CN113996306A - Catalyst for catalyzing dehydrogenation reaction of 1, 4-butanediol and preparation method and application thereof - Google Patents
Catalyst for catalyzing dehydrogenation reaction of 1, 4-butanediol and preparation method and application thereof Download PDFInfo
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- CN113996306A CN113996306A CN202111435541.3A CN202111435541A CN113996306A CN 113996306 A CN113996306 A CN 113996306A CN 202111435541 A CN202111435541 A CN 202111435541A CN 113996306 A CN113996306 A CN 113996306A
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 17
- 239000011701 zinc Chemical class 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Chemical class 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 10
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 9
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 239000008399 tap water Substances 0.000 description 10
- 235000020679 tap water Nutrition 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- 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
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of a catalyst for catalyzing dehydrogenation reaction of 1, 4-butanediol, which comprises the following steps: dissolving metal salts of copper, zinc, nickel, aluminum and cerium in water to obtain a metal salt solution; then slowly adding an anhydrous sodium carbonate solution into the metal salt solution, controlling the temperature to be 60-70 ℃, continuously detecting the pH value of the solution in the adding process, and stopping dropwise adding when the pH value reaches 8.5-9.5 to obtain a suspension; continuing stirring the turbid liquid, then precipitating and aging at the constant temperature of 65 ℃, and introducing mixed gas of hydrogen and nitrogen into the turbid liquid in the precipitation and aging process to obtain mixed precipitation liquid; and finally, washing and suction-filtering the mixed precipitate, drying, and then roasting in a muffle furnace at 500-550 ℃ for 4-6 h to obtain the metal oxide catalyst. The catalyst can reduce the proper dehydrogenation temperature to 190-200 ℃, thereby being beneficial to energy conservation and consumption reduction in the production process, high efficiency and environmental protection.
Description
Technical Field
The invention relates to the field of 1, 4-butyrolactone production, in particular to a catalyst for 1, 4-butyrolactone production, and more particularly to a catalyst for catalyzing 1, 4-butanediol dehydrogenation reaction to produce 1, 4-butyrolactone, and a preparation method and application of the catalyst.
Background
The 1, 4-butyrolactone can participate in the synthesis of various chemical products as a common fine chemical raw material, is an intermediate of various perfume drugs, can be used as an environment-friendly low-toxicity organic solvent in a certain scene due to high boiling point and stable property, can be used as a curing agent of a polyurethane coating, and has wide application.
At present, the synthesis process of 1, 4-butyrolactone mainly has 2 routes: the first is a 1, 4-butanediol dehydrogenation method, and the second is a maleic anhydride hydrogenation method; the last step of the maleic anhydride method is hydrogenation dehydration of succinic anhydride, the pressure required by the reaction is high, even if a noble metal catalyst is used, the pressure is often more than 8Mpa, and meanwhile, the material of equipment is required to be resistant to acid corrosion, so that the equipment cost is greatly increased. The 1, 4-butanediol dehydrogenation method is a normal pressure reaction with few byproducts, can reduce product separation and equipment cost, and is gradually becoming the main production method of the 1, 4-butyrolactone at present.
The catalyst used for preparing 1, 4-butyrolactone by dehydrogenation of 1, 4-butanediol is commonly a metal composite oxide catalyst, such as Cu/ZnO/Al2O3Some catalysts incorporate Cr, which is a toxic metal, or Pt, which is a noble metal. Although some catalysts can achieve higher 1, 4-butanediol conversion rate and 1, 4-butyrolactone selectivity, the appropriate temperature for 1, 4-butanediol dehydrogenation is basically maintained at 230-280 ℃, the catalytic dehydrogenation reaction temperature is higher, the production energy consumption is correspondingly high, and the industrial production is not facilitated.
The Chinese patent with the publication number of CN1562473A discloses a catalyst for preparing gamma-butyrolactone by 1, 4-butanediol dehydrogenation, which adopts CuO, ZnO and Ce2O3The dehydrogenation reaction temperature is reduced in a certain range, but needs to be further improved.
