CN1101269C - Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation - Google Patents
Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation Download PDFInfo
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- CN1101269C CN1101269C CN99120519A CN99120519A CN1101269C CN 1101269 C CN1101269 C CN 1101269C CN 99120519 A CN99120519 A CN 99120519A CN 99120519 A CN99120519 A CN 99120519A CN 1101269 C CN1101269 C CN 1101269C
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Abstract
The present invention discloses a catalyst for synthesizing methylisobutyl ketone by using acetone and hydrogen and a preparation method of the catalyst. The catalyst uses ion exchange resin as a carrier; and solvent extraction and purification treatment are carried out firstly before palladium is loaded. Metal palladium is active metal; and the content of the metal palladium is from 0.1 to 0.6w%. The catalyst overcomes the defect that the loss of sulfoacid roots is large in the primary stage of the operation of the existing catalyst, relieves corrosion to devices and simultaneously makes the catalyst have high activity and high stability; and the preparation method can reduce the production cost of MIBK.
Description
The present invention relates to a kind of Catalysts and its preparation method by acetone and hydrogen synthesize methyl-isobutyl ketone.
Methyl iso-butyl ketone (MIBK) (being called for short MIBK) is a kind of important organic solvent, is mainly used in paint, resin, coating, also is the organic synthesis raw material, generates methyl isobutyl alcohol through hydrogenation.The conventional production methods of MIBK is a three-step approach, and as US3,666,816 described methods owing to problems such as the production route are long, and intermediate is purified difficult, and productive rate is low, are progressively replaced by one-step synthesis process.Catalyst system therefor is divided into two classes in the one-step synthesis process, and the first kind is an organic catalyst, and as CN1069674A and US3,666,816 have just used Pd/Al respectively in methylisobutanone synthesized from acetone
2O
3With the Pd/ molecular sieve catalyst.Such catalyst advantage is that palladium be difficult for to run off, etching apparatus not, catalyst runs initial activity higher (especially in the 1000h); But such catalyst also has distinct disadvantage, and it is very fast that promptly organic catalyst is met the decline of water intensity.Owing to generate water in the synthetic MIBK reaction of acetone, after running to 1000h, its intensity descends rapidly the organic catalyst that is used for this reaction generally speaking, and organic catalyst reaches more than the 2000h rare running life.Because the existence of such this deadly defect of catalyst makes it that industrial application value not arranged, and does not see that so far any mineral-type catalyst carries out the report of commercial Application.
Second class is an organic catalyst, i.e. the Pd/ resin catalyst.This class catalyst is the catalyst that is used for the synthetic MIBK of acetone one-step method the earliest, also is unique so far catalyst that carries out industrial applications, as at US3,953, disclose a kind of Pd/ resin catalyst in 517, this catalyst advantage is that conversion ratio, selectivity are all better, and the life-span is also longer; But its shortcoming be in the operation process on the resin sulfonate radical loss is arranged, equipment is corrosive, the palladium that supports on the resin also has loss, and is influential service life to catalyst.
Purpose of the present invention is exactly for solving the shortcoming that the Pd/ resin catalyst exists, disclose a kind of loss that had both overcome the palladium sulfonate radical, alleviating the corrosion to equipment; Can improve conversion ratio and Catalysts and its preparation method optionally again.
Catalyst disclosed in this invention carries an amount of palladium by cationic ion-exchange resin to be made.Wherein used hydrogen type cation exchange resin is an ion exchange resin for the strongly acidic styrene, and its preparation method is US4, is introduced in 269,943.The Pd/ resin catalyst and the performance indications of the present invention's preparation are as follows: the exchange capacity of resin butt is 4.00～4.20meg/g, wet density 0.69～0.75g/ml, percentage of water loss 58～62w%, pore volume 0.36～0.39ml/g, average pore size 180～200 * 10
-10M, palladium content is 0.1～0.6w%, is preferably 0.2～0.5w%.
