CN102698804A - Preparation method for palladium supported resin catalyst - Google Patents
Preparation method for palladium supported resin catalyst Download PDFInfo
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- CN102698804A CN102698804A CN2012101793177A CN201210179317A CN102698804A CN 102698804 A CN102698804 A CN 102698804A CN 2012101793177 A CN2012101793177 A CN 2012101793177A CN 201210179317 A CN201210179317 A CN 201210179317A CN 102698804 A CN102698804 A CN 102698804A
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Abstract
The invention discloses a preparation method for a palladium supported resin catalyst. The preparation method comprises the following steps of: introducing cupric ions and fluoride ions into a main chain of a styrene series cation exchange resin polymer, and then carrying out a palladium supported treatment process. The palladium supported resin catalyst prepared by the invention has the advantages that the palladium supporting effect is good, palladium is not easy to remove, the low-temperature activity is high, the strength is higher, and the service life is long.
Description
Technical field
The present invention relates to a kind of preparation technology of ion exchange resin, particularly the preparation technology of a kind of year palladium resin catalyst.
Technical background
The technology of development carried ion exchange resin palladium catalyst has some announcements both at home and abroad; Like GB1010260; The disclosed palladium of US3953517/strongly acidic ion-exchange resin catalyst uses palladium nitrate dipping strong-acid ion exchange resin; This resin catalyst is the main catalyst of synthesize methyl-isobutyl ketone, but catalytic activity is lower, and selectivity is lower; CN1457927 has announced a kind of palladium/strongly acidic ion-exchange resin catalyst, adopts the acid solution and the strongly acidic ion-exchange resin catalyst that contain palladium to carry out ion-exchange; CN1883793 has announced a kind of nano Pd catalyst and preparation method thereof, is by water-soluble inorganic palladium salt and the water soluble polymer polymer loaded with nano palladium catalyst that reaction obtains under 60～90 ℃ of conditions in the low-carbon alcohols solvent.
It is short that more than invention catalyst and existing commercially available catalizer variety generally have service life, active low shortcoming, and therefore how improving palladium ion and the stability of palladium atom in resin carrier is the decision key of success.It is the main cause of high appendix palladium catalyst inactivation that palladium runs off.In the hydrogenation reaction stage, palladium may form soluble complex compound and run off.To concentrate on the resin surface weight relevant for Pd crystal grain in the main cause that palladium runs off in the palladium-carbon catalyst and the manufacture process, infiltrates more shallowly, causes the Pd loss easily.
Patent of invention CN101486000 before the applicant discloses a kind of year palladium resin catalyst and preparation method thereof, and said catalyst is mainly used in acetone and hydrogen and does in the technology that raw material synthesizes MIBK.The present invention adopts and in the palladium salting liquid, adds chelating agent formation palladium chelate, and a palladium resin catalyst is carried in the method preparation that evenly is adsorbed on then on the resin.It is even that said year palladium resin catalyst has the palladium of carrying, characteristics such as high, the active height of selectivity, long service life.Chelating agent adopts amino oxalic acid, aminotriacetic acid, and amino tetraacethyl, dimethylglyoxime, diphenylthiocarbazones etc. can improve carried palladium catalyst service life to a certain extent.But there is synthetic difficulty in these parts and problem such as cost an arm and a leg.
Summary of the invention
To the deficiency of prior art, the applicant finds, can pass through on styrene type cation exchange resin, to introduce the C-F key; Because the bond energy of C-F key is bigger in the fluoropolymer; More stable, fluorine atom not only combines firmly with carbon atom, and in the outer arrangement of carbon skeleton very closely. make main chain inside avoid the erosion of ultraviolet irradiation and chemical reagent; Prevented the exposure of carbon atom and carbochain effectively, so fluorocarbon polymer shows remarkable chemical stability.In addition, the applicant also finds, through introducing copper and fluorine on the main chain of above-mentioned resinous polymer, and then carries the palladium treatment process, can make the stable coordination structure of formation between copper and fluorine and the palladium, and the stability of palladium is improved.Because polymer strength (being chemical stability) improves, the stability of palladium improves, the service life of also just having improved year palladium resin catalyst.
According to above discovery; On the one hand; The invention provides a kind of raising and carry the method in the service life of palladium resin catalyst, this method is included in introduces copper and fluorine on the main chain of styrene type cation exchange resin polymer, and then carries the palladium treatment process; Wherein fluorine exists with the structure of C-F key, forms stable coordination structure between copper and fluorine and the palladium.
Be not limited thereto, the copper ion in this method comes from the acrylic acid copper that adds in the polymerization; Fluorine ion comes from the Fluorine containing olefine that adds in the polymerization, and said Fluorine containing olefine is the Fluorine containing olefine that can on resin, form the C-F key arbitrarily, for example is selected from tetrafluoroethene, vinylidene or CTFE.
On the other hand, the invention provides the preparation method of a kind of year palladium resin catalyst, may further comprise the steps:
1) preparation of the styrene type cation exchange resin carrier of cupric and fluorine:
The preparation styrene type cation exchange resin; Styrene type cation exchange resin preparation technology described here is a styrene type cation exchange resin production technology well known in the art; Be with the difference of existing production technology; Add the acrylic acid copper that accounts for weight percent monomer 1～10% in the polymerization single polymerization monomer, 0.5～5% Fluorine containing olefine is participated in polymerization, obtains the styrene type cation exchange resin of copper ions and C-F key; To neutral (being that the pH value is 7), remove the inner free acid of resin with poach;
2) carrying palladium handles:
With 1) in the resin handled well add in the agitated reactor, add the water of weight resin 40～80%, evenly stir, temperature is raised to 20～50 ℃, add the palladium saline solution, wherein palladium ion mass percent concentration scope is 0.5～5%, is preferably 1%; The weight of palladium saline solution and the ratio of weight resin are 1～5:1, are preferably 1:1, and stirring reaction 1～5 hour is removed reaction residue, and the cooling blowing obtains said year palladium resin catalyst.
Wherein, palladium salt can be selected from palladium bichloride, palladium nitrate or palladium.
Fluorine containing olefine is the Fluorine containing olefine that can on resin, form the C-F key arbitrarily, for example is selected from tetrafluoroethene, vinylidene or CTFE.
For the ease of understanding the present invention, provide the wherein general structure of end product at present, can find out that in this general formula, F exists with the form of C-F key, and forms coordination structure between copper and fluorine and the palladium.But should be noted that it is feedstock production that this general formula only is to use certain styrene type cation exchange resin well known in the art, just is used to explain the coordination form of C-F key and Cu-Pd-F, and is not used in restriction the present invention.In fact, so long as adopt above preparation technology, be initiation material with styrene type cation exchange resin well known in the art, all belong within the scope of the present invention.
Wherein, R is selected from-C ,-CCL ,-CHF or-CF
2
The beneficial effect of the invention
1). it is effective that year palladium resin catalyst of the present invention's preparation carries palladium, and palladium is difficult for removing.
2). this resin catalyst intensity is higher, long service life;
3). technology is simple, easy operating, cost is low, and reactivity is high, and pollute and lack, product yield, purity is high.
The specific embodiment
Following instance only is to further specify the present invention, is not the scope of restriction the present invention protection.
Embodiment 1:
Adopt known styrene type cation exchange resin production technology; Like D001 production of resins technology; Difference just adds the acrylic acid copper that accounts for weight percent monomer 5% in polymerization single polymerization monomer, 0.5% tetrafluoroethene is participated in polymerization, obtains styrene type cation exchange resin; Boil to colourless with pure water, remove the inner free acid of resin.
The 100g resin is added in the agitated reactor, add the water of weight resin 60%, evenly stir; Temperature is raised to 20 ℃, adds the palladium chloride solution 100g of palladium ion weight concentration 1% fast, stirring reaction 2.5 hours; Remove reaction residue, the cooling blowing obtains said year palladium resin catalyst.Sample number into spectrum K01.
Embodiment 2:
In polymerization single polymerization monomer, add the acrylic acid copper that accounts for monomer degree 1%, other step and embodiment 1 are identical, sample number into spectrum K02.
Embodiment 3:
In polymerization single polymerization monomer, add the acrylic acid copper that accounts for monomer degree 10%, other step and embodiment 1 are identical, sample number into spectrum K03.
Embodiment 4:
In polymerization single polymerization monomer, add the Fluorine containing olefine that accounts for monomer degree 5% and participate in polymerization, other step and embodiment 1 are identical, sample number into spectrum K04.
Embodiment 5:
In polymerization single polymerization monomer, add the Fluorine containing olefine that accounts for monomer degree 5% and participate in polymerization, other step and embodiment 2 are identical, sample number into spectrum K05.
Embodiment 6:
In polymerization single polymerization monomer, add the Fluorine containing olefine that accounts for monomer degree 5% and participate in polymerization, other step and embodiment 3 are identical, sample number into spectrum K06.
Embodiment 7:
In polymerization single polymerization monomer, add the Fluorine containing olefine that accounts for monomer degree 2% and participate in polymerization, other step and embodiment 1 are identical, sample number into spectrum K07.
Embodiment 8:
In polymerization single polymerization monomer, add the Fluorine containing olefine that accounts for monomer degree 2% and participate in polymerization, other step and embodiment 2 are identical, sample number into spectrum K08.
Embodiment 9:
In polymerization single polymerization monomer, add the Fluorine containing olefine that accounts for monomer degree 2% and participate in polymerization, other step and embodiment 3 are identical, sample number into spectrum K09.
Embodiment 10:
Palladium chloride solution palladium ion concentration 2%, other step and embodiment 1 are identical, sample number into spectrum K10.
Embodiment 11:
Palladium chloride solution palladium ion concentration 2%, palladium chloride solution 500g, other step and embodiment 2 are identical, sample number into spectrum K11.
Embodiment 12:
Palladium chloride solution palladium ion concentration 2%, other step and embodiment 3 are identical, sample number into spectrum K12.
Embodiment 13:
Change palladium solution into, other step and embodiment 1 are identical, sample number into spectrum K13.
Embodiment 14:
Change palladium solution into, other step and embodiment 2 are identical, sample number into spectrum K14.
Embodiment 15:
Change palladium solution into, other step and embodiment 3 are identical, sample number into spectrum K15.
Embodiment 16:
Fluorine containing olefine changes vinylidene into, and other step and embodiment 1 are identical, sample number into spectrum K16.
Embodiment 17:
Fluorine containing olefine changes vinylidene into, and other step and embodiment 2 are identical, sample number into spectrum K17.
Embodiment 18:
Fluorine containing olefine changes vinylidene into, and other step and embodiment 3 are identical, sample number into spectrum K18.
Embodiment 19:
Fluorine containing olefine changes CTFE into, and other step and embodiment 1 are identical, sample number into spectrum K16.
Embodiment 20:
Fluorine containing olefine changes CTFE into, and other step and embodiment 2 are identical, sample number into spectrum K17.
Embodiment 21:
Fluorine containing olefine changes CTFE into, and other step and embodiment 3 are identical, sample number into spectrum K18.
Comparative Examples 1
Do not add acrylic acid copper in the polymerization single polymerization monomer, Fluorine containing olefine is participated in polymerization, and other step and embodiment 1 are identical, sample number into spectrum K22.
Comparative Examples 2
Do not add acrylic acid copper in the polymerization single polymerization monomer, Fluorine containing olefine is participated in polymerization, and other step and embodiment 2 are identical, sample number into spectrum K23.
Comparative Examples 3
Do not add acrylic acid copper in the polymerization single polymerization monomer, Fluorine containing olefine is participated in polymerization, and other step and embodiment 3 are identical, sample number into spectrum K24.
Comparative Examples 4
Only add acrylic acid copper in the polymerization single polymerization monomer, do not add Fluorine containing olefine and participate in polymerization, other step and embodiment 1 are identical, sample number into spectrum K25.
Comparative Examples 5
Only add Fluorine containing olefine in the polymerization single polymerization monomer, do not add acrylic acid copper and participate in polymerization, other step and embodiment 1 are identical, sample number into spectrum K26.
The result of use evaluation:
Get the catalyst among 50g embodiment 1-21 and the Comparative Examples 1-5 respectively, the quartz sand that following dress was handled, the 5L stainless steel reactor of internal diameter 20mm is put in layering, feeds hydrogen earlier palladium ion is reduced to the palladium atom; Behind the 16h, add acetone, water, air speed 1.2L/h, 120 ℃ of reaction temperatures; Pressure 6.0MPa, hydrogen recycles, and moves 10 months continuously; Record acetone conversion, mill back rate of small round spheres such as following table, see the following form:
| The test batch | Sample number into spectrum | Acetone conversion % | Mill back rate of small round spheres % |
| Embodiment 1 | K01 | 43 | 98 |
| Embodiment 2 | K02 | 48 | 98 |
| Embodiment 3 | K03 | 47 | 97 |
| Embodiment 4 | K04 | 44 | 98 |
| Embodiment 5 | K05 | 46 | 98 |
| Embodiment 6 | K06 | 43 | 96 |
| Embodiment 7 | K07 | 45 | 97 |
| Embodiment 8 | K08 | 51 | 97 |
| Embodiment 9 | K09 | 47 | 99 |
| Embodiment 10 | K10 | 51 | 99 |
| Embodiment 11 | K11 | 49 | 98 |
| Embodiment 12 | K12 | 44 | 98 |
| Embodiment 13 | K13 | 43 | 98 |
| Embodiment 14 | K14 | 46 | 96 |
| Embodiment 15 | K15 | 45 | 98 |
| Embodiment 16 | K16 | 42 | 98 |
| Embodiment 17 | K17 | 44 | 97 |
| Embodiment 18 | K18 | 41 | 98 |
| Embodiment 19 | K19 | 45 | 98 |
| Embodiment 20 | K20 | 41 | 98 |
| Embodiment 21 | K21 | 41 | 97 |
| Comparative Examples 1 | K22 | 26 | 82 |
| Comparative Examples 2 | K23 | 23 | 88 |
| Comparative Examples 3 | K24 | 24 | 81 |
| Comparative Examples 4 | K25 | 32 | 92 |
| Comparative Examples 5 | K26 | 35 | 92 |
Can know that by last table the resin carried palladium catalyst sample of each embodiment used 10 months continuously among the present invention, had following effect:
1. add acrylic acid copper and Fluorine containing olefine sample afterwards, this resin catalyst intensity significantly is higher than sample in the Comparative Examples that does not add.
2. add acrylic acid copper and Fluorine containing olefine sample afterwards, use continuously more than 10 months, still can keep advantages of high catalytic activity, explain that the good stability of this resin catalyst palladium, activity significantly improve, rise appreciably service life.
3. add acrylic acid copper or Fluorine containing olefine separately; Stability, activity and the service life of this resin catalyst intensity and palladium; All good not as acrylic acid copper and the Fluorine containing olefine resin catalyst after all adding; Coordination effect between this explanation copper, fluorine and palladium can improve the stability of handle, and the C-F key is to the effect with raising of polymer strength.
Carried palladium catalyst prepared in accordance with the present invention is after ten months long-term use, and acetone conversion is greater than 40%, and mill back rate of small round spheres explains that its catalytic activity is good, long service life, a kind of comparatively desirable catalyst of can yet be regarded as greater than 97%.
Claims (9)
1. one kind is improved the palladium resin catalyst method in service life of carrying; Be included in and introduce copper ion and C-F bond structure on the main chain of styrene type cation exchange resin polymer; And then said polymer is carried palladium handle, the stable coordination structure of formation between copper and fluorine and the palladium wherein.
2. the said method of claim 1, the source of palladium is selected from palladium bichloride, palladium nitrate or palladium.
3. the said method of claim 1, the source of fluorine is selected from tetrafluoroethene, vinylidene or CTFE.
4. preparation method of carrying the palladium resin catalyst may further comprise the steps:
1) preparation of the styrene type cation exchange resin carrier of cupric and fluorine:
The preparation styrene type cation exchange resin; Wherein, In polymerization single polymerization monomer, add the acrylic acid copper that accounts for weight percent monomer 1～10%, 0.5～5% Fluorine containing olefine is participated in polymerization, obtains the styrene type cation exchange resin of copper ions and C-F bond structure; To pH=7, remove the inner free acid of resin with poach;
2) carrying palladium handles:
The resin of handling well in the step 1) is added in the agitated reactor; The water that adds weight resin 40～80%; Evenly stir, temperature is raised to 20～50 ℃, add the palladium saline solution; Wherein palladium ion mass percent concentration scope is 0.5～5%, and the weight of palladium saline solution and the ratio of weight resin are 1～5:1; Stirring reaction 1～5 hour is removed reaction residue, and the cooling blowing obtains said year palladium resin catalyst.
5. the said method of claim 4, wherein, palladium salt is selected from palladium bichloride, palladium nitrate or palladium.
6. the said method of claim 4, wherein, Fluorine containing olefine is selected from tetrafluoroethene, vinylidene or CTFE.
7. arbitrary method of claim 4-6, wherein, palladium ion mass percent concentration scope is 1%, the weight of palladium saline solution and the ratio of weight resin are 1:1.
8. the said method preparation of a claim 4-7 carries the palladium resin catalyst.
9. described year palladium resin catalyst of claim 8, its general formula is expressed as:
Wherein, R is selected from-C ,-CCL ,-CHF or-CF
2
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| CN201210179317.7A CN102698804B (en) | 2012-06-01 | 2012-06-01 | Preparation method for palladium supported resin catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722145A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenated nitrile-butadiene rubber |
| CN107722147A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of process for selective hydrogenation of polar polymer |
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| US20040102631A1 (en) * | 2001-03-12 | 2004-05-27 | Yasuhiro Uozumi | Solid-phase-supported transition metal catalysts |
| CN1709925A (en) * | 2005-04-18 | 2005-12-21 | 中国海洋大学 | Resin of zinc acrylate or copper acrylate containing capsaicin function group, its preparation and use |
| CN101486000A (en) * | 2009-02-12 | 2009-07-22 | 凯瑞化工有限责任公司 | Catalyst for synthesizing MIBK and preparation method thereof |
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
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2012
- 2012-06-01 CN CN201210179317.7A patent/CN102698804B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040102631A1 (en) * | 2001-03-12 | 2004-05-27 | Yasuhiro Uozumi | Solid-phase-supported transition metal catalysts |
| CN1709925A (en) * | 2005-04-18 | 2005-12-21 | 中国海洋大学 | Resin of zinc acrylate or copper acrylate containing capsaicin function group, its preparation and use |
| CN101486000A (en) * | 2009-02-12 | 2009-07-22 | 凯瑞化工有限责任公司 | Catalyst for synthesizing MIBK and preparation method thereof |
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722145A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenated nitrile-butadiene rubber |
| CN107722147A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of process for selective hydrogenation of polar polymer |
| CN107722147B (en) * | 2016-08-10 | 2020-06-09 | 中国石油化工股份有限公司 | Selective hydrogenation method of polar polymer |
| CN107722145B (en) * | 2016-08-10 | 2020-07-24 | 中国石油化工股份有限公司 | Preparation method of hydrogenated nitrile rubber |
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