CN109772352B - Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof - Google Patents
Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof Download PDFInfo
- Publication number
- CN109772352B CN109772352B CN201711119047.XA CN201711119047A CN109772352B CN 109772352 B CN109772352 B CN 109772352B CN 201711119047 A CN201711119047 A CN 201711119047A CN 109772352 B CN109772352 B CN 109772352B
- Authority
- CN
- China
- Prior art keywords
- copper
- bismuth
- zinc
- oxide
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title claims abstract description 19
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005470 impregnation Methods 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- GFAWQOJYGFJWNJ-UHFFFAOYSA-N [Bi].[Zn].[Cu] Chemical compound [Bi].[Zn].[Cu] GFAWQOJYGFJWNJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 7
- 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 7
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001621 bismuth Chemical class 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 229910052593 corundum Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and a preparation method and application thereof, wherein the catalyst comprises 40-70 wt% of a carrier, 30-60 wt% of a copper bismuth zinc composite oxide, and the copper bismuth zinc composite oxide is loaded on the carrier, wherein the carrier is at least one of an SBA-15 molecular sieve, alumina, titanium oxide, a molecular sieve, zinc oxide, zirconium oxide and silicon-containing alumina; the preparation method of the catalyst comprises the steps of impregnating a carrier with a solution containing zinc, copper and bismuth, drying and roasting after impregnation to obtain the final catalyst. The catalyst has the advantages of high activity, good long-period running stability, high propiolic alcohol yield and the like, and the preparation method is simple.
Description
Technical Field
The invention relates to a catalyst for preparing 1, 4-butynediol and coproducing propiolic alcohol, a preparation method and application thereof, in particular to a supported catalyst for preparing 1, 4-butynediol and coproducing propiolic alcohol by formaldehyde ethynylation, and a preparation method and application thereof.
Background
The process for industrially producing the 1, 4-butynediol is mainly an acetylenic aldehyde method (Reppe method), and domestic production enterprises such as Shanxi three-dimensional, Sichuan Tianhua, Xinjiang Meike chemical industry, China electric China petrochemical Ningxia energy chemical industry, Xinjiang Tianye, inner Mongolian Guyidong, Sichuan Weini wheel factories and the like all adopt the technology. 70 years of 20 th centuryInstead, a modified Reppe process was developed, using slurry or suspension bed technology, with the reaction being carried out at atmospheric or low pressure. However, the improved Reppe process requires higher catalyst and process operating conditions. In an industrial device, in order to avoid catalyst deactivation, the mass percentage concentration of formaldehyde serving as a reaction raw material is generally lower during reaction, and due to the existence of a large amount of water in a reaction liquid, copper ions on the surface of the catalyst are continuously washed by the water and are easier to wash away by the water. The catalyst used in industry at present has a small amount of Cu in the reaction liquid under normal operation conditions2+There is a slight fluctuation in operating conditions, which results in more Cu2+Loss of Cu not only affecting the activity of the alkyne hydroformylation reaction2+The reaction product flows into a subsequent reaction section and is adsorbed on the surface of the nickel-aluminum alloy catalyst, so that the number of active centers on the surface of the nickel-aluminum alloy is reduced, and the activity of the catalyst is reduced. In addition, the profit of enterprises is reduced continuously due to the continuous reduction of the price of the 1, 4-butynediol in recent years, and the profit of enterprises is increased as the price of the propiolic alcohol is higher due to the continuous increase of the downstream product market, so that the more the propiolic alcohol is co-produced while the 1, 4-butynediol is produced.
US4110249 and US4584418 and CN1118342A disclose unsupported malachite, unsupported copper/bismuth oxide catalysts, respectively, which are not attrition resistant and are prone to metal component loss.
US3920759 and CN102125856A disclose a copper bismuth supported catalyst using zinc silicate and kaolin as carriers, respectively, for catalytic reaction of synthesizing 1, 4-butynediol by the reaction of formaldehyde and acetylene. However, the catalyst has the following defects: (1) the carrier zinc silicate is unstable and can be dissolved in a reaction system, so that the service life is short; (2) the catalyst has more dosage and higher content of metal copper oxide, is easy to agglomerate, cannot fully exert the catalytic effect of each active center, and causes the waste of copper resources.
