CN107486207A - A kind of aldehyde liquid phase hydrogenating catalyst - Google Patents
A kind of aldehyde liquid phase hydrogenating catalyst Download PDFInfo
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- CN107486207A CN107486207A CN201710748259.8A CN201710748259A CN107486207A CN 107486207 A CN107486207 A CN 107486207A CN 201710748259 A CN201710748259 A CN 201710748259A CN 107486207 A CN107486207 A CN 107486207A
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention belongs to catalyst technical field, and in particular to a kind of aldehyde liquid phase hydrogenating catalyst.The mass content of the nickel of the catalyst is 15% ~ 30%.This method carries out catalyst preparation using coprecipitation method：(1) nickel nitrate solution configured is added in the reactor with stirring slurry and is heated to 50 DEG C ~ 70 DEG C, carried out neutralization precipitation with alkaline precipitating agent, neutralize 15 minutes ~ 30 minutes time, endpoint pH 7.0 ~ 7.3；Then it is aged 20 minutes ~ 50 minutes at 60 DEG C ~ 75 DEG C, fixed crystal formation；（2）Sediment adds Ludox after aging, is stirred 30 minutes ~ 80 minutes at 60 DEG C ~ 90 DEG C, Ludox is combined the slurry that precipitation forms stable and uniform with sediment；（3）Filter cake is obtained after washing, filtering to be dried, dried filter cake is ground, adds water and binding agent extruded moulding, is calcined again at being then 400 DEG C ~ 700 DEG C in temperature, obtains aldehyde hydrogenating catalyst.Preparation process simply easily realizes, it is unstable to solve conventional catalyst production process control, the problem of causing catalyst performance unstable.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of aldehyde liquid phase hydrogenating catalyst.
Background technology
Octyl alconyl is important Organic Chemicals.2,830,000 tons of world's n-butanol yield in 2006.World's octanol in 2006
2,970,000 tons of yield.380,000 tons of China's n-butanol yield in 2006, it is contemplated that China's butanol demand will be at 1,100,000 tons in 2015.
The demand of China's octanol in 2006 is 800,000 tons, and insufficiency of supply-demand is still very big.It is expected that China's octanol demand-expected amount in 22015
For 970,000-100 ten thousand tons.
With petrochemical industry and the development of carbonylation synthesis technology, early stage starchiness agricultural byproducts fermentative routes and acetaldehyde condensation route
Eliminate in succession, oxo synthesis（That is hydroformylation of propene method）Production octyl alconyl develops rapidly, and its production process is propylene
And synthesis gas（Carbon monoxide and hydrogen）The thick aldehyde of carbonylation synthesis, is refining to obtain n-butanal and isobutylaldehyde；Hydrogenation obtains product respectively
N-butanol and isobutanol；Two molecule n butyraldehyde aldolizations dehydration generation octenal, hydrogenation obtain product octanol.According to carbonylation
The difference of pressure and catalyst, oxo synthesis can be divided into the techniques such as high pressure cobalt method, middle-pressure process, low-pressure process.No matter which kind of is used
Technique, is then required for aldehyde Hydrogenation butanol and octanol, and aldehyde hydrogenation has two kinds of liquid phase method and vapor phase method.Liquid-phase hydrogenatin typically uses
Nickel catalyst, because it has the characteristics of hydrogenation activity temperature is low and operation energy consumption is few, and the nickel system aldehyde of liquid phase method adds at present
The equal import of hydrogen catalyst, expensive, technology blockage, although domestic have many research, have no the report of application of result.
The company of current external development and production aldehyde gas phase hydrogenation catalyst mainly has：UCC, BASF, Hirst, Huels,
Exxon and ICI etc..Nickel catalyst is also obtained with the characteristics of its hydrogenation activity temperature is low, operation energy consumption is few in aldehyde field of hydrogenation
To being widely applied.The high-pressure process of early stage prepares Ni series catalysts in the technique of octyl alconyl and is used for liquid-phase hydrogenatin, and it is operated
Pressure is higher, and some external chemical enterprises successively develop a series of aldehydes using Ni as main active component before and after nineteen ninety
Hydrogenation catalyst.
The Ni systems Ni-ZrO/SiO2 aldehyde hydrogenating catalysts that German Hoechst house journals EP.421196 is introduced, the said firm
The Ni systems aldehyde hydrogenating catalyst introduced in an other patent, it is as auxiliary agent using alkaline-earth metal Mg.German BASF patents DE.
