CN103801409A - Preparation method for sulfuration palladium/alumina catalyst - Google Patents
Preparation method for sulfuration palladium/alumina catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method for a sulfuration palladium/alumina catalyst. The method comprises the following steps: preparing an impregnating solution containing palladium and impregnating an alumina carrier in a part of the impregnating solution containing palladium; then adding a proper amount of a sodium alkyl xanthate solution drop by drop, wherein a catalyst intermediate is obtained after impregnation; and impregnating the catalyst intermediate in the rest impregnating solution containing palladium and carrying out drying and roasting so as to obtain the sulfuration palladium/alumina catalyst. The method provided by the invention overcomes the disadvantage of mismatching between a hydrogenation function and a condensation dehydration function of a conventional oxidized palladium/alumina catalyst for synthesis of methyl isobutyl ketone from acetone, and when used for synthesis of methyl isobutyl ketone from acetone, the prepared catalyst has superior reaction activity than catalysts used in conventional processes.
Description
Technical field
The present invention relates to a kind of preparation method of vulcanization type palladium/aluminium oxide catalyst, especially a kind of preparation method of methylisobutanone synthesized from acetone catalyst.
Background technology
Methyl iso-butyl ketone (MIBK) (being called for short MIBK) is a kind of important water, is mainly used in paint, cold coating, waxy oil dewaxing, is also one of raw material of producing by rubber antioxidant 4020, of many uses.
Traditional production method is three-step approach, has the problems such as contaminated environment, production cost is high, flow process is numerous and diverse, is eliminated gradually.One-step method is the state-of-the-art technology of methylisobutanone synthesized from acetone, and this technical requirement catalyst must have difunctional activated centre, i.e. condensation dehydration acid centre and hydrogenation sites.
Pd/ resin catalyst is to synthesize MIBK commercial plant for acetone through one-step method the earliest.Such catalyst generally adopts storng-acid cation exchange resin to immerse that ion-exchange obtains containing carrying out in the aqueous solution of palladium.So in the time of ion-exchange, the H on resin on some sulfonate radical
+by Pd
2+exchange is got off, Pd
2+after hydrogen reducing as hydrogenating function center, the H on another part sulfonate radical
+as the condensation function center of catalyst.The advantage of such catalyst is production technology maturation, conversion ratio, selectively also better; Shortcoming is that sulfonate radical easily comes off, and palladium easily runs off, and catalyst life is shorter.
The another kind of catalyst for the synthetic MIBK of acetone through one-step method is mineral-type catalyst, as Pd/Al
2o
3with Pd/ molecular sieve, such catalyst advantage is that palladium is difficult for running off, and not etching apparatus, as CN1069674A, US3666816, CN1255404A, CN1385241A.The conversion ratio of Pd/ molecular sieve catalyst, selectively relatively can, in the synthetic MIBK course of reaction of acetone, generate water, catalyst is met water intensity and active decline comparatively fast in reaction, and catalyst cost is higher, cause methyl iso-butyl ketone (MIBK) production cost to raise, due to this deadly defect of such catalyst, make it there is no industrial application value.
Pd/Al
2o
3catalyst is for methylisobutanone synthesized from acetone, catalyst initial stage hydrogenation activity is higher, cause and difunctionally do not mate, as under same conversion ratio, this catalyst selectivity is lower than Pd/ molecular sieve catalyst, generally when acetone conversion >40mol%, product selectivity < 95mol %.
For the Pd/Al of methylisobutanone synthesized from acetone
2o
3catalyst adopts the method for presulfurization in device conventionally, is about to the Pd/Al that adopts conventional method to prepare
2o
3catalyst packs in reactor, first after reduction, then carries out presulfurization in device, so that the too high part palladium atom passivation of hydrogenation activity is selective to improve, such as the disclosed method of CN99113289.0.This technical process is complicated, and cure time is long, and operating cost is high, affects the operating efficiency of device.
Summary of the invention
The problem existing for prior art, the invention provides a kind of vulcanization type Pd/ Al
2o
3the preparation method of catalyst.By the method gained catalyst, when by methylisobutanone synthesized from acetone course of reaction, its activity, selective and life-span all increase than existing method.
Vulcanization type Pd/ Al of the present invention
2o
3the preparation method of catalyst, comprising:
(1) preparation is containing the maceration extract of palladium, and maceration extract is acid,
(2) alumina support is immersed in to part containing in the maceration extract of palladium, then drips alkyl xanthogenic acid sodium solution, after dipping finishes, filter, be dried, obtain catalyst intermediate,
(3) catalyst intermediate is joined and flood remaining containing in the maceration extract of palladium, dry, roasting, obtain vulcanization type Pd/ Al
2o
3catalyst;
Wherein, the concentration of alkyl xanthogenic acid sodium solution is 0.1wt% ~ 1.0wt%, is preferably 0.3 wt% ~ 0.6 wt%, and in alkyl xanthogenic acid sodium and step (2) maceration extract used, the mol ratio of palladium atom is 2.0:1.0 ~ 3.0:1.0; The ratio of step (2) the maceration extract volume containing palladium used and step (3) the maceration extract volume containing palladium used is 1.0:1.0 ~ 1.0:3.0, preferably 1.0:1.5 ~ 1.0:2.5.
The carbon number of the alkyl in described alkyl xanthogenic acid sodium is 2 ~ 4.
Described vulcanization type Pd/ Al
2o
3in catalyst, the weight content of palladium is counted 0.1wt% ~ 0.7wt% with metal, preferably 0.2wt% ~ 0.6wt%.
Described alumina support, is generally gamma-aluminium oxide carrier, and its character is preferably as follows: specific area 140 ~ 260m
2/ g, preferably 180 ~ 200m
2/ g; Pore volume 0.3～0.8 mL/g, preferably 0.3～0.6mL/g; The shape of described alumina support can be spherical or strip, can be also other any suitable shape.
The described maceration extract containing palladium can adopt conventional method preparation, such as by soluble in water soluble palladium salt, preferably deionized water, it is acid regulating the pH value of maceration extract with inorganic acid again, preferably pH value is 2 ~ 4, in maceration extract, the concentration of palladium is 0.1wt% ~ 1.0wt%, preferably 0.1 wt% ~ 0.6 wt%.Described inorganic acid can be one or more in nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid etc.Described soluble palladium salt is one or more in palladium nitrate, palladium bichloride etc.
The inventive method step (2) detailed process is as follows: alumina support is immersed in to part containing in the maceration extract of palladium 2 ~ 4 hours, then drips alkyl xanthogenic acid sodium solution, then flood 2 ~ 4 hours, filter, dry after dipping finishes, obtain catalyst intermediate.In the inventive method, the described dipping of step (2) adopts supersaturation or saturated infusion process.When the alkyl xanthogenic acid sodium of described dropping, the temperature of reaction system is 60 ~ 80 ℃.After described immersion filtration, the dry of catalyst is to be dried 4～8 hours at 105～120 ℃,
The method of the dipping residual metallic palladium described in step (3) adopts conventional dipping method, i.e. supersaturation or saturated infusion process.The catalyst intermediate that step (2) is obtained is put into remaining acid maceration extract, floods 4 ~ 8 hours, after finishing, at 105～110 ℃, is dried 4～8 hours, and sintering temperature is 350～480 ℃, and roasting time 4～8 hours, obtains final catalyst prod.
The vulcanization type Pd/ Al of the inventive method gained
2o
3catalyst, will process through reduction before use, and this method of reducing can adopt conventional method of reducing, preferably adopts hydrogen reducing, and reducing condition is as follows: pressure 1.0～6.0MPa, 100～120 ℃ of temperature, 4～8 hours time, gas agent volume ratio 300 ~ 500.
In the synthetic MIBK reaction of acetone through one-step method, condensation dehydration acid centre and the distribution situation of hydrogenation sites on catalyst directly affect the coupling of two functions in catalyst.Palladium catalyst too high levels, hydrogenation activity strengthens, and easily causes acetone directly to be generated isopropyl alcohol by hydrogenation.The acid centre too high levels of catalyst, palladium content is too low, easily cause the isopropylidene acetone part that condensation dehydration generates on acid site not generated MIBK by hydrogenation, thereby affect the activity and selectivity of catalyst, and along with the growth of catalyst runs time, carbon distribution can make partial hydrogenation activated centre poisoning, and therefore palladium content is too low, also affects the life-span of catalyst.
Therefore, the present invention is in catalyst preparation process, step (2) adopts alumina support containing flooding certain hour in the acid maceration extract of palladium, make the palladium ion in maceration extract adsorb and be impregnated in alumina support duct in acid maceration extract, drip again excessive alkyl xanthogenic acid sodium solution and continue dipping, the alkyl xanthogenic acid sodium dripping in dipping process, palladium ion and alkyl xanthogenic acid sodium in carrier hole are reacted in carrier hole, the palladium sulfide uniform deposition generating is in carrier duct, be conducive to like this deposition of palladium salt, thereby prepare support type sulphurized catalyst intermediate, the catalyst intermediate in step (3), step (2) being obtained is flooded in acid palladium nitrate maceration extract, dry, roasting, can make palladium crystal grain high degree of dispersion be carried on alumina support surfaces externally and internally, and then palladium and palladium sulfide are evenly distributed on the surfaces externally and internally of carrier, be that even type distributes, but not eggshell type distributes.
Find after deliberation, in catalyst preparation process, first use excessive vulcanizing agent to vulcanize the Metal Palladium of carrier loaded certain component, make sulfuration more even, abundant, vulcanization type Metal Palladium decentralization is high, then load residual metallic component, the catalyst obtaining like this has good presulfurization effect, vulcanization type palladium in the passivation of catalyst initial stage the hydrogenation activity of palladium, make difunctional coupling better of catalyst, thereby improved the activity and selectivity of catalyst.Along with the growth of the duration of runs, vulcanization type palladium can progressively be converted into active palladium in atmosphere of hydrogen, and catalyst life is extended.
The catalyst of the inventive method gained is applicable to methylisobutanone synthesized from acetone process.
Catalyst of the present invention does carrier with gama-alumina, cheap, has good heatproof effect, and range of reaction temperature is widened, and extend service cycle, and catalyst preparation process is easy, has reduced the production cost of product.
The specific embodiment
Below in conjunction with embodiment, the present invention is done to further detailed explanation; it should be noted; following examples are not limiting the scope of the invention; those skilled in the art is in conjunction with description of the present invention and can do suitable expansion in full, and these expansions should be all protection scope of the present invention.In the present invention, v% is volume fraction, and wt% is mass fraction.
Embodiment 1
(1), the preparation of maceration extract
By Pd (NO
3)
22H
2o is put in 200 ml beakers, adds deionized water to dissolve, and by nitric acid adjusting maceration extract pH value to 4, is mixed with the dipping solution containing palladium 0.15wt%.
(2), load vulcanization type active component
Palladium amount 0.5wt% is carried in Catalyst Design.
Sodium ethylxanthate is put in 200 ml beakers, adds deionized water to dissolve, be mixed with the solution containing sodium ethylxanthate 0.5wt%.
Measure containing 14 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, get 10g gama-alumina (specific area 189m
2/ g, pore volume 0.4mL/g) pour into wherein, flood 3 hours, then beaker is put into water-bath, 65 ℃ of heating-up temperatures, drip containing 11 milliliters of the solution of sodium ethylxanthate 0.5wt%, the molar ratio of sodium ethylxanthate and palladium is 2.0:1, stirs dipping 3 hours gently, removes by filter residual solution, be dried 6 hours at 115 ℃, obtain catalyst intermediate.
(3) load oxidized form active component
Measure containing 23 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, step (2) is obtained to such an extent that catalyst intermediate is poured into wherein, flood 6 hours, filter, be dried 6 hours at 105 ℃, 400 ℃ of roastings 6 hours, obtain finished catalyst M-1.
Embodiment 2
(1) with embodiment 1
(2), load vulcanization type active component
Palladium amount 0.40wt% is carried in Catalyst Design.
Propyl group sodium xanthogenate is put in 200 ml beakers, adds deionized water to dissolve, be mixed with the solution containing propyl group sodium xanthogenate 0.5wt%
Measure containing 10 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, getting 10g gama-alumina (character is with embodiment 1) pours into wherein, flood 4 hours, then beaker is put into water-bath, 70 ℃ of heating-up temperatures, drip containing 10 milliliters of the solution of propyl group sodium xanthogenate 0.5wt%, the molar ratio of propyl group sodium xanthogenate and palladium is 2.3:1, stirs dipping 4 hours gently, removes by filter residual solution, be dried 6 hours at 115 ℃, obtain catalyst intermediate.
(3) load oxidized form active component
Measure containing 17 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, step (2) is obtained to such an extent that catalyst intermediate is poured into wherein, conventional dipping 3 hours, filters, 105 ℃ dry 6 hours, 400 ℃ of roastings 7 hours, obtain finished catalyst M-2.
Embodiment 3
(1) with embodiment 1
(2), load vulcanization type active component
Palladium amount 0.30wt% is carried in Catalyst Design.
Sodium ethylxanthate is put in 200 ml beakers, adds deionized water to dissolve, be mixed with the solution containing sodium ethylxanthate 0.5wt%.
Measure containing 6 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, getting 10g gama-alumina (character is with embodiment 1) pours into wherein, flood 3 hours, then beaker is put into water-bath, 65 ℃ of heating-up temperatures, drip containing 6 milliliters of the solution of sodium ethylxanthate 0.5wt%, the molar ratio of sodium ethylxanthate and palladium is 2.2:1, stirs dipping 4 hours gently, removes by filter residual solution, be dried 6 hours at 115 ℃, obtain catalyst intermediate.
(3) load oxidized form active component
Measure containing 14 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, step (2) is obtained to such an extent that catalyst intermediate is poured into wherein, conventional dipping 5 hours, filters, 105 ℃ dry 6 hours, 450 ℃ of roastings 6 hours, obtain finished catalyst M-3.
Embodiment 4
(1) with embodiment 1
(2), load vulcanization type active component
Palladium amount 0.25wt% is carried in Catalyst Design.
Sodium n-butyl-xanthate is put in 200 ml beakers, adds deionized water to dissolve, be mixed with the solution containing sodium n-butyl-xanthate 0.5wt%.
Measure containing 6 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, getting 10g gama-alumina (character is with embodiment 1) pours into wherein, flood 3 hours, then beaker is put into water-bath, 65 ℃ of heating-up temperatures, drip containing 6 milliliters of the solution of sodium n-butyl-xanthate 0.5wt%, the molar ratio of sodium n-butyl-xanthate and palladium is 2.0:1, stirs gently 4 hours, removes by filter residual solution, be dried 8 hours at 115 ℃, obtain catalyst intermediate.
(3) load oxidized form active component
Measure containing 11 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, step (2) is obtained to such an extent that catalyst intermediate is poured into wherein, conventional dipping 5 hours, filters, 105 ℃ dry 6 hours, 450 ℃ of roastings 7 hours, obtain finished catalyst M-4.
Example executes 5
(1) with embodiment 1
(2), load vulcanization type active component
Palladium amount 0.6wt% is carried in Catalyst Design.
Sodium n-butyl-xanthate is put in 200 ml beakers, adds deionized water to dissolve, be mixed with the solution containing sodium n-butyl-xanthate 0.5wt%.
Measure containing 14 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, getting 10g gama-alumina (character is with embodiment 1) pours into wherein, flood 3 hours, then beaker is put into water-bath, 75 ℃ of heating-up temperatures, drip containing 14 milliliters of the solution of sodium n-butyl-xanthate 0.5wt%, the molar ratio of sodium n-butyl-xanthate and palladium is 2.0:1, stirs dipping 4 hours gently, removes by filter residual solution, be dried 8 hours at 115 ℃, obtain catalyst intermediate.
(3) load oxidized form active component
Measure containing 26 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, step (2) is obtained to such an extent that catalyst intermediate is poured into wherein, conventional dipping 7 hours, filters, 105 ℃ dry 6 hours, 450 ℃ of roastings 7 hours, obtain finished catalyst M-5.
Comparative example 1
(1) with embodiment 1
(2) load oxidized form active component
Palladium amount 0.5wt% is carried in Catalyst Design.
Measure containing 34 milliliters of the dipping solutions of palladium 0.15wt% in 200 ml beakers, get 10g gama-alumina (character is with embodiment 1) and pour into wherein, stir gently 5 hours, remove by filter residual solution, be dried 7 hours at 105 ℃, 400 ℃ of roastings 6 hours, obtain finished catalyst DM-1.
Embodiment 6 ~ 10
The reaction unit of evaluate catalysts is internal diameter 8mm, the continuous microreactor of stainless steel tubular type of long 300mm, reaction upper feeding, reaction mass flows out from reactor bottom, enters separator after cooling, gas phase circulation of tail gas or metering emptying, liquid phase timing sampling, uses gas chromatographic analysis.
Get the each 5g of catalyst prepared in embodiment 1 ~ 5 (being broken into 8 ~ 24 orders mixes with 5mL 24 ~ 40m object quartz sand), be respectively charged in reactor, airtight qualified after, first logical hydrogen (the electrolytic cleaning hydrogen of 99v%) carries out the reduction of catalyst, and reducing condition is: 100 ℃ of reduction temperatures; Pressure 4.0MPa; Gas agent volume ratio 500; 4 hours time.
After reduction finishes, enter acetone raw material, be warming up to gradually reaction temperature, react by reaction condition.Operating condition and the results are shown in Table 1.
Comparative example 2
Evaluate reaction unit, Catalyst packing and the reducing condition of comparative example DM-1 oxidation catalyst with embodiment 6, after reduction finishes, enter the presulfurization stage.Detailed process: (1) formulating vulcanization oil, accurately take dimethyl disulfide 0.0044g and be dissolved in 20mL acetone, mix, acetone consumption is 4 times of catalyst volume, wherein the molar ratio of sulphur and palladium is 0.4:1, (2) presulfurization, 120 ℃ of curing temperatures; Pressure 3.5MPa; Sulfuration air speed 2.0h
-1.Sulfurized oil has entered rear switching raw material acetone and has transferred the normal reaction stage to.Operating condition and the results are shown in Table 1.
