction tube, and the upper end and the lower end of a catalyst bed layer are fixed by quartz cotton; reducing the catalyst for 6h at 400 ℃ by using 99.9% hydrogen under the condition of normal pressure, then reducing the temperature to the reaction temperature, pumping mixed solution of maleic anhydride and gamma-butyrolactone in a mass ratio of 1:9 into the catalyst by a high-pressure plunger pump, and inputting hydrogen from a total hydrogen pipeline.
Further, the reaction temperature is 100-: 100.
further, the reaction temperature is 240 ℃, the reaction pressure is 2.0MPa, and the molar ratio of the hydrogen anhydride is 100.
Further, the liquid phase product after the reaction was analyzed using a hydrogen Flame Ionization Detector (FID).
The invention takes nickel salt, copper salt, urea, sodium dodecyl sulfate and derivatives thereof as raw materials, and adopts a hydrothermal synthesis method to prepare the binary metal catalyst, wherein the sodium dodecyl sulfate provides a hydrophobic functional group, a mesoporous template agent and a Na auxiliary agent source. The introduction of hydrophobic functional group (long chain alkyl group) solves the problem of by-product dibasic acid, avoids the loss of active metal caused by acidosis and prolongs the service life of the catalyst. In addition, the catalyst has uniform particles, rich mesoporous structure and good catalytic activity, the selectivity of the succinic anhydride and the gamma-butyrolactone can be adjusted according to any proportion of reaction conditions, a two-stage hydrogenation process is omitted, the equipment investment cost is obviously reduced, and the industrial production is easy to realize.
The invention has the beneficial effects that:
1. the problem of rapid removal of water in the C ═ O hydrogenation product is solved, and the selectivity of succinic anhydride and maleic anhydride hydrolysis products (dibasic acid) is reduced;
2. a binary metal catalyst, Ni hydrogenation C ═ C bond, Cu hydrogenation C ═ O bond;
3. a hydrothermal synthesis method is adopted to synthesize a metal catalyst containing three elements of Ni and Cu, the proportion of Ni and Cu can be adjusted at will, the catalyst is uniform nano-particles, and the performance of the catalyst is stable;
4. the hydrophobic template agent is sodium dodecyl sulfate and derivatives thereof, generates mesopores after being calcined, and can provide hydrophobic property;
5. urea acts as a weak electrolyte precipitant that precipitates the metal and silicon into uniform nanoparticles.
Drawings
FIG. 1 shows the results of IR tests on the product obtained in example 1;
figure 2 is the XRD measurement of the product obtained in example 1.
Detailed Description
The present invention is illustrated in detail below by way of examples and comparative examples, but the scope of the present invention is not limited to the following description.
Examples 1 to 4 were carried out by the following methods
(1) Preparation of the catalyst
Taking nickel salt, copper salt, urea, a hydrophobic template agent and water according to a formula, mixing at a high temperature, stirring for 5min, filling the mixed solution into a hydrothermal kettle, performing static crystallization, repeatedly washing with deionized water for multiple times, drying, and roasting in an inert gas atmosphere to obtain the super-hydrophobic Ni-Cu hydrogenation catalyst for later use.
(2) Use of the catalyst
Tabletting and granulating the super-hydrophobic Ni-Cu hydrogenation catalyst under the pressure of 30MPa for 10min, and mixing with a proper amount of quartz sand for later use, wherein the granulation size is 20-40 meshes.
Fully mixing a 20-40-mesh catalyst and quartz sand by adopting a continuous fixed bed reaction device, wherein the mass ratio of the catalyst to the quartz sand is 1:1, filling the mixture into the middle part of a reaction tube, and fixing the upper end and the lower end of a catalyst bed layer by using quartz cotton; reducing the catalyst for 6h at 500 ℃ by using 99.9% hydrogen under the condition of normal pressure, then reducing the reaction temperature to 100 ℃, pumping mixed solution of maleic anhydride and gamma-butyrolactone according to the mass ratio of 1:9 into the catalyst by a high-pressure plunger pump, and inputting hydrogen through a total hydrogen pipeline.
