CN104549348B - A kind of catalyst of acetone synthesis diisobutyl ketone and preparation method thereof - Google Patents
A kind of catalyst of acetone synthesis diisobutyl ketone and preparation method thereof Download PDFInfo
- Publication number
- CN104549348B CN104549348B CN201310495783.0A CN201310495783A CN104549348B CN 104549348 B CN104549348 B CN 104549348B CN 201310495783 A CN201310495783 A CN 201310495783A CN 104549348 B CN104549348 B CN 104549348B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- salt
- mno
- hours
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
Catalyst of a kind of acetone synthesis diisobutyl ketone that the invention discloses and preparation method thereof, including active component Ni and carrier ZrO2‑ MnO2, with overall catalyst weight gauge, active component Ni counts content as 1wt%～10wt%, preferably 3wt%～6wt%, MnO with element2Content be 1wt%～20wt%, preferably 5wt%～10wt%, surplus is ZrO2.The catalyst of the present invention synthesizes diisobutyl reactive ketone for acetone, has raw material acetone conversion ratio high, and the selectivity of product diisobutyl ketone is good, i.e. the yield high of purpose product diisobutyl ketone.
Description
Technical field
The present invention relates to catalyst and the preparation method of a kind of acetone through one-step method synthesis diisobutyl ketone.
Background technology
Diisobutyl ketone is a kind of excellent solvent and chemical intermediate.The boiling point of diisobutyl ketone is high, evaporation rate is fast,
Dissolving power is strong, can improve film levelling, gloss, recoatability, good to the wettability of plastic bottom material, increases sorptive force, available nitro
Spray paint, ethenoid resin paint and the solvent of other synthetic resin coatings, can improve its moisture protection.It also is used as manufacturing organic gas
The dispersant of colloidal sol and food refine with solvent and some drugs, the intermediate of insecticide, be also used in rare metal extraction and
Purification separates metallic salt.
At present, the report about introduction synthesis diisobutyl ketone being is the most few.Great majority are to introduce synthesizing methyl isobutyl group
The method of ketone coproduction diisobutyl ketone.Totally seeing, if product for the purpose of diisobutyl ketone, its yield awaits improving.
CN101712606A discloses a kind of Ni/MgO-Al2O3ZrO2Catalyst, this catalyst consists of: Ni:6wt%,
MgO:60wt%, Al2O3: 21wt%, Ni:13wt%, catalyst is prepared by NiMgAlZr four-component hydrotalcite compound.Acetone turns
Rate is 60%, and the selectivity of diisobutyl ketone reaches 24%, and the yield of diisobutyl ketone is 14.4%.
CN102806085A discloses the catalyst of a kind of acetone hydrogenation coproduction isopropanol and diisobutyl ketone, catalyst bag
Salic carrier and be supported on γ-Al2O3Ni, Mg on carrier, in terms of the gross weight of catalyst, containing 20～the Ni of 25%, 8
～the Mg of 12%.Acetone conversion is 92.8%, and the selectivity of diisobutyl ketone reaches 25.6%, and the yield of diisobutyl ketone is
23.8%。
CN1566060A discloses the process of a kind of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone and diisobutyl ketone.
The method uses Pd/ZrO2As catalyst, Pd content is 0.5wt%, normal pressure, fixed bed reactors.Acetone conversion is
When 65.13%, the selectivity of diisobutyl ketone is up to 61.34%, and now the yield of diisobutyl ketone is 40.01%.
Document " Ni, Ni/Al2O3To acetone hydrogenation one-step synthesis methyl iso-butyl ketone (MIBK) Performance comparision " (institution of higher education's Science of Chemistry
Report, 1997, o. 11th, page 1865) report, during acetone hydrogenation one-step synthesis methyl iso-butyl ketone (MIBK), use Ni-
Ce/Al2O3During catalyst, the conversion ratio of acetone is 81.7%, and the selectivity of diisobutyl ketone is 50.05%, now diisobutyl ketone
Yield be up to 40.9%.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide the catalyst of a kind of acetone synthesis diisobutyl ketone
And preparation method thereof, the catalyst of the present invention synthesizes diisobutyl reactive ketone for acetone, has raw material acetone conversion ratio high, produces
The selectivity of product diisobutyl ketone is good, i.e. the yield high of purpose product diisobutyl ketone.
