CN101455978B - Shape-selective catalyst preparation method - Google Patents
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Abstract
The invention relates to a method for preparing a shape-selective alkylation catalyst, in particular to a method for preparing high-selectivity synthetic p-diethylbenzene catalyst by use of rare earth modification. The method has a main technical characteristic that rare earth modification is completed in two mutually linked steps, namely hot impregnation and cold impregnation. The high-selectivity catalyst prepared by the method has the advantages of high activity, long single-pass reaction period and good regeneration repeatability.
Description
Technical field
The invention belongs to the petrochemical catalyst technical field, relate generally to a kind of Preparation of catalysts method that is used for ethylbenzene/ethene (or ethanol) direct synthesis of high purity p-Diethylbenzene of form selected methylation (p-DEB).
Background technology
P-Diethylbenzene is used as the strippant of paraxylene in the technical process of adsorbing separation production paraxylene, the p-Diethylbenzene purity that existing market is sold will reach more than 98%.
The method that obtains p-Diethylbenzene has two kinds, and a kind of is to adopt adsorption method of separation to separate from mix diethylbenzene to obtain.This technology by Uop Inc. take the lead in the invention and in the mid-1970s industrialization of 20th century, this technology adopts zeolite adsorbents, toluene strippant and the simulation moving-bed device of metal ion exchanged to carry out p-Diethylbenzene production, there is the big and shortcoming such as equipment investment is big, and raw material sources are limited of energy consumption.
The industrial production technology of another kind of p-Diethylbenzene product be utilize the shape selective catalysis performance of silica-rich zeolite molecular sieve make ethylbenzene pass through disproportionated reaction (two molecule ethylbenzene generate a part benzene and a part diethylbenzene) or by with the directly synthetic p-Diethylbenzene of the alkylated reaction of ethene (or ethanol).In shape selective catalysis ethylbenzene disproportionation and ethylbenzene ethylation reaction, two other isomers of p-Diethylbenzene a-position and ortho position diethylbenzene are bigger because of molecular dimension, and its diffusion motion in molecular sieve pore passage is subjected to spatial constraints, thereby are difficult to generate.Molecular sieve shape selective catalysis method that Here it is is the principle of synthetic p-Diethylbenzene directly.Phase late 1970s, American Kaeding etc. in U.S. Pat 4094921 reported first on the ZSM-5 of modification type zeolite molecular sieve catalyst the result of study of the synthetic p-Diethylbenzene of ethylbenzene and ethylene alkylation highly selective, caused extensive interest both domestic and external thus.
Up to now, relevant shape selective catalysis directly synthetic p-Diethylbenzene main patent situation is as follows both at home and abroad:
Chinese invention patent 90101436.2 (nineteen ninety) has disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene.Its major technique is characterized as, and adopts Al, Mg bimetallic ion modification ZSM-5 zeolite molecular sieve.Wherein, metal A l ion modification is finished with the precipitation method.That is, Hydrogen ZSM-5 zeolite is contacted with aluminum nitrate solution, add ammonia precipitation process (pH=7-8) then.The modification of metal M g ion is finished with the magnesium nitrate solution normal temperature dipping.Selectivity with catalyst p-Diethylbenzene in the reaction of ethylbenzene ethanol alkylation of this method preparation can reach 95-98%, but conversion of ethylbenzene (only being 5-10%) on the low side, and the catalyst regeneration poor repeatability that shows in the practical application, be not suitable for commercial Application.
Disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in the Chinese invention patent 94110202.5 (1994).Its major technique is characterized as, and adopts Si (or Mg)-mishmetal modified ZSM-5 zeolite molecular sieve, the synthetic p-Diethylbenzene catalyst of preparation.This method is actually and is made of the rapid modification of multistep.Comprising using steam earlier at 400-700 ℃ of following Passivation Treatment Hydrogen ZSM-5 zeolite; Exchange Hydrogen ZSM-5 zeolite 1 hour with mixeding acid rare-earth (lanthanum-oxides/rare earth oxide 〉=40%) solution down at 20-90 ℃ then, perhaps use mixeding acid rare-earth (lanthanum-oxides/rare earth oxide 〉=40%) solution impregnation Hydrogen ZSM-5 zeolite 2-40 hour down at 0-30 ℃; At last, with methyl silicate or ethyl ester above-mentioned modified catalyst being carried out silanized surface again modifies.The gained modified catalyst can be used for the synthetic p-Diethylbenzene of ethylbenzene ethene (or ethanol) alkylation, and the p-Diethylbenzene conversion ratio can reach 8-19%, and p-Diethylbenzene can reach 95%.The shortcoming of this method is: the p-Diethylbenzene selectivity is difficult to reach more than 98%; The silanization modification procedure that wherein relates to need be used organic solvents such as toluene, dimethylbenzene, n-hexane or cyclohexane, and is unfriendly to environment.
Chinese invention patent 95118372.9 has disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in (nineteen ninety-five).Its major technique is characterized as, and adopts the solution impregnation modified zsm-5 zeolite of two or more slaine among B, Mg, Al, Si, P, Ca, Zn, Ti, the Zr and utilizes the synthetic p-Diethylbenzene of ethylbenzene disproportionation reaction.Wherein, various modified components are B in the content of oxide
2O
33-5%, MgO 1-3%, Al
2O
32-5%, SiO
21.5-2.5%, P
2O
53-7%, CaO 0.5-2%, ZnO 2-5%, TiO
22.5-5%, ZrO
22.5-5%, the maceration extract temperature is between 10-95 ℃, and the dipping modification need repeat 1-3 time.The conversion of ethylbenzene of prepared catalyst in the ethylbenzene disproportionation reaction reaches 10-30%, and the p-Diethylbenzene selectivity reaches 95-99%, and the p-Diethylbenzene yield is 7-15wt%, and one way surpasses 720 hours service life, and regeneration back performance reaches usage level first.Because the ethylbenzene disproportionation reaction mainly utilizes transition state control to select the directly synthetic p-Diethylbenzene of shape principle, utilize the directly synthetic p-Diethylbenzene of product diffusion-restricted principle to differ widely with ethylbenzene and ethene (ethanol) alkylation process, can not be applicable to the ethylbenzene alkylated reaction so be applicable to the shape-selective catalyst of ethylbenzene disproportionation reaction.
Disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene among the Chinese invention patent 200310116628.X (2003).Its major technique is characterized as, adopting the Hydrogen ZSM-5 zeolite molecular sieve of nanocrystalline granularity is parent, at first the Hydrogen parent is carried out the high-temperature vapor Passivation Treatment, adopt one or both component obtain solutions among La, Si, P, the Mg again the catalyst precursor after the passivation to be flooded modification then.The finished catalyst of making is used for the synthetic p-Diethylbenzene of ethylbenzene ethylene alkylation.Wherein, the water vapor passivation modification is carried out under 500-600 ℃, and passivation time is 6 hours; La, P, the modification of Mg dipping are carried out at normal temperatures, and 5 hours times spent, at 90 ℃ of following evaporate to dryness maceration extracts, drying and calcination process obtain modified product more afterwards.La
2O
3, P
2O
5, MgO modifier consumption is respectively in 1-9%, 2-12% and 5-12% scope.SiO
2Silanization method, SiO are adopted in modification
2Load capacity is in the 5-25% scope.Gained catalyst conversion of ethylbenzene in the alkylated reaction of continuous 244 hours ethylbenzene ethene is 16.50-10.35%, and the p-Diethylbenzene selectivity is 97.02-98.40%.But above-mentioned method of modifying has the following disadvantages: the dipping modification is at room temperature carried out, and is consuming time longer; Maceration extract is excessive, must be at 90 ℃ of following evaporates to dryness, time consumption and energy consumption and constantly concentrating along with maceration extract in the evaporate to dryness process, the catalyst of contact concentrate and do not reach between the catalyst of concentrate and bigger load capacity difference can occur, cause the catalyst performance heterogeneity, the preparation poor repeatability is unfavorable for commercial Application; In addition, when adopting the silanization modification, relate to the environmental problem of with an organic solvent bringing equally.
Disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in the Chinese invention patent 200410020397.9 (2004).Its major technique is characterized as, having adopted a kind of Si/Al mol ratio is that 50 H-ZSM-5 zeolite molecular sieve is a parent, and adopted B, Mg, three kinds of elements of Co to divide the above-mentioned parent of three step modifications to make catalyst, be used for the synthetic p-Diethylbenzene of ethylbenzene and ethanol alkylation reaction.Wherein, the presoma of B, Mg, three kinds of modifying elements of Co is respectively boric acid, magnesium nitrate and cobalt nitrate.With, the modifier consumption of B, Mg, Co atom meter is respectively 1-3%, 0.1-1% and 1-3%.During modification, zeolite molecular sieve is contacted 10 hours with first kind, second kind, the precursor solution of the third modifying element successively under room temperature and stirring condition, then at 80-120 ℃ of following evaporate to dryness.After three elements all load on the molecular sieve in identical mode, again with the gained solid 450-550 ℃ of following roasting 4 hours.The catalyst that so makes is in the reaction of ethylbenzene ethanol alkylation, conversion of ethylbenzene can reach 15-20%, and the p-Diethylbenzene selectivity can reach more than 99%, and the p-Diethylbenzene yield can reach more than 14%, but do not have long-time operation result, do not have the catalyst regeneration experimental result yet.The problem that this patented method exists comprises: on the one hand, need to go on foot and stir for a long time dip operation with three; On the other hand, three kinds of element modified evaporates to dryness that all need are operated, and not only time consumption and energy consumption is unfavorable for the processability uniform catalyst, and can discharge a large amount of acid water steams in the above modification liquid of evaporate to dryness process, causes equipment corrosion serious.
In addition, disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in the U.S. Pat 4094921.Its major technique is characterized as, and adopting grain size is that ZSM-5 zeolite more than 1 micron is a parent, by the high-temperature vapor passivation with give carbon deposit and make the zeolite parent possess high selectivity.
Disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in the U.S. Pat 4100217 (1978).Its major technique is characterized as, and adopting the ZSM-23 zeolite is parent, by ethylbenzene and the synthetic p-Diethylbenzene of ethylene alkylation.
Disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in the U.S. Pat 4128592 (1978).Its major technique is characterized as, adopt that grain size is more than 0.5 micron, silica alumina ratio greater than 12, the duct restricted index is that the zeolite of 1-12 is parent (being mainly the ZSM-5 zeolite), modification procedure comprises: (1) is at 250-1000 ℃ of following water vapor passivation more than 0.5 hour; Dipping at least 0.25% phosphorous oxide; Dipping at least 0.25% magnesia; Give deposition at least 1% charcoal.Prepared catalyst is used for the alkylated reaction of ethylbenzene and ethene, and the p-Diethylbenzene selectivity can reach 99%.
U.S. Pat 4365104 has disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in (nineteen eighty-two).Its major technique is characterized as, adopt silica alumina ratio greater than 12, the duct restricted index is that zeolite such as the ZSM-5 ,-11 ,-12 ,-23 ,-35 ,-38 ,-48 of 1-12 is parent, at first make the zeolite parent carry out modification, then the catalyst of above-mentioned modification is further handled down at 50-500 ℃ with hydrogen sulfide or sulfur dioxide again through the phosphorous oxide of water vapor passivation and load 0.25-25% or magnesia or phosphorous oxide and magnesian mixture.