CN201210157882.3 discloses a copper bismuth catalyst and a preparation method thereof, the steps of which are as follows: dripping alcohol solution of organic silicon source into mixed solution containing copper salt, bismuth salt, zinc salt and dispersant, regulating pH value of the mixed solution with alkali solution to obtain mixed precipitate, further ageing, washing the precipitate with dispersant as medium, and roasting in inert atmosphere. The catalyst has high activity, but has high cost and poor mechanical strength, and is difficult to realize industrialization.
CN20121039739X discloses a catalyst for the production of 1, 4-butynediol and a preparation method thereof, wherein nano-silica is adopted as a carrier, and copper and bismuth are adsorbed on the carrier by a precipitation deposition method. The catalyst prepared by the method has better activity and selectivity, but because urea is used as a precipitator, the reaction process is slow, a large amount of ammonia gas can be generated, and the environmental pollution is caused.
CN103157500A discloses a preparation method of a supported catalyst, which adopts a mesoporous molecular sieve as a carrier, and utilizes an impregnation method to load soluble copper salt and bismuth salt on the carrier, wherein the particle size of the prepared catalyst is 10-80 nanometers. CN103480382A discloses a catalyst for producing 1, 4-butynediol and a preparation method thereof, wherein the method adopts acidified nano-silica as a carrier, copper and bismuth are adsorbed on the carrier by impregnation and deposition precipitation methods, and then the finished product of the catalyst is obtained by drying and roasting. The activity stability of the above catalyst is to be improved.
In summary, the supported catalyst for producing 1, 4-butynediol in the prior art generally has the defects of low activity, especially, the stability of the activity in long-period operation needs to be further improved, and the yield of the propargyl alcohol co-produced while producing 1, 4-butynediol is very small.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a supported catalyst for preparing 1, 4-butynediol and coproducing propiolic alcohol, and a preparation method and application thereof. The catalyst has the advantages of high activity, good long-period running stability, high propiolic alcohol yield and the like, and the preparation method is simple.
The catalyst for preparing the 1, 4-butynediol and the propargyl alcohol is characterized in that the weight content of a carrier is 40-70 wt%, preferably 45-65 wt%, further preferably 55-60 wt%, the content of a copper-bismuth-zinc composite oxide is 30-60 wt%, preferably 35-55 wt%, further preferably 40-45 wt%, the copper-bismuth-zinc composite oxide is loaded on the carrier, the carrier is at least one of an SBA-15 molecular sieve, aluminum oxide, titanium oxide, a molecular sieve, zinc oxide, zirconium oxide and silicon-containing aluminum oxide, preferably silicon-containing aluminum oxide, further preferably silicon-containing aluminum oxide with the silicon content of 25-35%, the copper-bismuth-zinc composite oxide contains 20-60 wt% of copper oxide and 1.0-10.0 wt% of bismuth oxide, 0.5-3.5 wt% of zinc oxide, preferably 25-50 wt% of copper oxide, 2.5-6.5 wt% of bismuth oxide, 1.0-2.5 wt% of zinc oxide, further preferably 30-40 wt% of copper oxide, 4.0-5.0 wt% of bismuth oxide and 1.5-2.0 wt% of zinc oxide.
A method for preparing a catalyst for co-production of 1, 4-butynediol and propargyl alcohol comprises the steps of impregnating a carrier with a solution containing zinc, copper and bismuth, drying and roasting after impregnation to obtain the final catalyst.
In the above method, the zinc in the solution containing zinc, copper and bismuth is derived from zinc salt, and is selected from at least one of zinc nitrate, zinc sulfate and zinc chloride, preferably zinc nitrate. The molar concentration of the zinc salt in the solution is 0.15-0.55 mol/L, preferably 0.25-0.40 mol/L. The copper is derived from copper salt, is selected from at least one of copper sulfate, copper nitrate, copper acetate or copper chloride, and is preferably copper nitrate, and the molar concentration of the copper salt is controlled to be 1.0-8.0 mol/L, and is preferably 2.5-7.0 mol/L; the bismuth is derived from bismuth salt, is selected from at least one of bismuth nitrate, bismuth sulfate and bismuth acetate, and is preferably bismuth nitrate. The molar concentration of the bismuth salt is controlled to be 0.03-0.25 mol/L, preferably 0.05-0.20 mol/L. The pH value of the solution is 0-2.0, preferably 0.5-1.0.