Disclosure of Invention
Based on the technical problems, the invention provides a catalyst for catalyzing dehydrogenation reaction of 1, 4-butanediol, and a preparation method and application of the catalyst.
The technical solution adopted by the invention is as follows:
a catalyst for catalyzing dehydrogenation reaction of 1, 4-butanediol comprises metal components of Cu, Zn, Ni, Al and Ce, wherein the mass ratio of the metal components of Cu to Zn to Ni to Al to Ce is (5-12): 3-9): 1-2): 5-7: 0.5-1.
A preparation method of a catalyst for catalyzing dehydrogenation reaction of 1, 4-butanediol comprises the following steps:
(1) dissolving metal salts of copper, zinc, nickel, aluminum and cerium in water, and stirring and dissolving at 60-70 ℃ to obtain a metal salt solution;
(2) adding anhydrous sodium carbonate into deionized water, and stirring and dissolving at 60-70 ℃ to obtain a sodium carbonate solution;
(3) transferring the metal salt solution prepared in the step (1) into a reaction kettle, continuously stirring, controlling the temperature of the reaction kettle to be 60-70 ℃ through a water bath, and then slowly adding the sodium carbonate solution prepared in the step (2) into the reaction kettle; continuously detecting the pH value of the solution in the reaction kettle in the adding process, and stopping dropwise adding when the pH value reaches 8.5-9.5 to obtain a suspension;
(4) continuously stirring the turbid liquid obtained in the step (3), then precipitating and aging at the constant temperature of 65 ℃, and introducing mixed gas of hydrogen and nitrogen into the turbid liquid in the precipitation and aging process to obtain mixed precipitation liquid;
(5) and (4) repeatedly washing and filtering the mixed precipitation solution obtained in the step (4) with water, drying the obtained filtrate in a constant-temperature drying box, and finally roasting in a muffle furnace at 500-550 ℃ for 4-6 h to obtain the metal oxide catalyst.
Preferably, in step (1): the copper salt is selected from copper nitrate trihydrate, the zinc salt is selected from zinc sulfate heptahydrate, the nickel salt is selected from nickel nitrate hexahydrate, the aluminum salt is selected from aluminum nitrate nonahydrate, and the cerium salt is selected from cerium nitrate hexahydrate.
Preferably, in step (2): the concentration of the sodium carbonate solution is 0.8-1.2 mol/L.
Preferably, in step (3): the stirring speed is 200 r/min-400 r/min, and the adding time of the sodium carbonate solution is controlled to be 1-1.5 hours.
Preferably, in step (4): continuously stirring the suspension for 0.5-1 hour; the precipitation aging time is 2-2.5 hours.
Preferably, in step (4): the volume ratio of hydrogen in the mixed gas is 10%.
Preferably, in step (5): the washing and suction filtration times are 3-5 times, the stirring time is more than 40 minutes for the 1 st washing, and the remaining times are more than 20 minutes, so that the pH value after washing is 7-7.3; the drying temperature of the filtrate in the constant-temperature drying oven is 80-100 ℃, and the drying time is 10-12 hours.
The application of the catalyst in catalyzing dehydrogenation reaction of 1, 4-butanediol to prepare 1, 4-butyrolactone specifically comprises the following steps:
filling a catalyst into a fixed bed quartz tube reactor, wherein the pressure is normal pressure, the reaction temperature is 160-230 ℃, a temperature programming controller is adopted for controlling, data is detected every 10 ℃, and the mixed gas of hydrogen and 1, 4-butanediol is used for 1000-2500 h at a volume space velocity-1And (3) introducing the mixture into a quartz tube reactor, wherein the molar ratio of the mixed gas to 1, 4-butanediol (10-25) to 1 is hydrogen.
More preferably, the reaction temperature is 190-200 ℃.
The beneficial technical effects of the invention are as follows:
(1) the catalyst for the dehydrogenation reaction of the 1, 4-butanediol, which is developed by the invention, can realize high dispersion of active substances by matching of various metal oxides, further reduce the temperature of the dehydrogenation reaction of the 1, 4-butanediol, and reduce the proper dehydrogenation temperature to 190-200 ℃, thereby being beneficial to energy conservation and consumption reduction in the production process, high efficiency and environmental protection.