Disclosed a kind of preparation method who is used for the shape-selective catalyst of synthetic p-Diethylbenzene in the U.S. Pat 4465886 (1984).Its major technique is characterized as, adopt silica alumina ratio greater than 12, the duct restricted index is that zeolite such as the ZSM-5 ,-11 ,-12 ,-23 ,-35 ,-38 ,-48 of 1-12 is parent, adopt molecular dimension silicones big, that can not enter zeolite cavity that above-mentioned zeolite is carried out outer surface and cover modification, make zeolite have shape selectivity.After this, U.S. Pat 4950835 (nineteen ninety) the method modified ZSM-5 zeolite that disclosed the positive esters of silicon acis deposition of silica of a kind of usefulness prepares the catalyst of high shape selectivity; U.S. Pat 5406015 (nineteen ninety-five) and US5530170 (1996) have proposed silicon-containing organic compounds such as use silane that the ZSM-5 zeolite molecular sieve is carried out silica are deposition modified, obtain the method for high shape selectivity catalyst.
Up to now, directly the situation of the main open source literature both at home and abroad of synthetic p-Diethylbenzene is as follows for relevant shape selective catalysis:
1989 18 the 2nd phases of volume of open source literature " petrochemical industry " have been reported a kind of ethylbenzene ethanol alkylation and synthetic p-Diethylbenzene Preparation of catalysts method of ethylbenzene disproportionation of being used for, and its major technique feature is, with magnesium-modified HZSM-5 zeolite.Wherein, magnesium-modified employing nitrate solution infusion process, maceration extract is evaporated to dried in water-bath.The conversion of ethylbenzene of gained catalyst can reach more than 25%, and the diethylbenzene selectivity can reach more than 99%.But above result only is 1-6 hour gained of reaction, does not have the result of long-time running, does not also have the reaction result of regenerated catalyst.
1991 the 12nd the 3rd phases of volume of open source literature " catalysis journal " have reported that a kind of ethylbenzene vinyl alkyl that is used for is combined to p-Diethylbenzene Preparation of catalysts method, and its major technique feature is: with the solution impregnation modified HZSM-5 zeolite of rare earth lanthanum nitrate.But do not disclose the modification details, the highest of the p-Diethylbenzene selectivity of catalyst reaches about 80%.
1992 the 21st the 5th phases of volume of open source literature " petrochemical industry " have been reported a kind of synthetic p-Diethylbenzene Preparation of catalysts method of ethylbenzene ethanol alkylation that is used for, its major technique feature is: catalyst floods modification with the soluble salt of Mg, Ca, Sr and Ce, and the modifier solution consumption is by the water absorption decision of HZSM-5 zeolite molecular sieve parent.Emphasize that bimetallic-modified is effective, but do not disclose the details of modified component.Prepared catalyst has been used on the industrial installation.
2008 the 36th the 3rd phases of volume of open source literature " Chemical Engineering " have reported that a kind of ethylbenzene vinyl alkyl that is used for is combined to p-Diethylbenzene Preparation of catalysts method, its major technique feature is: prepare the purpose catalyst with magnesium-modified HZSM-5 molecular sieve, be used for industrial production, but do not disclosed the catalyst modification details.
Reported that a kind of ethylbenzene disproportionation synthesizes p-Diethylbenzene Preparation of catalysts method among open source literature Journal of Molecular Catalysis A:Chemical 181 (2002) 41-55.Its major technique is characterized as: with tetraethyl orthosilicate is modifier, prepares the purpose catalyst by gas-solid phase reaction deposition of silica on the HZSM-5 outer surface of zeolite.
Reported among open source literature Catalysis Today 73 (2002) 65-73 that a kind of ethylbenzene ethanol alkylation synthesizes p-Diethylbenzene Preparation of catalysts method.Its major technique is characterized as: with tetraethyl orthosilicate is modifier, and estersil is dissolved in toluene-methanol solution, prepares the purpose catalyst with above-mentioned solution by gas-solid phase reaction deposition of silica on the HZSM-5 outer surface of zeolite then.
Reported that a kind of ethylbenzene disproportionation synthesizes p-Diethylbenzene Preparation of catalysts method among open source literature Journal of Molecular Catalysis A:Chemical 217 (2004) 185-191.Its major technique is characterized as: with tetraethyl orthosilicate is modifier, estersil is dissolved in toluene-methanol solution, prepare the purpose catalyst with above-mentioned solution by liquid and solid phase reaction deposition of silica on the HZSM-5 outer surface of zeolite then, liquid and solid phase reaction continues 12 hours down at 80 ℃.
Open source literature Journal of Molecular Catalysis A:Chemical 217 (2004) 185-191 and ChemicalEngineering Research and Design 82 (A10): reported among the 2004:1391-1396 that a kind of ethylbenzene disproportionation synthesizes p-Diethylbenzene Preparation of catalysts method.Its major technique is characterized as: with tetraethyl orthosilicate is modifier, estersil is dissolved in toluene-methanol solution, prepare the purpose catalyst with above-mentioned solution by liquid and solid phase reaction deposition of silica on the HZSM-5 outer surface of zeolite then, liquid and solid phase reaction continues 12 hours down at 80 ℃.
Reported that a kind of ethylbenzene ethanol alkylation synthesizes p-Diethylbenzene Preparation of catalysts method among 2005 the 26th the 8th phases of volume of open source literature " catalysis journal " and Journal of Molecular Catalysis A:Chemical248 (2006) 220-225.Its major technique is characterized as: with ammonia is modifier, makes aluminium on the HZSM-5 by nitrogenize by gas-solid phase reaction, thereby eliminates the effects of the act optionally strong acid center of p-Diethylbenzene, preparation purpose catalyst.It should be noted that the nitride in the catalyst is in use unstable, in catalyst regeneration process, may become oxide form again again, so this kind method of modifying has only theory significance.
Reported among open source literature Applied Catalysis A:General 299 (2006) 157-166 that a kind of ethylbenzene ethanol alkylation synthesizes p-Diethylbenzene Preparation of catalysts method.Its major technique is characterized as: with the ethanolic solution dipping HZSM-5 zeolite of rare earth element lanthanum nitrate or cerous nitrate, maceration extract stirred after 1 hour, again standing over night.Then the ethanol reduction vaporization in the maceration extract is removed catalyst solid roasting 10 hours in 550 ℃ and air atmosphere.It should be noted that with this method p-Diethylbenzene selectivity of catalyst when the lanthana load capacity reaches 30% and still only reach about 90%.As seen, the modified effect of its lanthana is poor.
