CN100421791C - Catalyst carried by Nano carbon fiber in use for refining terephthalic acid through hydrogen added - Google Patents
Catalyst carried by Nano carbon fiber in use for refining terephthalic acid through hydrogen added Download PDFInfo
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- CN100421791C CN100421791C CNB2005100245207A CN200510024520A CN100421791C CN 100421791 C CN100421791 C CN 100421791C CN B2005100245207 A CNB2005100245207 A CN B2005100245207A CN 200510024520 A CN200510024520 A CN 200510024520A CN 100421791 C CN100421791 C CN 100421791C
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Abstract
The present invention discloses a catalyst with nanometer carbon fiber as a carrier for hydrofining terephthalic acid. A carrier is nanometer 90 to 98.9% of carbon fiber, and an active ingredient is 0.1 to 5% of metal palladium and 1 to 9.9% transition metal according to weight percentage. The catalyst of the present invention can be used for hydrofining terephthalic acid. The conversion rate of carboxyl benzaldehyde can be up to more than 96.1% under the condition of laboratory examination. Compared with the prior art, the present invention is characterized in that a specifically large middle hole structure is adopted; the nanometer carbon fiber which does not contain or contains few micro-pores is used as the catalyst carrier. By means of a conventional and simple catalyst preparation method, a novel catalyst with high catalytic performance is obtained in a TA hydrofining process.
Description
Technical field
The present invention relates to a kind of hydrorefined catalyst of terephthalic acid (TPA) that is used for, particularly be used for the hydrogenation catalyst of the carbon nano-fiber carried metal palladium of crude terephthalic acid unifining process.
Background technology
Contain in the crude terephthalic acid of suitability for industrialized production carboxyl benzaldehyde impurity such as (being called for short 4-CBA), can be by changing other compound behind the hydrogenation into, so that further separate purification with subsequent technique processes such as crystallizations.
Palladium/the activated-carbon catalyst of support type is mainly used in the selective hydrogenation of unsaturated compounds, is particularly useful for crude terephthalic acid (being called for short TA) process for refining.At typical patent example USP4, in 415,479, the refining hydrogenation catalyst that uses of TA is the Pd/C catalyst, and its carrier is 4～8 purpose cocoanut active charcoals.The specific area of this catalyst reaches 1000m
2More than/the g, bulk density is about 0.45g/cm
3, average pore size is 2nm, pore volume reaches 0.7cm
3/ g, wherein the aperture accounts for more than 75% less than the pore volume of 2nm.
From the exploitation of TA hydrofining technology, the research of relevant catalyst is being carried out always, though year surplus having gone through 40, the Pd/C catalyst is the main catalyst of PTA industrial production subtractive process always.This mainly is because refining system has high corrosion, the many carrier materials of aqueous terephthalic acid solution solubilized of heat, be included in metal oxide and salt in the carrier as natural and artificial synthetic aluminium oxide, silica, diatomite, baked clay, zirconium carrier and some other, therefore hindered the research and development of non-charcoal carried catalyst.AMOCO company is at USP4,743, developed new carrier in 577, introduced metallic elements such as Ti, Ni and be carrier or be carrier, overcome the active carbon intensity difference, worn away high shortcoming with titanium oxide etc., but because such catalyst carrier specific area is less, only be 0.55 and 1.21m2/, its catalytic performance of the catalyst after the load can not satisfy the hydrorefined requirement of TA, though obtained certain progress, but also be in the development stage, as yet not industrialization.