(2) By screening the proportion of the active components and the like, the invention can effectively reduce the cost of the catalyst on the basis of keeping the original catalytic activity, simultaneously increase the strength and the wear resistance of the catalyst and effectively reduce the cost of a complete set of equipment.
(3) The catalyst prepared by the method has low activation temperature and high conversion rate and selectivity, and can greatly improve the production efficiency and reduce the related cost when being applied to industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a metal oxide catalyst prepared by the process of the present invention; apparent Al can be seen from the figure2O3A crystalline form;
FIG. 2 is a graph showing activity evaluations of catalyst A prepared in example 1 of the present invention and catalyst I prepared in comparative example 1, and catalyst J prepared in comparative example 2, wherein (a) shows 1, 4-butanediol conversion, (b) shows 1, 4-butyrolactone selectivity;
FIG. 3 is a graph showing the evaluation of the catalytic activity of the catalyst obtained after changing the pH of the filtrate washing in the present invention, wherein (a) shows the conversion of 1, 4-butanediol and (b) shows the selectivity of 1, 4-butyrolactone;
FIG. 4 is an activity evaluation graph of a catalyst obtained by changing the distribution ratio of active components in the present invention, wherein (a) shows the conversion rate of 1, 4-butanediol and (b) shows the selectivity of 1, 4-butyrolactone;
FIG. 5 is a diagram showing activity evaluation of a catalyst obtained by changing the compounding ratio of a carrier and an auxiliary in the present invention, wherein (a) shows the conversion of 1, 4-butanediol, and (b) shows the selectivity of 1, 4-butyrolactone.
Detailed Description
Example 1
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and heated with stirring in a constant temperature magnetic stirrer set at 65 ℃. 69.5g of aluminum nitrate nonahydrate, 26.6g of copper nitrate trihydrate, 22g of zinc sulfate heptahydrate, 9.9g of nickel nitrate hexahydrate and 3.1g of cerium nitrate hexahydrate were added to a beaker, and uniformly dissolved with stirring to obtain a metal salt solution. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3Dropwise adding the solution into the metal salt solution, controlling the mixing time to be 1 hour, simultaneously controlling the reaction kettle to be 65 ℃ through a water bath, adjusting the pH of the suspension to be about 9, stopping dropwise adding, and continuously stirring the mixed solution for 1 hour. After stirring is stopped, precipitating and aging for 2 hours at the constant temperature of 65 ℃, and introducing H with the volume fraction of 10 percent into the suspension in the process2H of (A) to (B)2And N2To obtain mixed precipitation liquid. Repeatedly washing and filtering the mixed precipitation solution with tap water for four times,the water consumption for each time is 2600ml, the stirring time for the first washing is one hour, and the time for each washing is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. Then, the mixture was calcined at 550 ℃ for 4 hours in a muffle furnace to obtain a metal oxide catalyst A (Cu: Zn: Ni: Al: Ce ═ 7:5:2:5: 1).
The prepared metal oxide catalyst powder is pressed and ground, particles of 40-60 meshes are screened out, 0.2g of catalyst particles are weighed and put into a fixed bed quartz tube reactor to carry out an activity evaluation test for simulating 1, 4-butanediol dehydrogenation reaction gas, and the air pressure is normal pressure. Mixing the mixed gas with the molar ratio of hydrogen to 1, 4-butanediol being 25:1 at a volume space velocity of 2000h-1And introducing the mixture into a reaction tube, controlling the reaction temperature to be 160-230 ℃ by adopting a programmed temperature controller, and detecting data every 10 ℃. And (3) carrying out online gas quantitative analysis by adopting a gas chromatograph of an FID detector, and further obtaining the conversion rate of the 1, 4-butanediol and the selectivity of the 1, 4-butyrolactone. The results of the experiment are shown in FIG. 2. From figure 2 it can be seen that almost complete conversion can be achieved at 190 c with high conversion and lower catalytic temperature than the existing cost-equivalent catalysts.
