CN1695802A - Preparing alcohol catalyst through adding hydrogen to aldehyde in gas phase of Cu-Zn series and its prepn. process - Google Patents
Preparing alcohol catalyst through adding hydrogen to aldehyde in gas phase of Cu-Zn series and its prepn. process Download PDFInfo
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- CN1695802A CN1695802A CN 200510013552 CN200510013552A CN1695802A CN 1695802 A CN1695802 A CN 1695802A CN 200510013552 CN200510013552 CN 200510013552 CN 200510013552 A CN200510013552 A CN 200510013552A CN 1695802 A CN1695802 A CN 1695802A
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Abstract
A CuZn-series hydrocatalyst for preparing alcohol from gas-phase aldehyde features high activity and thermal stability, and large specific surface area. Its preparing process features use of the two-step neutralizing and the special metallic element for modifying it.
Description
Technical field the present invention relates to catalyst technical field, is a kind of adding hydrogen to aldehyde in gas phase of Cu-Zn series catalyst for preparing alcohol and preparation method thereof.
Background technology aldehyde hydrogenation system alcohol is the technology of relatively knowing at present, and the aldehyde hydrogenation generally is to realize in the presence of hydrogenation catalyst.The catalyzer of relatively selecting the superior at present is copper-zinc system catalyst or its improved system of producing with coprecipitation method.From the aqueous solution of soluble copper salt and zinc salt, adopt the subsalt of alkali precipitation agent co-precipitation copper zinc, obtain mixed oxide through calcination process again.Disclosed employing yellow soda ash is made the subsalt that precipitation agent co-precipitation from the aqueous solution of soluble copper salt and zinc salt obtains copper zinc in U.S. Pat 4762817, roasting in 287～371 ℃ of following air atmospheres, and compression molding makes catalyzer again.This preparation method sprays into step realization in the yellow soda ash to mantoquita and zinc solution, and the physical structure of catalyst Precursors is more single, and does not introduce auxiliary agent and handle, and by-products content is than higher in the product.In U.S. Pat 31926129, with being selected from one or more basic metal in sodium, potassium, lithium, the caesium and a kind of modified catalyst parent in cobalt, nickel and their mixture, reduced the generation of by product effectively, but the realization of its process is to prepare catalyst Precursors earlier, carries out modification again.In Chinese patent ZL9812047.3, the contriver replaces the alkali precipitation agent with organic acid, has saved water washing process, and the copper zinc precipitation structure of realization is single, the preparation good reproducibility.But because method is limit, copper zinc yield has problems, and product cost is higher.
Summary of the invention the present invention at first is in optimizing and technology, directly introduces in addition modification of auxiliary agent in N-process, prepares the catalyst process process and realizes that easily the catalyzer target product yield of preparation obviously improves.And properties-correcting agent is common plain metal salt, and cost is lower, and does not have the secondary pollution problem substantially.
The present invention is a kind of catalyzer of adding hydrogen to aldehyde in gas phase of Cu-Zn series system alcohol, and being characterized as with catalyst weight per-cent is benchmark, comprises that cupric oxide is 25～55%, and zinc oxide is 40～70%; The weight ratio of cupric oxide and zinc oxide is 1: 1～1: 5; The auxiliary agent that adds is a kind of or combination that is selected from Mg, Ca, Mn, the Al ion, and content counts 0.8～10.0% with ion; The BET specific surface area is 30～80m
2/ g, pore volume are 0.15～0.30cm
3/ g, mean pore size is 15～30nm.
The present invention also provides a kind of Preparation of catalysts method of adding hydrogen to aldehyde in gas phase of Cu-Zn series system alcohol, is characterised in that through following steps:
Obtain certain density copper, zinc solution with sour dissolved copper, zinc; The concentration of copper salt solution counts 8～15% with the cupric oxide weight percent; The concentration of zinc solution counts 9～20% with the zinc oxide weight percent; Get 1/5th to 1/4th of total zinc solution amount, in the ion addition is 0.8～10.0% of catalyzer total amount, mix with the nitrate solution a kind of or combination in Mg, Ca, Mn, the Al ion, under agitation with alkali precipitation agent and stream neutralization, co-precipitation, aging, solid-liquid separation obtains filter cake.