People such as Bankmann (Catalysis Today Vol.1992,12:225-242) the proposition titanium dioxide (TiO of high-specific surface area in 1992
2) make the carrier of catalyst, and carried out extensive studies, as: the extrusion forming process of the high specific surface area titanic oxide of preparation and raw material, additive, bonding agent and extrusion forming process parameter etc. are to the influence of final titania support catalytic action.But the technology that the document provides is carried out selective hydrogenation with above-mentioned moulding titanium dioxide carrier supported palladium, platinum or rhodium, exists the hydrogenation unstable result, the very big defective of carrier loaded reactive metal back end hydrogenation effect difference that different moulding process obtain;
Along with further investigation to load type palladium catalyst, people recognize that gradually the character of carrier may produce considerable influence to the distribution and the hydrogenation process itself of palladium, result of study shows, with porous and the non-porous type absorbent charcoal carrier supported palladium that combines, its hydrogenation activity is a twice of only using non-porous type active carbon, but the porous type active carbon has bigger voidage, have more palladium and be closed in inside, hole, can not contribute to activity of such catalysts, and along with the carrying out of hydrogenation reaction, the duct that these ducts, especially aperture are less will contaminated and obstruction.Therefore, patent USP3,953,369 when the preparation catalyst, prevent reactive metal dark excessively infiltration in the duct by the surfactant that adds macromolecule, and USP4,256, porous activated carbon contacted (surface tension that reduces solution) at 609 o'clock with the aqueous solutions of organic solvent that certain IX pure gold belongs to solution, active component is deposited at micropore surface by evaporating solvent.But, because active carbon especially is applied to the hydrorefined cocoanut active charcoal preparation process complexity of TA and is difficult to control, therefore a large amount of existence of micropore are inevitable, even adopt the technology of this Patent publish can not make full use of the reactive metal of load, therefore exist when being applied to the crude terephthalic acid unifining process defective that the 4-CBAde conversion ratio is lower.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind ofly to be used for terephthalic acid (TPA) hydrorefined to be the catalyst of carrier with the carbon nano-fiber, to overcome the defective that prior art exists, to satisfy the needs of the parties concerned;
Another technical issues that need to address of the present invention are to disclose the application of described catalyst in terephthalic acid (TPA) hydrofinishing.
Technical conceive of the present invention is such:
Non-ly think that all catalytic reaction extensively is present in oil and chemical industry field, the feature of reaction system is the reaction between a kind of reactant of solid catalyst surface generation fluid phase.Therefore the performance of catalyst carrier has largely influenced the performance of catalyst, and the surface of catalyst carrier and the interaction between the reactive metal will influence the activity, selectivity, life-span of catalytic reaction etc.
For the TA unifining process, because it all is the big molecule of band phenyl ring that the key reaction thing 4-CBA and the product p-methylbenzoic acid (being called for short 4-PT) of hydrogenation reaction take place, if the duct of catalyst mostly is microchannel, then big reactant molecule carries out in the process in catalytic reaction, diffuse into the catalyst duct and on the catalyst inner surface, react and the duct is shifted out in afterproduct diffusion, certainly exist very big diffusional resistance, its apparent reflection is that catalytic activity reduces, and reaction speed is slack-off.And the cocoanut active charcoal that present technology adopts just micropore account for a large amount of porous active carbons.
The present invention imagines the employing new carbon---and carbon nano-fiber is as a kind of carrier, and it has comparatively special pore structure feature.Compare with cocoanut active charcoal, the micropore of carbon nano-fiber is considerably less, average pore size can reach more than the 10nm, average pore size than conventional cocoanut active charcoal is big more than 5 times, and chemical composition homogeneous, the purity height, do not contain active carbon that natural crop obtains the inevitable elements such as S, N that exist, and one of reason that the activated carbon supported just catalyst of the latter is poisoned easily, the life-span is short.
Carbon nano-fiber (diameter is roughly between 50～200nm) is the found a kind of novel carbon structures of a kind of 1991, because its special physicochemical performance becomes hot research in recent years, is the brand-new material that a kind of extremely has application prospect.It is applied to catalytic field as catalyst or catalyst carrier, it mainly is the graphite marginal texture that utilizes the orderly arrangement of carbon nano-fiber, the pore structure of the uniqueness of carbon fiber, and the interaction between the metal of the pi-electron of the graphite linings of formation carbon fiber and area load etc.Carbon nano-fiber is compared with the immediate active carbon of composition and character as catalyst carrier, and more advantage is arranged, and will produce active influence to activity of such catalysts, selectivity, life-span etc. behind its carried metal.Many achievement (R.Gao, C.D.Tan and R.T.Baker, Cataly.Today 65:19,2001 have been obtained through research at present with application prospect; M.S.Hoogenraad, M.F.Onwezen, A.J.van Dillen, J.W.Geus.Stud.Surf.Sci.Catal., 101:1331,1996; Toebes Marjolein L., Prinsloo Frans F., Bitter Johannes H., van Dillen A.Jos, Krijn P.de Jong.J.Catal., 214:78-87,2003; Marc J.ledoux, et al.Journal ofMolecular Catalysis A:Chemical, 170:155-163,2001).