Table 1
| ? | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 2 |
| Catalyst numbering | M-1 | M-2 | M-3 | M-4 | M-5 | DM-1 |
| Reaction temperature, ℃ | 160 | 170 | 160 | 180 | 150 | 160 |
| Reaction pressure, MPa | 6.0 | 5.0 | 5.0 | 6.0 | 6.0 | 6.0 |
| Air speed, h -1 | 2.0 | 1.5 | 1.5 | 1.0 | 1.0 | 2.0 |
| The duration of runs, h | 500 | 500 | 500 | 500 | 500 | 500 |
| H 2/AC，(v) | 500 | 600 | 700 | 800 | 800 | 500 |
| Conversion ratio, mol% | ?45.98 | 46.52 | 44.65 | 45.81 | 47.91 | 45.14 |
| MIBK is selective, mol% | 97.77 | 97.59 | 97.79 | ?97.86 | 97.66 | 97.57 |
Claims (14)
1. a vulcanization type Pd/ Al
2o
3the preparation method of catalyst, comprising:
(1) preparation is containing the maceration extract of palladium, and maceration extract is acid,
(2) alumina support is immersed in to part containing in the maceration extract of palladium, then drips alkyl xanthogenic acid sodium solution, after dipping finishes, filter, be dried, obtain catalyst intermediate,
(3) catalyst intermediate is joined and flood remaining containing in the maceration extract of palladium, dry, roasting, obtain vulcanization type Pd/ Al
2o
3catalyst;
Wherein, the concentration of alkyl xanthogenic acid sodium solution is 0.1wt% ~ 1.0wt%, and in alkyl xanthogenic acid sodium and step (2) maceration extract used, the mol ratio of palladium atom is 2.0:1.0 ~ 3.0:1.0; The ratio of step (2) the maceration extract volume containing palladium used and step (3) the maceration extract volume containing palladium used is 1.0:1.0 ~ 1.0:3.0.
2. the concentration that in accordance with the method for claim 1, it is characterized in that described alkyl xanthogenic acid sodium solution is 0.3 wt% ~ 0.6 wt%.
3. in accordance with the method for claim 1, it is characterized in that step (2) the maceration extract volume containing palladium used and the ratio of step (3) the maceration extract volume that contains palladium used are 1.0:1.5 ~ 1.0:2.5.
4. the carbon number that in accordance with the method for claim 1, it is characterized in that the alkyl in described alkyl xanthogenic acid sodium is 2 ~ 4.
5. the gross weight content that in accordance with the method for claim 1, it is characterized in that palladium in described catalyst is counted 0.1wt% ~ 0.7wt% with metal.
6. in accordance with the method for claim 1, it is characterized in that described alumina support is gamma-aluminium oxide carrier, its character is as follows: specific area 140 ~ 260m
2/ g; Pore volume 0.3～0.8 mL/g.
7. in accordance with the method for claim 1, it is characterized in that the described the equipment of dipping liquid method containing palladium is as follows: by soluble in water soluble palladium salt, then to regulate the pH value of maceration extract with inorganic acid be acidity, and in maceration extract, the concentration of palladium is 0.1wt% ~ 1.0wt%.
8. in accordance with the method for claim 1, it is characterized in that described inorganic acid is one or more in nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid; Described soluble palladium salt is one or more in palladium nitrate, palladium bichloride.
9. the pH value that in accordance with the method for claim 1, it is characterized in that the described maceration extract containing palladium is 2 ~ 4.
10. in accordance with the method for claim 1, it is characterized in that in step (2), alumina support is immersed in to part containing in the maceration extract of palladium 2 ~ 4 hours, then drip alkyl xanthogenic acid sodium solution, flood again 2 ~ 4 hours, after dipping finishes, filter, be dried, obtain catalyst intermediate.
11. in accordance with the method for claim 1, and while it is characterized in that the middle dropping of described step (2) alkyl xanthogenic acid sodium solution, the temperature of reaction system is 60 ~ 80 ℃.
12. in accordance with the method for claim 1, it is characterized in that the described dipping of step (2) and step (3) adopts supersaturation or saturated infusion process.
13. in accordance with the method for claim 1, it is characterized in that described dry of step (2) is at 105～120 ℃ dry 4～8 hours.
14. in accordance with the method for claim 1, it is characterized in that described dry of step (3) is at 105～110 ℃ dry 4～8 hours, and described roasting condition is as follows: sintering temperature is 350～480 ℃, roasting time 4～8 hours.
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