Reported that a kind of ethylbenzene disproportionation synthesizes p-Diethylbenzene Preparation of catalysts method among open source literature Journal of Molecular Catalysis A:Chemical 248 (2006) 152-158.Its major technique is characterized as: earlier with the hexane solution of many phenyl methyls siloxanes by liquid and solid phase reaction deposition of silica on the HZSM-5 outer surface of zeolite, ethanol-water solution with magnesium acetate at room temperature floods silicon modified HZSM-5 zeolite then, obtains the purpose catalyst.This catalyst can keep 98.6% p-Diethylbenzene selectivity up to 28% o'clock at conversion of ethylbenzene.But, do not have long-time service data of catalyst and regeneration afterreaction data.An obvious problem of this method is silanization modifier costliness.
From above-mentioned patent and open source literature report as can be seen, up to the present, the preparation para-selectivity is in the existing several different methods of the synthetic p-Diethylbenzene catalyst more than 98%, mainly can be divided into silanization method (as, U.S. Pat 4950835 (nineteen ninety)) and load multi-element metal-nonmetal oxide method (as, Chinese invention patent 90101436.2 (nineteen ninety)).Though this two classes method of modifying has all been realized commercial Application,, prepare catalyst with the Silicane Method modification and exist modifier to cost an arm and a leg and problem such as organic solvent harm environment; Load multi-element metal-nonmetal oxide method has been avoided the problem of silanization method.But the synthetic p-Diethylbenzene catalyst of existing load multi-element metal-nonmetal oxide method preparation all exists regenerability poor in actual applications, catalyst short problem in service life.
Summary of the invention
The present invention aims to provide a kind of method for preparing high p-Diethylbenzene catalysts selective with the rare earth compound modification.
We recognize through studying for a long period of time, are whole acid centres of (1) elimination outer surface of zeolite to force synthetic reaction to be carried out in zeolite cavity with the catalyst key of the synthetic p-Diethylbenzene of zeolite molecular sieve (as ZSM-5) preparation high selectivity.This is because the acid site on the outer surface is present in the open geometric space, does not have the shape selective catalysis effect; Strong acid center on the outer surface can make in the hole p-Diethylbenzene product that generates change into by the secondary isomerization reaction between position and ortho position accessory substance, then can directly generate the ortho position accessory substance in the weak acid by the primary first-order equation alkylation; (2) by dwindling zeolite port size and duct size, suitably increase the molecular diffusion resistance in zeolite crystal internal capillary road, thereby position and the diffusion velocity of ortho position diethylbenzene product in zeolite micropore between limiting effectively, simultaneously by suitably eliminating the strong acid center in the zeolite micropore, and the moderate strength acid site of reservation right quantity, reach the coking deactivation that both suppresses catalyst, can utilize isomerization reaction position and ortho position diethylbenzene product between diffusion hindered isomery again to be become the purpose of p-Diethylbenzene purpose product again.
But, make high-selectivity catalyst possess good activity and stable simultaneously, then need under the prerequisite that has effectively suppressed the carbon deposit reaction in the zeolite cavity, in the duct, keep more acid site as far as possible; Also need be between effectively having limited under the prerequisite of position and ortho position diethylbenzene diffusion velocity in the duct, make the maintenance of zeolite cavity and aperture unimpeded as far as possible; On the other hand, prepare the good catalyst of regenerability, need then to avoid that employed modifying element (high temperature, have steam to exist) under the harsh conditions of regeneration runs off, migration or solid phase reaction.
We get catalyst and have realized commercial Application by multi-element metal-nonmetal oxide modification legal system that employing contains rare earth compound in patent in early stage (Chinese invention patent 94110202.5 (1994)).But because this patented method has adopted silanization and magnesium-modified simultaneously, the former improves the Preparation of Catalyst cost and the harm environment, the latter cause catalyst activity and bad stability and partly offset rare earth compound to the effect that improves catalyst regeneration repeatability (magnesium ion under the high temperature of regeneration with catalyst in alumina catalyst support between formed spinelle MgAl mutually
2O
4, changed the catalyst phase gradually), so catalyst performance still can not satisfy the demand in market from now on.
The oxide of rare-earth elements of lanthanum, cerium, praseodymium etc. has stronger alkalescence and bigger size, and this regulates zeolite acidity for it and the duct port size provides advantage; On the other hand, the oxide itself of rare-earth elements of lanthanum, cerium, praseodymium etc. is all more stable, they generally do not exist losss, migration problem under the coexistence of high temperature and steam, generally also not can with carrier generation high temperature solid state reaction, this provides advantage for it prepares the good catalyst of regenerability.Therefore, theoretically, merely with the rare-earth element modified all good synthetic p-Diethylbenzene catalyst of combination property of just can preparing.But, from open source literature Applied CatalysisA:General 299 (2006) 157-166, be not difficult to find out, simple with rare-earth element modified, even the very big p-Diethylbenzene catalyst (the p-Diethylbenzene selectivity of prepared catalyst also only reaches about 90% when the lanthana load capacity reaches 30%) that also is difficult to prepare high selectivity of modifier consumption.
We are through discovering, with existing rare earth loaded modified method (as, open source literature Applied Catalysis A:General299 (2006) 157-166; Chinese invention patent 94110202.5 (1994) is at 0-30 ℃ of following dipping) reason that is difficult to obtain the synthetic p-Diethylbenzene catalyst of high selectivity is, rare earth ion is larger-size hydrated ion at normal temperatures, is difficult to enter the zeolite cavity (as the ZSM-5 duct) of ten-ring.If therefore the modification of supported rare earth ion is at room temperature carried out, rare earth ion can not successfully enter zeolite cavity, also just can not effectively regulate, can only play the effect of eliminating the outer surface of zeolite acid site and the effect of dwindling the aperture acid strength in the zeolite pore and duct size; In addition, if (flooding down at 20-90 ℃ as Chinese invention patent 94110202.5 (1994)) carried out in the modification of supported rare earth ion under higher temperature, the hydrated rare-earth ion can reduce size because of hydrauture reduces on the one hand, may and increase size and reduce the ion-exchange activity because of the aggravation of self hydrolysis on the other hand, be difficult to equally acid strength in the zeolite pore and duct size are effectively regulated.