Of the present inventionly be used for terephthalic acid (TPA) hydrorefined to be the catalyst of carrier with the carbon nano-fiber, to it is characterized in that carrier is a carbon nano-fiber, active component is Metal Palladium and transition metal, and percentage by weight is:
Carbon nano-fiber 90～98.9%
Metal Palladium 0.1～5%
Transition metal 1～9.9%
The diameter of said carbon nano-fiber is 50～200nm, and total specific area is 150～250m
2/ g, external surface area are 120～220m
2/ g, average pore size is 8～12nm, wherein the aperture is 0～5% less than the percentage that the pore volume of 2nm accounts for total pore volume;
Said carbon nano-fiber can adopt the present technique field known method of those of ordinary skill to prepare, or adopts the commercially available prod;
Carbon nano-fiber can preferably adopt the organic mode of gas phase catalysis thermal cracking low carbon chain to obtain, and this method comprises the steps:
To be warming up to 550～650 ℃ with 1～5 ℃/min as the iron group transition metal oxide powder of catalyst, with hydrogen reducing 3～5 hours, feed the low carbon chain organic matter, 700～1000ml/min, hydrogen 100～300ml/min, grew 7～11 hours, and promptly obtained said carbon nano-fiber;
Preferred transition metal is Ni, Co or Fe, and low carbon chain organic matter organic matter is selected from a kind of in methane, ethene, ethane, carbon monoxide, propane or the benzene, preferred ethane or carbon monoxide, and reaction temperature is 500～1100 ℃, is preferably 600～800 ℃;
Said method has had disclosed report in CN03114990.1 and CN03114989.8, also be called chemical gaseous phase catalytic cracking solution;
The carbon nano-fiber of method for preparing owing to be that to adopt transition metal oxide be catalyst, therefore wherein contains weight concentration and is 0.5～10% transition metal.
One of Preparation of catalysts method of the present invention comprises the steps:
Adopt conventional equivalent impregnation or excessive dipping method, the compound palladium of palladium is loaded on the carbon nano-fiber, obtain catalyst precarsor; Equivalent impregnation or excessive dipping method (" the catalyst engineering introduction " of Wang Shangdi, Sun Junquan work, Chemical Industry Press, 2001) in the literature are disclosed methods;
The compound of said palladium is selected from halide, acetate, nitrate, the acid of chlorine palladium and the basic salt thereof of palladium, the complex of palladium ammonia, is preferably acid of chlorine palladium or palladium amine complex, and concentration is 1.0～3.0mmol/L, and the method for recommendation is excessive infusion process;
Carbon nano-fiber prepares for adopting the organic mode of gas phase catalysis thermal cracking low carbon chain;
Acid of said chlorine palladium or palladium amine complex refer to H
2PdCl
4, Pd (NH
3)
4Cl
2
Then catalyst precarsor was worn out 1～12 hour in air.
Catalyst precarsor after aging is handled with the reducing agent reduction, comprises the steps:
Catalyst precarsor after aging places reducing agent, under 20～300 ℃ temperature, reduces preferred 2～4 hours 1～10 hour;
Said reducing agent is selected from formic acid, sodium formate, hydrazine hydrate, glucose or hydrogen;
Preferred aqueous sodium formate solution liquid-phase reduction or the hydrogen vapour phase reduction of adopting;
Preparation method's of the present invention two comprises the steps:
Adopt conventional equivalent impregnation or excessive dipping method, the compound palladium and the iron group of palladium is transition metal compound loaded on carbon nano-fiber, obtain catalyst precarsor; Equivalent impregnation or excessive dipping method (" the catalyst engineering introduction " of Wang Shangdi, Sun Junquan work, Chemical Industry Press, 2001) in the literature are disclosed methods;
The compound of said palladium is selected from halide, acetate, nitrate, the acid of chlorine palladium and the basic salt thereof of palladium, the complex of palladium ammonia, is preferably acid of chlorine palladium or palladium amine complex, and concentration is 1.0～3.0mmol/L, and the method for recommendation is excessive infusion process;
Said iron group metal compound is selected from halide, nitrate, sulfate and the iron cyanide of nitrate, sulfate, halide or iron of nickel or halide, nitrate or the sulfate of cobalt;
Then catalyst precarsor was worn out 1～12 hour in air.