The catalyst of the acetone synthesis diisobutyl ketone of the present invention, including active component Ni and carrier ZrO2- MnO2, to urge
Agent gross weight meter, active component Ni counts content as 1wt%～10wt%, preferably 3wt%～6wt%, MnO with element2Content
For 1wt%～20wt%, preferably 5wt%～10wt%, surplus is ZrO2。
The preparation method of the catalyst of the acetone synthesis diisobutyl ketone of the present invention, including following content:
(1) mixed solution of the soluble-salt containing zirconium and the soluble-salt of manganese is added drop-wise in aqueous slkali, control ph
It is 8 ~ 11, drips complete, stir 15 ~ 60 minutes, aging, obtain Zr (OH)4With Mn (OH)2Mixing water gel, washs, is dried, roasts
Burning, molding, obtain ZrO2-MnO2Carrier；
(2) ZrO that step (1) is obtained2-MnO2Carrier impregnation active component Ni, dry, roasting obtains catalyst n i/
ZrO2-MnO2；Wherein impregnation liquid is containing ammonium salt and the mixed solution of the soluble-salt of nickel.
In the inventive method, the soluble-salt of the zirconium described in step (1) is zirconium oxychloride and zirconium nitrate, preferably oxychlorination
Zirconium, the soluble-salt of manganese is manganese nitrate, manganese sulfate and manganese chloride, preferably manganese chloride.
In the inventive method, described solution is generally aqueous solution, it is also possible to be C4Following alcoholic solution, such as methanol, second
Alcohol, propanol or isopropanol etc., or be the mixed solution of water and alcohol.
In the inventive method, in the mixed solution of Zr Yu Mn described in step (1), tenor is 0.02～1.5mol/L,
Preferably 0.2～1.0mol/L, depending on concrete Zr Yu Mn concentration is according to Zr Yu Mn ratio in prepared catalyst.
In the inventive method, the aging generally room temperature described in step (1) is aging, and ageing time is 20 ~ 30 hours.
In the inventive method, Zr (OH) in step (1)4With Mn (OH)2Mixing water gel is washed with deionized to without Cl-
Exist.
In the inventive method, the drying condition described in step (1) is: be dried 4～8 hours at 100～120 DEG C；Roasting bar
Part is: roasting 6～10 hours at 200～500 DEG C.
In the inventive method, the carrier molding described in step (1) can drip ball forming, spin pelletize, extruded and pressure
Sheet molding etc., support shapes is bar shaped (cylindrical, trilobal and quatrefoil etc.), spherical or sheet shape.
In the inventive method, the soluble-salt of the described nickel described in step (2) is nitrate and acetate, and ammonium salt is nitric acid
Salt, sulfate, carbonate, acetate and chloride, the soluble-salt of the identical ammonium salt of preferred anionic and nickel.
In the inventive method, the dip time described in step (2) is 20～25 hours.
In the inventive method, the drying condition described in step (2) is: 100～115 DEG C are dried 3～4 hours；Roasting condition
For: 300～500 DEG C of roastings 8～10 hours.
In the inventive method, in step (2) impregnation liquid, the content of Ni is calculated as 0.05～1.5mol/L, preferably 0.2 with element
～1.0mol/L；NH in impregnation liquid4 +Content be 0.01～1.0mol/L, preferably 0.05～0.5mol/L.
In the inventive method, depending on active component content is according to response situation.
Ni/ZrO of the present invention2-MnO2Catalyst is applied to acetone synthesis diisobutyl reactive ketone, and the generic condition of reaction is:
Reaction temperature 150～250 DEG C, preferably 150～200 DEG C, reaction pressure is normal pressure, and acetone feed air speed is 0.25～2.5h-1
(V), preferably 0.5～2.0h-1(V), H2/ acetone (V/V) is 200～500, preferably 300～400.
Catalyst of the present invention loads reactor before use, uses reducing process reduction in device.Reducing condition is: reduction temperature
Being 300 DEG C, reduction pressure normal pressure, the time is 5～8 hours, and the catalyst isolation air after reduction preserves.