In the above method, the solution containing zinc, copper and bismuth further contains C8F17SO2NH(CH2)3N(CH2COO) Na is marked as C8F17, and the concentration of the C8F17 in the solution is 20-100 g/L, preferably 40-80 g/L. The impregnation liquid containing C8F17 can improve the hydrophobic property of the catalyst and reduce the influence of water on the surface of the catalystAnd the stability of the catalyst in long-period operation is obviously improved.
In the method, the impregnation process adopts one or more times of impregnation, and the specific times of impregnation are determined by a skilled person according to the loading amount. The impregnation can be over-volume impregnation, equal volume impregnation or spray impregnation.
In the above method, when the siliceous alumina is used, the carrier is preferably subjected to impregnation treatment with an acid solution.
In the above method, the impregnation is followed by drying in an oven. The drying temperature is 100-180 ℃, preferably 120-140 ℃. The drying time is 2-8 hours, preferably 3-5 hours; the roasting temperature is 300-550 ℃, and preferably 350-400 ℃. The temperature rise rate of the catalyst is 50-100 ℃/h, preferably 60-80 ℃/h. The roasting time is 2-8 hours, preferably 3-5 hours.
The method for preparing the 1, 4-butynediol and coproducing the propiolic alcohol by using the catalyst comprises the following steps: the reaction temperature is 100-180 ℃, preferably 120-150 ℃, the reaction pressure is 0.5-2.0 MPa, preferably 1.0-1.5 MPa, the flow rate of acetylene is 40-120 ml/min, preferably 60-100 ml/min, the mass concentration of the formaldehyde aqueous solution is 1.0-5%, preferably 2-4%, and the mass-volume ratio of the catalyst to the added formaldehyde aqueous solution is 1: 10-1: 40, preferably 1: 20-1: 30.
The catalyst of the invention loads the copper bismuth zinc composite oxide on the carrier, and because the zinc oxide has a special semiconductor electronic structure, the catalyst can properly capture H dissociated in the reactant in the reaction process in the ethynylation reaction+Thereby inhibiting the further reaction of the propiolic alcohol and improving the selectivity of the propiolic alcohol; in addition, zinc oxide crystal grains are uniformly distributed among the copper microcrystals, so that the stability of the catalyst is improved.
Detailed Description
The technical solutions of the present invention are further illustrated by the following examples and comparative examples, but the scope of the present invention is not limited by the examples. The wear resistance of the catalyst is subjected to ultrasonic treatment by a cell disruptor and then analyzed by a BT-9300ST laser particle size analyzer in Dandongboet, the ultrasonic treatment frequency is 3000 times, and the power of the ultrasonic disruptor is 600W. The evaluation of the reactivity of the catalyst is carried out on a slurry bed, a formaldehyde and acetylene reaction system is adopted, the reaction temperature is 130 ℃, the reaction pressure is 1.0MPa, the acetylene flow rate is 90mL/min, the catalyst dosage is 20g, and the formaldehyde addition with the concentration of 3 wt% is 600 mL. The catalyst reacted for 3 months was discharged from the reactor, washed, and then incinerated at 800 ℃ using a high temperature incinerator, and composition analysis was performed using XRF, and table 3 shows the% loss of copper oxide after 3 months of catalyst operation. The following examples and comparative examples are all% by mass unless otherwise specified.
Example 1
(1) Weighing 450g of Al2O3Dry glue powder (containing 30wt% silicon) was placed in 1800mL containing 18% concentration
Treating in dilute nitric acid solution at 20 deg.c for 4 hr.
(2) And filtering the treated alumina, and then washing the catalyst by using deionized water at the temperature of 30 ℃, wherein the using amount of the washing water is 10L.
(3) The treated alumina was slurried to 37% dry basis and spray dried at 200 ℃.
Then the mixture is placed in a roasting furnace at 700 ℃ for roasting for 4 hours.
(4) 36.4g of zinc nitrate was measured, 700mL of deionized water was added, while 700g of copper nitrate, 60.5g of bismuth nitrate and 58.9g of nitric acid were added, and the temperature was raised to 50 ℃ and dissolved with stirring.