In the application process of Pd/ resin catalyst, also exist two problems at present: 1, sulfonate radical (SO in the reaction operation process
3H) run off, especially 300h runs off comparatively fast before the initial reaction stage, is lost to that sulfonate radical has corrosiveness to equipment in the reactant liquor.2, palladium runs off in the operation process, is that 300h runs off very fast before the start of run equally.These two problems of Pd/ resin catalyst are studied, and the result shows: start of run (about preceding 300h) sulfonic acid group runs off very fast, is because the used h type resin of preparation catalyst lacks due to the preliminary treatment.The storng-acid cation exchange resin building-up process has a sulfonating reaction step, and normal sulfonating reaction can make sulfonate radical be in the polymerization matrix.As scheme the position shown in the A.
But except that reaction (A), sulfonate radical can also combine with polymerization matrix or polymer fragment shown in figure (B)～(D) by different modes, and these sulfonate radicals with improper mode combination all are unstable structures under reaction condition, easily come off having under the water condition, that part of faster sulfonate radical of initial reaction stage sulfonate radical falling speed is exactly this part sulfonate radical.Palladium is downloaded on the sulfonate radical with ion-exchange on the Pd/ resin catalyst, because the existence of unstable sulfonate radical is combined in the unstable naturally easily loss of palladium on this part, it is exactly this reason that initial reaction stage part palladium easily runs off.If there is a kind of method before resin carries palladium, it to be carried out preliminary treatment, those unstable sulfonate radicals are removed, so both can reduce the corrosion of sulfonic acid to equipment, can overcome the loss of palladium again, prolong the service life of catalyst.
In addition, though ion exchange resin is insoluble basically, but, the complexity of the characteristics of macromolecular structure and molecular function fundamental reaction, crosslinked incomplete, strictly say always be mingled with the low-molecular-weight polymer that generates in the building-up process, reaction reagent in the new product, paraffin, soluble impurities such as sweller.The product that generally dispatches from the factory does not all pass through preliminary treatment.So, if utilize a kind of solvent, under certain condition soluble impurity in the resin duct and polymer fragment are developed, will make the resin duct unimpeded like that, inner surface increases, and also can improve the conversion ratio of catalyst, reduces the production cost of MIBK.
The present invention just is based on the preparation method that above-mentioned principle has proposed the Pd/ resin catalyst, its step is as follows: 1, solvent extraction: get a certain amount of sodium type cationic ion-exchange resin, place the Sha Shi extractor, be incorporated as 1～5 times of resin volume, be preferably 2～4 times solvent to it.This solvent boiling point is 70～130 ℃ alcohol and/or a ketone series solvent, is preferably methyl iso-butyl ketone (MIBK), MEK and/or n-butanol, resin is carried out solvent extraction handle, and treatment temperature is 70～130 ℃, is preferably 80～120 ℃; Processing time is 1.0～4.0h; Be preferably 2.0～3.0h.2, purified treatment: the resin after the extracting is placed 0.5～3.0mol, be preferably in the NaCl aqueous solution of 1.0～2.0mol, soak 4.0～8.0h, NaCl liquid consumption is 1～5 times of resin, be preferably 2～3 times,, handle 1.0～5.0h at 80～120 ℃, be preferably in 90～100 ℃, handle 2.0～4.0h.3, acid treatment: the sodium type resin after the purified treatment is adopted conventional acid treatment method, make it transfer h type resin to.4, carry palladium: h type resin is immersed dipping year palladium in the palladium saline solution, and palladium saline solution wherein is palladium nitrate or palladium chloride aqueous solution preferably.Stir 1.0～5.0h simultaneously, leach resin afterwards, be washed till neutrality with distilled water.Can obtain catalyst of the present invention.
The catalyst palladium on the resin before use needs become Metal Palladium with hydrogen reduction, and method of reducing can use the conventional reduction method, normal temperature or add thermal reduction all can, but can not surpass 80 ℃ at reduction temperature, but normal pressure during reduction can pressurize, can not ingress of air but reduce rear catalyst.
Course of reaction can adopt the fixed bed continuous feed, also can adopt the tank reactor intermittent feeding.