The present invention is by introducing metal Mn in the carrier, and metal Mn is finally with MnO2State exist, can effectively hinder
Only W metal crystallite on carrier melts, more preferable divided active component, thus improves activity and the stability of catalyst.With
Time, MnO2Alcohol oxidation is generated ketone there is catalytic action, so MnO in catalyst2Existence inhibit the generation of by-product alcohol,
Be conducive to improving the selectivity of purpose product diisobutyl ketone.And, auxiliary agent Mn joins in carrier in the way of co-precipitation, keeps away
Exempt from Mn at carrier ZrO2Upper formation eggshell adsorbs, and thus causes active component Ni to adsorb the phenomenon being obstructed on carrier to send out
Raw, adsorb on carrier in active component Ni effectively.In the present invention, complex catalyst precursor is impregnated into the nickel nitrate containing ammonium nitrate
In solution mixed solution so that Ni ion and NH4 +Forming competitive Adsorption, beneficially Ni on catalyst precursor can be more uniform
Load to the presoma of catalyst, thus improve conversion ratio and the selectivity of catalyst.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described, but and is not so limited the present invention.
Embodiment 1
By 262g ZrOCl2·8H2O and 8g MnCl2·4H2O is dissolved in 1000mL deionized water, is made into mixed solution.
It is in 0.2mol/L ammonia spirit that mixing salt solution is added drop-wise to 800mL concentration, and is simultaneously added dropwise 0.2mol/L NaOH solution control
PH value processed is 11.Stir 40 minutes after dropping, more aging 24 hours of static precipitation in mother solution at normal temperatures, prepare Zr
(OH)4With Mn (OH)2Mixing water gel.Zr(OH)4With Mn (OH)2Mixing water gel is washed with deionized to without Cl-Exist, mistake
Filter is precipitated thing, and precipitate is dried 6 hours at 110 DEG C, and at 300 DEG C, roasting 8 hours, obtain ZrO2-MnO2Support C-1.
By 16gNi (NO3)2·6H2O and 3gNH4NO3It is dissolved in 130mL distilled water and is made into impregnation liquid, 100gC-1 is impregnated
In impregnation liquid, impregnate 24 hours, remove upper strata clear water, dry 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.Prepare and urge
Agent A-1.The MnO of this catalyst2Content be 3wt%, Ni content be 3wt%.
Embodiment 2
By 185gZrCl4And 16gMnCl2·4H2O is dissolved in 1000mL deionized water, is made into mixed solution.By salt-mixture
It is in 0.2mol/L ammonia spirit that solution is added drop-wise to 800mL concentration, and is simultaneously added dropwise 0.2mol/L NaOH solution control ph and is
11.Stir 40 minutes after dropping, more aging 24 hours of static precipitation in mother solution at normal temperatures, prepare Zr (OH)4With Mn
(OH)2Mixing water gel.Zr(OH)4With Mn (OH)2Mixing water gel is washed with deionized to without Cl-Existing, it is heavy to be filtrated to get
Shallow lake thing, precipitate dries 6 hours at 110 DEG C, and at 300 DEG C, roasting 8 hours, obtain ZrO2-MnO2Support C-2.
By 22gNi (NO3)2·6H2O and 3gNH4NO3It is dissolved in 130mL distilled water and is made into impregnation liquid, 100gC-3 is impregnated
In this impregnation liquid, impregnate 24 hours, remove upper strata clear water, dry 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.Prepare
Catalyst A-2.The MnO of this catalyst2Content be 6wt%, Ni content be 4wt%.
Embodiment 3
By 250gZrOCl2·8H2O and 28gMn (NO3)2·4H2O is dissolved in 1000mL deionized water, is made into mixed solution.
It is in 0.2mol/L ammonia spirit that mixing salt solution is added drop-wise to 800mL concentration, and is simultaneously added dropwise 0.2mol/L NaOH solution control
PH value processed is 11.Stir 40 minutes after dropping, more aging 24 hours of static precipitation in mother solution at normal temperatures, prepare Zr
(OH)4With Mn (OH)2Mixing water gel.Zr(OH)4With Mn (OH)2Mixing water gel is washed with deionized to without Cl-Exist, mistake
Filter is precipitated thing, and precipitate is dried 6 hours at 110 DEG C, and at 300 DEG C, roasting 8 hours, obtain ZrO2-MnO2Support C-3.
By 24gNi (CH3COO)2·4H2O and 3.5g CH3COONH4It is dissolved in 150mL distilled water and is made into impregnation liquid, will
100gC-3 is impregnated in this impregnation liquid, impregnates 24 hours, removes upper strata clear water, dries 3 hours in 110 DEG C, roasts in 400 DEG C
Burn 8 hours.Prepare catalyst A-3.The MnO of this catalyst2Content be 8wt%, Ni content be 5wt%.
Embodiment 4
ZrO2-MnO2The preparation of support C-4 is with embodiment 1.
