CN1052664C - Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof - Google Patents
Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof Download PDFInfo
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- CN1052664C CN1052664C CN95108208A CN95108208A CN1052664C CN 1052664 C CN1052664 C CN 1052664C CN 95108208 A CN95108208 A CN 95108208A CN 95108208 A CN95108208 A CN 95108208A CN 1052664 C CN1052664 C CN 1052664C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 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 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 150000001621 bismuth Chemical class 0.000 claims description 9
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229960004643 cupric oxide Drugs 0.000 claims description 5
- 238000005649 metathesis reaction Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 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
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960003280 cupric chloride Drugs 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
- 239000002245 particle Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000008098 formaldehyde solution Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229940036348 bismuth carbonate Drugs 0.000 description 4
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- -1 alcohol ester Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NWYRNCMKWHKPAI-UHFFFAOYSA-N C(=O)=O.[Na] Chemical compound C(=O)=O.[Na] NWYRNCMKWHKPAI-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 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 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for slurry bed reaction of formaldehyde and acetylene for synthesizing 1, 4-butynediol, which is characterized by no carrier, simple preparation method, high activity and easy regeneration and recycling.
Description
The present invention relates to a kind of production 1, the unsupported catalyst of 4-butynediol, more particularly, it is synthetic 1 to relate to a kind of formaldehyde and acetylene of can be used for, the unsupported catalyst of the slurry-bed reaction of 4-butynediol.
1, the 4-butynediol is a kind of at widely used industrial chemicals of industry such as chemical industry, medicine and plating, by its hydrogenation make 1, the 4-butyleneglycol is to produce mutual-phenenyl two acid bromide two alcohol ester (PBT), urethane (PU), tetrahydrofuran (THF) (THF) and the gamma-butyrolactone (important source material of Chemicals such as γ-BL).As far back as the forties initial stage, just having occurred with formaldehyde and acetylene is raw material, and fixed bed high pressure Rui Bofa (REPPE) is synthetic 1, the technology of 4-butynediol, use be the alkynes copper catalyst that loads on the carrier.This catalyzer manufacturing processed is long, technical sophistication, and work-ing life is short, changes difficulty, be difficult for reclaiming, and reaction is in pressurization (0.5MPa) operation down, has increased the danger of acetylene pressurized blast.
Succeed in developing again behind the seventies novel synthetic 1, the catalyzer of 4-butynediol, this granules of catalyst is little, and is active high, and improved operational condition, makes 1, the synthetic technology of 4-butynediol improves to some extent.This type of catalyzer generally is to be the copper bismuth catalyst of carrier with aluminum oxide, silica gel, Magnesium Silicate q-agent, malachite, activated carbon, float stone, diatomite etc.For example: U.S. Pat 39920759 discloses a kind of synthetic 1 by formaldehyde and acetylene, the supported catalyst of 4-butynediol, and this catalyzer is carrier with the Magnesium Silicate q-agent, and the content of copper is 5～20% in the catalyzer, and the content of bismuth is 0～3%.There is following shortcoming in this catalyzer, and (1) because the existence of carrier is unfavorable for the regeneration and the recycling of catalyzer, the life-span is shorter; (2) preparation method's more complicated.
The objective of the invention is to overcome the defective that exists in the above-mentioned prior art, provide a kind of formaldehyde and acetylene of being used for synthetic 1, the slurry-bed reaction of 4-butynediol active higher, be convenient to the unsupported catalyst for preparing and reclaim.
Catalyzer of the present invention is the mixture of a kind of cupric oxide and bismuth oxide, and the weight ratio between copper and the bismuth is 100: 1～100: 40, and its preparation method is as follows:
(1) with distilled water water miscible mantoquita and bismuth salt are made the aqueous solution respectively, in metal, the weight percent concentration of solution is 1～35%;
(2) with distilled water water miscible carbonate being made weight percent concentration is 5～25% the aqueous solution;
(3) replacement(metathesis)reaction is carried out in copper salt solution, bismuth salts solution and the carbonate solution mixing of above-mentioned preparation, generate precipitation.