(5) Treated Al2O3Putting into the aqueous solution containing copper, bismuth and zinc, and carrying out one or more times of impregnation.
(6) Impregnating Al2O3Filtering, drying in an oven at 120 deg.C for 3 hr.
(7) The mixture is put into a roasting furnace and is heated to 400 ℃ at the heating rate of 70 ℃/h for 4 hours. And preparing the copper-bismuth supported catalyst. Sample number is a, sample composition is: 38.2% of CuO and Bi2O34.8 percent and 1.8 percent of ZnO. The particle size distribution of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
Example 2
(1) 480g of Al are weighed2O3The dried rubber powder (containing 30wt% of silicon) is put into a roasting furnace at 750 ℃ for roasting for 4 hours.
(2) 38.1g of zinc nitrate is measured, 800mL of deionized water is added, and 715g of copper nitrate, 64.8g of bismuth nitrate, 53.9g of nitric acid and 32gC are added8F17And the temperature was raised to 50 ℃ and dissolved with stirring.
(5) Mixing Al2O3Putting into water solution containing copper, bismuth and zinc and surfactant, and soaking for one or more times. (6) Impregnating Al2O3Filtering, drying in an oven at 120 deg.C for 3 hr.
(7) The mixture is put into a roasting furnace and is roasted for 4 hours at the temperature rising speed of 70 ℃/h to 450 ℃. And preparing the copper-bismuth supported catalyst. Sample number B, sample composition: 31.1% of CuO and Bi2O34.1 percent and 1.5 percent of ZnO. The particle size distribution of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
Example 3
(1) 468g of Al are weighed2O3Dry glue powder (containing 30wt% silicon) was placed in 2000mL containing 15% concentration
Treating in dilute nitric acid solution at 20 deg.c for 4 hr.
(2) And filtering the treated alumina, and then washing the catalyst by using deionized water at the temperature of 30 ℃, wherein the using amount of the washing water is 15L.
(3) The treated alumina was slurried to 33% dry basis and spray dried at 190 ℃.
Then the mixture is placed in a roasting furnace at 730 ℃ for roasting for 4 hours.
(4) 40.0g of zinc nitrate was measured and 800mL of deionized water was added, along with 692g of copper nitrate, 61.3g of bismuth nitrate, 52.9g of nitric acid, and 28g of C8F17And the temperature was raised to 50 ℃ and dissolved with stirring.
(5) Treated Al2O3Putting into the aqueous solution containing copper, bismuth and zinc, and carrying out one or more times of impregnation.
(6) Impregnating Al2O3Filtering, drying in an oven at 120 deg.C for 3 hr.
(7) The mixture is put into a roasting furnace and is roasted for 4 hours at the temperature rising speed of 70 ℃/h to 450 ℃. And preparing the copper-bismuth supported catalyst. Sample number is C, sample composition is: 31.0% of CuO and Bi2O34.0 percent and 1.6 percent of ZnO. The particle size distribution of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
Example 4
(1) Weighing 434g of Al2O3Dry glue powder (containing 30wt% silicon) was placed in 2000mL containing 14% concentration
Treating in dilute nitric acid solution at 20 deg.c for 4 hr.
(2) And filtering the treated alumina, and then washing the catalyst by using deionized water at the temperature of 30 ℃, wherein the using amount of the washing water is 15L.
(3) The treated alumina was slurried to 32% dry basis and spray dried at 200 ℃.
Then the mixture is placed in a roasting furnace at 550 ℃ for roasting for 4 hours.
(4) 43.0g of zinc nitrate was measured and 800mL of deionized water was added, along with 692 copper nitrate, 64.2g of bismuth nitrate, 51.6g of nitric acid, and 30g of C8F17And the temperature was raised to 50 ℃ and dissolved with stirring.
(5) Treated Al2O3Putting into the aqueous solution containing copper, bismuth and zinc, and carrying out one or more times of impregnation.
(6) Impregnating Al2O3Filtering, drying in an oven at 120 deg.C for 3 hr.