Discover more than comprehensive, technical scheme of the present invention is: according to a conventional method MFI type shape-selective molecular sieve is carried out earlier the stripper plate agent and handle, for the carrier extruded moulding is handled, steam high temperature Passivation Treatment, carry out the nitric acid rare earth modification with hot dipping stain and cold soaking stain method successively with the aluminium oxide then.Wherein, in the hot dipping stain of at first carrying out, make the nitrate maceration extract of rare earth be highly acid to suppress the hydrolysis of rare earth ion in hydrothermal solution by adding a small amount of nitric acid.Concrete operations are as follows:
(1) the former powder of shape-selective molecular sieve (referring to ZSM-5, any mixture of ZSM-11 or ZSM-5 and ZSM-11) that will have the MFI structure burns the agent of amine removal template, then with the molecular screen primary powder, the Al that measure
2O
3Mix with the sesbania powder, and, mix and pinch, last extrusion, drying, roasting moulding with the dilute nitric acid solution making beating.The condition of molding that the present invention recommends to use is: the molecular sieve of metering and Al
2O
3Butt than for 65/35-80/20, the sesbania powder accounts for molecular sieve and Al
2O
3Butt weight and 2-6%, the concentration of rare nitric acid adopts 5～15% (volumes), dryly carries out drying time 〉=3 hour under 110 ℃; Roasting is carried out in 450～650 ℃ temperature range, and roasting time is 2～6 hours.The silica alumina ratio preferable range of the MFI molecular sieve parent that the present invention recommends is 20～200, and the grain size preferable range is 0.5～5 micron.
(2) with molded molecular sieve routinely the ammonium switching method make the ammonium type, and be prepared into Hydrogen by dry, roasting, then the hydrogen type molecular sieve catalyst is handled with conventional water vapor passivation method.The ammonium give-and-take conditions that the present invention recommends are: ammonium nitrate solution concentration 0.4～1.0mol/L, ammonium nitrate solution is 1: 1～20: 1 (ml/g) with the ratio of granular solids, ammonium exchange is at room temperature carried out, 0.5～10 hour swap time of each ammonium, repeated exchanged 1～5 time; Dry under 110 ℃, carry out drying time 〉=3 hour; Roasting is carried out in 550～650 ℃ temperature range, and roasting time is 6～10 hours; Water vapor passivation adopts 100% steam, and passivation temperature is in 400～700 ℃ of scopes, and passivation time selects 1～20 hour, water vapor flux with water count 0.1～30 the gram (hour)
-1(gram catalyst)
-1
(3) will in rare earth nitrate solution, carry out the modification of hot dipping stain through the hydrogen type molecular sieve catalyst after the water vapour passivation, and drying and roasting.The hot dipping stain condition that the present invention recommends is: temperature range is 60-95 ℃, and dip time is 0.1～40 hour; In 1～10% scope, the pH value is 2～5 with the oxide weight timing for rare earth element total content in the rare earth nitrate solution, and the rare earth nitrate solution consumption is 1～100ml (a gram catalyst)
-1, hot dipping stain number of times is got 1～3 time.When adopting repeatedly hot dipping stain, need drying and roasting between twice hot dipping stain.In 2～7% scopes, wherein, used rare earth nitrades is lanthanum nitrate or lanthanum rich mischmetal nitrate (lanthanum-oxides/rare earth oxide weight ratio 〉=40%) to rare earth element total amount by the load of hot dipping stain during the hot dipping stain with the oxide weight timing.Dry under 110 ℃, carry out drying time 〉=3 hour; Roasting is carried out in 450～650 ℃ temperature range, and roasting time is 2～4 hours.
(4) the rare earth modified catalyst after the hot dipping stain is further at room temperature carried out the modification of equal-volume cold soaking stain with rare earth nitrate solution, and dry, roasting.The cold soaking stain modified condition that the present invention recommends is: temperature range is 5-30 ℃, and dip time is 0.1～10 hour; Rare earth element total content in the rare earth nitrate solution in 5～25% scopes, adopts equal-volume cold soaking stain with the oxide weight timing, and the dipping number of times is got 1～3 time.When adopting repeatedly the cold soaking stain, need drying and roasting between twice dipping.Rare earth element total amount by the load of cold soaking stain with the oxide weight timing in 7～20% scopes.Used rare earth nitrades was lanthanum nitrate or lanthanum rich mischmetal nitrate (lanthanum-oxides/rare earth oxide weight ratio 〉=40%) when wherein, cold soaking steeped.Dry under 110 ℃, carry out drying time 〉=3 hour; Roasting is carried out in 450～650 ℃ temperature range, and roasting time is 2～4 hours.
The invention has the beneficial effects as follows: the present invention is both fully sharp with the good advantage of rare earth modified catalyst regeneration performance, also solved in the past and simple rare earth modifiedly can not improve the catalyst para-selectivity effectively, the problem that must be aided with other modification procedure, long, the good regeneration repeatability of catalyst selectivity height, single-pass reaction period of the present invention's preparation possesses good activity and stable simultaneously.
The catalyst of the present invention's preparation is used for fixing bed bioreactor, and synthetic p-Diethylbenzene adopts the ethylbenzene alkylation, promptly uses ethylbenzene and ethene (ethanol) raw material.The typical reaction condition is: ethylbenzene and ethene (ethanol) mol ratio is 4.5: 1, and reaction pressure is a normal pressure, and reaction temperature is 340 ℃ (350 ℃), and the mass space velocity of ethylbenzene is 5h
-1
The specific embodiment
Be that example is described in further details the present invention with the ZSM-5 zeolite below, but do not influence protection scope of the present invention.