Mix with copper salt solution with remaining zinc solution, do precipitation agent with water soluble alkali solution, cocurrent adding material, in pH7.5～9.0,70～90 ℃ of following co-precipitation of temperature, aging, solid-liquid separation obtains filter cake.Two filter cakes that obtain of step are mixed, 40～60 ℃ of making beating washings down, solid-liquid separation, oven dry, at 350～400 ℃, roasting in 6～9 hours, catalyst Precursors.Make releasing agent with graphite, moulding on tablet machine gets the catalyzer finished product.
As preferable range of the present invention, it is characterized in that described aldehyde hydrogenating catalyst, be benchmark with catalyst weight per-cent, comprise cupric oxide 25～35%, zinc oxide is 60～65%, and the weight ratio of cupric oxide and zinc oxide is 1: 1.2～1: 3, and the BET specific surface area is 40～60m
2/ g, pore volume are 0.18～0.26cm
3/ g, mean pore size is 17～25mm.Auxiliary agent is a kind of or combination in Mg, Ca, Mn, the Al ion, and content is 1.0%～7.5%.
As preferable range of the present invention, it is characterized in that the preparation method of described aldehyde hydrogenating catalyst, the process following steps:
Obtain certain density copper, zinc solution with sour dissolved copper, zinc; The concentration of copper salt solution counts 10～13% with the cupric oxide weight percent; The concentration of zinc solution counts 11～18% with the zinc oxide weight percent; Get 1/5th to 1/4th of total zinc solution amount, in the ion addition is 1～7.5% of catalyzer total amount, mix with the nitrate solution a kind of or combination in Mg, Ca, Mn, the Al ion, under agitation with alkali precipitation agent and stream neutralization, co-precipitation, aging, solid-liquid separation obtains filter cake.
Mix with copper salt solution with remaining zinc solution, do precipitation agent with water soluble alkali solution, cocurrent adding material, in pH8～8.5,75～85 ℃ of following co-precipitation of temperature, aging, solid-liquid separation obtains filter cake.Two filter cakes that obtain of step are mixed, 45～55 ℃ of making beating washings down, solid-liquid separation, oven dry, at 350～370 ℃, roasting in 7～8 hours, catalyst Precursors.Make releasing agent with graphite, moulding on tablet machine gets the catalyzer finished product.
Characteristics of the present invention are: the one, N-process realizes in two steps, per step all with two kinds of solution in parallel header tank and stream add insulation and stir in and precipitate in the still; The 2nd, in N-process, directly introduced Mg, Mn, Ca, the Al ion makes it modification.The present invention has improved activity of such catalysts, selectivity and thermostability, has effectively reduced the generation of by product.Compared with prior art, the present invention has optimized N-process, and in N-process, introduce Mg, modification ion such as Mn, Ca, Al improved activity of such catalysts and selectivity.And copper zinc yield height in the N-process.
The principal reaction condition of adding hydrogen to aldehyde in gas phase:
Hydrogen aldehyde mol ratio 15～30, temperature of reaction are on the dew point of feed materials aldehydes, and generally at 120～260 ℃, more than 120 ℃, octenal is more than 150 ℃ as butyraldehyde, and reaction pressure is generally 0.3MPa～0.6MPa.Because the aldehyde hydrogenation is a strong exothermal reaction, the reaction solution air speed should be controlled at 1.0h
-1Below, that commonly used is 0.2～0.5h
-1
Catalyzer needs prereduction before use, reduction is preferably in the hydrogen atmosphere of allocating volume ratio 2～10% in the nitrogen into to be carried out, and strict control heat-up rate, and reduction temperature will carry out under 200 ℃～250 ℃, the highlyest be no more than 280 ℃, be preferably in 205～215 ℃ and carry out.