Example 2
Catalyst B (Cu: Zn: Ni: Al: Ce ═ 7:5:2:5:1) was prepared by changing the preparation method of the catalyst of example 1, washing the mixed precipitate with tap water to pH 7.5 to 7.8, and activity evaluation was performed under the same conditions as in example 1, except for the same conditions, and the experimental results were shown in fig. 3.
Example 3
Catalyst C (Cu: Zn: Ni: Al: Ce ═ 7:5:2:5:1) was prepared by changing the preparation of the catalyst of example 1, washing the mixed precipitate with tap water to pH 6.5 to 7, and the activity evaluation was performed under the same conditions as in example 1 except for the same conditions, and the experimental results were shown in fig. 3. As can be seen from the comparison in FIG. 3, the optimum washing pH value in the preparation method of the present invention is 7 to 7.3.
Example 4
100mL of deionized water is measured and poured into a 2000mL beaker, a magnetic stirring rod is added, and the mixture is stirred in a constant-temperature magnetic stirrerStirring and heating, and setting the temperature to 65 ℃. 69.5g of aluminum nitrate nonahydrate, 19g of copper nitrate trihydrate, 30.8g of zinc sulfate heptahydrate, 9.9g of nickel nitrate hexahydrate and 3.1g of cerium nitrate hexahydrate were added to a beaker, and uniformly dissolved with stirring to obtain a metal salt solution. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3Dropwise adding the solution into the metal salt solution, controlling the mixing time to be 1 hour, adjusting the pH of the suspension to be about 9 in a reaction kettle at 65 ℃ through a water bath, stopping dropwise adding, and continuously stirring the mixed solution for 1 hour. After stirring is stopped, precipitating and aging for 2H at the constant temperature of 65 ℃, and introducing H into the suspension in the process2Volume fraction of 10% H2H of (A) to (B)2And N2To obtain mixed precipitation liquid. And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The dried sample was then calcined in a muffle furnace at 550 ℃ for 4h to give metal oxide catalyst D (Cu: Zn: Ni: Al: Ce: 5:7:2:5: 1). The procedure of the activity evaluation test was the same as in example 1, and the results are shown in FIG. 4.
Example 5
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and stirred in a constant temperature magnetic stirrer at a set temperature of 65 ℃. 69.5g of aluminum nitrate nonahydrate, 26.6g of copper nitrate trihydrate, 26.4g of zinc sulfate heptahydrate, 4.9g of nickel nitrate hexahydrate and 3.1g of cerium nitrate hexahydrate were added to a beaker, and uniformly dissolved with stirring to obtain a metal salt solution. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Strip for heating and stirring in water bath at 65 DEG CStirring at a stirring paddle speed of 400r/min, and adding Na as precipitant2CO3Dropwise adding the solution into the metal salt solution, controlling the mixing time to be 1 hour, controlling the temperature of the reaction kettle to be 65 ℃ through a water bath, adjusting the pH value of the suspension to be about 9, stopping dropwise adding, and continuously stirring the mixed solution for 1 hour. After stirring is stopped, precipitating and aging for 2H at the constant temperature of 65 ℃, and introducing H into the suspension in the process2Volume fraction of 10% H2H of (A) to (B)2And N2The mixed gas of (1). And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The dried sample was calcined in a muffle furnace at 550 ℃ for 4 hours to obtain a metal oxide catalyst E (Cu: Zn: Ni: Al: Ce: 7:6:1:5: 1). The procedure of the activity evaluation test was the same as in example 1, and the results are shown in FIG. 4.