By 27gNi (NO3)2·6H2O and 3.2gNH4NO3It is dissolved in 160mL distilled water and is made into impregnation liquid, 100gC-4 is soaked
Stain, in this impregnation liquid, impregnates 24 hours, removes upper strata clear water, dries 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.System
Obtain catalyst A-4.The MnO of this catalyst2Content be 3wt%, Ni content be 5wt%.
Embodiment 5
ZrO2-MnO2The preparation of support C-5 is with embodiment 3.
By 32gNi (NO3)2·6H2O and 3.2gNH4NO3It is dissolved in 160mL distilled water and is made into impregnation liquid, 100gC-5 is soaked
Stain, in this impregnation liquid, impregnates 24 hours, removes upper strata clear water, dries 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.System
Obtain catalyst A-5.The MnO of this catalyst2Content be 8wt%, Ni content be 6wt%.
Comparative example 1
By 17gNi (NO3)2·6H2O is dissolved in 130mL distilled water and is made into aqueous solution, with this solution impregnation 100g zirconium oxide
Carrier Z-1, removes upper strata clear water, dries 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.Prepare catalyst B-1.This catalysis
The Ni content of agent is 3wt%.
Comparative example 2
By 17gNi (NO3)2·6H2O is dissolved in 130mL distilled water and is made into aqueous solution, with this solution impregnation 100g γ-Al2O3
Carrier Z-2, removes upper strata clear water, dries 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.Prepare catalyst B-2.This catalysis
The Ni content of agent is 3wt%.
Comparative example 3
By 11gMn (NO3)2·4H2O joins in 130mL distilled water and is made into aqueous solution, with this solution impregnation 100g γ-
Al2O3Carrier, impregnates 24 hours.Removing upper strata clear water, dry 3 hours in 110 DEG C, in 300 DEG C, roasting 8 hours, make and contain
The carrier Z-3 of manganese.
By 17gNi (NO3)2·6H2O is dissolved in 130mL distilled water and is made into aqueous solution, and 100gZ-3 is impregnated into this nickel solution
In, remove upper strata clear water, dry 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.Prepare catalyst B-3.This catalyst
Mn content be 3wt%, Ni content be 3wt%.
Comparative example 4
By 11gMn (NO3)2·4H2O joins in 130mL distilled water and is made into aqueous solution, by this solution impregnation 100gZrO2
Carrier, impregnates 24 hours.Removing upper strata clear water, dry 3 hours in 110 DEG C, in 300 DEG C, roasting 8 hours, make containing manganese
Carrier Z-4.
By 17gNi (NO3)2·6H2O is dissolved in 130mL distilled water and is made into aqueous solution, and 100gZ-4 is impregnated into this nickel solution
In, remove upper strata clear water, dry 3 hours in 110 DEG C, roasting 8 hours in 400 DEG C.Prepare catalyst B-4.This catalyst
MnO2Content be 3wt%, Ni content be 3wt%.
Embodiment 6
Catalyst C-1 is loaded reactor, uses reducing process reduction in device.Reducing condition is: reduction temperature is 300 DEG C,
Normal pressure reduces 8 hours, and during reduction, hydrogen gas space velocity is 120h-1.Answering temperature 180 DEG C, reaction pressure normal pressure, acetone feed air speed is
1.5, H2/ acetone (V/V) is 300.
Raw material acetone enters after reactor reaction, and product is cooled and gas-liquid separation, vapor phase hydrogen emptying or recycle,
Liquid-phase reaction product gas chromatographic analysis.The conversion ratio of result acetone is 49.78%, and the selectivity of diisobutyl ketone is
34.26%, yield is 17.05%.
Catalyst A-2, A-3, A-4, A-5, B-1, B-2, B-3, B-4 is evaluated respectively more different by the method for embodiment 6
The performance of catalyst, the results are shown in Table 1.
Table 1 catalyst performance evaluation.
As can be seen from the table, the present invention receipts of the activity of the catalyst obtained, selectivity and diisobutyl ketone
Rate compared with prior art has raising by a relatively large margin.