The Ni systems aldehyde hydrogenating catalyst introduced in 43100538, in addition to cu is added, is also added into third component Zr and the 4th component
Mo.The Ni systems aldehyde hydrogenating catalyst mentioned in German Huels house journals EP.394842, except adding people Cu as the first auxiliary agent,
Cr is added again as the second auxiliary agent.
Russian GurevichGs patents EP, 326674 describe two-step method production octyl alconyl technique and catalyst, its Ni
It is that Cr is added in liquid-phase hydrogenatin catalyst for refining as auxiliary agent.Mitsubishi chemical company patent JP, mention in 61172838
The advanced aldehyde hydrogenating catalyst of Ni systems is equally using Cr as auxiliary agent.The support type Ni- that Czech chemistry oil company Bednarz is introduced
Cr catalyst is used for corresponding aldehyde Hydrogenation for n-butanol, isobutanol and octanol.
Research institute of domestic Jilin Chemical company carried out the research work of octenal liquid phase hydrogenating catalyst, the catalyst of development in
In September, 1998 is applied to chemical fertilizer factory of Jilin Chemical Industrial Co. Ltd. butyl octanol unit, comes from the running situation of catalyst
See, exceed imported catalyst in service life, show to have made octenal liquid phase hydrogenating catalyst manufacture localization technology by oneself
Through maturation, but also there is a certain distance in the activity and selectivity of catalyst with imported catalyst.
The content of the invention
The purpose of the present invention is to propose to a kind of aldehyde liquid phase hydrogenating catalyst.
On the basis of catalyst keeps high activity, high selectivity, simplify the preparation method of catalyst so that catalyst
Preparation process is simpler, and process control is more easy to control, and the preparing raw material of catalyst is easy to get, is cheap, while catalyst system
It is standby more stable.
A kind of aldehyde liquid phase hydrogenating catalyst of the present invention：Catalyst preparation is carried out using co-precipitation, comprised the following steps that：
(1) nickel nitrate solution configured is added in the reactor with stirring slurry and is heated to 50 DEG C ~ 70 DEG C, sunk with alkalescence
Shallow lake agent carries out neutralization precipitation together, neutralizes 15 minutes ~ 30 minutes time, endpoint pH 7.0 ~ 7.3；It is then old at 60 DEG C ~ 75 DEG C
Change 20 minutes ~ 50 minutes, fixed crystal formation.
（2）Sediment adds Ludox after aging, is stirred 30 minutes ~ 80 minutes at 60 DEG C ~ 90 DEG C, makes Ludox with sinking
Starch forms the slurry of stable and uniform with reference to precipitation.
（3）Obtain filter cake after washing, filtering and be dried, dried filter cake is ground, add water and binding agent extrusion into
Type, it is calcined again at being then 400 DEG C ~ 700 DEG C in temperature, obtains aldehyde hydrogenating catalyst.
Usually, the alkaline precipitating agent is one kind or several in K2CO3, Na2CO3, NaHCO3, NaOH, KOH or ammoniacal liquor
Kind.
The Ludox is low sodium or sodium-free silica sol；One kind is typically JA-25 type Ludox.
The sintering temperature is 500 DEG C ~ 700 DEG C.
Aldehyde liquid phase hydrogenating catalyst prepared by the inventive method, the mass content of the nickel of catalyst is 15% ~ 30%, auxiliary agent matter
It is 0.2 ~ 5% to measure content, and remaining is SiO2.
The aldehyde liquid phase hydrogenating catalyst of the preparation, suitable for adding for the aliphatic chain list aldehydes such as propionic aldehyde, butyraldehyde, octenal
Hydrogen.
The catalyst prod prepared using the inventive method has the features such as intensity is good, and activity is high and selectivity is high.
Embodiment
The inventive method is described in detail in reference to embodiment, but is not limited to embodiment.
Example 1
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with sodium bicarbonate solution, controls about 50 DEG C of precipitation temperature, neutralizes 15 minutes time, terminal pH value 7.0, Ran Hou
Stirring ageing 30min, weighs 880gJA-25 type Ludox and is added in above-mentioned slurry at 60 DEG C, is stirred 50 minutes at 80 DEG C, after
Scrubbed, filtering, dry, grind, adding 180g deionized waters and 1.8g methylcellulose is mediated, extruded moulding, 500
DEG C roasting 2h, produce catalyst sample 1.