Catalyst precarsor after aging is handled with the reducing agent reduction, comprises the steps:
Catalyst precarsor after aging places reducing agent, under 20～300 ℃ temperature, reduces preferred 2～4 hours 1～10 hour;
Said reducing agent is selected from formic acid, sodium formate, hydrazine hydrate, glucose or hydrogen;
Preferred aqueous sodium formate solution liquid-phase reduction or the hydrogen vapour phase reduction of adopting;
Catalyst of the present invention can be used for terephthalic acid (TPA) hydrofinishing, can reach more than 96.1% to the conversion ratio of carboxyl benzaldehyde;
The catalyst activity evaluation method is as follows, press in the reactor in 0.5 rising, add said catalyst 1 gram, crude terephthalic acid 90 grams, wherein the content to carboxyl benzaldehyde is 3000ppm, deionized water 240ml, 280 ℃ of reaction temperatures, the hydrogen dividing potential drop is 0.7Mpa, in time is sampled to sampler behind the reaction time 30min.The question response still reaches the phased soln that flows with sample oven dry in the sampler and with ammoniacal liquor after being cooled to room temperature, adopts liquid chromatogram (HPLC) analysis.Catalytic activity is calculated with the conversion ratio to carboxyl benzaldehyde.
Compared with prior art, characteristics of the present invention have been to adopt a kind of special big central hole structure that has, the carbon nano-fiber that does not contain or contain micropore seldom is as catalyst carrier, adopt conventional simple method for preparing catalyst, obtained the high new catalyst of catalytic performance in the TA unifining process.
The specific embodiment
Embodiment 1
Take by weighing 2 gram superfine iron oxide powder, place in the quartz boat of accumbency in the reaction tube, be warming up to 600 ℃ with 3 ℃/min, with hydrogen reducing 4 hours, feed carbon monoxide 800ml/min, hydrogen 200ml/min grew 9 hours, obtain carbon nano-fiber 60 grams, its BET surface area is 232.95m2/g after measured, and wherein external surface area is 190.5m2/g, and average pore size is 9.8nm, total pore volume is 0.42cm3/g, and the aperture is that the following pore volume of 2nm is 0.013cm3/g.
Embodiment 2
With 5 gram carbon fibers be dispersed in the 100ml aqueous solution stir 30min after, splash into by 0.0423gPdCl
2Be dissolved in the chlorine palladium acid solution that the hydrochloric acid of 1.4ml 5mol/L obtains, 1 of per minute.Drip and finish back continuation stirring dipping 1 hour.Suction filtration spends deionised water then, and filter cake is delivered to 120 ℃ of baking ovens and spent the night.The catalyst that obtains carries out catalytically active assessment by aforementioned catalyst examination condition, and the conversion ratio of 4-CBA is 96.1%.
Embodiment 3
The catalyst precarsor that embodiment 2 dipping is obtained is in air after aging 12 hours, get 1% aqueous sodium formate solution, the amount of the aqueous solution is advisable with all catalyst of submergence just, 80 ℃ of reduction 120min, spending deionised water to filtrate then is neutral or detects less than till the chlorion with 0.1NAgNO3, filter cake is the gained catalyst, and carrying out the conversion ratio that active examination obtains 4-CBA is 96.5%.
Embodiment 4
Take by weighing carbon nano-fiber 5 grams, measuring its water absorption rate is 1.25ml/g, by the carbon fiber loaded palladium content 0.5% preparation palladium amine complex solution of 5 grams, splashes into palladium solution while stirring, and dries in air at room temperature.The catalyst that obtains is checked and rated, and the conversion ratio of 4-CBA is 90%.
