CN108067239B - A kind of bulky grain copper bismuth catalyst and its preparation method and application - Google Patents
A kind of bulky grain copper bismuth catalyst and its preparation method and application Download PDFInfo
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- CN108067239B CN108067239B CN201610990988.XA CN201610990988A CN108067239B CN 108067239 B CN108067239 B CN 108067239B CN 201610990988 A CN201610990988 A CN 201610990988A CN 108067239 B CN108067239 B CN 108067239B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- 239000002253 acid Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000032683 aging Effects 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001621 bismuth Chemical class 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 106
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- NMTBZBPWKJALHU-UHFFFAOYSA-N O=C.C#C Chemical group O=C.C#C NMTBZBPWKJALHU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- 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 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910000380 bismuth 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 48
- 239000012670 alkaline solution Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- -1 alkynes aldehyde Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 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
- 239000006193 liquid solution Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- ZLMJMSJWJFRBEC-BJUDXGSMSA-N potassium-38 Chemical compound [38K] ZLMJMSJWJFRBEC-BJUDXGSMSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of preparation method of bulky grain copper bismuth catalyst, comprising the following steps: (1) prepares the acid solution containing mantoquita and bismuth salt；(2) precipitant solution is prepared；(3) bottom water is added into reaction kettle, heating is heated to reaction temperature；(4) precipitant solution of the acid solution of step (1) and step (2) is added drop-wise in reaction kettle by the mode for taking cocurrent；(5) when remaining acid solution is that step (1) prepares the 4/5 ~ 9/10 of acid solution total amount, stop reaction, carry out aging；(6) after aging, continue to react and continue to be passed through gas CO from reactor bottom2；(7) when remaining acid solution is the 1/5-1/10 that step (1) prepares acid solution total amount, the flow for adding water to reaction system is improved；(8) it to after reaction, carry out aging, after aging, washs, filtering.The advantages that catalyst of this method preparation has wearability good, and catalyst particle size is uniformly moderate, activity stability is high, and the yield of propilolic alcohol is high.
Description
Technical field
The present invention relates to a kind of bulky grain copper bismuth catalysts and its preparation method and application, relate in particular to one kind and are used for
Formaldehyde acetylene is combined to the bulky grain copper bismuth catalyst and preparation method thereof of 1,4- butynediols coproduction propilolic alcohol.
Background technique
Industrialized production Isosorbide-5-Nitrae-butynediols technique is mainly acetylene-formaldehyde process (Reppe method), domestic manufacturing enterprise Ru Shan
Western three-dimensional, Sichuan day China, Xinjiang Meike chemical industry, state's electricity Sinopec Ningxia derived energy chemical, Xingjiang Tianye Co., Inner Mongol gouy east, four
Chuan Weinilun factory etc. is all made of such technology.In the 1970s, develop the Reppe method technique of improvement, using slurry bed or
Suspension bed technique, reaction carry out under normal pressure or lower pressure.But Reppe technique is improved to the more demanding of catalyst, is fitted
Closing industrialized particle size should be at 1 ~ 50 μm.The particle size of catalyst is greater than 50 μm, and activity will decline very much, but if
Less than 1 μm, filter relatively difficult.Since 1,4-butanediol price constantly declined in recent years, the profit of enterprise is caused constantly to reduce,
And propilolic alcohol causes it to hold at high price due to the continuous increase in downstream product market, so in production Isosorbide-5-Nitrae-butynediols
While, the more propilolic alcohol of coproduction, the profit of enterprise is bigger.
US4110249 and US4584418 and CN1118342A is individually disclosed with DNAcarrier free malachite, carrier-free
Copper oxide/bismuth oxide catalyst, these catalyst are not wear-resisting, and metal component is easy to be lost.
US3920759 and CN102125856A is individually disclosed to be urged using magnesium silicate, kaolin as the copper bismuth support type of carrier
Agent, for formaldehyde and acetylene reaction synthesis Isosorbide-5-Nitrae-butynediols catalysis reaction.But such catalyst has the disadvantage that
(1) carrier magnesium silicate is unstable, can dissolve in the reaction system, the service life is short；(2) catalyst amount is more, metal copper oxide
Content is higher, easily reunites, and cannot give full play to the catalytic effect in each activated centre, causes the waste of copper resource.
CN201210157882.3 discloses a kind of copper bismuth catalyst and preparation method, and its step are as follows: using organosilicon
The alcoholic solution in source is added drop-wise in the mixed liquor containing mantoquita, bismuth salt, magnesium salts and dispersing agent, and the pH of mixed solution is adjusted with aqueous slkali
Value obtains mixed sediment, through further aging, uses dispersing agent for the washing of medium progress sediment, and use inert atmosphere
It is roasted.The activity of the catalyst is higher, but higher cost, bad mechanical strength, it is difficult to realize industrialization.
CN201210397161.X is disclosed for Isosorbide-5-Nitrae-butynediols production catalyst and preparation method thereof, this method
Use nano silica for carrier, copper and bismuth are adsorbed on carrier by the method to precipitate deposition.The catalysis of the method preparation
Agent has preferable activity and selectivity, but due to using urea for precipitating reagent, reaction process is slower, can generate a large amount of ammonia
Gas causes environmental pollution, and the catalyst granules prepared is smaller, bad filtering.
CN103170342A discloses a kind of nanometer CuO-Bi for synthesizing 1,4- butynediols2O3Catalyst, feature exist
In, proper amount of surfactant and sodium hydroxide solution are separately added into copper bismuth acidic aqueous solution, at a certain temperature pyrolysis system
Standby nanocatalyst.Prepared 10 ~ 80nm of catalyst particle size.The catalyst reaction activity is higher, but due to catalyst
Particle it is small, be used for slurry bed or suspension bed, particle is small, sad filter.And nanometer CuO-Bi2O3Activated centre exposure is more, holds
Easy in inactivation.
CN103157500A discloses a kind of preparation method of loaded catalyst, and this method uses mesopore molecular sieve to carry
Body loads to soluble mantoquita and bismuth salt on carrier using infusion process, and the catalyst particle size of preparation is received for 10 ~ 80
Rice, the catalyst activity is higher, but catalyst granules is too small, sad filter.
CN103480382A disclose it is a kind of produce Isosorbide-5-Nitrae-butynediols catalyst and preparation method thereof, this method uses
Nano silica after acidification is carrier, is adsorbed on copper and bismuth on carrier with dipping and deposition sedimentation method, then does
It is dry, roast to obtain finished catalyst.The catalyst activity of this method preparation is preferable, and intensity is higher.But the catalysis of the method preparation
The particle size uniformity of agent powder is bad, and little particle is more, is unfavorable for the industrial operation of catalyst.
In conclusion production Isosorbide-5-Nitrae-butynediols catalyst is in the prevalence of catalyst particle size discomfort in the prior art
In, the wearability of catalyst and the technical problems such as stability is poor, active component is easy to be lost, and produce Isosorbide-5-Nitrae-butynediols
Meanwhile the yield very little of propilolic alcohol.
Summary of the invention
It is an object of the invention to overcome above-mentioned defect existing in the prior art, a kind of synthesis Isosorbide-5-Nitrae-butynediols is provided
The catalyst of bulky grain copper bismuth catalyst of coproduction propilolic alcohol and preparation method thereof, this method preparation has wearability good, catalysis
The advantages that agent even particle size is moderate, activity stability is high, and the yield of propilolic alcohol is high.
A kind of preparation method of bulky grain copper bismuth catalyst, comprising the following steps:
(1) acid solution containing mantoquita and bismuth salt is prepared；
(2) precipitant solution is prepared；
(3) bottom water is added into reaction kettle, heating is heated to reaction temperature；
(4) precipitant solution of the acid solution of step (1) and step (2) is added drop-wise to reaction by the mode for taking cocurrent
In kettle, gas CO is passed through from reactor bottom in reaction process2；
(5) when remaining acid solution is that step (1) prepares the 4/5 ~ 9/10 of acid solution total amount, stop reaction, carry out
Aging；
(6) after aging, continue to react and continue to be passed through gas CO from reactor bottom2, when remaining acid molten
When liquid is the 1/2-3/5 that step (1) prepares acid solution total amount, deionized water is added to reaction system, flow is acid molten
0.5-1.5 times of liquid and alkaline solution total flow；
(7) it when remaining acid solution is the 1/5-1/10 that step (1) prepares acid solution total amount, improves to reaction system
Add the flow of water, flow is 2-4 times of acid solution and alkaline solution total flow；
(8) it to after reaction, carry out aging, after aging, washs, filtering；
(9) deionized water containing potassium nitrate and calgon is added in filter cake to be spray-dried after mixing evenly
Copper bismuth catalyst is made.
In the method for the present invention step (1), mantoquita in copper sulphate, copper nitrate, copper acetate or copper chloride at least one
Kind, preferably copper nitrate.The molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L, preferably 1.0 ~ 2.5 mol/ in acid solution
L.Bismuth salt is selected from least one of bismuth nitrate, bismuth sulfate or bismuth acetate, preferably bismuth nitrate.Bismuth salt rubs in acid solution
You control in 0.01 ~ 0.05mol/L, preferably 0.02 ~ 0.04mol/L concentration.Acid solution pH value be 0 ~ 2.0, preferably 0.5 ~
1.0。
In step (2) of the present invention, precipitating reagent is selected from sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, ammonium hydroxide, bicarbonate
At least one of sodium, preferably sodium carbonate.The molar concentration of precipitating reagent be 0.1 ~ 3.0 mol/L, preferably 0.5 ~ 2.0
mol/L。
In step (3) of the present invention, be added bottom water into reaction kettle, additional amount be step (1) acid solution volume 0.15 ~
0.4 times, preferably 0.2 ~ 0.3 times.Heating is heated to 30 ~ 80 DEG C of reaction temperature, and optimal is 40~70 DEG C.It is constantly stirred in reaction process
It mixes.
In step (4) of the present invention, acid solution and alkaline solution are added in reaction kettle with certain speed cocurrent, are kept
The pH value of reaction is controlled 5.0~8.0, and optimal is 6.0~7.0, and reaction temperature is controlled at 30 ~ 80 DEG C, and optimal is 40~70 DEG C.
The bottom of reaction kettle is passed through CO2, CO2It is diluted using nitrogen, CO2Concentration be 20%~60%, optimal is 30%~50%.Flow is
150 ~ 1000ml/min, preferably 600 ~ 800ml/min.CO2Concentration is volumetric concentration.
In step (5) of the present invention, aging temperature is controlled at 30 ~ 80 DEG C, and optimal is 40~70 DEG C.The control of aging pH value exists
5.0~8.0, optimal is 6.0~7.0, and ageing time was controlled at 10~70 minutes, optimal 20 ~ 50 minutes.
In step (6) of the present invention, the pH value of reaction is controlled 5.0~8.0, and optimal is 6.0~7.0, reaction temperature control
At 30 ~ 80 DEG C, optimal is 40~70 DEG C.The CO of reaction kettle being passed through2Concentration is 20%~60%, and optimal is 30%~50%.Flow
For 150 ~ 1000ml/min, preferably 350 ~ 450ml/min, CO2Concentration is volumetric concentration.
In step (7) of the present invention, the pH value of reaction is controlled 5.0~8.0, and optimal is 6.0~7.0, reaction temperature control
At 30 ~ 80 DEG C, optimal is 40~70 DEG C.The CO of reaction kettle2Concentration is 20%~60%, and optimal is 30%~50%.Flow be 150 ~
1000ml/min, preferably 150 ~ 250ml/min, CO2Concentration is volumetric concentration.
In step (8) of the present invention, after reaction, ageing time is 0.5~4.0 hour, preferably 1.0~2.5 hours.
It is washed, is filtered using the deionized water of temperature same as aging.
In step (9) of the present invention, the deionized water containing potassium nitrate and calgon is added in filter cake, stirs evenly
Afterwards, it carries out being spray-dried obtained copper bismuth catalyst.Potassium nitrate additional amount is 1%~20% of water quality in slurries, preferably 5%
~15%.The butt of slurry is 15%~45%, preferably 25%~35%.Calgon additional amount is the 5% of catalyst weight
~ 25%, preferably 10% ~ 20%.
A kind of catalyst prepared using the above method, based on the weight of catalyst, the content of copper oxide be 30wt% ~
80wt%, preferably 40wt% ~ 70wt%, the content of bismuth oxide are the wt% of 1.0wt% ~ 10.0, the preferably wt% of 2.5 wt%~6.5,
The particle size of catalyst at least 93% or more is between 10-30um.
Above-mentioned catalyst is combined to Isosorbide-5-Nitrae-butynediols coproduction propilolic alcohol reaction, reaction temperature 80- for formaldehyde acetylene
100 DEG C, reaction pressure 0.5-1.5MPa, acetylene flow be 50-150mL/min, formalin mass concentration be 4% ~
25%, preferably 9% ~ 15%.Catalyst amount be added formalin mass volume ratio be 1:3 ~ 1:10, preferably 1:5 ~
1:7。
In above-mentioned application, diethylene glycol (DEG) can be added into reaction system, additional amount is the formalin quality being added
0.5% ~ 3.5%, preferably 0.8 ~ 2.0%.In alkynes aldehyde reaction, by the way that diethylene glycol (DEG) is added in the reaction system, further improve
The selectivity of propilolic alcohol, and the loss of metal is effectively inhibited, it is able to extend the service life of catalyst, there is good economy
Benefit.
The present invention is added not by several sections of coprecipitation reactions, and in the different phase of coprecipitation reaction into reaction system
The deionized water of same amount keeps the catalyst granules prepared larger to change the degree of supersaturation of reaction product, and is distributed collection
In, excellent wear-resisting property.In alkynes aldehyde reaction, the selectivity of propilolic alcohol can be improved, and effectively inhibit the loss of metal,
It is able to extend the service life of catalyst, it is with good economic efficiency.
Specific embodiment
Technical solution of the present invention is further illustrated below by embodiment and comparative example, but protection scope of the present invention is not
It is limited by example.Again using Dandong after the wear-resisting property of catalyst is ultrasonically treated using cell crushing instrument in the present invention
Hundred special BT-9300ST laser particle analyzer analyses, ultrasonic treatment number is 3000 times, and the power of Ultrasonic Cell Disruptor is 600W.
The reactivity evaluation of catalyst carries out in slurry bed, and using formaldehyde and acetylene reaction system, reaction temperature is 90 DEG C, reaction
Pressure is 0.75MPa, and acetylene flow is 80mL/min, and the formaldehyde additional amount of catalyst amount 30g, concentration 15wt% are
150ml。
Embodiment 1
(1) 715gCu (NO is weighed3)23H2O and 30g Bi (NO3)35H2O is put into the water containing 25g nitric acid, molten to its
2000ml is settled to after solution.
(2) 300 grams of Na are weighed2CO3It is configured to 2000ml solution.
(3) 500ml deionized water is added in a kettle, is stirred and heated to 50 DEG C.
(4) acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.0, reaction
Temperature is 50 DEG C.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow is
500ml/min。
(5) as the acid solution of step (1) 1700 ml of residue, stop reaction, carry out aging, aging condition and reaction
Condition is identical, and ageing time is 30 minutes.
(6) after aging, continue to react, when remaining acid solution is 1000 ml, in acid solution and alkali
Property solution cocurrent while be added, 1200 ml of deionized water is equably added into reaction kettle, the addition speed of water is 50 ml/
min.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, gas flow 400ml/
min。
(7) when remaining acid solution is 400 ml, while acid solution and alkaline solution cocurrent are added, uniformly
2400 ml of deionized water is added into reaction kettle for ground, and the addition speed of water is 150 ml/min.Reaction kettle during the reaction
Bottom, which is passed through, uses N2Diluted CO2, CO2Concentration is 40%, gas flow 200ml/min.
(8) to after reaction, temperature is reduced to 45 DEG C, carries out aging.After aging 1.5 hours, with 45 DEG C of deionizations
Water is washed, washing into cleaning solution without sodium ion in the presence of, stop washing.
(9) filter cake is added in 580 grams of water containing 60g potassium nitrate and 31 grams of calgons, water temperature is controlled 45
DEG C, mashing is uniform to material, and the drying of catalyst is carried out with spray-dried instrument.Sample number into spectrum is A, sample composition are as follows: CuO:
66.0%, Bi2O3:4.0%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 2
(1) 650gCu (NO is weighed3)23H2O and 33g Bi (NO3)35H2O is put into the water containing 25g nitric acid, molten to its
2000ml is settled to after solution.
(2) 300 grams of Na are weighed2CO3It is configured to 2000ml solution.
(3) 600ml deionized water is added in a kettle, is then stirred and heated to 45 DEG C.
(4) acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.5, reaction
Temperature is 45 DEG C.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow is
500ml/min。
(5) as the acid solution of step (1) 1600 ml of residue, stop reaction, carry out aging, aging condition and reaction
Condition is identical, and ageing time is 20 minutes.
(6) after aging, continue to react, when remaining acid solution is 1200 ml, in acid solution and alkali
Property solution cocurrent while be added, 1800 ml of deionized water is equably added into reaction kettle, the addition speed of water is 50 ml/
min.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, gas flow 400ml/
min。
(7) when remaining acid solution is 300 ml, while acid solution and alkaline solution cocurrent are added, uniformly
1800 ml of deionized water is added into reaction kettle for ground, and the addition speed of water is 150 ml/min.Reaction kettle during the reaction
Bottom, which is passed through, uses N2Diluted CO2, CO2Concentration is 40%, gas flow 200ml/min.
(8) to after reaction, temperature is reduced to 40 DEG C, carries out aging.After aging 1.5 hours, with 40 DEG C of deionizations
Water is washed, washing into cleaning solution without sodium ion in the presence of, stop washing.
(9) filter cake is added in 580 grams of water containing 65g potassium nitrate and 30 grams of calgons, water temperature is controlled 45
DEG C, mashing is uniform to material, and the drying of catalyst is carried out with spray-dried instrument.Sample number into spectrum is B, sample composition are as follows: CuO:
60.2%, Bi2O3:4.2%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 3
(1) 956gCu (NO is weighed3)23H2O and 42.5g Bi (NO3)35H2O is put into the water containing 40g nitric acid, to it
2000ml is settled to after dissolution.
(2) 320 grams of Na are weighed2CO3It is configured to 2000ml solution.
(3) 600ml deionized water is added in a kettle, is stirred and heated to 65 DEG C.
(4) acid solution and alkaline solution cocurrent are added in reaction kettle, the pH value for controlling reactant is 6.8, reaction
Temperature is 65 DEG C.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, and gas flow is
500ml/min。
(5) as the acid solution of step (1) 1800 ml of residue, stop reaction, carry out aging, aging condition and reaction
Condition is identical, and ageing time is 25 minutes.
(6) after aging, continue to react, when remaining acid solution is 1000 ml, in acid solution and alkali
Property solution cocurrent while be added, 1200 ml of deionized water is equably added into reaction kettle, the addition speed of water is 50 ml/
min.The bottom of reaction kettle, which is passed through, during the reaction uses N2Diluted CO2, CO2Concentration is 40%, gas flow 400ml/
min。
(7) when remaining acid solution is 400 ml, while acid solution and alkaline solution cocurrent are added, uniformly
2400 ml of deionized water is added into reaction kettle for ground, and the addition speed of water is 150 ml/min.Reaction kettle during the reaction
Bottom, which is passed through, uses N2Diluted CO2, CO2Concentration is 40%, gas flow 200ml/min.
(8) temperature is reduced to 60 DEG C, carries out aging.It after aging 2.0 hours, is washed, is washed with 60 DEG C of deionized waters
Into cleaning solution without sodium ion in the presence of, stop washing.