When course of reaction adopted the fixed bed continuous feed, reaction temperature was 100～150 ℃, and reaction pressure is 3.0～9.0Mpa, and the acetone feed volume space velocity is 0.5～3.0h
-1, H
2/ AC (v) is 300～1800; Being preferably reaction temperature is 115～140 ℃; Reaction pressure is 4.0～8.0MPa, and the feed volume air speed is 1.0～2.5h
-1, H
2/ AC (v) is 500～1500.
When employing tank reactor at intermittence, reaction temperature is 100～150 ℃, and reaction pressure is 3.0～9.0MPa, and the reaction time is 0.5～4.0h, H
2(v) be 300～1800, catalyst amount is 10～40 (v) % of acetone to/AC; Be preferably 110～140 ℃ of reaction temperatures, reaction pressure 4.0～8.0MPa, reaction time 1.0～3.5h, H
2/ AC (v) is 500～1500; Catalyst amount is 15～30 (v) % of acetone.
The used acetone of this reaction is industrial primes, content 〉=99w%; Hydrogen 〉=99v%.
Catalyst of the present invention is owing to adopted the step of extracting and purification in preparation process, make that unstable sulfonate radical seldom in this catalyst, therefore this catalyst reduces significantly in the loss of start of run sulfonate radical, has alleviated the corrosion to equipment, has overcome the loss of palladium; Simultaneously also make this catalyst have excellent activity and stability, and can reduce the MIBK production cost.
Embodiment 11, solvent extraction: get 100ml sodium type macroporous strong-acid cation-exchange resin and place the Sha Shi extractor, add 400ml methyl iso-butyl ketone (MIBK) (purity＞99w%) to it, resin is carried out solvent extraction handle 115 ℃ of extraction temperatures, extracting time 2.5h.2, purified treatment: the 100ml resin after the above-mentioned extracting is placed the 200ml 1mol NaCl aqueous solution, soak 4.0h, place the 1000ml autoclave afterwards, be heated to 100 ℃, constant temperature 3.5h is washed till neutrality afterwards.3, acid treatment: transfer the 100ml sodium type resin after the purified treatment to Hydrogen, promptly handle sodium type resin, make it to be converted to h type resin, be washed till neutrality with distilled water afterwards with 4 times 1mol hydrochloric acid solution.4, carry palladium: above-mentioned 100ml h type resin is immersed 200ml contain in the palladium nitrate aqueous solution of 0.06gPd, stir simultaneously and lasting 3.5h, leach resin afterwards, be washed till neutrality, promptly get and contain the Pd amount and be 0.2w% catalyst, called after MB-1 with distilled water.
Embodiment 2
Get 100ml sodium type resin, take with embodiment 1 in identical treatment step, different is in the step 1, and solvent changes MEK into that (purity＞99w%), consumption is 200ml, and treatment temperature is 80 ℃, and the processing time is 3h; Soak time is 6.0h in the step 2, and temperature is 95 ℃, and the NaCl solution concentration is 2.0mol, and consumption is 300ml, and the processing time is 2.0h; Gained 100ml h type resin is immersed in it in palladium chloride solution that contains palladium 0.08g again, and other is with embodiment 1, and it is 0.25w% that the catalyst that makes contains Pd, called after MB-2.
Embodiment 3
Get 100ml sodium type resin, take with embodiment 1 in identical treatment step, gained 100ml h type resin is immersed in it in palladium nitrate solution that contains palladium 0.12g again, the stirring duration that different is in the step 3 is 4.0h, other is with embodiment 1.It is 0.40w% that the catalyst that makes contains Pd, called after MB-3.
Embodiment 4
Get 100ml sodium type resin, take with embodiment 1 in identical treatment step, different is: solvent changes n-butanol into (purity＞99w%), consumption is 200ml, and treatment temperature is 118 ℃, and the processing time is 3h in the step 1; Soak time is 7.0h in the step 2, and treatment temperature is 95 ℃, and the NaCl solution concentration is 2.0mol, and consumption is 400ml, and the processing time is 2.0h; Gained 100ml h type resin is immersed in it in palladium nitrate solution that contains palladium 0.15g again, and the stirring duration that different is in the step 3 is 2.0h, and other is with embodiment 1, and it is 0.50w% that the catalyst that makes contains Pd, called after MB-4.