Example 2
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with sodium carbonate liquor, controls about 65 DEG C of precipitation temperature, neutralizes 20 minutes time, terminal pH value 7.2, then 70
Stirring ageing 40min, weighs 640gJA-25 type Ludox and is added in above-mentioned slurry at DEG C, is stirred 70 minutes at 75 DEG C, by
Washing, filtering, dry, grind, adding 170g deionized waters and 1.7g methylcellulose is mediated, extruded moulding, at 550 DEG C
2h is calcined, produces catalyst sample 2.
Example 3
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with sodium carbonate liquor, controls about 70 DEG C of precipitation temperature, neutralizes 30 minutes time, terminal pH value 7.3, then 70
Stirring ageing 75min, weighs 640gJA-25 type Ludox and is added in above-mentioned slurry at DEG C, is stirred 75 minutes at 60 DEG C, by
Washing, filtering, dry, grind, adding 170g deionized waters and 1.2g methylcellulose is mediated, extruded moulding, at 600 DEG C
2h is calcined, produces catalyst sample 3.
Example 4
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with sodium hydroxide solution, controls about 65 DEG C of precipitation temperature, neutralizes 25 minutes time, terminal pH value 7.1, Ran Hou
Stirring ageing 40min, weighs 640gJA-25 type Ludox and is added in above-mentioned slurry at 65 DEG C, is stirred 30 minutes at 90 DEG C, after
Scrubbed, filtering, dry, grind, adding 180g deionized waters and 1.5g methylcellulose is mediated, extruded moulding, 650
DEG C roasting 2h, produce catalyst sample 4.
Example 5
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with solution of potassium carbonate, controls about 50 DEG C of precipitation temperature, neutralizes 15 minutes time, terminal pH value 7.1, then 60
Stirring ageing 30min, weighs 480gJA-25 type Ludox and is added in above-mentioned slurry at DEG C, is stirred 60 minutes at 70 DEG C, by
Washing, filtering, dry, grind, adding 150g deionized waters and 1.2g methylcellulose is mediated, extruded moulding, at 550 DEG C
2h is calcined, produces catalyst sample 5.
Example 6
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with ammonia spirit, controls about 65 DEG C of precipitation temperature, neutralizes 20 minutes time, terminal pH value 7.3, then at 70 DEG C
Lower stirring ageing 40min, weighs 480gJA-25 type Ludox and is added in above-mentioned slurry, stirred 75 minutes at 80 DEG C, by washing
Wash, filter, dry, grind, add 150g deionized waters and 1.2g methylcellulose is mediated, extruded moulding, in 600 DEG C of roastings
2h is burnt, produces catalyst sample 6.
Example 7
Nickelous nitrate hexahydrate 200g is taken to add 1L deionized waters to be configured to solution, by nickel nitrate solution in the stillpot with stirring
It is co-precipitated with potassium hydroxide solution, controls about 65 DEG C of precipitation temperature, neutralizes 30 minutes time, terminal pH value 7.0, Ran Hou
Stirring ageing 40min, weighs 480gJA-25 type Ludox and is added in above-mentioned slurry at 70 DEG C, is stirred 60 minutes at 70 DEG C, after
Scrubbed, filtering, dry, grind, adding 140g deionized waters and 1.2g methylcellulose is mediated, extruded moulding, 700
DEG C roasting 2h, produce catalyst sample 7.
Reference test 1
In the tubular reactor used in laboratory, the sample and commercially available import aldehyde that respectively take the preparation of 50ml examples detailed above 1 ~ 7 add
The carry out activity rating activation of hydrogen catalyst, appreciation condition are：Reaction pressure 4.0MPa, material liquid air speed 1.1h-1, in raw material
Butyraldehyde is 1 with ratio of butanol：4, evaluation result is as shown in table 1.
The reference test 1 of table 1
。
Contrasted more than as can be seen that the characteristics of catalyst of the inventive method preparation is active and selective high.
Reference test 2
In the tubular reactor used in laboratory, the sample and commercially available import aldehyde that respectively take the preparation of 50ml examples detailed above 1 ~ 7 add
The carry out activity rating activation of hydrogen catalyst, appreciation condition are：Reaction pressure 4.0MPa, material liquid air speed 1.1h-1, in raw material
Positive propionic aldehyde and normal propyl alcohol ratio are 1:4, evaluation result is as shown in table 2.