The comparative example 1
(the zeolite crystal degree is the 1-2 micron, SiO to prepare Hydrogen HZSM-5 molecular sieve catalyst according to conventional method
2/ Al
2O
3=50, extruded moulding, granularity
Molecular sieve content 80%, alumina content 20%), and with its carry out the water vapour Passivation Treatment (adopt 100% steam, 550 ℃ of passivation temperatures, passivation time 3 hours, water vapor flux with water count 1 gram (hour)
-1(gram catalyst)
-1).Be that the lanthanum nitrate hexahydrate (in lanthana) of 6wt.% carries out hot dipping and steeps with concentration down at 80 ℃ then, dip time is 2 hours, does not add acid for adjusting pH value, and the rare earth nitrate solution consumption is 5ml (a gram catalyst)
-1, hot dipping stain number of times gets 1,2,3,4 respectively, 5 times.All carry out drying and calcination process behind each dipping.Drying is carried out 3 hours drying times under 110 ℃; Roasting is carried out under 550 ℃, and roasting time is 3 hours.The lanthana load capacity of gained catalyst is followed successively by 2.9wt%, 5.7wt%, 9.1wt%, 12.2wt%, 15.4wt%.The initial reaction performance of above-mentioned catalyst in the ethylbenzene ethylene alkylation is as follows:
Table 1
The comparative example 2
Repeat comparative example 1, but when hot dipping is steeped, use lanthanum rich mischmetal nitrate (lanthanum-oxides/rare earth oxide 〉=40%) instead.Then the oxide carried amount of the total rare earth (TRE) of gained catalyst is followed successively by 3.4wt%, 6.1wt%, 8.8wt%, 11.9wt%, 14.5wt%.The initial reaction performance of above-mentioned catalyst in the ethylbenzene ethylene alkylation is as follows:
Table 2
The comparative example 3
Repeat comparative example 1, but it is element modified to use cold infusion process supported rare earth instead.Said cold soaking stain refers to that dipping at room temperature carries out, as 25 ℃.Then the lanthana load capacity of gained catalyst is followed successively by 2.5wt%, 4wt%, 7wt%, 8.5wt%, 10.6wt%.The initial reaction performance of above-mentioned catalyst in the ethylbenzene ethylene alkylation is as follows:
Table 3
The comparative example 4
Repeat comparative example 3, but use lanthanum rich mischmetal nitrate (lanthanum-oxides/rare earth oxide 〉=40%) maceration extract instead.Then the lanthana load capacity of gained catalyst is followed successively by 2.3wt%, 3.8wt%, 6.6wt%, 8.0wt%, 10.2wt%.The initial reaction performance of above-mentioned catalyst in the ethylbenzene ethylene alkylation is as follows:
Table 4
Embodiment 1
(the zeolite crystal degree is the 1-2 micron, SiO to prepare Hydrogen HZSM-5 molecular sieve catalyst according to conventional method
2/ Al
2O
3=50, extruded moulding, granularity
Molecular sieve content 80%, alumina content 20%), and with its carry out the water vapour Passivation Treatment (adopt 100% steam, 550 ℃ of passivation temperatures, passivation time 3 hours, water vapor flux with water count 1 gram (hour)
-1(gram catalyst)
-1).Be that the lanthanum nitrate hexahydrate (in lanthana) of 6wt.% carries out the hot dipping stain with concentration down at 80 ℃ then, dip time is 2 hours, and a small amount of rare nitric acid of dropping is adjusted to the pH value between the 3-4 before the maceration extract heating, and the rare earth nitrate solution consumption is 5ml (a gram catalyst)
-1, hot dipping stain number of times gets 1,2,3,4 respectively, 5 times.All carry out drying and calcination process behind each dipping.Drying is carried out 3 hours drying times under 110 ℃; Roasting is carried out under 550 ℃, and roasting time is 3 hours.The lanthana load capacity of gained catalyst is followed successively by 3.5wt%, 6.7wt%, 9.6wt%, 13wt%, 16.2wt%.The initial reaction performance of above-mentioned catalyst in the ethylbenzene ethylene alkylation is as follows:
Table 5
Embodiment 2
(the zeolite crystal degree is the 1-2 micron, SiO to prepare Hydrogen HZSM-5 molecular sieve catalyst according to conventional method
2/ Al
2O
3=50, extruded moulding, granularity
Molecular sieve content 80%, alumina content 20%), and with its carry out the water vapour Passivation Treatment (adopt 100% steam, 550 ℃ of passivation temperatures, passivation time 3 hours, water vapor flux with water count 1 gram (hour)
-1(gram catalyst)
-1).Be that the lanthanum nitrate hexahydrate (in lanthana) of 6wt.% carries out the hot dipping stain with concentration down at 80 ℃ then, dip time is 2 hours, and a small amount of rare nitric acid of dropping is adjusted to the pH value between the 3-4 before the maceration extract heating, and the rare earth nitrate solution consumption is 5ml (a gram catalyst)
-1, hot dipping stain number of times is got respectively 2 times, all carries out drying and calcination process behind each dipping.Drying is carried out 3 hours drying times under 110 ℃; Roasting is carried out under 550 ℃, and roasting time is 3 hours.The lanthana load capacity of gained catalyst is 6.8wt%.Then, with the lanthana modification catalyst after the hot dipping stain further at room temperature (as, 25 ℃) carry out the equal-volume cold soaking with 10wt% lanthanum nitrate hexahydrate (in lanthana) and steep modification, dip time is 1 hour, flood 2 times, carry out drying and roasting behind each dipping, condition is the same.The lanthana accumulative total content of gained modified catalyst reaches 16.3wt%.The initial reaction performance of this catalyst in the ethylbenzene ethylene alkylation is conversion of ethylbenzene 18.29%, p-Diethylbenzene selectivity 98.15%; Reactivity worth in the ethylbenzene ethanol alkylation is a conversion of ethylbenzene 19.83%, p-Diethylbenzene selectivity 98.37%.
Embodiment 3
Repeat embodiment 2, but hot dipping stain and cold soaking are used lanthanum rich mischmetal nitrate (lanthanum-oxides/rare earth oxide 〉=40%) maceration extract instead when steeping.Then the rare earth oxide total load amount of gained modified catalyst reaches 15.6wt%.The initial reaction performance of this catalyst in ethylbenzene and ethanol alkylation reaction is conversion of ethylbenzene 21.66%, p-Diethylbenzene selectivity 96.64%; Initial reaction performance in the ethylbenzene ethylene alkylation is a conversion of ethylbenzene 22.77%, p-Diethylbenzene selectivity 96.32%.
Embodiment 4
Repeat embodiment 2, but hot dipping stain temperature changes 60 ℃ and 95 ℃ successively into.Then the lanthana total load amount of gained modified catalyst is followed successively by 15.5wt% and 16.7wt%.Above-mentioned catalyst is a conversion of ethylbenzene 24.58% in the initial reaction performance in ethylbenzene and ethanol alkylation reaction, p-Diethylbenzene selectivity 95.94%; Initial reaction performance in the ethylbenzene ethylene alkylation is a conversion of ethylbenzene 23.72%, p-Diethylbenzene selectivity 98.08%.
Embodiment 5
Repeat embodiment 2, but the hot dipping stain time changes 0.1 hour successively into, 20 hours and 40 hours.Then the lanthana total load amount of gained modified catalyst is followed successively by 16wt%, 16.2wt% and 16.1wt%.Above-mentioned catalyst initial reaction performance in the ethylbenzene ethylene alkylation is:
Table 6
Embodiment 6
Repeat embodiment 2, but the pH value of lanthanum nitrate hexahydrate changes 2-3 and 4-5 successively into during the hot dipping stain.Then the lanthana total load amount of gained modified catalyst is followed successively by 16wt% and 15.4wt%.The initial reaction performance of above-mentioned catalyst in the ethylbenzene ethylene alkylation is:
Table 7
Embodiment 7
Repeat embodiment 2, but lanthanum nitrate hexahydrate concentration changes 1% into during the hot dipping stain, hot dipping stain number of times changes into 3 times, then the lanthana amount about 2% by the load of hot dipping stain.Be that 20% lanthanum nitrate hexahydrate carries out cold soaking stain modification 2 times to the gained catalyst with concentration again, the lanthana total load amount of gained modified catalyst is 19wt%.The initial reaction performance of this catalyst in the ethylbenzene ethylene alkylation is that conversion of ethylbenzene is 15.62%, and the p-Diethylbenzene selectivity is 99.48%.
Embodiment 8
Repeat embodiment 2, but lanthanum nitrate hexahydrate concentration changes 10% into during the hot dipping stain, hot dipping stain number of times changes into 1 time, then the lanthana amount about 5.3% by the load of hot dipping stain.Be that 20% lanthanum nitrate hexahydrate carries out cold soaking stain modification 1 time to the gained catalyst with concentration again, the lanthana total load amount of gained modified catalyst is 14.2wt%.The initial reaction performance of this catalyst in the ethylbenzene ethylene alkylation is that conversion of ethylbenzene is 23.76%, and the p-Diethylbenzene selectivity is 98.28%.
Embodiment 9
Repeat embodiment 2, but the lanthanum nitrate hexahydrate consumption changes 1ml (gram catalyst) successively into during the hot dipping stain
-1, 50ml (gram catalyst)
-1And 100ml (gram catalyst)
-1, the sintering temperature of catalyst changes 650 ℃ into, and roasting time changes 2 hours into.Then the lanthana total load amount of gained modified catalyst is 15.32wt%, and the initial reaction performance of catalyst in the ethylbenzene ethylene alkylation is that conversion of ethylbenzene is 22.47%, and the p-Diethylbenzene selectivity is 97.56%.
Embodiment 10
Repeat embodiment 2, but the lanthanum nitrate hexahydrate consumption changes 1ml (gram catalyst) successively into during the hot dipping stain
-1, 50ml (gram catalyst)
-1And 100ml (gram catalyst)
-1, the roasting condition of catalyst changed 650 ℃ of following roastings 2 hours and 450 ℃ of following roastings respectively into 4 hours.Then the lanthana total load amount of gained modified catalyst is 15.83wt%, and the initial reaction performance of catalyst in the ethylbenzene ethylene alkylation is that conversion of ethylbenzene is 23.05%, and the p-Diethylbenzene selectivity is 97.98%.
Embodiment 11
Repeat embodiment 2, but temperature changes 5 ℃ into during the cold soaking stain, dip time changes 0.1 hour respectively into and 10 hours, and the cold lanthanum nitrate hexahydrate concentration that is immersed in is repetition in 7% o'clock 3 times, and the catalyst drying is carried out under 110 ℃, gets drying time 6 hours; Roasting continues 4 hours down at 450 ℃.Then the lanthana total load amount of gained modified catalyst is 18.76wt%, and the initial reaction performance of catalyst in the ethylbenzene ethylene alkylation is that conversion of ethylbenzene is 17.34%, and the p-Diethylbenzene selectivity is 98.25%.
Embodiment 12
Behavior in service is as follows continuously in the ethylbenzene ethylene alkylation for the catalyst of preparation in embodiment 2:
Table 8
Embodiment 13
After the catalyst of preparation was regenerated through 10 carbon deposits in embodiment 2, the successive reaction performance of regenerative agent in the ethylbenzene ethylene alkylation was as follows:
Table 9
Embodiment 14
The continuous behavior in service of catalyst in the ethylbenzene ethanol alkylation of preparation is as follows in embodiment 2:
Table 10
Claims (2)
1. the preparation method of a shape-selective catalyst, it is characterized in that, according to a conventional method MFI type shape-selective molecular sieve being carried out earlier the stripper plate agent handles, take in the aluminium oxide as the processing of carrier extruded moulding, steam high temperature Passivation Treatment, carry out lanthanum nitrate or the modification of lanthanum rich mischmetal nitrate solution with hot dipping stain and cold soaking stain method successively then, wherein, hot dipping stain and cold soaking steep lanthanum-oxides/rare earth oxide weight ratio 〉=40% in the used lanthanum rich mischmetal nitrate, and concrete operations are as follows:
(1) the former powder of shape-selective molecular sieve that will have the MFI structure burns the agent of amine removal template, then with the molecular screen primary powder, the Al that measure
2O
3Mix with the sesbania powder, and, mix and pinch with the dilute nitric acid solution making beating, last extrusion, drying, roasting moulding, condition of molding is: the molecular sieve of metering and Al
2O
3Butt than for 65/35-80/20, the sesbania powder accounts for molecular sieve and Al
2O
3Butt weight and 2-6%, the volume by volume concentration of rare nitric acid is 5～15%, dry carries out drying time 〉=3 hour under 110 ℃; Roasting is carried out in 450～650 ℃ temperature range, and roasting time is 2～6 hours, and the silica alumina ratio with shape-selective molecular sieve parent of MFI structure is 20～200, and grain size is 0.5～5 micron;
(2) with molded molecular sieve routinely the ammonium switching method make the ammonium type, and be prepared into Hydrogen by dry, roasting, then the hydrogen type molecular sieve catalyst is handled with conventional water vapor passivation method, the ammonium give-and-take conditions are: ammonium nitrate solution concentration 0.4～1.0mol/L, ammonium nitrate solution is 1: 1～20: 1 (ml/g) with the ratio of molded molecular sieve, ammonium exchange is at room temperature carried out, 0.5～10 hour swap time of each ammonium, repeated exchanged 1～5 time; Dry under 110 ℃, carry out drying time 〉=3 hour; Roasting is carried out in 550～650 ℃ temperature range, and roasting time is 6～10 hours; Water vapor passivation adopts 100% steam, and passivation temperature is in 400～700 ℃ of scopes, and passivation time selects 1～20 hour, water vapor flux with water count 0.1～30 the gram (hour)
-1(gram catalyst)
-1
(3) will in lanthanum nitrate or lanthanum rich mischmetal nitrate solution, carry out the modification of hot dipping stain through the hydrogen type molecular sieve catalyst after the water vapour passivation, and drying and roasting, hot dipping stain condition is: temperature range is 60-95 ℃, dip time is 0.1～40 hour; In 1～10% scope, the pH value is 2～5 with the oxide weight timing for rare earth element total content in lanthanum nitrate or the lanthanum rich mischmetal nitrate solution, and lanthanum nitrate or lanthanum rich mischmetal nitrate solution consumption are 1～100ml (gram catalyst)
-1, hot dipping stain number of times is got 1～3 time, when adopting repeatedly hot dipping stain, need drying and roasting between twice hot dipping stain, rare earth element total amount by the load of hot dipping stain, is dryly carried out under 110 ℃ in 2～7% scopes with the oxide weight timing, drying time 〉=3 hour; Roasting is carried out in 450～650 ℃ temperature range, and roasting time is 2～4 hours;
(4) the rare earth modified catalyst after the hot dipping stain is further at room temperature carried out the modification of equal-volume cold soaking stain with lanthanum nitrate or lanthanum rich mischmetal nitrate solution, and dry, roasting, cold soaking stain modified condition is: temperature range is 5-30 ℃, and dip time is 0.1～10 hour; Rare earth element total content in lanthanum nitrate or the lanthanum rich mischmetal nitrate solution with the oxide weight timing in 5～25% scopes, adopt equal-volume cold soaking stain, the dipping number of times is got 1～3 time, when adopting repeatedly the cold soaking stain, need drying and roasting between twice dipping, rare earth element total amount by the load of cold soaking stain, is dryly carried out under 110 ℃ in 7～20% scopes with the oxide weight timing, drying time 〉=3 hour; Roasting is carried out in 450～650 ℃ temperature range, and roasting time is 2～4 hours.
2. the preparation method of a kind of shape-selective catalyst according to claim 1 is characterized in that, the shape-selective molecular sieve of the described MFI of having structure is any mixture of ZSM-5, ZSM-11 or ZSM-5 and ZSM-11.
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| CN103785472A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst used for preparation of olefins through catalytic cracking, and preparation method and application thereof |
| CN104588075B (en) * | 2013-10-30 | 2017-02-08 | 中国石油化工股份有限公司 | Preparation method for alkylation catalyst |
| CN106179348B (en) * | 2016-07-26 | 2018-09-28 | 江苏正丹化学工业股份有限公司 | A kind of catalyst, preparation method and the usage for producing divinylbenzene |
| CN106582788B (en) * | 2016-12-06 | 2019-04-23 | 中触媒新材料股份有限公司 | A kind of modified zsm-5 zeolite and preparation method and catalysis prepare the synthetic method of 3- methyl-3-butene-1-alcohol |
| CN107376991B (en) * | 2017-06-20 | 2019-09-17 | 中国科学院大连化学物理研究所 | A kind of alkylation catalyst and preparation method thereof generated to methyl-ethyl benzene |
| CN107913727B (en) * | 2017-10-31 | 2020-05-29 | 中海油天津化工研究设计院有限公司 | Preparation method of catalyst for preparing p-diethylbenzene by efficiently alkylating ethylbenzene |
| CN110961143B (en) * | 2018-09-29 | 2023-05-26 | 中国石油天然气股份有限公司 | Molecular sieve catalyst, preparation method thereof and application thereof in ethylbenzene dealkylation reaction and xylene isomerization reaction |
| CN109704958B (en) * | 2018-12-19 | 2022-09-20 | 万华化学集团股份有限公司 | Method for preparing ethyl butyrate and catalyst used in method |
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