(9) filter cake is added in 700 grams of water containing 75g potassium nitrate and 38 grams of calgons, water temperature is controlled 60
DEG C, mashing is uniform to material, and the drying of catalyst is carried out with spray-dried instrument.Sample number into spectrum is A, sample composition are as follows: CuO:
55.4%, Bi2O3:3.6%.Size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Embodiment 4
The preparation method of catalyst is shown in Table 1 with embodiment 3, sample number into spectrum D, size distribution.The evaluation condition of catalyst:
30 grams of catalyst are weighed, the formalin 150ml that mass concentration is 15% is added into reactor, the content that diethylene glycol (DEG) is added is
It is added the 10% of formalin quality, is stirred continuously.Acetylene gas is then passed to, gas flow is 80 ml/min, by reactor
Temperature rises to 100 DEG C, and reaction pressure is controlled in 0.75 MPa, is reacted, sampling analysis after reaction 6 hours.The result is shown in
Table 2.
Comparative example 1
There is by the technical solution preparation of CN201210397161.X embodiment 1 with embodiment 3 catalyst of same composition,
Sample number into spectrum is E, and size distribution is shown in Table 1, and evaluation result is shown in Table 2.
Comparative example 2
CO is not passed through in step (4) (6) (7) with 3 difference of embodiment2, sample number into spectrum F, size distribution is shown in Table
1, evaluation result is shown in Table 2.
Comparative example 3
With embodiment 3, the difference is that deionized water is no longer added into reaction kettle during the reaction.Sample number into spectrum
For G, size distribution is shown in Table 1, and evaluation result is shown in Table 2.
The distribution of particles of 1 catalyst of table
The evaluation result of 2 catalyst of table
Claims (13)
1. a kind of preparation method of bulky grain copper bismuth catalyst, it is characterised in that: the following steps are included:
(1) acid solution containing mantoquita and bismuth salt is prepared；
(2) precipitant solution is prepared；
(3) deionized water is added into reaction kettle, heating is heated to reaction temperature；
(4) precipitant solution of the acid solution of step (1) and step (2) is added drop-wise in reaction kettle by the mode for taking cocurrent,
Gas CO is passed through from reactor bottom in reaction process2；
(5) when remaining acid solution is that step (1) prepares the 4/5 ~ 9/10 of acid liquor capacity total amount, stop reaction, carry out
Aging；
(6) after aging, continue to react and continue to be passed through gas CO from reactor bottom2, when remaining acid solution is step
Suddenly when (1) prepares the 1/2-3/5 of acid liquor capacity total amount, deionized water is added to reaction system, flow is acid solution
With 0.5-1.5 times of precipitant solution total flow；
(7) it when remaining acid solution is the 1/5-1/10 that step (1) prepares acid liquor capacity total amount, improves to reaction system
Add the flow of water, flow is 2-4 times of acid solution and precipitant solution total flow；
(8) it to after reaction, carry out aging, after aging, washs, filtering；
(9) deionized water containing potassium nitrate and calgon is added in filter cake, after mixing evenly, carries out spray drying and is made
Copper bismuth catalyst.
2. according to the method described in claim 1, it is characterized by: mantoquita is selected from copper sulphate, copper nitrate, acetic acid in step (1)
At least one of copper or copper chloride, the molar concentration of mantoquita is controlled in 0.6 ~ 3.0mol/L in acid solution, and bismuth salt is selected from
At least one of bismuth nitrate, bismuth sulfate or bismuth acetate, in acid solution the molar concentration control of bismuth salt 0.01 ~
0.05mol/L, acid solution pH value are 0 ~ 2.0.
3. according to the method described in claim 1, it is characterized by: in step (2), precipitating reagent be selected from sodium carbonate, sodium hydroxide,
At least one of potassium carbonate, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, the molar concentration of precipitating reagent are 0.1 ~ 3.0 mol/L.
4. according to the method described in claim 1, it is characterized by: deionized water being added into reaction kettle, adds in step (3)
Enter 0.15 ~ 0.4 times that amount is step (1) acid solution volume, heating is heated to 30 ~ 80 DEG C of reaction temperature.