The reference test 2 of table 2
。
Contrasted more than as can be seen that the characteristics of catalyst of the inventive method preparation is active and selective high.
Reference test 3
In the tubular reactor used in laboratory, the sample and commercially available import aldehyde that respectively take the preparation of 50ml examples detailed above 1 ~ 7 add
The carry out activity rating activation of hydrogen catalyst, appreciation condition are：Reaction pressure 4.0MPa, material liquid air speed 1.1h-1, in raw material
2- ethyl hexenals and 2-Ethylhexyl Alcohol ratio are 1:5, evaluation result is as shown in table 3.
The reference test 3 of table 3
。
Claims (8)
1. a kind of aldehyde liquid phase hydrogenating catalyst, it is characterized in that carrying out catalyst preparation using coprecipitation method, comprise the following steps that：
(1) nickel nitrate solution configured is added in the reactor with stirring and is heated to 50 DEG C ~ 70 DEG C, with alkaline precipitating agent
Neutralization precipitation is carried out together, neutralizes 15 minutes ~ 30 minutes time, endpoint pH 7.0 ~ 7.3；Then 20 are aged at 60 DEG C ~ 75 DEG C
Minute ~ 50 minutes, fixed crystal formation；
（2）Sediment adds Ludox after aging, is stirred 30 minutes ~ 80 minutes at 60 DEG C ~ 90 DEG C, makes Ludox and sediment
The slurry of stable and uniform is formed with reference to precipitation；
（3）Filter cake is obtained after washing, filtering to be dried, and dried filter cake is ground, adds water and binding agent extruded moulding, so
It is calcined again at being afterwards 400 DEG C ~ 700 DEG C in temperature, obtains aldehyde hydrogenating catalyst.
A kind of 2. aldehyde liquid phase hydrogenating catalyst as claimed in claim 1, it is characterised in that alkaline precipitating agent be K2CO3, Na2CO3,
One or more in NaHCO3, NaOH, KOH or ammoniacal liquor.
3. a kind of aldehyde liquid phase hydrogenating catalyst as claimed in claim 1, it is characterised in that Ludox is low sodium or sodium-free silica sol.
A kind of 4. aldehyde liquid phase hydrogenating catalyst as claimed in claim 3, it is characterized in that Ludox is JA-25 type Ludox.
5. a kind of aldehyde liquid phase hydrogenating catalyst as claimed in claim 1, it is characterised in that sintering temperature is 500 DEG C ~ 700 DEG C.
6. a kind of aldehyde liquid phase hydrogenating catalyst as claimed in claim, it is characterised in that described binding agent is methylcellulose.
7. aldehyde liquid phase hydrogenating catalyst prepared by method as claimed in claim 1, it is characterised in that the quality of the nickel of catalyst contains
Measure as 15% ~ 30%, remaining is SiO2.
8. aldehyde liquid phase hydrogenating catalyst prepared by method as claimed in claim 1, it is characterised in that catalyst is applied to propionic aldehyde, fourth
The hydrogenation of aldehyde, octenal aliphatic chain list aldehydes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710748259.8A CN107486207A (en) | 2017-08-28 | 2017-08-28 | A kind of aldehyde liquid phase hydrogenating catalyst |
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| CN201710748259.8A CN107486207A (en) | 2017-08-28 | 2017-08-28 | A kind of aldehyde liquid phase hydrogenating catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876812A (en) * | 2019-01-25 | 2019-06-14 | 武汉聚川科技有限公司 | A kind of preparation method of nickel-base hydrogenation catalyst |
| CN111482166A (en) * | 2019-01-28 | 2020-08-04 | 中国石油化工股份有限公司 | Nano carbon-based material and preparation method thereof and etherification method of propylene oxide |
-
2017
- 2017-08-28 CN CN201710748259.8A patent/CN107486207A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876812A (en) * | 2019-01-25 | 2019-06-14 | 武汉聚川科技有限公司 | A kind of preparation method of nickel-base hydrogenation catalyst |
| CN111482166A (en) * | 2019-01-28 | 2020-08-04 | 中国石油化工股份有限公司 | Nano carbon-based material and preparation method thereof and etherification method of propylene oxide |
| CN111482166B (en) * | 2019-01-28 | 2023-03-10 | 中国石油化工股份有限公司 | Nano carbon-based material and preparation method thereof and etherification method of propylene oxide |
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