(4) with throw out washing, dry, calcining, obtain catalyzer.
Above-mentioned mantoquita can be a kind of of any water miscible mantoquita, or their mixture, and for example: cupric chloride, copper sulfate, cupric nitrate etc. are best with cupric nitrate.
Above-mentioned bismuth salt can be a kind of of any water miscible bismuth salt, or their mixture, and for example: bismuth chloride, bismuth sulfate, Bismuth trinitrate, Bismuth carbonate etc. are best with Bismuth trinitrate.
Above-mentioned carbonate can be a kind of of any water miscible alkaline carbonate or alkali metal hydrocarbonate, or their mixture, for example: yellow soda ash, sodium bicarbonate etc.
Above-mentioned copper and the weight ratio between the bismuth are 100: 1～100: 40, are preferably 100: 4～100: 25, are preferably 100: 8～100: 18.The weight percent concentration of above-mentioned mantoquita and bismuth salt brine solution (in metal) is 1～35%, is preferably 5～30%, is preferably 23～27%.
The weight percent concentration of above-mentioned carbonate aqueous solution is 5～25%, is preferably 7～15%, is preferably 10～12%.
Above-mentioned soluble copper salt, bismuth salt and carbonate carry out replacement(metathesis)reaction, generate the mixed precipitation of copper carbonate and Bismuth carbonate, and precipitated solid is told from solution, obtains thick copper carbonate and Bismuth carbonate.Precipitation process can adopt discontinuous or continous way operation.In the discontinuous operation, two kinds of solution can any order add together, but should carry out under good agitation condition, and the replacement(metathesis)reaction temperature is controlled at 15～55 ℃, is preferably 20～50 ℃, and the best is 40～45 ℃.The pH value that reaction ends should be controlled at 6.5～7.5, is preferably 6.8～7.2.And in continous way operation, except control and temperature and pH value identical during above-mentioned discontinuous is operated, should note keeping the pH value approximately constant of reaction system constantly, change and will in time adjust.
The particle diameter of wherein said catalyzer is 1-180 μ.
Copper carbonate that makes as stated above and Bismuth carbonate throw out can filter from reaction solution immediately after precipitation process is finished and tell, and place a few hours and separate but be preferably in, and can preferably should not be less than 2 hours storage period between 1～8 hour.
The carbonate deposition of telling from solution is used water purification and deionized water wash successively, removes water-soluble impurity, and the bath water temperature control is preferably used 40～50 ℃ hot water between normal temperature to 80 ℃.
Filter cake after the washing can take any form to carry out drying, calcining then, and the incinerating temperature is controlled at 200～800 ℃, is preferably 300～600 ℃, and the best is 400～500 ℃.After calcining, obtain black or little brownish black meal, promptly obtain unsupported catalyst.Activated processing earlier when this catalyzer uses.So-called activation treatment is dispersed in catalyzer in the formaldehyde solution exactly, blasts acetylene then, makes cupric oxide generate the alkynes copper complex with catalytic activity.
Activation treatment can synthesize 1 at acetylene and formaldehyde, and carry out in the original place in the reactive system of 4-butynediol, also can carry out in other containers.Concrete method is: in the reactor with stirring and condensing works, add the formaldehyde solution of 5～45% concentration, preferably use the formaldehyde solution of 8～15% concentration.Then, put into non-activated catalyzer, start stirring, feed and be mixed with 20～30%N
2, and begin reactant is heated.When the temperature of reaction solution was raised to 70 ℃, the control heat-up rate made temperature be controlled between 1～15 hour by 70 ℃ of times that are elevated to 90 ℃, preferably is no less than 7 hours.Then 90 ℃ of constant temperature 4～6 hours.The acetylene tolerance that feeds in reactor should guarantee enough excessive, at this moment tail gas can return a part as unstripped gas, and along with the lengthening in reaction times, acetylene content progressively improves in the gas, when temperature reached 90 ℃, activation was with not mixing other rare gas element again in the acetylene gas.
