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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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 |
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| 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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Families Citing this family (22)
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| 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 |
| CN102875332B (en) * | 2012-10-12 | 2014-08-13 | 隆昌天康精细化工有限公司 | Process for synthesizing 3-hexyne-2,5-diol through slurry bed based on low pressure method |
| CN102950014B (en) * | 2012-10-18 | 2014-04-16 | 大连瑞克科技有限公司 | Catalyst for production of 1,4-butynediol and preparation method of catalyst |
| CN105709757A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for catalyst used for production of 1,4-butynediol |
| CN106669699A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | 1,4-butyne-diol catalyst preparation method |
| CN106669690B (en) * | 2015-11-09 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of copper bismuth catalyst and preparation method thereof and its application in synthesis 1,4- butynediols |
| CN106669692A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation of 1,4-butynediols catalyst and preparation method and application thereof |
| CN106669701A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | 1,4-butyne diol catalyst preparation method |
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| CN106669688B (en) * | 2015-11-09 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of copper bismuth catalyst and its preparation method and application |
| CN106669695A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of copper bismuth silicon catalyst |
| CN105413711A (en) * | 2015-11-20 | 2016-03-23 | 苏英慧 | Regeneration preparing method for supported copper-bismuth catalyst |
| CN107537506B (en) * | 2016-06-23 | 2019-11-15 | 中国石油化工股份有限公司 | Synthesize the catalyst precursor of 1,4- butynediols, by its catalyst synthesized and preparation method thereof |
| CN108069826B (en) * | 2016-11-11 | 2020-11-10 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for synthesizing 1, 4-butynediol |
| CN110876939A (en) * | 2019-11-27 | 2020-03-13 | 大连瑞克科技有限公司 | Catalyst for synthesizing 1, 4-butynediol by reacting formaldehyde with acetylene |
| CN111068692B (en) * | 2019-12-26 | 2022-12-16 | 湖北吉和昌化工科技有限公司 | Catalyst for synthesizing N, N-diethyl propargylamine and preparation method thereof |
| CN111939919A (en) * | 2020-08-25 | 2020-11-17 | 巴斯夫公司 | Copper-aluminum catalyst for preparing 1, 4-butynediol |
| CN113233959B (en) * | 2021-04-19 | 2023-01-24 | 邢彩虹 | BYD reaction and catalyst separation and regeneration method and device |
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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1995
- 1995-07-19 CN CN95108208A patent/CN1052664C/en not_active Expired - Fee Related
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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