Claims (15)
1. the catalyst of an acetone synthesis diisobutyl ketone, it is characterised in that: by active component Ni and carrier ZrO2-MnO2Group
Becoming, with overall catalyst weight gauge, active component Ni counts content as 1wt%～10wt%, MnO with element2Content be 1wt%～
20wt%, surplus is ZrO2；The preparation method of described catalyst is as follows: (1) is by the soluble-salt containing zirconium and the solubility of manganese
The mixed solution of salt is added drop-wise in aqueous slkali, and control ph is 8 ~ 11, drips complete, stirs 15 ~ 60 minutes, aging, obtains Zr
(OH)4With Mn (OH)2Mixing water gel, wash, be dried, roasting, molding, obtain ZrO2-MnO2Carrier；(2) step (1) is obtained
The ZrO arrived2-MnO2Carrier impregnation active component Ni, dry, roasting obtains catalyst n i/ZrO2-MnO2；Wherein impregnation liquid is for containing
There is the mixed solution of the soluble-salt of ammonium salt and nickel.
2. according to the catalyst described in claim 1, it is characterised in that: active component Ni with element count content as 3wt%～
6wt%, MnO2Content be 5wt%～10wt%.
3. the preparation method of the catalyst described in claim 1 or 2, it is characterised in that include following content: (1) is by containing zirconium
The mixed solution of the soluble-salt of soluble-salt and manganese is added drop-wise in aqueous slkali, and control ph is 8 ~ 11, drips complete, stirs 15
~ 60 minutes, aging, obtain Zr (OH)4With Mn (OH)2Mixing water gel, wash, be dried, roasting, molding, obtain ZrO2-MnO2
Carrier；(2) ZrO that step (1) is obtained2-MnO2Carrier impregnation active component Ni, dry, roasting obtains catalyst n i/ZrO2-
MnO2；Wherein impregnation liquid is containing ammonium salt and the mixed solution of the soluble-salt of nickel.
The most in accordance with the method for claim 3, it is characterised in that: the soluble-salt of the zirconium described in step (1) is zirconium oxychloride
With one or both mixing in zirconium nitrate；The soluble-salt of manganese is one or more in manganese nitrate, manganese sulfate and manganese chloride.
The most in accordance with the method for claim 3, it is characterised in that: the mixed solution described in step (1) and step (2) is water-soluble
Liquid, C4Following alcoholic solution or be the mixed solution of water and alcohol.
The most in accordance with the method for claim 3, it is characterised in that: metal in the mixed solution of Zr Yu Mn described in step (1)
Content is 0.02～1.5mol/L.
The most in accordance with the method for claim 3, it is characterised in that: aging aging for room temperature described in step (1), ageing time
It it is 20 ~ 30 hours.
The most in accordance with the method for claim 3, it is characterised in that: the drying condition described in step (1) is: at 100～120 DEG C
It is dried 4～8 hours；Roasting condition is: roasting 6～10 hours at 200～500 DEG C.
The most in accordance with the method for claim 3, it is characterised in that: the soluble-salt of the described nickel described in step (2) is nitric acid
In salt and acetate one or both；Ammonium salt be nitrate, sulfate, carbonate, acetate and chloride one or more.
10. according to the method described in claim 3 or 9, it is characterised in that: ammonium salt is identical with the anion of the soluble-salt of nickel.
11. in accordance with the method for claim 3, it is characterised in that: the dip time described in step (2) is 20～25 hours.
12. in accordance with the method for claim 3, it is characterised in that: the drying condition described in step (2) is: 100～115 DEG C
It is dried 3～4 hours；Roasting condition is: 300～500 DEG C of roastings 8～10 hours.
13. in accordance with the method for claim 3, it is characterised in that: in step (2) impregnation liquid, the content of Ni is calculated as with element
0.05～1.5mol/L, NH in impregnation liquid4 +Content be 0.01～1.0mol/L.
Catalyst described in 14. claim 1 or 2 is applied to acetone synthesis diisobutyl reactive ketone.