Embodiment 5
Get MB-2 catalyst 100ml, internal diameter Φ 25mm, long in the white steel pipe type reactor of 1000mm packs into after mixing with 100ml 10～40 order quartz sands, raw material acetone, hydrogen enters from reactor head, product is through cooling and gas-liquid separation, vapor phase hydrogen recycles or emptying, and the liquid-phase product composition is used gas chromatographic analysis, and liquid-phase product sulfonate radical content is analyzed with chemical method.The operating condition of MB-2 catalyst and the results are shown in Table 1.
Table 1, the operating condition of MB-2 catalyst and result
| Reaction temperature, ℃ | ?140 | ||||
| Reaction pressure, MPa | ?6.0 | ||||
| Air speed, h -1 | ?2.5 | ||||
| H 2/AC，v | ?800 | ||||
| Conversion ratio, mol% | ?45.77 | ?45.71 | ?45.11 | ?45.08 | ?45.10 |
| The MIBK selectivity, mol% | ?92.44 | ?92.34 | ?92.71 | ?92.01 | ?92.21 |
| Sulfonate radical concentration in the product, ppm | ?57 | ?42 | ?37 | ?24 | ?24 |
| Accumulated running time, h | ?10 | ?100 | ?200 | ?300 | ?350 |
Embodiment 6～8
Get catalyst 100ml, with 100ml 10～40 order quartz sands internal diameter Φ 25mm that packs into after the dilution that is mixed, length is in the white steel pipe type reactor of 1000 mm, and other is with embodiment 5, concrete operating condition and the results are shown in Table 2.
The operating condition of table 2 embodiment 6～8 and result
| Embodiment | 6 | ?7 | ?8 |
| The catalyst numbering | MB-4 | ?MB-1 | ?MB-3 |
| Reaction temperature, ℃ | 115 | ?120 | ?130 |
| Reaction pressure, MPa | 5.0 | ?8.0 | ?4.0 |
| Air speed, h -1 | 1.0 | ?2.5 | ?2.5 |
| H 2/AC，v | 500 | ?1000 | ?1500 |
| Conversion ratio, mol% | 47.02 | ?36.18 | ?41.21 |
| The MIBK selectivity, mol% | 92.03 | ?96.09 | ?94.42 |
Embodiment 9～12
Get a certain amount of catalyst, acetone and pack in the 100ml autoclave, estimate, other is with embodiment 5, reaction condition and the results are shown in Table 3.
Table 3 batch process reaction condition and result
| Embodiment | 9 | ?10 | ?11 | ?12 |
| The catalyst numbering | MB-4 | ?MB-1 | ?MB-3 | ?MB-2 |
| Reaction temperature, ℃ | 110 | ?120 | ?120 | ?140 |
| Reaction pressure, MPa | 4.0 | ?6.0 | ?5.0 | ?8.0 |
| Reaction time, h | 2.5 | ?1.0 | ?3.5 | ?1.0 |
| H 2/ catalyst, v | 500 | ?400 | ?800 | ?1500 |
| The acetone consumption, ml | 30 | ?30 | ?60 | ?30 |
| Catalyst amount, ml | 10 | ?10 | ?10 | ?10 |
| Conversion ratio, mol% | 34.26 | ?28.51 | ?49.35 | ?32.77 |
| The MIBK selectivity, mol% | 90.32 | ?94.71 | ?91.08 | ?89.74 |
Embodiment 13
Get the internal diameter Φ 25mm that packs into after MB-4 catalyst 100ml and 100ml 10～40 order quartz sands are mixed, in the white steel pipe type reactor of long 1000ml, carry out the stability experiment of 1500h, other is with embodiment 5.The condition of stability experiment and the results are shown in Table 4.