Catalyst activated is told from solution, gives over to synthesize 1, the catalyzer of 4-butynediol.The catalyzer that has activated has inflammable and explosive character, can not do drying treatment, also not before use the shelf time long.
Unsupported catalyst of the present invention is mainly used in formaldehyde and acetylene synthesizes 1, the slurry-bed reaction of 4-butynediol.Cupric oxide in the catalyzer and formaldehyde and acetylene reaction generate the alkynes copper complex; to acetylene and formaldehyde synthetic 1; the 4-butynediol plays katalysis; the main effect of bismuth oxide then is that issuable acetylene polymerization is paid reaction in the inhibited reaction process; so not only protect the stability of catalyzer, and can also reduce the consumption of acetylene and the generation of impurity.During application, the formaldehyde concentration that is weight percentage is 5～45% the aqueous solution, and the weight ratio of catalyzer and formaldehyde solution is 1: 6～1: 25.The temperature of building-up reactions is 75～105 ℃, and the pressure of building-up reactions is normal pressure or pressurization.
Unsupported catalyst of the present invention compared with prior art has the following advantages:
1, unsupported catalyst of the present invention, consumption is few, and is active high, and normal pressure or pressurization operation down all can obtain good reaction result.Simultaneously, catalyzer can use repeatedly, is easy to replenish and change.
2, unsupported catalyst of the present invention can be operated under normal pressure, has reduced the acetylene pressurized widely and has decomposed the danger that causes blast.
3, unsupported catalyst of the present invention owing to there is not carrier, is easy to regeneration and recycles, and this just makes the cost of catalyzer reduce greatly, and recovery cost only is 1/4～1/5 of a raw catalyst.Simultaneously, the recovery of catalyzer has also reduced the pollution of alkynes copper.
4, unsupported catalyst of the present invention for the scope of application broad of the concentration of raw material formaldehyde solution, is convenient to industrial applying.
5, unsupported catalyst of the present invention can be used for batch reaction system, also can be used for the continuous reaction system.
Embodiment
Example 1: the copper nitrate solution 590g of cupric 13.6%, the bismuth nitrate solution 126g and the distilled water 45g of bismuth-containing 11.2% are mixed.Take by weighing the 1000g weight percent concentration and be 10% Carbon Dioxide sodium water solution and put into beaker, under agitation drip the solution of above-mentioned cupric, bismuth, be neutral pH=7 to solution and stop.The elimination mother liquor, precipitation obtains catalyzer with distilled water wash, drying, calcining.
After above-mentioned catalyzer is activated, get catalyzer 9g, in agitated bed, estimate.The formalin 200g of adding 36% feeds enough acetylene, and normal pressure, 90 ℃ of following reactions 8 hours, the transformation efficiency of formaldehyde is 76.3%.
Example 2: the mixing solutions of the Bismuth trinitrate of the cupric nitrate of cupric 14.4% and bismuth-containing 2.5%, be added to continuously by a certain percentage in the 500ml reactor with 10～15% sodium carbonate solutions, reaction solution continuously outflows under violent stirring, control pH value=7.Reaction solution is placed after-filtration and is separated, and precipitation obtains catalyzer with distilled water wash, drying, calcining.After this catalyzer is activated, in 7 liters of stirring tanks through three sections reactions, the add-on of catalyzer is 10% of a formaldehyde solution, 90 ℃ of temperature of reaction, and normal pressure feeds acetylene down, 20～22 hours residence time, 30～32% formaldehyde is transformed more than 98%, 1, the selectivity of 4-butynediol is greater than 96%, space-time yield is 5～5.5Kg1,4-butynediol/Kg catalyzer sky.