(7) The mixture is put into a roasting furnace and is roasted for 4 hours at the temperature rising speed of 70 ℃/h to 450 ℃. And preparing the copper-bismuth supported catalyst. Sample number D, sample composition: 30.2% of CuO and Bi2O34.1 percent and 1.7 percent of ZnO. The particle size distribution of the catalyst is shown in Table 1, and the evaluation results are shown in Table 2.
Comparative example 1
The difference from example 3 is that zinc nitrate was not added in step (4), sample No. E, particle size distribution shown in Table 1, and evaluation results shown in Table 2.
Comparative example 2
The difference from example 3 is that no surfactant is added in step (4), the dilute nitric acid treatment of alumina in step (1) is omitted, sample number is F, particle size distribution is shown in Table 1, and evaluation results are shown in Table 2.
Comparative example 3
A catalyst having the same composition as in example 3 was prepared according to the technical scheme of cn201210397351. x example 1, with sample number G, particle size distribution as shown in table 1, and evaluation results as shown in table 2.
TABLE 1 particle distribution of the catalyst
TABLE 2 evaluation results of initial Activity of catalyst
TABLE 3 copper loss in catalyst (catalyst run 3 months)
Claims (12)
1. A catalyst, characterized by: the catalyst is used for preparing 1, 4-butynediol and propargyl alcohol, and comprises 40-70 wt% of a carrier, 30-60 wt% of a copper bismuth zinc composite oxide, wherein the copper bismuth zinc composite oxide is loaded on the carrier, the carrier is at least one of an SBA-15 molecular sieve, aluminum oxide, titanium oxide, a molecular sieve, zinc oxide, zirconium oxide and silicon-containing aluminum oxide, the copper bismuth zinc composite oxide comprises 20-60 wt% of copper oxide, 1.0-10.0 wt% of bismuth oxide and 0.5-3.5 wt% of zinc oxide.
2. The catalyst of claim 1, wherein: according to the weight content of the final catalyst, the content of the carrier is 45-65 wt%, the content of the copper bismuth zinc composite oxide is 35-55 wt%, the carrier is silicon-containing alumina, and the copper bismuth zinc composite oxide contains 25-50 wt% of copper oxide, 2.5-6.5 wt% of bismuth oxide and 1.0-2.5 wt% of zinc oxide.
3. The catalyst of claim 2, wherein: according to the weight content of the final catalyst, the content of the carrier is 55-60 wt%, the content of the copper bismuth zinc composite oxide is 40-45 wt%, the carrier is silicon-containing aluminum oxide with the silicon content of 25-35 wt%, and in the copper bismuth zinc composite oxide, the content of copper oxide is 30-40 wt%, the content of bismuth oxide is 4.0-5.0 wt%, and the content of zinc oxide is 1.5-2.0 wt%.
4. A process for preparing a catalyst as claimed in any one of claims 1 to 3, characterized in that: impregnating the carrier with a solution containing zinc, copper and bismuth, drying and roasting to obtain the final catalyst.
5. The method of claim 4, wherein: the solution containing zinc, copper and bismuth is characterized in that zinc in the solution is selected from at least one of zinc nitrate, zinc sulfate and zinc chloride, and the molar concentration of the zinc salt in the solution is 0.15-0.55 mol/L.
6. The method of claim 4, wherein: the solution containing zinc, copper and bismuth is characterized in that copper in the solution is selected from at least one of copper sulfate, copper nitrate, copper acetate or copper chloride, and the molar concentration of copper salt is controlled to be 1.0-8.0 mol/L.
7. The method of claim 4, wherein: the solution containing zinc, copper and bismuth is characterized in that bismuth in the solution is selected from at least one of bismuth nitrate, bismuth sulfate or bismuth acetate, and the molar concentration of bismuth salt is controlled to be 0.03-0.25 mol/L.
8. The method of claim 4, wherein: the solution containing zinc, copper and bismuth contains C8F17SO2NH(CH2)3N(CH2COO) Na is marked as C8F17, and the concentration of the C8F17 in the solution is 20-100 g/L.
9. The method of claim 4, wherein: the impregnation process adopts one or more times of impregnation, over-volume impregnation or equal-volume impregnation or spray impregnation.
10. The method of claim 4, wherein: when the silicon-containing alumina is used as the carrier, the carrier is impregnated by using an acid solution.