Table 4 MB-4 catalyst stability experimental conditions and result
| Reaction temperature, ℃ | ?115 | ?120 | ?120 | ?120 | ?120 |
| Reaction pressure, MPa | ?6.0 | ?6.0 | ?6.0 | ?6.0 | ?6.0 |
| Air speed, h -1 | ?1.0 | ?2.5 | ?2.5 | ?2.5 | ?2.5 |
| H 2/AC，v | ?500 | ?500 | ?500 | ?500 | ?500 |
| Conversion ratio, mol% | ?47.44 | ?36.27 | ?35.58 | ?33.89 | ?38.92 |
| The MIBK selectivity, mol% | ?92.83 | ?96.19 | ?95.72 | ?94.12 | ?93.08 |
| Accumulated running time, h | ?350 | ?600 | ?900 | ?1300 | ?1500 |
Comparing embodiment 1
Get 100ml sodium type resin, omit 1,2 treatment steps among the embodiment 2, only handle by the step of 3,4 among the embodiment 2, other makes the catalyst that contains Pd 0.25w% with embodiment 2, called after B-1.B-1 catalyst 100ml and 100ml10～40 order quartz sands is evenly mixed, and the internal diameter Φ 25mm that packs in the white steel pipe type reactor of long 1000ml, is 140 ℃ in reaction temperature, and reaction pressure is 6.0MPa, and the liquid air speed is 2.5h
-1, H
2(v) be under 800 conditions, the B-1 catalyst to be estimated, other is with embodiment 5 for/AC.Evaluation result sees Table 5.
Table 5 B-1 catalyst result
| Conversion ratio, mol% | 40.71 | ?40.57 | ?39.81 | ?39.16 | |||
| The MIBK selectivity, mol% | 90.59 | ?90.22 | ?89.24 | ?89.01 | |||
| Contain sulfonate radical concentration in the product, ppm | 57 | ?128 | ?147 | ?120 | ?81 | ?25 | ?24 |
| Accumulated running time, h | 10 | ?100 | ?200 | ?300 | ?350 | ?400 | ?450 |
It is very little in start of run sulfonate radical concentration to further specify catalyst of the present invention by above embodiment, illustrates that sulfonate radical runs off seldom, has so just alleviated the corrosion to equipment; And can find out also that by the contrast of the data of table 1 and table 5 catalyst selectivity of the present invention and conversion ratio all are higher than the comparative catalyst.
Claims (10)
1, a kind of is the catalyst of raw material synthesize methyl-isobutyl ketone with acetone and hydrogen, with the hydrogen type cation exchange resin is carrier, Metal Palladium is an active component, this catalyst characteristics is: the butt exchange capacity of resin is 4.00～4.20meq/g, wet density is 0.69～0.75g/ml, percentage of water loss is 58～62w%, and pore volume is 0.36～0.39ml/g, and average pore size is 180～200 * 10
-10M, palladium content are 0.1～0.6w%; Catalyst adopts following method preparation:
(1) solvent extraction: get sodium type cationic ion-exchange resin, to the solvent that wherein is incorporated as 1～5 times of resin volume, this solvent is the alcohol and/or the ketone series solvent of 70～130 ℃ of boiling points, resin is carried out solvent extraction handle, treatment temperature is 70～130 ℃, and the processing time is 1.0～4.0h;
(2) purified treatment: the resin after the extracting is placed the NaCl aqueous solution of 0.5～3.0mol, soak 4.0～8.0h, the NaCl solution usage is 1～5 times of resin, handles 1.0～5.0h down at 80～120 ℃;
(3) acid treatment: with the sodium type resin after the purified treatment, make sodium type resin be converted to h type resin, be washed till neutrality with distilled water afterwards with conventional acid treatment method;
(4) carry palladium: h type resin is immersed dipping year palladium in the palladium saline solution, stir 1.0～5.0h simultaneously, leach resin afterwards, be washed till neutrality, can obtain catalyst of the present invention with distilled water.
2, according to the described catalyst of claim 1, wherein palladium content is 0.2～0.5w%.
3, according to the described catalyst of claim 1, it is characterized in that the described solvent of step (1) of method for preparing catalyst is methyl iso-butyl ketone (MIBK), MEK and/or n-butanol, consumption is 2～4 times of resin volume.