5. according to the method described in claim 1, it is characterized by: acid solution and precipitant solution cocurrent add in step (4)
Enter into reaction kettle, keep the pH value control of reaction 5.0~8.0, reaction temperature control is at 30 ~ 80 DEG C, the bottom of reaction kettle
It is passed through CO2, CO2It is diluted using nitrogen, CO2Volumetric concentration be 20%~60%, flow be 150 ~ 1000mL/min.
6. according to the method described in claim 1, it is characterized by: in step (5), aging temperature control is at 30 ~ 80 DEG C, aging
5.0~8.0, ageing time was controlled at 10~70 minutes for pH value control.
7. according to the method described in claim 1, it is characterized by: in step (6), the pH value control of reaction 5.0~8.0,
Reaction temperature control is at 30 ~ 80 DEG C, the CO of reaction kettle being passed through2Volumetric concentration is 20%~60%, and flow is 150 ~ 1000mL/
min。
8. according to the method described in claim 1, it is characterized by: in step (7), the pH value control of reaction 5.0~8.0,
Reaction temperature control is at 30 ~ 80 DEG C, the CO of reaction kettle2Volumetric concentration is 20%~60%, and flow is 150 ~ 1000mL/min.
9. according to the method described in claim 1, it is characterized by: in step (8), after reaction, ageing time is 0.5~
4.0 hour.
10. according to the method described in claim 1, containing potassium nitrate and six inclined phosphorus it is characterized by: being added in step (9) filter cake
The deionized water of sour sodium carries out being spray-dried obtained copper bismuth catalyst, potassium nitrate additional amount is water quality in slurries after mixing evenly
The 1%~20% of amount, the butt of slurry are 15%~45%, and calgon additional amount is the 5% ~ 25% of catalyst weight.
11. a kind of catalyst prepared using claims 1 to 10 either method, it is characterised in that: based on the weight of catalyst,
The content of copper oxide is 30wt% ~ 80wt%, and the content of bismuth oxide is the wt% of 1.0wt% ~ 10.0, and the particle size of catalyst is at least
93% or more between 10-30 microns.
12. catalyst described in claim 11 is combined to answering in the reaction of 1,4- butynediols coproduction propilolic alcohol in formaldehyde acetylene
With, it is characterised in that: reaction temperature is 80-100 DEG C, reaction pressure 0.5-1.5MPa, and acetylene flow is 50-150mL/min,
Formalin mass concentration is 4% ~ 25%, and catalyst amount is 1:3 ~ 1:10 with the formalin mass volume ratio being added.
13. application according to claim 12, it is characterised in that: diethylene glycol (DEG) is added into reaction system, additional amount is
The 0.5% ~ 3.5% of the formalin quality of addition.
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| CN102658158A (en) * | 2012-05-20 | 2012-09-12 | 山西大学 | Copper bismuth catalyst and preparation method thereof |
| CN103157500A (en) * | 2013-03-22 | 2013-06-19 | 新疆大学 | Preparation of supported catalyst for 1,4-butynediol |
| CN104069864A (en) * | 2014-07-10 | 2014-10-01 | 山西大学 | Magnetic copper and bismuth catalyst and preparation method thereof |
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| CN105121016A (en) * | 2013-03-15 | 2015-12-02 | 巴斯夫公司 | Novel ethynylation catalyst and method of making same |
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| CN101024195A (en) * | 2007-03-23 | 2007-08-29 | 福建师范大学 | Method for preparing molecular sieve composite oxide catalyst using HZSM5 as carrier and its use |
| CN102125856A (en) * | 2011-01-31 | 2011-07-20 | 华烁科技股份有限公司 | Supported catalyst for use in production of 1, 4-butynediol by Reppe method, preparation method thereof and application thereof |
| CN102658158A (en) * | 2012-05-20 | 2012-09-12 | 山西大学 | Copper bismuth catalyst and preparation method thereof |
| CN103157500A (en) * | 2013-03-22 | 2013-06-19 | 新疆大学 | Preparation of supported catalyst for 1,4-butynediol |
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