Embodiment 5
Embodiment 4 to catalyst further place 250 ℃ of Muffle furnace roastings 2.5 hours, and in the 20H2/Ar gaseous mixture 300 ℃ of reductase 12s hour, and under argon shield, be cooled to room temperature.Catalyst that obtains such as embodiment 1 carry out the activity examination, and the conversion ratio of 4-CBA is 97.5%.
Comparative example
Commercially available cocoanut active charcoal was dropped into the stirring of 4M salpeter solution after 24 hours, be washed with water to neutral back drying, prepare activated carbon loaded palladium catalyst by embodiment 2,3 steps, and check and rate catalyst under similarity condition, the conversion ratio of 4-CBA is 93.6%.
The hydrorefined catalyst CBA-300 of TA that is used for of commercially available Engelhard company is checked and rated its catalytic activity in the laboratory under same reaction condition, the conversion ratio of 4-CBA is 94.5%.
Above-mentioned discussion and embodiment are intended to can not think limitation of the present invention as explanation of the present invention.For being familiar with one of skill in the art, within the scope of the present invention, still can carry out other variations.
Claims (4)
- One kind to be used for terephthalic acid (TPA) hydrorefined be the method for preparing catalyst of carrier with the carbon nano-fiber, it is characterized in that, comprise the steps: to adopt conventional equivalent impregnation or excessive dipping method, with the compound of palladium and transition metal compound loaded on carbon nano-fiber, obtain catalyst precarsor, then catalyst precarsor was worn out 1～12 hour in air; Catalyst precarsor after aging is handled with the reducing agent reduction;In active component Metal Palladium and transition metal, percentage by weight is:Carbon nano-fiber 90～98.9%Metal Palladium 0.1～5%Transition metal 1～9.9%;Said transition metal is Ni, Co or Fe.
- 2. preparation method according to claim 1 is characterized in that, the compound of said palladium is selected from the complex of the halide of palladium, acetate, nitrate, the acid of chlorine palladium and basic salt thereof or palladium ammonia, and concentration is 1.0～3.0mmol/L.
- 3. method according to claim 1, it is characterized in that, the catalyst precarsor that catalyst precarsor reduction after aging is handled after comprising the steps: to wear out places reducing agent, under 20～300 ℃ temperature, reduced 1～10 hour, said reducing agent is selected from formic acid, sodium formate, hydrazine hydrate, glucose or hydrogen.
- 4. method according to claim 1 is characterized in that, the diameter of said carbon nano-fiber is 50～200nm, and total specific area is 150～250m 2/ g, external surface area are 120～220m 2/ g, average pore size is 8～12nm, wherein the aperture is 0～5% less than the percentage that the pore volume of 2nm accounts for total pore volume.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442110A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920195B (en) * | 2009-06-09 | 2012-09-05 | 中国石油化工股份有限公司 | Preparation method of terephthalic acid hyrorefining catalyst by using carbon nanofibers as vector |
| CN102218328A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Aromatic aldehyde selective hydrogenating catalyst used for refining terephthalic acid |
| CN102219671B (en) * | 2010-04-15 | 2014-04-23 | 中国石油化工股份有限公司 | Method for selective hydrogenation of aromatic aldehydes for refining terephthalic acid |
| CN102513080B (en) * | 2011-11-23 | 2014-01-15 | 华东理工大学 | Preparation method of homopolymer or copolymer of cyclohexyl ethylene and catalyst |
| CN103657644A (en) * | 2013-10-31 | 2014-03-26 | 内蒙古工业大学 | Preparation method of novel porous carbon nano fiber loaded palladium nanoparticle composite catalyst |
| CN105126925A (en) * | 2015-09-18 | 2015-12-09 | 苏州顺唐化纤有限公司 | Catalyst for hydrogenation synthesis reaction |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107442110A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
| CN107442110B (en) * | 2016-05-30 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for hydrofining crude terephthalic acid and preparation method thereof |
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