4,, it is characterized in that the treatment temperature described in the step (1) of method for preparing catalyst is 80～120 ℃, processing time 2.0～3.0h according to the described catalyst of claim 1.
5, according to the described catalyst of claim 1, it is characterized in that the NaCl concentration of aqueous solution described in the step (2) of method for preparing catalyst is 1.0～2.0mol, solution usage is 2～3 times of resin volume, handles 2.0～4.0h down at 90～100 ℃.
6,, it is characterized in that the palladium saline solution described in the step (4) of method for preparing catalyst is palladium nitrate or palladium chloride aqueous solution according to the described catalyst of claim 1.
7, a kind of preparation method of methyl iso-butyl ketone (MIBK) adopts the fixed bed continuous feed, and reaction temperature is 100～150 ℃, and reaction pressure is 3.0～9.0MPa, and the acetone feed volume space velocity is 0.5～3.0h
-1, H
2/ AC volume ratio is 300～1800, it is characterized in that catalyst is the described catalyst of claim 1.
8, according to the described preparation method of claim 7, it is characterized in that described reaction temperature is 115～140 ℃, reaction pressure is 4.0～8.0MPa, the acetone feed volume space velocity is 1.0～2.5h
-1, H
2/ AC volume ratio is 500～1500.
9, a kind of preparation method of methyl iso-butyl ketone (MIBK) adopts intermittently tank reactor, and reaction temperature is 100～150 ℃, and reaction pressure is 3.0～9.0MPa, and the reaction time is 0.5～4.0h, H
2/ AC volume ratio is 300～1800, and the volume ratio of catalyst amount and amounts of acetone is 10～40%, it is characterized in that catalyst is the described catalyst of claim 1.
10, according to the described preparation method of claim 9, it is characterized in that described reaction temperature is 110～140 ℃, reaction pressure is 4.0～8.0MPa, the reaction time is 1.0～3.5h, H
2/ AC volume ratio is 500～1500, and the volume ratio of catalyst amount and amounts of acetone is 15～30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99120519A CN1101269C (en) | 1999-09-17 | 1999-09-17 | Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99120519A CN1101269C (en) | 1999-09-17 | 1999-09-17 | Catalyst for synthesizing methyl isobutyl ketone with acetone and its preparation |
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| Publication Number | Publication Date |
|---|---|
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| CN1101269C true CN1101269C (en) | 2003-02-12 |
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Families Citing this family (3)
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|---|---|---|---|---|
| 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 |
| TWI457175B (en) * | 2010-06-30 | 2014-10-21 | Dow Global Technologies Llc | Mixed bed polymeric catalyst and use thereof |
| CN104588098B (en) * | 2013-11-01 | 2017-05-31 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of synthesizing methyl isobutyl ketone catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953517A (en) * | 1967-09-08 | 1976-04-27 | Veba-Chemie Aktiengesellschaft | Process for preparing methyl isobutyl ketone and catalyst |
| JPS615038A (en) * | 1984-06-18 | 1986-01-10 | Sumitomo Chem Co Ltd | Process for direct conversion of diacetone alcohol to methyl isobutyl ketone |
| CN1080564A (en) * | 1993-05-04 | 1994-01-12 | 中国石油化工总公司抚顺石油化工研究院 | The Catalysts and its preparation method of synthesize methyl-isobutyl ketone |
-
1999
- 1999-09-17 CN CN99120519A patent/CN1101269C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953517A (en) * | 1967-09-08 | 1976-04-27 | Veba-Chemie Aktiengesellschaft | Process for preparing methyl isobutyl ketone and catalyst |
| JPS615038A (en) * | 1984-06-18 | 1986-01-10 | Sumitomo Chem Co Ltd | Process for direct conversion of diacetone alcohol to methyl isobutyl ketone |
| CN1080564A (en) * | 1993-05-04 | 1994-01-12 | 中国石油化工总公司抚顺石油化工研究院 | The Catalysts and its preparation method of synthesize methyl-isobutyl ketone |
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