Reaction should be adopted the continuous charging mode, and aldehyde gasification back enters on the catalyzer of the present invention with hydrogen, and is timely for preventing temperature runaway and heat exchange, preferably adopts and splits tubular reactor.
Embodiment further specifies this patent below by embodiment.
Embodiment 1
This example is prepared reference catalyst with the method for US4876402.
The solution of 417 gram copper (adding with the cupric nitrate form) and 858 gram zinc (with the adding of zinc nitrate form) are heated to about 43 ℃ for 16 liters, spray into and be in mechanical stirring and constant temperature in the sodium carbonate solution of 60 ℃ 15.7% (weight).The last pH value of precipitation mixture is 7.9～8.5.After precipitation, copper zinc subcarbonate is filtered, with 37.8～48.8 ℃ deionized water making beating washing, filter so repeatedly, pull an oar and wash four times then, make that the sodium content in the filter cake after the roasting reduces to 0.1～0.15% (weight).Drying, roasting, the mixture of cupric oxide, zinc oxide, catalyst Precursors and an amount of graphite are mixed, compression molding, reduction is at last handled and is promptly got reference catalyst.
Embodiment 2
Nitric acid dissolve copper must contain 450 ml solns of cupric oxide 40.7 grams, must contain 900 ml solns of zinc oxide 100.7 grams with nitric acid dissolve zinc.Get 180 milliliters of zinc nitrate solutions and mix with 5.2 gram magnesium nitrates, 41 gram aluminum nitrate aqueous solutions, with the sodium carbonate solution of 15.7% weight 75 ℃～85 ℃ and stream neutralization, keep the pH value 7.9～8.5,60 ℃ of aging half an hour, solid-liquid separation gets filter cake 1; Remaining zinc solution mixes with copper salt solution, and sodium carbonate solution same and 15.7% weight also flows neutralization at 75 ℃～85 ℃, keeps the pH value 7.9～8.5, and 60 ℃ of aging half an hour, solid-liquid separation gets filter cake 2.Two kinds of filter cakes are mixed, making beating washing quadruplication in 45～60 ℃ of water, with filtration cakes torrefaction, 350 ℃, roasting in 9 hours adds the graphite compression molding and gets catalyzer.
Embodiment 3
Copper zinc feed ratio is with example 2, and introducing auxiliary agent is manganous nitrate and aluminum nitrate, and add-on is respectively 5.8 grams and 25 grams, and the preparation method is with embodiment 2, but at 400 ℃, roasting in 6 hours adds the graphite compression molding and gets catalyzer.
Embodiment 4
Be respectively 85 grams and 193 nitrate solutions that restrain in order to cupric oxide, zinc oxide content, introduce magnesium nitrate and aluminum nitrate, dosage is 10 grams, and the preparation method is with example 2.
Embodiment 5
Copper zinc charging capacity is only introduced magnesium nitrate with example 2, and dosage is 15 grams, and all the other preparation methods are with example 3, but at 370 ℃, roasting in 7.5 hours.
Each catalyzer physical index of example 1～5 preparation is listed in table 1
| Embodiment | Specific surface area, m 2/g | Pore volume, cm 3/g | Mean pore size, nm | Side pressure strength (N/cm) |
| ????1 | ?????40.4 | ?????0.17 | ?????16.8 | ???????156 |
| ????2 | ?????46.3 | ?????0.22 | ?????19.3 | ???????176 |
| ????3 | ?????45.8 | ?????0.20 | ?????17.8 | ???????173 |
| ????4 | ?????41.6 | ?????0.21 | ?????20.1 | ???????174 |
| ????5 | ?????53.8 | ?????0.24 | ?????18.1 | ???????173 |
Embodiment 6
This routine comparing embodiment 1 and 2,3,4,5 hydrogenation of n-butyraldehyde performance.