Table 1: the amounts (molar ratios) of the respective raw materials used in examples 1 to 4
| Numbering | Nickel salt | Copper salts | Urea | Hydrophobic template agent | Water (I) |
| Example 1 | 1 | 1 | 4 | 0.005 | 83 |
| Example 2 | 1 | 0 | 4 | 0.005 | 83 |
| Example 3 | 0 | 1 | 4 | 0.005 | 83 |
| Example 4 | 1 | 1 | 4 | 0 | 83 |
In examples 1 to 4, nickel chloride was used as the nickel salt, copper chloride was used as the copper salt, and sodium dodecylsulfate was used as the hydrophobic template.
Table 2: test results of examples 1 to 4
Combining the data in table 2, it can be seen that examples 2 and 3, which have no copper salt or nickel salt added thereto, result in higher selectivity of a single product than example 1. The product predominated on succinic anhydride in the absence of Cu catalyst, indicating that the Ni catalyst significantly promoted hydrogenation of the C ═ C double bonds. In the absence of Ni-based catalysts, Cu-based catalysts hydrogenate both C ═ C and C ═ O double bonds, but the conversion is significantly lower. Example 4 the total acid content was significantly increased without the addition of a hydrophobic template, demonstrating that the hydrophobic catalyst has a key effect on reducing the acid content, greatly improving the catalytic performance of the catalyst.
In examples 5 to 10, the raw material ratio and the production method of example 1 were used, but the conditions for using the catalyst were adjusted as shown in Table 3 (normal pressure was 101KPa or 0.1 MPa). The total acid selectivity comprises 1, 4-succinic acid, maleic acid, propionic acid and butyric acid.
Table 3: test results of examples 5 to 10
It can be seen from the data in Table 3 that examples 6-9 have higher reaction pressure than example 5, wherein the maleic anhydride conversion is significantly increased when 260 ℃ is used in example 8, which indicates that at 260 ℃, the catalytic performance of the catalyst is optimal, the catalyst activity is reduced at too low temperature, and the by-product acid may be promoted at too high temperature.
Example 10 increased the reaction pressure, and as the reaction pressure increased due to the addition of hydrogen during the hydrogenation reaction, the selectivity to succinic anhydride continued to decrease and the yield of gamma-butyrolactone decreased, both due to the excessive hydrogenation, and tetrahydrofuran was produced as a by-product. Therefore, based on the data in Table 3, the hydrogenation catalytic performance of the catalyst of the present invention was optimized using a reaction temperature of 260 ℃ and a reaction pressure of 1.0 MPa.
FIGS. 1 and 2 below show the results of IR and XRD measurements, respectively, of the product obtained in example 1.
FIG. 1 results of IR test of the product obtained in example 1, the IR data showing that the wave number is 3500cm -1 The vicinity is a hydroxyl peak. 2950 and 2850cm -1 Sp of C-H 3 Vibration peak at 1380-1360 and 1420cm -1 The peak is the in-plane bending vibration peak of the C-H bond. Low wave number 430- -1 Are the vibrational peaks of metal-oxygen (Ni-O and Cu-O). It is shown that hydrophobic functions such as C-H are formed on the metal oxide.
FIG. 2 XRD test results of the product obtained in example 1 show that the obtained catalyst has better crystallinity.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as described within the scope thereof and the invention is defined by the claims appended hereto without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (17)
1. A super-hydrophobic Ni-Cu hydrogenation catalyst is characterized in that: the catalyst is prepared from the following raw materials: the composite material comprises nickel salt, copper salt, urea, a hydrophobic template agent and water, wherein the molar ratio of the nickel salt to the copper salt to the urea is 1:0.1-2:0.1-4, and the molar mass of the hydrophobic template agent is 0.01-0.5% of the total molar mass of the nickel salt to the copper salt to the urea.
2. The hydrogenation catalyst of claim 1, wherein: the nickel salt is selected from one or more of nickel chloride, nickel nitrate and nickel sulfate; the copper salt is selected from one or more of copper chloride, copper nitrate and copper sulfate; the hydrophobic template agent is sodium dodecyl sulfate and derivatives thereof.