11. The method of claim 4, wherein: drying at 100-180 ℃ for 2-8 hours after dipping; the roasting temperature is 300-550 ℃, and the roasting time is 2-8 hours.
12. A process for the preparation of 1, 4-butynediol with the co-production of propargyl alcohol using a catalyst according to any one of claims 1 to 3, characterized in that: the reaction temperature is 100-180 ℃, the reaction pressure is 0.5-2.0 MPa, the flow rate of acetylene is 40-120 ml/min, the mass concentration of the formaldehyde aqueous solution is 1.0-5%, and the mass volume ratio of the dosage of the catalyst to the mass volume ratio of the added formaldehyde aqueous solution is 1: 10-1: 40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711119047.XA CN109772352B (en) | 2017-11-14 | 2017-11-14 | Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711119047.XA CN109772352B (en) | 2017-11-14 | 2017-11-14 | Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109772352A CN109772352A (en) | 2019-05-21 |
| CN109772352B true CN109772352B (en) | 2021-08-31 |
Family
ID=66493331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711119047.XA Active CN109772352B (en) | 2017-11-14 | 2017-11-14 | Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772352B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113813978B (en) * | 2021-09-17 | 2022-11-11 | 山西大学 | Nitrogen-doped carbon-coated multi-center synergistic nano-reactor catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989471A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Multi-metal oxide catalyst and preparation method thereof |
| WO2016112455A1 (en) * | 2015-01-13 | 2016-07-21 | British Columbia Cancer Agency Branch | Heterocyclic compounds for cancer imaging and treatment and methods for their use |
-
2017
- 2017-11-14 CN CN201711119047.XA patent/CN109772352B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989471A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Multi-metal oxide catalyst and preparation method thereof |
| WO2016112455A1 (en) * | 2015-01-13 | 2016-07-21 | British Columbia Cancer Agency Branch | Heterocyclic compounds for cancer imaging and treatment and methods for their use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109772352A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109772425B (en) | Supported catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof | |
| WO2018010359A1 (en) | Method for preparing dual-function catalyst and application thereof | |
| CN109772350B (en) | Supported catalyst for co-production of propynol by producing 1, 4-butynediol and preparation method and application thereof | |
| CN106000450A (en) | Preparation method of catalyst for hydrating cyclohexene | |
| CN109772353B (en) | Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method thereof | |
| CN115041188B (en) | Modification method of supported platinum-copper alloy catalyst and application of supported platinum-copper alloy catalyst in propylene preparation by propane dehydrogenation | |
| CN109772352B (en) | Catalyst for preparing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof | |
| CN103043773A (en) | Catalytic wet oxidation method of flue gas desulfurization waste liquor | |
| KR100882016B1 (en) | Catalyst for Dehydrogenation of Cyclohexanol and Method for Preparation Thereof | |
| CN109772351B (en) | Catalyst for producing 1, 4-butynediol and co-producing propiolic alcohol and preparation method and application thereof | |
| CN105642300B (en) | A kind of copper bismuth catalyst preparation method for synthesizing 1,4 butynediols | |
| CN108069827A (en) | A kind of method for preparing 1,4- butynediols coproduction propilolic alcohols | |
| CN114292167B (en) | Preparation method of vanillin | |
| CN108069830B (en) | Method for synthesizing 1, 4-butynediol and coproducing propiolic alcohol by formaldehyde ethynylation | |
| CN106669698B (en) | It is a kind of to be used to synthesize copper bismuth catalyst of 1,4- butynediols and preparation method thereof | |
| CN108069826B (en) | Method for synthesizing 1, 4-butynediol | |
| CN105642301B (en) | A kind of preparation method for being used to synthesize the copper bismuth catalyst of 1,4 butynediols | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
| CN111939919A (en) | Copper-aluminum catalyst for preparing 1, 4-butynediol | |
| CN112264026A (en) | Preparation method of high-activity high-selectivity methanol synthesis catalyst | |
| CN107224976B (en) | Nano catalyst and preparation method thereof | |
| CN105566050A (en) | Method for producing ethylbenzene from ethylene and benzene | |
| CN111097427A (en) | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone | |
| CN112125809B (en) | Method for continuously preparing pentanediamine by decarboxylation of lysine | |
| CN110882689B (en) | Preparation and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231009 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |