CN1457927A - Process for preparing palladium-resin catalyst - Google Patents
Process for preparing palladium-resin catalyst Download PDFInfo
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- CN1457927A CN1457927A CN 02109663 CN02109663A CN1457927A CN 1457927 A CN1457927 A CN 1457927A CN 02109663 CN02109663 CN 02109663 CN 02109663 A CN02109663 A CN 02109663A CN 1457927 A CN1457927 A CN 1457927A
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- palladium
- resin
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Abstract
The present invention discloses the preparation process of Pd/ resin catalyst, and is especially the preparation process of Pd/ resin catalyst for the one-step process to synthesize methyl isobutyl ketone. Pd-containing acid solution and resin are made to produce ion exchange to obtain the catalyst with high activity and high selectivity. The present invention has raised Pd utilization, and the catalyst may be used in hydroetherification of gasoline, synthesis of methyl isobutyl ketone with acetone and other reaction process.
Description
1, technical field
The present invention relates to a kind of preparation method of palladium-resin catalyst, especially for the preparation method of the palladium-resin catalyst of acetone and hydrogen synthesize methyl-isobutyl ketone.
2, background technology
With acetone and hydrogen one-step method synthesize methyl-isobutyl ketone technology is the state-of-the-art technology of producing methyl iso-butyl ketone (MIBK), and the catalyst that is used for this technology also has polytype.
Ger.Pat.123853 introduces a kind of one-step method synthesizing methyl isobutyl ketone catalyst, and with Hydrogen ion exchange resin and the active carbon mixing conduct of carrying palladium, the conversion ratio of its acetone is low.
Problems such as JP119436 discloses a kind of usefulness and carried the catalyst that the activated alumina of palladium is made synthetic methyl iso-butyl ketone (MIBK), sees according to its disclosed material, and there is the reaction temperature height in this catalyst, and conversion ratio is low, and the selectivity of product methyl iso-butyl ketone (MIBK) is bad.
US5684207 introduces a kind of ZSM-5 zeolite of handling with acid medium and prepares the synthesize methyl-isobutyl ketone catalyst, but when using this catalyst synthesize methyl-isobutyl ketone, selectivity is lower.It is the carried palladium catalyst synthesize methyl-isobutyl ketone technology of carrier with the organosilicon that US5149881 discloses a kind of, also fails to improve simultaneously the selectivity of product and the conversion ratio of acetone.
Disclosed palladium/the strong acid cation exchange resin catalyst of GB1010260, US3953517 is the main catalyst for application type of synthesize methyl-isobutyl ketone, wherein Preparation of catalysts is a palladium nitrate aqueous solution dipping strong-acid ion exchange resin, the activity of such catalysts that this method obtains, selectivity are hanged down and are all awaited further raising, and the utilization rate of palladium is lower in the catalyst preparation process.
3, summary of the invention
The present invention is directed to problems of the prior art, the preparation method of the palladium-resin catalyst that a kind of Metal Palladium utilization rate height, catalyst activity and selectivity all further improve is provided, and the catalyst of the inventive method preparation has active advantage such as get well low temperature under simultaneously.
The preparation method of palladium-resin catalyst of the present invention is: adopt solution and the ion exchange resin contain palladium to carry out ion-exchange, filter then, wash and obtain palladium-resin catalyst, wherein containing palladium solution is the acid solution that contains palladium.Above H in the described acid solution
+Concentration is 0.01～5.0mol/L, and suitable concentration is 0.2～3.0mol/L, is preferably 0.2～1.5mol/L.Acid medium can be inorganic acid and C such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid
1～C
5Organic acid etc.Ion-exchange time is generally 10～100 minutes.
Resin used in the present invention can be various suitable ion exchange resin, preferred strong-acid ion exchange resin, as strongly acidic styrene type cation exchange resin etc., the content that palladium accounts for catalyst is 0.01%～3.0% (butt weight, down together), suitable content is 0.05%～2.0%, is preferably 0.1%～1.0%.
By in ion exchange process, adding certain density H
+, can change the competitive Adsorption state in the ion exchange process, help palladium and exchange to and help more that it is active and optionally in the resin structure.The catalyst that adopts the inventive method to obtain under the suitable situation of palladium content, has improved the utilization rate of palladium.In methylisobutanone synthesized from acetone technology, when other condition is identical, use its feed stock conversion of catalyst of the present invention and purpose product yield all to be significantly improved, illustrate that the catalyst of the inventive method preparation has higher activity and selectivity.
4, the specific embodiment
The preparation method of palladium-resin catalyst of the present invention, ion exchange process is carried out in employing in acid medium, adopt ion-exchange commonly used, the difference that contains the palladium amount according to prepared catalyst, the palladium salt in the control palladium saline solution and the concentration of acid medium, acid medium preferably with used palladium salt anionic same acids.
The palladium-resin catalyst that the inventive method obtains can be used for various suitable chemical reactions, as catalytically cracked gasoline ether hydro-etherification, acetone and hydroformylation step method synthesize methyl-isobutyl ketone etc.Carry the palladium resin catalyst in use, the palladium of ionic state will become Metal Palladium with hydrogen reducing, and method of reducing can adopt conventional hydrogen reducing, normal temperature reduction or add thermal reduction all can, but temperature can not surpass 120 ℃, but normal pressure during reduction, can pressurize, the catalyst after the reduction is not wanted ingress of air yet.
When the catalyst that the present invention extensively obtains uses, can adopt continuous reaction or intermittent reaction.When being used for acetone and hydrogen synthesize methyl-isobutyl reactive ketone, adopt charging fixed bed reactors down, reaction temperature preferably is controlled at 100～140 ℃ at 60～160 ℃; Reaction pressure is preferably in 5.0～7.0MPa at 4.0～8.0MPa; The acetone feed volume space velocity is at 0.5～2.5h
-1Be preferably in 0.5～1.5h
-1The inlet amount of hydrogen can change on a large scale, but hydrogen ketone is than not being lower than 0.5 (mol).
Further specify the result of use of the inventive method and acquisition product below by embodiment and Comparative Examples.
Embodiment 1
200ml Hydrogen resin cation and 200ml deionized water are added in the container, add 45mlPd then
2+Concentration is that the palladium nitrate of 0.076mol/L---nitric acid---water ternary solution carries out ion-exchange, H in the solution
+Concentration is 0.3mol/L.Be 30 minutes swap time, stirs, leaches waste liquid, extremely neutral with the deionized water washing after carrying out then.Obtain containing the catalyst of palladium 0.2% (heavy), be numbered S-1 butt.
Comparative Examples 1
Employing is with the identical method of embodiment 1, and just ion exchanged soln is a palladium nitrate aqueous solution, does not wherein contain acid, makes the catalyst D-1 that contains palladium 0.2%.
Embodiment 2
200ml Hydrogen resin cation and 200ml deionized water are added in the container, add 40ml Pd then
2+Concentration is palladium nitrate-nitric acid of 0.15mol/L---the water ternary solution carries out ion-exchange, H in the solution
+Concentration is 0.5mol/L.Operation must contain the catalyst S-2 of palladium 0.38% with embodiment 1
Comparative Examples 2
Employing is with the identical method of embodiment 2, and just ion exchanged soln is a palladium nitrate aqueous solution, does not wherein contain acid, makes the catalyst D-2 that contains palladium 0.38%.
More above-mentioned four kinds of catalyst palladium nitrate utilization rates relatively see Table 1.From table 1 data as can be seen, use the inventive method, the utilization rate of palladium has had comparatively significantly raising, and the post processing that is beneficial to exchange solution also can reduce cost.
Table 1
Catalyst drops into Pd
2+The residual Pd of amount exchange
2+Amount Pd
2+
* 10
-4(mol) * 10
-6(mol) utilization rate %
S-1 3.24 2.04 99.37
D-1 3.30 7.97 97.54
S-2 6.12 5.69 99.07
D-2 6.28 11.67 98.11
Embodiment 3:
Prepare catalyst S-3, wherein H with hydrochloric acid, palladium chloride aqueous solution
+Concentration is 3.0mol/L, and the preparation method is identical with enforcement 1.It is 0.2% that catalyst contains the palladium amount.
Embodiment 4:
With acetic acid is that acid medium prepares catalyst S-4, wherein H
+Concentration is 0.1mol/L, and the preparation method is identical with enforcement 1.It is 0.2% that catalyst contains the palladium amount.
Embodiment 5:
With nitric acid is that acid medium prepares catalyst S-5, wherein H
+Concentration is 0.05mol/L, and the preparation method is identical with enforcement 1.It is 0.05% that catalyst contains the palladium amount.
Embodiment 6:
With nitric acid is that acid medium prepares catalyst S-6, wherein H
+Concentration is 0.05mol/L, and the preparation method is identical with enforcement 1.It is 0.08% that catalyst contains the palladium amount.
Embodiment 7:
With 100ml S-1 catalyst, be divided into four fens in proportion, mix with the quartz sand of handling, mixed cumulative volume is 200ml.The internal diameter of packing into is in the stainless steel reactor of 25mm.Raw material acetone hydrogen enters from reaction bottom, and product is through cooling and gas-liquid separation, vapor phase hydrogen emptying or recycle the liquid-phase reaction product gas chromatographic analysis.Reaction temperature is 120 ℃, and pressure comes 6.0MPa, and the acetone feed air speed is 1.0h
-1The conversion ratio of acetone is 44.62% as a result, and the selectivity of methyl iso-butyl ketone (MIBK) is 96.48%.
Embodiment 8:
The acetone feed air speed is 4.0h
-1, other condition with embodiment 7 evaluate catalysts S-6 as a result the conversion ratio of acetone be 26.35%, the selectivity of methyl iso-butyl ketone (MIBK) is 97.29%.
Method difference evaluate catalysts S-2, S-3, S-4, S-5, D-1, D-2 with embodiment 7.Relatively the performance of different catalysts the results are shown in Table 2.From table 2 data as can be seen, activity of such catalysts that the inventive method obtains and selectivity compared with prior art all have raising by a relatively large margin.
Table 2
Palladium catalyst content (w) % acetone conversion % methyl iso-butyl ketone (MIBK) selectivity %
S-1 0.2 44.62 96.48
S-2 0.38 46.03 94.47
S-3 0.2 43.72 96.37
S-4 0.2 43.81 96.51
S-5 0.05 35.24 96.38
D-1 0.2 35.24 92.74
D-2 0.38 38.76 91.15
Claims (10)
1, a kind of preparation method of palladium-resin catalyst adopts to contain palladium solution and resin carries out ion-exchange, filters then, washs and make catalyst prod, it is characterized in that the described palladium solution that contains is that acidity contains palladium solution.
2,, it is characterized in that described resin is a strong-acid ion exchange resin according to the preparation method of the described palladium-resin catalyst of claim 1.
3,, it is characterized in that described resin is a strongly acidic styrene type cation exchange resin according to the preparation method of claim 1 or 2 described palladium-resin catalysts.
4,, it is characterized in that described acidity contains the H in the palladium solution according to the preparation method of the described palladium-resin catalyst of claim 1
+Concentration is 0.01～5.0mol/L.
5,, it is characterized in that described acidity contains the H in the palladium solution according to the preparation method of claim 1 or 4 described palladium-resin catalysts
+Concentration is 0.2～3.0mol/L.
6,, it is characterized in that described acidity contains the H in the palladium solution according to the preparation method of claim 1 or 4 described palladium-resin catalysts
+Concentration is 0.2～1.5mol/L.
7,, it is characterized in that the acid medium that described acidity contains palladium solution is nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid or C according to the preparation method of claim 1 or 4 described palladium-resin catalysts
1～C
5Organic acid.
8,, it is characterized in that the acid medium that described acidity contains palladium solution is the acid identical with the palladium salt anionic according to the preparation method of claim 1 or 4 described palladium-resin catalysts.
9,, it is characterized in that it is 0.01%～3.0% that prepared catalyst contains palladium in butt weight according to the preparation method of the described palladium-resin catalyst of claim 1.
10,, it is characterized in that it is 0.1%～1.0% that prepared catalyst contains palladium in butt weight according to the preparation method of claim 1 or 9 described palladium-resin catalysts.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109663 CN1211160C (en) | 2002-05-15 | 2002-05-15 | Process for preparing palladium-resin catalyst |
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|---|---|---|---|
| CN 02109663 CN1211160C (en) | 2002-05-15 | 2002-05-15 | Process for preparing palladium-resin catalyst |
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| CN1211160C CN1211160C (en) | 2005-07-20 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348505C (en) * | 2004-05-20 | 2007-11-14 | 哈尔滨工业大学 | Hydrogenation and deoxidization method for palladium ion type catalytic resin |
| CN100448543C (en) * | 2006-01-09 | 2009-01-07 | 中国石油化工股份有限公司 | Preparation method of Pd/resin catalyst |
| CN102309989A (en) * | 2010-06-30 | 2012-01-11 | 陶氏环球技术有限公司 | The mixed bed polyalcohol catalyst |
| CN103801409A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for sulfuration palladium/alumina catalyst |
| CN114436794A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for synthesizing methyl isoamyl ketone |
| CN115215718A (en) * | 2021-04-21 | 2022-10-21 | 中国石油化工股份有限公司 | Process for isobutene metathesis and use |
-
2002
- 2002-05-15 CN CN 02109663 patent/CN1211160C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348505C (en) * | 2004-05-20 | 2007-11-14 | 哈尔滨工业大学 | Hydrogenation and deoxidization method for palladium ion type catalytic resin |
| CN100448543C (en) * | 2006-01-09 | 2009-01-07 | 中国石油化工股份有限公司 | Preparation method of Pd/resin catalyst |
| CN102309989A (en) * | 2010-06-30 | 2012-01-11 | 陶氏环球技术有限公司 | The mixed bed polyalcohol catalyst |
| US8471069B2 (en) | 2010-06-30 | 2013-06-25 | Rohm And Haas Company | Mixed bed polymeric catalyst |
| CN102309989B (en) * | 2010-06-30 | 2014-12-31 | 陶氏环球技术有限公司 | Mixed bed polymeric catalyst |
| CN103801409A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method for sulfuration palladium/alumina catalyst |
| CN103801409B (en) * | 2012-11-08 | 2016-03-30 | 中国石油化工股份有限公司 | The preparation method of vulcanization type palladium/aluminium oxide catalyst |
| CN114436794A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for synthesizing methyl isoamyl ketone |
| CN115215718A (en) * | 2021-04-21 | 2022-10-21 | 中国石油化工股份有限公司 | Process for isobutene metathesis and use |
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|---|---|
| CN1211160C (en) | 2005-07-20 |
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Granted publication date: 20050720 |