3. The hydrogenation catalyst of claim 1, wherein: the molar ratio of the nickel salt to the copper salt to the urea is 1:1:4, and the molar mass of the hydrophobic template agent is 0.083% of the total molar mass of the nickel salt to the copper salt to the urea.
4. A preparation method of a super-hydrophobic Ni-Cu hydrogenation catalyst is characterized by comprising the following steps:
the super-hydrophobic Ni-Cu hydrogenation catalyst is directly synthesized in one step by a hydrothermal method:
weighing nickel salt, copper salt, urea, a hydrophobic template agent and water according to the formula ratio, mixing at room temperature, stirring for 5min, filling the mixed solution into a hydrothermal kettle, performing static crystallization, repeatedly washing with deionized water for multiple times, drying, and roasting in an inert gas atmosphere to obtain the super-hydrophobic Ni-Cu hydrogenation catalyst.
5. The method of claim 4, wherein: the temperature of the static crystallization is 100 ℃, and the time is 12 h.
6. The method of claim 4, wherein: the washing is repeated by using deionized water, wherein the temperature of the deionized water is 40 ℃, and the washing times are 3 times.
7. The method of claim 4, wherein: the drying is carried out at 120 ℃ for 12 h.
8. The method of claim 4, wherein: the roasting temperature is 200-500 ℃.
9. The method of claim 4, wherein: the roasting temperature is 300 ℃.
10. The method of claim 4, wherein: the roasting equipment is a muffle furnace, and the roasting time in the muffle furnace is 6-24 h.
11. A super-hydrophobic Ni-Cu hydrogenation catalyst is characterized in that: the super-hydrophobic Ni-Cu hydrogenation catalyst prepared by the preparation method of any one of claims 4 to 10.
12. The application of the super-hydrophobic Ni-Cu hydrogenation catalyst is characterized in that: the super-hydrophobic Ni-Cu hydrogenation catalyst as defined in any one of claims 1-3 and 11 or the super-hydrophobic Ni-Cu hydrogenation catalyst prepared by the preparation method as defined in any one of claims 4-10 is applied to catalyzing maleic anhydride hydrogenation for coproducing succinic anhydride and gamma-butyrolactone.
13. A use method of a super-hydrophobic Ni-Cu hydrogenation catalyst is characterized by comprising the following steps: adding a super-hydrophobic Ni-Cu hydrogenation catalyst into a reaction tube, and catalyzing maleic anhydride hydrogenation to co-produce succinic anhydride and gamma-butyrolactone under a proper reaction condition; wherein the super-hydrophobic Ni-Cu hydrogenation catalyst is the hydrogenation catalyst of any one of claims 1 to 3 and 11, or the super-hydrophobic Ni-Cu hydrogenation catalyst prepared by the preparation method of any one of claims 4 to 10.
14. Use according to claim 13, characterized in that: and tabletting and granulating the super-hydrophobic Ni-Cu hydrogenation catalyst, wherein the tabletting pressure is 30MPa, the tabletting time is 10min, the granulation size is 20-40 meshes, and the super-hydrophobic Ni-Cu hydrogenation catalyst is mixed with a proper amount of quartz sand for later use.
15. Use according to claim 14, characterized in that: fully mixing a 20-40-mesh catalyst and 20-40-mesh quartz sand by adopting a continuous fixed bed reaction device, wherein the mass ratio of the catalyst to the quartz sand is 1:1, filling the mixture into the middle part of a reaction tube, and fixing the upper end and the lower end of a catalyst bed layer by using quartz cotton; under the condition of normal pressure, reducing the catalyst for 6 hours at 500 ℃ by using 99.9% hydrogen, then reducing the temperature to the reaction temperature, pumping mixed solution of maleic anhydride and gamma-butyrolactone according to the mass ratio of 1:9 into the catalyst by a high-pressure plunger pump, and inputting hydrogen by a total hydrogen pipeline.
16. Use according to claim 15, characterized in that: the reaction temperature is 100-400 ℃, the reaction pressure is 0.1-5.0MPa, and the molar ratio of the hydrogen anhydride is 100: 1.
17. Use according to claim 15, characterized in that: the reaction temperature is 240 ℃, the reaction pressure is 1.0MPa, and the molar ratio of the hydrogen anhydride is 100.
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