Example 6
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and stirred in a constant temperature magnetic stirrer at a set temperature of 65 ℃. 69.5g of aluminum nitrate nonahydrate, 30.4g of copper nitrate trihydrate, 22g of zinc sulfate heptahydrate, 4.9g of nickel nitrate hexahydrate and 3.1g of cerium nitrate hexahydrate were added to a beaker, and uniformly dissolved with stirring to obtain a metal salt solution. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3Dropwise adding the solution into the metal salt solution, controlling the mixing time to be 1 hour, controlling the temperature of the reaction kettle to be 65 ℃ through a water bath, adjusting the pH value of the suspension to be about 9, stopping dropwise adding, and continuously stirring the mixed solution for 1 hour. After stirring is stopped, precipitating and aging for 2H at the constant temperature of 65 ℃, and introducing H into the suspension in the process2Volume fraction of 10% H2H of (A) to (B)2And N2To obtain a mixtureAnd (4) combining the precipitation solution. And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The dried sample was calcined in a muffle furnace at 550 ℃ for 4h to obtain a metal oxide catalyst F (Cu: Zn: Ni: Al: Ce: 8:5:1:5: 1). The activity evaluation test procedure is the same as that of example 1, the experimental result is shown in FIG. 4, and comparison shows that several catalysts have better reaction activity and conversion rate.
Example 7
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and stirred in a constant temperature magnetic stirrer at a set temperature of 65 ℃. 69.5g of aluminum nitrate nonahydrate, 26.6g of copper nitrate trihydrate, 22g of zinc sulfate heptahydrate, 4.9g of nickel nitrate hexahydrate and 6.2g of cerium nitrate hexahydrate were added to a beaker, and uniformly dissolved with stirring to obtain a metal salt solution. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3The solution is dropwise added into the metal salt solution, the mixing time is controlled to be 1 hour, the temperature of the reaction kettle is controlled to be 65 ℃ through a water bath, the pH value of the suspension is adjusted to be about 9, and then the dropwise addition is stopped. The mixed solution was stirred for 1 h. After stirring is stopped, the precipitate is aged for 2 hours at the constant temperature of 65 ℃, and H is introduced into the suspension in the process2Volume fraction of 10% H2H of (A) to (B)2And N2To obtain mixed precipitation liquid. And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The dried sample was calcined at 550 ℃ for 4 hours in a muffle furnace to obtain a metal oxide catalyst G (Cu: Zn: Ni: Al: Ce: 7:5:1: 5):2). The procedure of the activity evaluation test was the same as in example 1, and the results are shown in FIG. 5.
Example 8
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and heated with stirring in a constant temperature magnetic stirrer set at 65 ℃. 55.6g of aluminum nitrate nonahydrate, 26.6g of copper nitrate trihydrate, 22g of zinc sulfate heptahydrate, 9.9g of nickel nitrate hexahydrate and 6.2g of cerium nitrate hexahydrate were added to a beaker, and uniformly dissolved with stirring to obtain a metal salt solution. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3Dropwise adding the solution into the metal salt solution, controlling the mixing time to be 1 hour, controlling the temperature of the reaction kettle to be 65 ℃ through a water bath, adjusting the pH value of the suspension to be about 9, stopping dropwise adding, and continuously stirring the mixed solution for 1 hour. After stirring is stopped, the precipitate is aged for 2 hours at the constant temperature of 65 ℃, and H is introduced into the suspension in the process2Volume fraction of 10% H2H of (A) to (B)2And N2To obtain mixed precipitation liquid. And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The sample was calcined in a muffle furnace at 550 ℃ for 4H to obtain metal oxide catalyst H (Cu: Zn: Ni: Al: Ce ═ 7:5:2:5: 1). The procedure of the activity evaluation test was the same as in example 1, and the results are shown in FIG. 5. As can be seen from the comparison in fig. 5, higher nickel content can maintain activity and conversion over a greater temperature range.
Comparative example 1
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and stirred in a constant temperature magnetic stirrer at a set temperature of 65 ℃. 83.4g of aluminum nitrate nonahydrate, 30.4g of copper nitrate trihydrate, 26.4g of zinc sulfate heptahydrate were added toAnd stirring and dissolving the mixture uniformly in a beaker. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3The solution is dropwise added into the metal salt solution, the mixing time is controlled to be 1 hour, the temperature of the reaction kettle is controlled to be 65 ℃ through a water bath, the pH value of the suspension is adjusted to be about 9, and then the dropwise addition is stopped. The mixed solution was stirred for 1 h. After stirring is stopped, the precipitate is aged for 2 hours at the constant temperature of 65 ℃, and H is introduced into the suspension in the process2Volume fraction of 10% H2H of (A) to (B)2And N2To obtain mixed precipitation liquid. And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The sample was calcined in a muffle furnace at 550 ℃ for 4 hours to obtain metal oxide catalyst I (Cu: Zn: Al ═ 4:3: 3). The rest of the procedure is the same as in example 1, and the experimental results are shown in FIG. 2.
Comparative example 2
100mL of deionized water was measured and poured into a 2000mL beaker, and a magnetic stir bar was added and stirred in a constant temperature magnetic stirrer at a set temperature of 65 ℃. 30.4g of copper nitrate trihydrate, 31.7g of zinc sulfate heptahydrate and 2.5g of cerium nitrate hexahydrate are added into a beaker and stirred to be dissolved uniformly. 1500mL of deionized water is weighed and added into a 2000mL beaker, a magnetic stirring rod is added, the mixture is stirred and heated in a constant-temperature magnetic stirrer, the temperature is set to be 65 ℃, 157g of anhydrous sodium carbonate is weighed and placed into the beaker, and a sodium carbonate solution is obtained. Heating in water bath at 65 deg.C under stirring with stirring paddle rotating speed of 400r/min, adding Na as precipitant2CO3The solution is dropwise added into the metal salt solution, the mixing time is controlled to be 1 hour, the temperature of the reaction kettle is controlled to be 65 ℃ through a water bath, the pH value of the suspension is adjusted to be about 9, and then the dropwise addition is stopped. The mixed solution was stirred for 1 h. After the stirring is stopped,precipitating and aging at 65 deg.C for 2H, and introducing H into the suspension2Volume fraction of 10% H2H of (A) to (B)2And N2To obtain mixed precipitation liquid. And repeatedly washing and suction-filtering the mixed precipitate for four times by using tap water, wherein the water consumption is 2600ml each time, the stirring time of the first washing is one hour, and the washing time is half an hour later. Wash to pH 7 to 7.3. The filtrate was dried overnight in a constant temperature oven at 100 ℃. The sample was calcined in a muffle furnace at 550 ℃ for 4h to obtain metal oxide catalyst J (Cu: Zn: Ce ═ 50:45: 5). The rest of the procedure is the same as in example 1, and the experimental results are shown in FIG. 2.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the scope of the claims.
Claims (10)
1. A catalyst for catalyzing the dehydrogenation of 1, 4-butanediol, comprising: the catalyst contains metal components of Cu, Zn, Ni, Al and Ce, and the mass ratio of the metal components is (5-12): 3-9): 1-2): 5-7): 0.5-1.
2. The method of claim 1 for preparing a catalyst for catalyzing the dehydrogenation of 1, 4-butanediol comprising the steps of:
(1) dissolving metal salts of copper, zinc, nickel, aluminum and cerium in water, and stirring and dissolving at 60-70 ℃ to obtain a metal salt solution;
(2) adding anhydrous sodium carbonate into deionized water, and stirring and dissolving at 60-70 ℃ to obtain a sodium carbonate solution;
(3) transferring the metal salt solution prepared in the step (1) into a reaction kettle, continuously stirring, controlling the temperature of the reaction kettle to be 60-70 ℃ through a water bath, and then slowly adding the sodium carbonate solution prepared in the step (2) into the reaction kettle; continuously detecting the pH value of the solution in the reaction kettle in the adding process, and stopping dropwise adding when the pH value reaches 8.5-9.5 to obtain a suspension;
(4) continuously stirring the turbid liquid obtained in the step (3), then precipitating and aging at the constant temperature of 65 ℃, and introducing mixed gas of hydrogen and nitrogen into the turbid liquid in the precipitation and aging process to obtain mixed precipitation liquid;
(5) and (4) repeatedly washing and filtering the mixed precipitation solution obtained in the step (4) with water, drying the obtained filtrate in a constant-temperature drying box, and finally roasting in a muffle furnace at 500-550 ℃ for 4-6 h to obtain the metal oxide catalyst.