15. according to the reaction described in claim 14, it is characterised in that: the condition of reaction is: reaction temperature 150～250 DEG C, instead
Answering pressure is normal pressure, and acetone feed volume space velocity is 0.25～2.5h-1, H2The volume ratio of/acetone is 200～500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495783.0A CN104549348B (en) | 2013-10-22 | 2013-10-22 | A kind of catalyst of acetone synthesis diisobutyl ketone and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310495783.0A CN104549348B (en) | 2013-10-22 | 2013-10-22 | A kind of catalyst of acetone synthesis diisobutyl ketone and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549348A CN104549348A (en) | 2015-04-29 |
| CN104549348B true CN104549348B (en) | 2016-11-16 |
Family
ID=53067053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310495783.0A Active CN104549348B (en) | 2013-10-22 | 2013-10-22 | A kind of catalyst of acetone synthesis diisobutyl ketone and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549348B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566060A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Technological process for synthesizing methyl isobutyl ketone and diisobutyl ketone with acetone |
| CN1733360A (en) * | 2004-08-09 | 2006-02-15 | 中国科学院大连化学物理研究所 | The catalyst of a kind of synthesizing methyl nezukone and diethyl ketone and method for making and application |
| WO2012073082A1 (en) * | 2010-11-30 | 2012-06-07 | Rhodia Poliamida E Especialidades Ltda | Process for producing dibk |
| CN102698761A (en) * | 2012-01-17 | 2012-10-03 | 中国海洋石油总公司 | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application |
| CN102806085A (en) * | 2012-08-13 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for co-generating of isopropanol and diisobutyl ketone through acetone hydrogenation and application |
-
2013
- 2013-10-22 CN CN201310495783.0A patent/CN104549348B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566060A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Technological process for synthesizing methyl isobutyl ketone and diisobutyl ketone with acetone |
| CN1733360A (en) * | 2004-08-09 | 2006-02-15 | 中国科学院大连化学物理研究所 | The catalyst of a kind of synthesizing methyl nezukone and diethyl ketone and method for making and application |
| WO2012073082A1 (en) * | 2010-11-30 | 2012-06-07 | Rhodia Poliamida E Especialidades Ltda | Process for producing dibk |
| CN102698761A (en) * | 2012-01-17 | 2012-10-03 | 中国海洋石油总公司 | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application |
| CN102806085A (en) * | 2012-08-13 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for co-generating of isopropanol and diisobutyl ketone through acetone hydrogenation and application |
Non-Patent Citations (3)
| Title |
|---|
| 以纳米二氧化锆为载体的Pd 催化剂制备及还原缩合性能研究;刘晓红等;《精细化工》;20031231;第20卷(第12期);727页右栏第2段 * |
| 改性ZrO2-MnO2基整体式催化剂上NH3选择性催化还原NO;邱春天等;《催化学报》;20111231;第32卷(第7期);1227-1233 * |
| 纳米二氧化错催化剂的制备与应用;刘丽娟等;《精细石油化工进展》;20050831;第6卷(第8期);46-48 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549348A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106861703B (en) | A kind of preparation method of the catalyst for cis-butenedioic anhydride liquid-phase hydrogenatin synthetic gamma butyrolactone | |
| CN113000049B (en) | Method for preparing Ni-Al-based oxide catalyst | |
| CN101264453A (en) | Titanium-silicon molecular sieve/tripolite composite catalyst and preparation | |
| CN107774263B (en) | A kind of preparation method of catalst for synthesis of methanol | |
| CN107790137B (en) | A kind of preparation method of copper zinc catalyst | |
| CN108722420A (en) | A kind of preparation method of copper silicon systems catalyst | |
| CN102698761A (en) | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application | |
| CN107519881B (en) | Preparation method of cyclohexyl acetate hydrogenation catalyst, prepared hydrogenation catalyst and cyclohexyl acetate hydrogenation method | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN106861704B (en) | A kind of preparation method and application of nickel-auxiliary agent-alumina-silica Zr catalyst | |
| KR101584399B1 (en) | Method for preparing dimethyl carbonate using supported catalyst | |
| CN103301849A (en) | Catalyst for preparing dicarbon oxygen compounds by utilizing synthesis gas and preparation method of catalyst | |
| CN104907074B (en) | Ester through hydrogenation catalyst and preparation method thereof and the method for ester through hydrogenation reaction | |
| CN104549348B (en) | A kind of catalyst of acetone synthesis diisobutyl ketone and preparation method thereof | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| KR20130048716A (en) | Catalysts and processes for the hydrogenolysis of glycerol and other organic compounds for producing polyols and propylene glycol | |
| CN104028267A (en) | Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation | |
| CN106140199B (en) | Acid resistant form ester through hydrogenation catalyst and its preparation method and application and ester through hydrogenation method | |
| CN105732329B (en) | Synthetic method of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol | |
| CN107159263A (en) | Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone catalyst and preparation method | |
| CN111482181A (en) | Reforming hydrogen production composite catalyst and preparation method and application thereof | |
| CN105727954B (en) | A kind of preparation method of synthesis gas preparing natural gas catalyst | |
| CN111054339A (en) | Catalyst composition for preparing glycol | |
| CN106140200A (en) | Acid resistant form ester through hydrogenation catalyst and its preparation method and application and ester through hydrogenation method | |
| CN107115865B (en) | A kind of preparation method of copper zinc-aluminium Zr catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |