CN1114585C - Bimetal resin type catalyst and its preparing process - Google Patents

Bimetal resin type catalyst and its preparing process Download PDF

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Publication number
CN1114585C
CN1114585C CN98111252A CN98111252A CN1114585C CN 1114585 C CN1114585 C CN 1114585C CN 98111252 A CN98111252 A CN 98111252A CN 98111252 A CN98111252 A CN 98111252A CN 1114585 C CN1114585 C CN 1114585C
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bimetal
resin
palladium
resin type
catalyst
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CN1232015A (en
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吴惠兴
余布谷
丁国来
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Sinopec Jinling Petrochemical Co Ltd
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Sinopec Jinling Petrochemical Co Ltd
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Abstract

The present invention relates to a bimetal resin type catalyst used for the one-step synthesis of methyl isobutyl ketone (MIBK) and a preparing method thereof. The catalyst is formed in a mode that hydrogen type cation transformation resin is used as a supporter and metal palladium and a transition metal element, palladium and a lanthanide series metal element and palladium and an alkali earth metal element as active components, wherein the content of metallic elements if from 0.05 to 1.00%(a weight percent). The catalyst has the advantages of high activity and high selectivity and improves the defect that ions of sulfoacid roots easily drop off in the use course of a palladium resin catalyst.

Description

Bimetal resin type catalyst and preparation method thereof
The present invention relates to a kind of bimetal resin type catalyst that is used for acetone single stage method synthesize methyl-isobutyl ketone (MIBK) and preparation method thereof.
Methyl iso-butyl ketone (MIBK) (MIBK) is a kind of medium-boiling solvent, is widely used in coating, medicine process solvent, caking agent, agricultural chemicals, rubber antioxidant etc.It is reported that the commercial catalysts by acetone single stage method synthesize methyl-isobutyl ketone is palladium-resin type catalyzer (US3,953,517) at present, palladium-resin type catalyzer has higher activity and selectivity.But this catalyzer thermostability is not enough, has the easy obscission of sulfonate ion.
The object of the invention provides a kind of bimetal resin type catalyst that is used for acetone single stage method synthesize methyl-isobutyl ketone and preparation method thereof.
Bimetal resin type catalyst of the present invention is to be carrier with the hydrogen type cation exchange resin, by palladium metal and a kind of transition metal, palladium and a kind of lanthanide element, palladium and a kind of alkali earth metal is that active ingredient is formed, and wherein the content of metallic element is 0.05-1.00% (weight percentage)
The preparation of bimetal resin type catalyst of the present invention is: commercially available Zeo-karb is through pre-treatment, acidifying, use Palladous nitrate, a kind of metal nitrate then, add nonionogenic tenside (alkylphenol polyoxyethylene) simultaneously and be mixed with mixed solution, carry out ion-exchange, resin after the exchange obtains bimetal resin type catalyst with deionized water wash, hydrogen reducing.
The concrete steps of Preparation of Catalyst are as follows:
1, the pre-treatment of Zeo-karb carrier:
Get commercially available Hydrogen D72 resin, soaked 24 hours, use the clear water rinsing again to PH=6-7 with 2.5% hydrochloric acid (HCl).Use 5% sodium hydroxide (NaOH) to soak then 24 hours, use the clear water rinsing again to PH=7-8.
2, acidifying:
Acidifying is to carry out in the acidifying post, and the hydrochloric acid of 1 equivalent (1N) is entered by the column bottom, and superficial linear velocity is the 0.2-0.5 mm/second.When import and export hydrochloric acid (HCl) when concentration is identical acidifying finish, 1 liter of resin needs 1 equivalent (1N) hydrochloric acid (HCl) about 8 liters.There is not chlorion (Cl with washed with de-ionized water to exporting waste liquid then -) exist [with 0.1 equivalent (0.1N) Silver Nitrate (AgNO 3) check].
3, ion-exchange (is example with the Pd-Co/ resin type catalyst):
Exchange liquid preparation: take by weighing 1.00 gram palladium sponges, with nitric acid (HNO 3) dissolve, and be diluted to 500 milliliters (ml) with deionized water, add 2.7 gram cobalt nitrate hexahydrate [Co (NO again 3) 26H 2O] and 1.00 gram alkylphenol polyoxyethylene, be stirred to and be dissolved as ion exchange liquid fully, standby.
Exchange and washing: get after the acidifying 1 liter of Hydrogen D72 resin, place the exchange still, drip exchange liquid while stirring, added in 30 minutes, restir is after 30 minutes, with deionized water wash to PH=6-7.
4, hydrogen reducing:
With above-mentioned washing rear catalyst after air-dry, the reactor of packing into, logical hydrogen reducing 4-8 hour of normal temperature and pressure (also can pressurize), the Pd-Co/ bimetal resin type catalyst.
The evaluation of catalyzer is to carry out on the microreactor testing apparatus.Catalyzer one-time pad amount is 2 milliliters (ml).
Processing condition: air speed: 2 hours -1
Reaction pressure: 4.0Mpa
Temperature of reaction: 120 ℃
H 2/ acetone: 500: 1 (volume ratio)
The present invention is used for the bimetal resin type catalyst of acetone single stage method synthesize methyl-isobutyl ketone, and under identical processing condition, its catalyst activity and selectivity are better than palladium-resin type catalyzer, experiment show the sulfonate ion obscission be improved significantly.
Following embodiment is to explanation of the present invention, is not limitation of the invention.
Embodiment 1.
The preparation of Pd-Co bimetal resin type catalyst:
Carrier adopts the D72 of Nankai University Zeo-karb, and Preparation of Catalyst obtains the Pd-Co bimetal resin type catalyst by pre-treatment, acidifying, exchange, reduction.
Pre-treatment:
Soaked 24 hours with 2.5% hydrochloric acid (HCl), use the clear water rinsing again to PH=6-7.Use 5% sodium hydroxide (NaOH) to soak then 24 hours, use the clear water rinsing again to PH=7-8.
Acidifying:
Acidifying is to carry out in the acidifying post, and the hydrochloric acid of 1 equivalent (1N) is entered by the column bottom, and superficial linear velocity is the 0.2-0.5 mm/second.When import and export hydrochloric acid (HCl) when concentration is identical acidifying finish, 1 liter of resin needs 1 equivalent (1N) hydrochloric acid (HCl) about 8 liters.There is not chlorion (Cl with washed with de-ionized water to exporting waste liquid then -) exist [with 0.1 equivalent (0.1N) Silver Nitrate (AgNO 3) check].
Exchange:
Take by weighing 1.00 gram palladium sponges nitric acid (HNO 3) dissolving, be diluted to 500 milliliters (ml) with deionized water, add 2.7 gram cobalt nitrate hexahydrate [Co (NO again 3) 26H 2O] and 1.00 gram alkylphenol polyoxyethylene, be stirred to and be dissolved as ion exchange liquid fully, standby.
Get after the acidifying 1 liter of Hydrogen D72 resin, place the exchange still, drip above-mentioned exchange liquid while stirring, added in 30 minutes, restir is after 30 minutes, with deionized water wash to PH=6-7.
4, hydrogen reducing:
Catalyzer after air-dry, in the reactor of packing into, logical hydrogen reducing 4-8 hour of normal temperature and pressure (also can pressurize), the Pd-Co bimetal resin type catalyst.
The evaluation of catalyzer is to carry out on the microreactor testing apparatus.Catalyzer one-time pad amount is 2 milliliters (ml).
Processing condition: air speed: 2 hours -1
Reaction pressure: 4.0Mpa
Temperature of reaction: 120 ℃
H 2/ acetone: 500: 1 (volume ratio)
Evaluation result (seeing Table-1 bimetal resin type catalyst evaluation result):
Acetone conversion is 42.77%
The methyl iso-butyl ketone (MIBK) selectivity is 95.70%
Embodiment 2.
The preparation of Pd-Ce bimetal resin type catalyst:
The preparation method sees embodiment 1.
Resin carries out the Pd-Ce exchange after pre-treatment, acidifying.
The preparation of exchange liquid: palladium nitrate solution adds 7.72 grams, six water cerous nitrate [Ce (NO 3) 36H 2O] and 1.00 gram alkylphenol polyoxyethylene, be mixed with 500 milliliters of exchange liquid that contain palladium, cerium and tensio-active agent.Ion-exchange then, hydrogen reducing obtain the Pd-Ce bimetal resin type catalyst.
The catalyzer microreactor testing apparatus of packing into is carried out evaluation test, estimate processing condition and see embodiment 1.
Evaluation result (seeing Table-1 bimetal resin type catalyst evaluation result):
Acetone conversion is 39.02%
The methyl iso-butyl ketone (MIBK) selectivity is 94.85%
Embodiment 3.
The preparation of Pd-Ni bimetal resin type catalyst:
The preparation method sees embodiment 1.
The preparation of exchange liquid: palladium nitrate solution adds 2.78 grams, six water nickelous nitrate [Ni (NO 3) 26H 2O] and 1.00 gram alkylphenol polyoxyethylene, be mixed with 500 milliliters of exchange liquid that contain palladium, nickel and tensio-active agent.Ion-exchange then, hydrogen reducing obtain the Pd-Ni bimetal resin type catalyst.
The catalyzer microreactor testing apparatus of packing into is carried out evaluation test, estimate processing condition and see embodiment 1.
Evaluation result (seeing Table-1 bimetal resin type catalyst evaluation result):
Acetone conversion is 45.50%
The methyl iso-butyl ketone (MIBK) selectivity is 94.15%
Embodiment 4.
The preparation of Pd-Mg bimetal resin type catalyst:
The preparation method sees embodiment 1.
The preparation of exchange liquid: palladium nitrate solution adds 9.64 gram magnesium nitrate hexahydrate [Mg (NO 3) 26H 2O] and 1.00 gram alkylphenol polyoxyethylene, be mixed with 500 milliliters of exchange liquid that contain palladium, magnesium and tensio-active agent.Ion-exchange then, hydrogen reducing obtain the Pd-Mg bimetal resin type catalyst.
The catalyzer microreactor testing apparatus of packing into is carried out evaluation test, estimate processing condition and see embodiment 1.
Evaluation result (seeing Table-1 bimetal resin type catalyst evaluation result):
Acetone conversion is 43.06%
The methyl iso-butyl ketone (MIBK) selectivity is 94.71%
Embodiment 5.
Reference test, the preparation of Pd/ resin type catalyst:
Method for preparing catalyst is seen embodiment 1, and exchange liquid contains palladium (Pd) 2 mg/ml, does not contain other metal ion and tensio-active agent.Ion-exchange then, hydrogen reducing obtain the Pd/ resin type catalyst.The catalyzer microreactor testing apparatus of packing into is estimated, and the test evaluation processing condition are seen embodiment 1.
Evaluation result (seeing Table-1 bimetal resin type catalyst evaluation result):
Acetone conversion is 38.70%
The methyl iso-butyl ketone (MIBK) selectivity is 93.07%
Table one bimetal resin type evaluating catalyst result
Embodiment Catalyzer Acetone conversion (%) Methyl iso-butyl ketone (MIBK) selectivity (%)
1 The Pd-Co bimetal resin type 42.77 95.70
2 The Pd-Ce bimetal resin type 39.02 94.85
3 The Pd-Ni bimetal resin type 45.50 94.15
4 The Pd-Mg bimetal resin type 43.06 94.71
5 The Pd/ resin type 38.70 93.07
By above-mentioned table one as seen, activity of bimetal resin type catalyst (transformation efficiency) and selectivity are better than the Pd/ resin type catalyst.
Embodiment 6.
The test that comes off of bimetal resin type catalyst sulfonate ion:
Get respectively 100 milliliters of Pd-Co/ resin in the foregoing description, Pd-Ce/ resin, Pd-Ni/ resin, Pd-Mg/ resin, 5 kinds of catalyzer of Pd/ resin, place Erlenmeyer flask respectively, add 500 ml deionized water, in 100 ℃ of water, boiled 3 hours, normal temperature to be chilled to (25 ℃) after-filtration, the elimination catalyzer is used acid number in the determination of acid-basetitration water again.Investigate 5 kinds of catalyzer sulfonate ion dropping situations in water, the results are shown in Table-2.
The acid number that table-2 sulfonate ions come off in water
Embodiment Catalyzer Acid number (mgKOH/ restrains stem-based catalyst)
1 The Pd-Co bimetal resin type 0.078
2 The Pd-Ce bimetal resin type 0.155
3 The Pd-Ni bimetal resin type 0.058
4 The Pd-Mg bimetal resin type 0.058
5 The Pd/ resin type 0.213
By table-2 as seen, bimetal resin type catalyst sulfonate ion obscission be improved significantly.
Embodiment 7.
The catalyst stability test:
Pd/ resin type catalyst and Pd-Co bimetal resin type catalyst are moved 4000 hours respectively, its processing condition on 1000 tons of/year methyl iso-butyl ketone (MIBK) production equipments:
600 liters of loaded catalysts
Temperature of reactor 100-105 ℃
Reaction pressure 6.0Mpa
H 2/ acetone is than (V, volume ratio) 200 (H 2Be 75% hydrogen and nitrogen gas)
Air speed 1 hour -1
4000 hours working times
The results are shown in Table-3, scheme-1.
The test of table-3 catalyst stabilities
Working time (hour) Transformation efficiency (%)
Pd-Co bimetal resin catalyzer The Pd/ resin catalyst
50 31.5
100 29.76 30.2
150 27.3
200 35.04 25.6
240 30.85
300 26.8
480 28.77 24.2
720 29.96
960 24.37 22.7
1320 29.21
1500 30.55 20.5
1680 28.68
1920 28.20 18.4
2160 26.89 15.2
2500 29.09 14.5
2640 30.69
3000 28.23
4000 27.98
Figure-1 dotted line is the Pd/ resin type catalyst.By dotted line as seen, when catalyzer ran to about 2000 hours, transformation efficiency descends very fast, and 2500 hours transformation efficiencys only 14.5% can not be kept ordinary production.Solid line is the Pd-Co bimetal resin type catalyst, and catalyzer is in operational process, and it is not obvious that transformation efficiency descends, illustrate this catalyzer sulfonate ion obscission be improved significantly.Prolonged catalyst life.

Claims (5)

1. bimetal resin type catalyst that is used for acetone single stage method synthesize methyl-isobutyl ketone, it is characterized in that with the hydrogen type cation exchange resin being carrier, by palladium metal and a kind of transition metal or palladium and a kind of lanthanide element or palladium and a kind of alkali earth metal is that active ingredient is formed, and wherein the content of metallic element is 0.05～1.00 weight %; Wherein Zeo-karb is through pre-treatment, acidifying, mixed solution with Palladous nitrate, a kind of metal nitrate and nonionogenic tenside carries out ion-exchange then, resin deionized water wash after the exchange, hydrogen reducing obtains bimetal resin type catalyst.
2. catalyzer according to claim 1 is characterized in that a kind of transition metal is nickel or cobalt.
3. catalyzer according to claim 1 is characterized in that a kind of lanthanide element is a cerium.
4. catalyzer according to claim 1 is characterized in that a kind of alkali earth metal is a magnesium.
5. catalyzer according to claim 1 is characterized in that used nonionogenic tenside is an alkylphenol polyoxyethylene.
CN98111252A 1998-04-16 1998-04-16 Bimetal resin type catalyst and its preparing process Expired - Fee Related CN1114585C (en)

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JP5554201B2 (en) * 2009-11-25 2014-07-23 ローム アンド ハース カンパニー Metal alloy catalyst composition
TWI457175B (en) * 2010-06-30 2014-10-21 Dow Global Technologies Llc Mixed bed polymeric catalyst and use thereof
CN103801397B (en) * 2012-11-07 2016-03-30 中国石油化工股份有限公司 A kind of bimetal resin Catalysts and its preparation method
CN104549501B (en) * 2013-10-28 2017-05-17 中国石油化工股份有限公司 Ethylidene diacetate method vinyl acetate catalyst and vinyl acetate synthesis method
CN107469865A (en) * 2017-09-18 2017-12-15 吉林市道特化工科技有限责任公司 A kind of method for preparing high degree of dispersion palladium resin catalyst and application
CN107675003B (en) * 2017-10-10 2019-10-08 江西理工大学 A method of the Enrichment purification rare earth from southern ion type rareearth ore leachate

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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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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