3. The method for preparing a catalyst for catalyzing dehydrogenation of 1, 4-butanediol according to claim 2, wherein in the step (1): the copper salt is selected from copper nitrate trihydrate, the zinc salt is selected from zinc sulfate heptahydrate, the nickel salt is selected from nickel nitrate hexahydrate, the aluminum salt is selected from aluminum nitrate nonahydrate, and the cerium salt is selected from cerium nitrate hexahydrate.
4. The method for preparing a catalyst for catalyzing dehydrogenation of 1, 4-butanediol according to claim 2, wherein in the step (2): the concentration of the sodium carbonate solution is 0.8-1.2 mol/L.
5. The method for preparing a catalyst for catalyzing dehydrogenation of 1, 4-butanediol according to claim 2, wherein in the step (3): the stirring speed is 200 r/min-400 r/min, and the adding time of the sodium carbonate solution is controlled to be 1-1.5 hours.
6. The method for preparing a catalyst for catalyzing dehydrogenation of 1, 4-butanediol according to claim 2, wherein in the step (4): continuously stirring the suspension for 0.5-1 hour; the precipitation aging time is 2-2.5 hours.
7. The method for preparing a catalyst for catalyzing dehydrogenation of 1, 4-butanediol according to claim 2, wherein in the step (4): the volume ratio of hydrogen in the mixed gas is 10%.
8. The method for preparing a catalyst for catalyzing dehydrogenation of 1, 4-butanediol according to claim 2, wherein in the step (5): the washing and suction filtration times are 3-5 times, the stirring time is more than 40 minutes for the 1 st washing, and the remaining times are more than 20 minutes, so that the pH value after washing is 7-7.3; the drying temperature of the filtrate in the constant-temperature drying oven is 80-100 ℃, and the drying time is 10-12 hours.
9. The application of the catalyst of any one of claims 1 to 8 in the preparation of 1, 4-butyrolactone by catalyzing dehydrogenation of 1, 4-butanediol, specifically comprising the following steps:
filling a catalyst into a fixed bed quartz tube reactor, wherein the pressure is normal pressure, the reaction temperature is 160-230 ℃, a temperature programming controller is adopted for controlling, data is detected every 10 ℃, and the mixed gas of hydrogen and 1, 4-butanediol is used for 1000-2500 h at a volume space velocity-1And (3) introducing the mixture into a quartz tube reactor, wherein the molar ratio of the mixed gas to 1, 4-butanediol (10-25) to 1 is hydrogen.
10. Use of the catalyst of claim 9 for the catalytic dehydrogenation of 1, 4-butanediol to produce 1, 4-butyrolactone, wherein: the reaction temperature is 190-200 ℃.
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Citations (4)
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| CN1139106A (en) * | 1995-06-26 | 1997-01-01 | 中国石油化工总公司 | Preparation of Gamma-butyrolactone |
| US5637735A (en) * | 1994-08-10 | 1997-06-10 | China Petrochemical Corporation | Process for the preparation of gamma-butyrolactone |
| CN102029156A (en) * | 2009-10-07 | 2011-04-27 | Sk能源株式会社 | Process for preparing of [gamma]-butyrolactone and n-methyl pyrrolidone from 1,4-butanediol |
| CN104984751A (en) * | 2015-06-15 | 2015-10-21 | 广西新晶科技有限公司 | Metallic oxide catalyst and preparation method thereof |
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2021
- 2021-11-29 CN CN202111435541.3A patent/CN113996306A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637735A (en) * | 1994-08-10 | 1997-06-10 | China Petrochemical Corporation | Process for the preparation of gamma-butyrolactone |
| CN1139106A (en) * | 1995-06-26 | 1997-01-01 | 中国石油化工总公司 | Preparation of Gamma-butyrolactone |
| CN102029156A (en) * | 2009-10-07 | 2011-04-27 | Sk能源株式会社 | Process for preparing of [gamma]-butyrolactone and n-methyl pyrrolidone from 1,4-butanediol |
| CN104984751A (en) * | 2015-06-15 | 2015-10-21 | 广西新晶科技有限公司 | Metallic oxide catalyst and preparation method thereof |
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