Estimate on 20 milliliters of fixed-bed reactor evaluating apparatus, reductive condition is: hydrogen reducing, and 205 ℃ of reduction temperatures, 6 hours recovery times, reduction finishes to lower the temperature with nitrogen.Appreciation condition is: 125 ℃ of feeding temperatures, hydrogen and butyraldehyde volume ratio are 5000: 1, reaction velocity 0.5h
-1, reaction pressure is 0.4MPa.From cold-trap, collect separating liquid, the employing helium is carrier gas, is stationary liquid with poly-ethanol nonyl phenylate, is stationary phase with the female Sha Bai w of chromium (chromosorb w), with the thermal conductivity cell is the gas chromatograph analysis of identifier, calculates the relative content of each component in the product with area normalization method.
The results are shown in table 2
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 |
| Transformation efficiency, weight % | ????98.1 | ????99.9 | ????99.7 | ????99.6 | ????99.3 |
| The propyl carbinol selectivity, % | ????98.9 | ????99.7 | ????99.4 | ????99.5 | ????99.1 |
Embodiment 7
This routine comparing embodiment 1 and 2,3,4,5 octenal hydrogenation performance.
Testing sequence is identical with embodiment 6.Raw material is industrial octenal, 160 ℃ of feeding temperatures.
Reaction pressure: 0.5MPa; Air speed 0.30h
-1Hydrogen-aldehyde rate: 28: 1 (mol).
The results are shown in table 3
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 |
| Transformation efficiency, weight % | ????99.5 | ????100 | ????99.9 | ????99.7 | ????99.8 |
| The octanol selectivity, % | ????98.6 | ????99.9 | ????99.5 | ????99.3 | ????99.4 |
Claims (4)
1. the catalyzer of an adding hydrogen to aldehyde in gas phase of Cu-Zn series system alcohol, being characterized as with catalyst weight per-cent is benchmark, comprises that cupric oxide is 25～55%, zinc oxide is 40～70%; The weight ratio of cupric oxide and zinc oxide is 1: 1～1: 5; The auxiliary agent that adds is a kind of or combination that is selected from Mg, Ca, Mn, the Al ion, and content counts 0.8～10.0% with ion; The BET specific surface area is 30～80m
2/ g, pore volume are 0.15～0.30cm
3/ g, mean pore size is 15～30nm.
2. the Preparation of catalysts method of an adding hydrogen to aldehyde in gas phase of Cu-Zn series system alcohol is characterised in that through following steps:
Obtain certain density copper, zinc solution with sour dissolved copper, zinc; The concentration of copper salt solution counts 8～15% with the cupric oxide weight percent; The concentration of zinc solution counts 9～20% with the zinc oxide weight percent; Get 1/5th to 1/4th of total zinc solution amount, in the ion addition is 0.8～10.0% of catalyzer total amount, mix with the nitrate solution a kind of or combination in Mg, Ca, Mn, the Al ion, under agitation with alkali precipitation agent and stream neutralization, co-precipitation, aging, solid-liquid separation obtains filter cake;
Mix with copper salt solution with remaining zinc solution, do precipitation agent with water soluble alkali solution, cocurrent adding material, in pH7.5～9.0,70～90 ℃ of following co-precipitation of temperature, aging, solid-liquid separation, obtain filter cake, the filter cake that two steps were obtained mixes, 40～60 ℃ of making beating washings down, solid-liquid separation, the oven dry, at 350～400 ℃, the roasting of 6～9 hours time, get catalyst Precursors, make releasing agent with graphite, moulding on tablet machine gets the catalyzer finished product.
3. according to the described vapor hydroformylation catalyst of claim 1, it is characterized in that with catalyst weight per-cent be benchmark, comprise cupric oxide 25～35%, zinc oxide is 60～65%, the weight ratio of cupric oxide and zinc oxide is 1: 1.2～1: 3, and the BET specific surface area is 40～60m
2/ g, pore volume are 0.18～0.26cm
3/ g, mean pore size is 17～25nm, and auxiliary agent is a kind of or combination in Mg, Ca, Mn, the Al ion, and content is 1.0%～7.5%.
4. according to the preparation method of the described vapor hydroformylation catalyst of claim 2, it is characterized in that through following steps:
Obtain certain density copper, zinc solution with sour dissolved copper, zinc; The concentration of copper salt solution counts 10～13% with the cupric oxide weight percent; The concentration of zinc solution counts 11～18% with the zinc oxide weight percent; Get 1/5th to 1/4th of total zinc solution amount, in the ion addition is 1～7.5% of catalyzer total amount, mix with the nitrate solution a kind of or combination in Mg, Ca, Mn, the Al ion, under agitation with alkali precipitation agent and stream neutralization, co-precipitation, aging, solid-liquid separation obtains filter cake;
Mix with copper salt solution with remaining zinc solution, do precipitation agent with water soluble alkali solution, cocurrent adding material, in pH8～8.5,75～85 ℃ of following co-precipitation of temperature, aging, solid-liquid separation obtains filter cake.Two filter cakes that obtain of step are mixed, 45～55 ℃ of making beating washings down, solid-liquid separation, oven dry, at 360～390 ℃, the roasting of 7～8 hours time, catalyst Precursors, make releasing agent with graphite, moulding on tablet machine, the catalyzer finished product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012078393A1 (en) | 2010-12-06 | 2012-06-14 | Sud-Chemie Inc. | Promoted copper/zinc catalyst for hydrogenating aldehydes to alcohols |
| CN105080549A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for preparing 2-ethylhexyl alcohol through gas phase hydrogenation of octenal and preparation method of catalyst |
| CN106268972A (en) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc-base hydrogenation catalyst |
| WO2023125060A1 (en) * | 2021-12-29 | 2023-07-06 | 中国石油天然气股份有限公司 | Gas-phase aldehyde hydrogenation catalyst, preparation method therefor and application thereof |
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2005
- 2005-05-25 CN CN 200510013552 patent/CN1695802A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012078393A1 (en) | 2010-12-06 | 2012-06-14 | Sud-Chemie Inc. | Promoted copper/zinc catalyst for hydrogenating aldehydes to alcohols |
| US8399718B2 (en) | 2010-12-06 | 2013-03-19 | Sud-Chemie Inc. | Promoted copper/zinc catalyst for hydrogenating aldehydes to alcohols |
| CN103476492A (en) * | 2010-12-06 | 2013-12-25 | 科莱恩公司 | Promoted copper/zinc catalyst for hydrogenating aldehydes to alcohols |
| CN103476492B (en) * | 2010-12-06 | 2016-06-22 | 科莱恩公司 | For aldehyde being hydrogenated the promoted cu zn catalyst for alcohol |
| TWI549751B (en) * | 2010-12-06 | 2016-09-21 | 科萊恩公司 | Promoted copper/zinc catalyst for hydrogenating aldehydes to alcohols, process for preparing the same and process of hydrogenating aldehydes to alcohols using the same |
| KR101932780B1 (en) | 2010-12-06 | 2018-12-27 | 클라리언트 코포레이션 | Promoted copper/zinc catalyst for hydrogenating aldehydes to alcohols |
| CN105080549A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for preparing 2-ethylhexyl alcohol through gas phase hydrogenation of octenal and preparation method of catalyst |
| CN106268972A (en) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc-base hydrogenation catalyst |
| CN106268972B (en) * | 2015-06-08 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc-base hydrogenation catalyst |
| WO2023125060A1 (en) * | 2021-12-29 | 2023-07-06 | 中国石油天然气股份有限公司 | Gas-phase aldehyde hydrogenation catalyst, preparation method therefor and application thereof |
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