Example 3: in having 300 milliliters of glass reactors of agitator and condenser, the catalyzer 15g that adds 36% formaldehyde solution 135g and example 1 preparation, under normal pressure, 90 ℃ the reaction 7 hours, tell solid catalyst after the cooling, reaction soln is carried out (gas-chromatography) to be analyzed, formaldehyde 3.7%, formic acid 0.2%, 1,4-butynediol 40.96%, propiolic alcohol 1.2% and impurity 0.1%.Calculate formaldehyde transformation efficiency 85.7%, generate 1,4-butynediol selectivity 97.4%, space-time yield 13.7kg product/kg catalyzer sky.
Example 4: the catalyzer that on example 3 described devices, adds different amounts, be respectively 4.67%, 6.47%, 7.68% and 9.9% catalyzer of formaldehyde solution weight, under same reaction conditions, the formaldehyde transformation efficiency is respectively 72.4%, 86.8%, 91.1% and 97.6%.
Example 5:1,4-butynediol synthetic reaction device and reaction conditions are with example 3, change temperature of reaction, under 80 ℃, 85 ℃, 90 ℃ and 95 ℃, react, the transformation efficiency of formaldehyde is respectively 62.9%, 72.5%, 73.4% and 75.7%, and impurity is respectively 0,0.1%, 0.2% and 0.3%.
Claims (8)
1. produce 1 for one kind, the unsupported catalyst of 4-butynediol is to be main active constituent with cupric oxide, it is characterized in that: this catalyzer carrier free;
Wherein said unsupported catalyst is the mixture of cupric oxide and bismuth oxide, and the weight ratio between copper and the bismuth is 100: 1-100: 40.
2. unsupported catalyst according to claim 1 is characterized in that: the particle diameter of catalyzer is 1-180 μ.
3. the preparation method of the described unsupported catalyst of claim 1 is as follows:
(1) with distilled water water miscible mantoquita or bismuth salt are made the aqueous solution respectively, in metal, the weight percent concentration of solution is 1-35%;
(2) with distilled water water miscible carbonate is made the aqueous solution that weight percent concentration is 5-25%;
(3) replacement(metathesis)reaction is carried out in copper salt solution, bismuth salts solution and the carbonate solution mixing of above-mentioned preparation, generate precipitation;
(4) with throw out washing, dry, calcining, obtain catalyzer.
4. method according to claim 3 is characterized in that: described mantoquita is selected from a kind of of cupric chloride, copper sulfate, cupric nitrate, or their mixture.
5. method according to claim 3 is characterized in that: described bismuth salt is selected from a kind of of bismuth chloride, bismuth sulfate, Bismuth trinitrate, or their mixture.
6. method according to claim 3 is characterized in that: described carbonate is alkaline carbonate or alkali metal hydrocarbonate.
7. method according to claim 3 is characterized in that: the temperature of described replacement(metathesis)reaction is 15-55 ℃, and the final pH value of reaction is 6.5-7.5.
8. claim 1 or one of 2 described catalyzer are synthetic 1 at formaldehyde and acetylene, the application in the slurry-bed reaction of 4-butynediol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95108208A CN1052664C (en) | 1995-07-19 | 1995-07-19 | Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95108208A CN1052664C (en) | 1995-07-19 | 1995-07-19 | Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1118342A CN1118342A (en) | 1996-03-13 |
| CN1052664C true CN1052664C (en) | 2000-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95108208A Expired - Fee Related CN1052664C (en) | 1995-07-19 | 1995-07-19 | Unsupported catalyst for producing 1, 4-butynediol and preparation method and application thereof |
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| CN (1) | CN1052664C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19924020A1 (en) * | 1999-05-26 | 2000-11-30 | Basf Ag | Process for the preparation of alkynediols |
| CN102125856B (en) * | 2011-01-31 | 2012-11-28 | 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 |
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| US4110249A (en) * | 1976-08-05 | 1978-08-29 | E. I. Du Pont De Nemours And Company | Preparation of bismuth modified spheroidal malachite |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110249A (en) * | 1976-08-05 | 1978-08-29 | E. I. Du Pont De Nemours And Company | Preparation of bismuth modified spheroidal malachite |
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| CN1118342A (en) | 1996-03-13 |
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