CN102441420B - C8 aromatic hydrocarbon isomerization catalyst, preparation method and application thereof - Google Patents
C8 aromatic hydrocarbon isomerization catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a C8 aromatic hydrocarbon isomerization catalyst which comprises a rare earth-modified molecular sieve, a halogen-modified inorganic melting-resisting oxide and at least one VIII-family precious metal, wherein the molecular sieve is an EUO molecular sieve, the weight ratio of the rare earth-modified molecular sieve to the halogen-modified inorganic melting-resisting oxide is 10:90-90:10, in the catalyst, the content of the VIII-family precious metal is 0.1-10 percent by weight, in the rare earth-modified molecular sieve, the mass content of the rare earth oxide is 0.5-60.0 percent, and in the halogen-modified inorganic melting-resisting oxide, the mass content of the halogen is 0.5-20.0 percent. Compared with the prior art, the catalyst can ensure that the dimethylbenzene is isomerized and ethylbenzene is selectively transformed into paraxylene when used in C8 aromatic hydrocarbon isomerization and the concentration of the paraxylene in the catalyst in dimethylbenzene reaches or approaches a thermodynamic equilibrium value, and has high yield of the dimethylbenzene.
Description
Technical field
The present invention relates to C
8Catalytic converting catalyst of aromatic hydrocarbons and its preparation method and application particularly relates to Catalysts and its preparation method and application that a kind of ortho-xylene and meta-xylene tautomerize to paraxylene, also relates to C
8The conversion of ethylbenzene in aromatic hydrocarbons.
Background technology
In petrochemical production process, the C that obtains from various techniques
8In aromatic hydrocarbons, except to,, adjacent three kinds of dimethylbenzene, also contain ethylbenzene.As raw material, by joint operations such as isomerization, rectifying and adsorbing separation, can obtain the paraxylene product.Due to ethylbenzene and the dimethylbenzene boiling point very approaching, separation difficulty causes in the combined unit recycle stream ethylbenzene accumulation, causes isomerization combined unit logistics internal circulating load to improve, the operating severity of adsorbing separation increases, and but can not increase the output capacity of device.For avoiding above situation to occur, improve the production efficiency of device, just the part ethylbenzene conversion must be removed.Mainly contain at present two kinds of ethylbenzene conversion approach: a kind of is to be converted into dimethylbenzene by isomerization, and this approach is due to the yield that can improve purpose product dimethylbenzene, and is subject to the favor in market always; Another kind is to generate benzene by taking off ethyl, due to benzene cut boiling point and the dimethylbenzene difference enough large, be easy to by rectifying, it be separated, the production efficiency of device is effectively improved.
At present a lot of about the patent of ethylbenzene conversion, the zeolite catalyst of general one or more metals of multipurpose load of prior art, the multiplex aluminium oxide of its carrier, and the multiplex modenite of zeolite or ZSM series zeolite.As US4,482,773 have proposed the ZSM-5 catalyst of year Pt and Mg, and conversion of ethylbenzene is less than 45%.US4,487,731 have proposed ZSM-5 catalyst, the US4 of year Pt and Bi, 939,110 have proposed ZSM-5 catalyst, the US5 of year Pt and Pb, 077,254 proposed the mordenite catalyst of year Pt (Pd), also the composite zeolite catalyst that uses simultaneously ZSM-5 and modenite arranged, as US4,467,129 have reported ZSM-5 and the mordenite catalyst that is loaded with a kind of metal in RE, Mo, W, V.The dimethylbenzene yield is 95～98.5%, ethylbenzene generate benzene selectively less than 90%.Above prior art has a potential problem to be: the ethylbenzene in raw material is converted into benzene and C via dealkylation
2Cut subsequently must be with benzene and C
2Cut is separated from process-stream or it is transformed.Thereby each large refinery all will face a large amount of benzene byproducts, and according to the selling market market, the price of benzene will be lower than the price of desirable paraxylene product.And that CN200480009963.2 discloses is a kind of be used to making the raw material that comprises ethylbenzene and xylene different structure mixture that isomerized method occur, the method is to use two kinds of catalyst combination, at first raw material contacts with the first carbon monoxide-olefin polymeric, to produce the paraxylene intermediate product of relative raw material ratio higher concentration, then this intermediate product is contacting with the second carbon monoxide-olefin polymeric, and the ethylbenzene isomerization reaction mainly occurs.Although the method can make the paraxylene equilibrium concentration in product increase, the method causes xylene loss many, the deficiencies such as product yield reduction.
Summary of the invention
For overcoming deficiency of the prior art, the invention provides a kind of catalyst, can be ethylbenzene conversion dimethylbenzene, simultaneously ortho-xylene and meta-xylene is converted into paraxylene, the paraxylene that contains about equilibrium quantity in product stream has conversion of ethylbenzene and dimethylbenzene yield high.The present invention also provides the preparation method and application of this catalyst.
C of the present invention
8The aromatic hydrocarbons heterogeneous catalyst comprises: rare earth modified molecular sieve and halogen modified inorganic refractory oxide and at least a VIII family noble metal form, described molecular sieve is the molecular sieve of EUO structure, the weight ratio of rare-earth modified molecular-sieve and halogen modified inorganic refractory oxide is 10: 90～90: 10, be preferably 30: 70～80: 20, in catalyst, VIII family bullion content counts 0.1%～10% with weight metal, is preferably 0.2%～5.0%.Wherein in rare-earth modified molecular-sieve, rare earth oxide (RE
2O
3) mass content be 0.5%～60.0%, be preferably 10.0%～40.0%; In halogen modified inorganic refractory oxide, the mass content of halogen is 0.5%～20.0%, is preferably 1.0%～10.0%.
The physicochemical property of catalyst of the present invention is as follows: specific surface is 80～150m
2/ g, pore volume are 0.25～0.60ml/g (adopting ASAP2400 nitrogen absorption under low temperature instrument to record specific surface and pore volume).
Described molecular sieve is the EUO structure molecular screen, and the EUO molecular sieve has one dimension micropore canals structure, contains ten-ring straight-through duct (0.58 * 0.41nm) and twelve-ring side pocket (0.68 * 0.58 * 0.81nm) structure of vertical UNICOM with it.Directly synthetic EUO molecular sieve generally contains the cation of alkali metal or alkaline-earth metal, needs to obtain Hydrogen EUO molecular sieve by the method for roasting after the ammonium ion exchange of routine.
Described rare earth is selected from one or more in lanthanum, cerium, praseodymium and neodymium, is preferably lanthanum or/and cerium, more preferably lanthanum.
Described halogen is one or more in fluorine, chlorine and bromine, is preferably chlorine.
Described VIII family noble metal is preferably platinum and/or palladium, most preferably is platinum.
Described inorganic refractory oxide is one or more that are selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, is preferably aluminium oxide and/or kaolin, more preferably aluminium oxide.
Described catalyst is applied to xylene isomerization process, and meta-xylene and/or ortho-xylene are tautomerized to paraxylene.The process conditions of using are generally as follows: reaction temperature is 350～420 ℃, and reaction pressure is 0.8MPa～1.5MPa, and hydrogen/hydrocarbon raw material mol ratio is 2～10, and the hydrocarbon feed weight space velocity is 5～50h
-1
Before reaction, catalyst is carried out reduction activation, active noble metals is existed with simple substance form, reducing condition is as follows: under hydrogen existed, 100 ℃～500 ℃ kept 1～12 hour, and pressure is 0.5MPa～10MPa.Can contain in the isomerization raw material in meta-xylene, ortho-xylene and ethylbenzene any or several, C in preferred industry
8Aromatic hydrocarbons is rich in the mixed material of meta-xylene, ortho-xylene and ethylbenzene after adsorption stripping dimethyl benzene.
C of the present invention
8The preparation method of aromatic hydrocarbons heterogeneous catalyst comprises:
(1) preparation rare-earth modified molecular-sieve;
(2) prepare halogen modified inorganic refractory oxide;
(3) rare-earth modified molecular-sieve, halogen modified inorganic refractory oxide are made catalyst carrier;
(4) supported active metal component makes final isomerization catalyst.
Then catalyst of the present invention and preparation method make catalyst carrier by the modification respectively of two kinds of catalysis materials, the final load active metal component, and the catalyst that obtains is used for C
8During aromatics isomerization, the concentration of paraxylene in mixed xylenes is reached or near thermodynamic equilibrium value, the dimethylbenzene yield is high, can make ethylbenzene conversion simultaneously is dimethylbenzene, improve the yield of high value added product, reduced the energy consumption of separated process.
The key component of catalyst of the present invention is rare earth modified EUO molecular sieve and halogen modified inorganic refractory oxide.Because rare earth element can act on sour position with the B of molecular sieve, the acid strength of molecular sieve is reduced, and can produce more sour position, when providing more active sites for catalyst, avoided the side reactions such as the coking of strong acidic site and carbon distribution, the activity of catalyst and stability all are significantly improved.Can produce a large amount of L acid sites through halogen modified inorganic oxide, the effect that is subjected to Electronic Performance can improve catalyst and aromatic hydrocarbons that L is sour, thereby the touch opportunity of active sites on increase reactant and catalyst, the reactivity worth of raising catalyst.Synergy by rare-earth modified molecular-sieve and halogen modified inorganic refractory oxide, make catalyst when having desirable xylene isomerization function, can reduce dimethylbenzene and take off the side reactions such as alkyl, compare with existing catalyst, obviously reduce the loss of dimethylbenzene.
The specific embodiment
The below provides a kind of concrete preparation method of catalyst of the present invention, but is not limited to the method, and concrete steps are:
(1) with rare earth loaded to molecular sieve, through super-dry and roasting, obtain rare-earth modified molecular-sieve;
(2) halogen is loaded on inorganic refractory oxide, through super-dry and roasting, obtain halogen modified inorganic refractory oxide;
(3) rare-earth modified molecular-sieve, halogen modified inorganic refractory oxide, extrusion aid, water and the abundant kneading of peptizing agent are become plastic paste, extruded moulding through super-dry and roasting, obtains catalyst carrier of the present invention.
(4) will contain active metal component with conventional infusion process and load on carrier, then by dry, calcination process, obtain xylene isomerization catalyst of the present invention.
Rare earth loaded described in step (1) can be adopted ion-exchange, infusion process or kneading method to molecular sieve, when wherein adopting ion-exchange or infusion process, the solution compounds containing rare earth used that preparation contains rare earth are selected from one or more in oxide, chloride, nitrate, sulfate and carbonate, be preferably and be selected from chloride and/or nitrate, more preferably nitrate.When adopting kneading method, that solution with compounds containing rare earth fully mixes with molecular sieve, compounds containing rare earth are to be selected from one or more in oxide, chloride, nitrate, sulfate and carbonate, are preferably oxide and/or nitrate, more preferably oxide.
The described halogen of step (2) loads on inorganic refractory oxide and can adopt infusion process or kneading method, when wherein adopting infusion process, prepare halogen-containing solution compound used and be and be selected from one or more in hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and hydrofluoric acid, be preferably hydrochloric acid and/or ammonium chloride, more preferably ammonium chloride.When adopting kneading method, that solution with halogen contained compound fully mixes with the precursor of inorganic refractory oxide, wherein halogen contained compound is to be selected from one or more in hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and hydrofluoric acid, be preferably hydrochloric acid and/or ammonium chloride, more preferably ammonium chloride.Inorganic refractory oxide is one or more that are selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, be preferably aluminium oxide and/or kaolin, aluminium oxide more preferably, the precursor of aluminium oxide can be selected from boehmite, boehmite, diaspore, gibbsite and visit one or more in aluminium stone.
The described peptizing agent of step (3) is inorganic acid or organic acid, is preferably inorganic acid, and more preferably hydrochloric acid and nitric acid, most preferably be nitric acid; Wherein the mass concentration of salpeter solution used is 1.0%～30.0%, is preferably 1.0%～5.0%, and consumption is can make the kneading material be as the criterion as plastic block.Step (3) in order to be beneficial to extruded moulding, can adopt extrusion aid in the shaping of catalyst process, such as graphite, starch, cellulose and sesbania powder etc.
The mode that the described noble metal of step (4) is added in catalyst can adopt infusion process or ion-exchange, is preferably infusion process.Activity component impregnation solution commonly used is the aqueous solution that contains the reactive metal soluble compound, for example platinum acid chloride solution, platinum amine complex solution, palladium amine complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof.
Drying condition described in step (1), (2), (3) and (4) is normal temperature～300 ℃ maintenance 1h～48h, step (1), step (2), step (3) and the described drying condition of step (4) can be identical, also can be different.The roasting condition of step (1), (2) and (3) is 400 ℃～900 ℃ maintenance 0.5h～10.0h, and step (1), step (2) and the described roasting condition of step (3) can be identical, also can be different.The described catalyst roasting condition of step (4) is 300 ℃～600 ℃ and keeps 1h～8h.
Below by embodiment, technology of the present invention is described further.
Feedstock property that use in the laboratory sees Table 1, and experiment is to complete on pilot-plant, and catalyst volume 100ml is packed into reactor with after 100ml quartz sand dilution, and catalyst reduces 4h under 653K hydrogen exists before charging.
Table 1 feedstock property (quality percentage composition)
| Ethylbenzene | 7.9％ |
| Paraxylene | 0.1％ |
| Meta-xylene | 70.2％ |
| Ortho-xylene | 21.8％ |
Embodiment 1
The preparation of catalyst E-1 of the present invention
(1) preparation of EUO molecular sieve.
The present invention's EUO molecular sieve used is the method preparation according to US Patent No. 6733658 embodiment 3, and the molecular sieve silica alumina ratio that obtains is 63, specific area 449m
2/ g, pore volume 0.19mL/g.
Above-mentioned synthetic zeolite contains the cation of alkali metal or alkaline-earth metal, exchange with ammonium cation, through roasting in the air of 316 ℃～540 ℃ 1～10 hour, the acidic molecular sieve of gained was numbered S-1 subsequently, and it is well known in the art that this kind forms acid zeolite.
(2) getting 1000 gram mass concentration is that the lanthanum nitrate hexahydrate of 20% (in lanthana) fully mixes with 800 gram S-1 molecular sieves, then under 130 ℃ of conditions dry 24 hours, under 750 ℃ of conditions, roasting is 3 hours, obtains the lanthana mass content and be 20% modification S-1 molecular sieve.Be numbered the LS-1 molecular sieve.
(3) be that ammonium chloride solution and 450 grams (in the aluminium oxide) aluminium hydroxide (German Condean company produce SB) of 10% (in halogen) fully mixes with 500 gram mass concentration, then under 50 ℃ of conditions dry 48 hours, under 400 ℃ of conditions, roasting is 8 hours, obtain the halogen mass content and be 6.8% modified aluminas, be numbered the GS-1 aluminium oxide.
(4) 100 gram LS-1 molecular sieves of step (1), 100 gram GS-1 aluminium oxide and the 10 gram sesbania powder of step (2) are mixed, then add 230ml water and 14ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), abundant kneading, make it to become the paste plastic, extrude the cylindrical bars that diameter is 1.5mm on banded extruder, cylindrical bars under 100 ℃ dry 16 hours, then 550 ℃ of roastings obtained catalyst carrier ES-1 of the present invention in 4 hours in air atmosphere.
(5) with 100 gram ES-1 with containing H
2PtCl
6The saturated dipping of solution, and then 100 ℃ of dryings 8 hours, 500 ℃ of roasting 3h in air atmosphere make the catalyst of the present invention that contains 0.6wt%Pt, are numbered E-1, and its physico-chemical property sees Table 2, and reaction result sees Table 3.
Embodiment 2
The preparation of catalyst E-2 of the present invention
The preparation process of catalyst E-2 of the present invention is with embodiment 1, and difference is to replace lanthanum nitrate with cerous nitrate, and the catalyst of the present invention of preparing is numbered E-2, and its physico-chemical property sees Table 2, and reaction result sees Table 3.
Embodiment 3
The preparation of catalyst E-3 of the present invention
The preparation process of catalyst E-3 of the present invention is with embodiment 1, and difference is that refractory aluminium oxide used is the mixture of kaolin and aluminium oxide, and halide is selected ammonium fluoride, the composition of the catalyst E-3 of the present invention for preparing sees Table 1, be numbered E-3, its physico-chemical property sees Table 2, and reaction result sees Table 3.
Embodiment 4～7
The preparation of catalyst E-4～E-7 of the present invention
The preparation process of catalyst E-4～E-7 of the present invention is with embodiment 1, and the amount of difference lanthanum nitrate used, molecular sieve, halogen and aluminium hydroxide is different, the catalyst E-4～E-7 of the present invention for preparing, and its physico-chemical property sees Table 2, and reaction result sees Table 3.
Comparative Examples 1
The preparation of comparative catalyst C-1 of the present invention.
The preparation method of catalyst is with embodiment 4, and difference is molecular sieve used without containing the rare earth element solution processing, and aluminium oxide is also processed without halogen.Be numbered C-1, its physico-chemical property sees Table 2, and reaction result sees Table 3.
The main physico-chemical property of table 2 catalyst
Annotate: there is no dated RE in (1) table 1
2O
3Be lanthana, molecular sieve is EUO type molecular sieve, and refractory oxide is aluminium oxide.1. take the modified molecular screen quality as benchmark; 2. take catalyst quality as benchmark; 3. take modification refractory oxide quality as benchmark; 4. take catalyst quality as benchmark; 5. cerium oxide; 6. 30wt% kaolin and surplus aluminium oxide.
(2) S represents specific area, and V represents pore volume.
Table 3 catalyst runs condition and result
[notes]: the percentage in table 2 is mass percent.
PX represents paraxylene, and ∑ X represents the dimethylbenzene total amount.
1. in this process, xylene content increases xylene loss for negative representative.
Result by table 3 can be found out, compares with the comparative catalyst, and catalyst conversion of ethylbenzene of the present invention has obviously improved xylene loss and obviously reduced, and reactivity worth is obviously due to the comparative catalyst.
Claims (10)
1. C
8The aromatic hydrocarbons heterogeneous catalyst, it is characterized in that: catalyst is comprised of rare earth modified molecular sieve and halogen modified inorganic refractory oxide and at least a VIII family noble metal, described molecular sieve is the molecular sieve of EUO structure, the weight ratio of rare-earth modified molecular-sieve and halogen modified inorganic refractory oxide is 10: 90～90: 10, in catalyst, VIII family bullion content counts 0.1%～10% with weight metal; Wherein in rare-earth modified molecular-sieve, the mass content of rare earth oxide is 0.5%～60.0%; In halogen modified inorganic refractory oxide, the mass content of halogen is 0.5%～20.0%.
2. according to catalyst claimed in claim 1, it is characterized in that: the weight ratio of rare-earth modified molecular-sieve and halogen modified inorganic refractory oxide is 30: 70～80: 20, and in catalyst, VIII family bullion content counts 0.2%～5.0% with weight metal.
3. according to catalyst claimed in claim 1, it is characterized in that: in rare-earth modified molecular-sieve, the mass content of rare earth oxide is 10.0%～40.0%; In halogen modified inorganic refractory oxide, the mass content of halogen is 1.0%～10.0%.
4. according to catalyst claimed in claim 1, it is characterized in that: the EUO molecular sieve is Hydrogen EUO molecular sieve.
5. according to catalyst claimed in claim 1, it is characterized in that: rare earth is selected from one or more in lanthanum, cerium, praseodymium and neodymium; Halogen is one or more in fluorine, chlorine and bromine; VIII family noble metal is platinum and/or palladium; Inorganic refractory oxide is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay.
6. the application of the described catalyst of the arbitrary claim of claim 1 to 5 in xylene isomerization process, reaction temperature is 350～420 ℃, and reaction pressure is 0.8MPa～1.5MPa, and hydrogen/hydrocarbon raw material mol ratio is 2～10.
7. according to application claimed in claim 6, it is characterized in that: hydrocarbon raw material is any or several hydrocarbon raw material that contains in meta-xylene, ortho-xylene and ethylbenzene.
8. the preparation method of the described catalyst of the arbitrary claim of claim 1 to 5 is characterized in that:
(1) with rare earth loaded to molecular sieve, through super-dry and roasting, obtain rare-earth modified molecular-sieve;
(2) halogen is loaded on inorganic refractory oxide, through super-dry and roasting, obtain halogen modified inorganic refractory oxide;
(3) rare-earth modified molecular-sieve, halogen modified inorganic refractory oxide, extrusion aid, water and the abundant kneading of peptizing agent are become plastic paste, extruded moulding through super-dry and roasting, obtains catalyst carrier;
(4) will contain active metal component with infusion process and load on carrier, then by dry, calcination process, obtain xylene isomerization catalyst.
9. it is characterized in that in accordance with the method for claim 8: step (1) middle rare earth loads to and adopts ion-exchange, infusion process or kneading method on molecular sieve; The halogen of step (2) loads to and adopts infusion process or kneading method on inorganic refractory oxide.
10. in accordance with the method for claim 8, it is characterized in that: the roasting condition of step (1), (2) and (3) is 400 ℃～900 ℃ maintenance 0.5h～10.0h, and the described catalyst roasting condition of step (4) is 300 ℃～600 ℃ and keeps 1h～8h.
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| CN104117369B (en) * | 2014-06-26 | 2017-04-12 | 江苏扬子催化剂有限公司 | Normal-paraffin isomerization catalyst, preparation method and application thereof |
| CN105833900A (en) * | 2016-04-06 | 2016-08-10 | 山东成泰化工有限公司 | Isomerization catalyst and preparation method thereof |
| CN107297221A (en) * | 2017-07-11 | 2017-10-27 | 太原大成环能化工技术有限公司 | A kind of ethylbenzene dealkylation catalyst and preparation method thereof |
| CN109835913B (en) * | 2017-11-29 | 2022-07-15 | 中国科学院大连化学物理研究所 | Synthesis method of rare earth EU-1 hierarchical pore molecular sieve |
| CN108435243A (en) * | 2018-04-20 | 2018-08-24 | 太原大成环能化工技术有限公司 | A kind of rare earth modified ethylbenzene dealkylation catalyst and preparation method thereof |
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| CN1156642A (en) * | 1995-07-24 | 1997-08-13 | 法国石油公司 | Catalyst using cerium modified mordenite as main component and its application in aromatic C8 fraction isomerization |
| CN1233531A (en) * | 1997-12-22 | 1999-11-03 | 法国石油公司 | Catalyst containing zeolite EUO and use of catalyst in process for isomerizing aromatic compounds containing 8 carbon atoms per molecule |
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