CN1058284C - Light hydrocarbon aromatization catalyst and its preparing process - Google Patents
Light hydrocarbon aromatization catalyst and its preparing process Download PDFInfo
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- CN1058284C CN1058284C CN98101358A CN98101358A CN1058284C CN 1058284 C CN1058284 C CN 1058284C CN 98101358 A CN98101358 A CN 98101358A CN 98101358 A CN98101358 A CN 98101358A CN 1058284 C CN1058284 C CN 1058284C
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Abstract
The present invention relates to an aromatization catalyst of light hydrocarbon, which comprises Zn, mixed rare earth and an HZSM-5 component. The aromatization catalyst measured by the catalyst weight is composed of 0.8 to 3.5 wt% of Zn, 0.2 to 1.5 wt% of mixed rare earth (measured by an oxide) and 95.0 to 99.0 wt% of carrier composed of 50 to 80 wt% of HZSM-5 zeolite and 20 to 50 wt% of gamma-aluminium oxide, wherein the mixed rare earth contains elements, such as lanthanum, cerium, praseodymium, neodymium, etc. In the catalyst, Zn is led in by using a [Zn(NH3)4]<2+> complex ion solution as impregnating liquid, and the catalyst is treated with water vapor at a high temperature under proper conditions so that the catalyst has the advantages of favorable aromatization activity, favorable aromatization selectivity, favorable stability and favorable regeneration performance.
Description
The present invention is a kind of aromatizing catalyst for light hydrocarbon and preparation method thereof, specifically, is a kind of C of being applicable to
2～C
12Lighter hydrocarbons, zinciferous aromatized catalyst and preparation method thereof.
A large amount of low-carbon (LC) lighter hydrocarbons of association and contain the gas mixture of low-carbon (LC) lighter hydrocarbons usually in oil field, natural-gas field and the refinery production, these low-carbon (LC) lighter hydrocarbons are converted into based on benzene, toluene and the dimethylbenzene aromatic hydrocarbons of (being called for short BTX) by catalyzed reaction, the a large amount of cheap hydrogen of by-product have good economic benefits simultaneously.And upload the aromatized catalyst that zinc or gallium make at the HZSM-5 zeolite, have the active high and good advantage of selectivity, but owing to carbon deposit, catalyst activity reduction is very fast, the one way life-span is short, has only a few to tens of hours usually, is difficult to promote the use of in fixed-bed reactor.Zinc runs off easily in the reducing atmosphere of this external aromatization, though gallium runs off soon not as zinc, prices are rather stiff for gallium.External employing moving-bed cyclic regeneration (as the CYCLAR technology of UOP and BP company) technology, though can realize the successive stable operation, because the facility investment height, scale is big, is difficult to promote at home.For adapting to the requirement of fixed bed operation, improve the stability of Zn-HZSM-5 aromatized catalyst, people mainly improve catalyzer from the following aspects.
Introducing second modified component with hydrogenation activity in the Zn-HZSM-5 catalyzer, mainly is to introduce noble metal platinum, to reduce catalyst carbon deposit.Disclose a kind of aromatizing catalyst for light hydrocarbon as CN1062100A, this activity of such catalysts component is platinum, zinc or gallium, and carrier is ZSM-5 zeolite and/or ZSM-11 and SiO
2And/or Al
2O
3Mixture is normal pressure, 500 ℃, during air speed 2.0
-1Condition under carry out C
5～C
8The aromatization of lighter hydrocarbons, the catalyzer one way life-span can reach 200 hours, can continue after aromatics yield 50%, catalyzer are repeatedly regenerated to use.
CN1070847A then discloses a kind of HZSM-5 catalyzer with gallium, zinc, platinum modification, and this activity of such catalysts consists of gallium 0.5～2.0%, zinc 0.5～2.0%, and platinum 0.1～0.5%, all the other are 40～100 HZSM-5 for silica alumina ratio.Active ingredient and moulding are 70: 30 with the weight ratio of caking agent.Its preparation method is to soak earlier gallium in HZSM-5, and extruded moulding is handled 1～3 hour with dealuminzation with the airflow that contains 15～20% water vapors down at 600～700 ℃ more then, soaks zinc and platinum at last.This catalyzer is normal pressure, 550 ℃, during weight space velocity 0.5
-1Condition under carry out C
5～C
8Light dydrocarbon aromatization reaction, the catalyzer one way life-span reaches 240 hours, and aromatics yield is not less than 40 heavy %.
Though the aromatized catalyst of modified with noble metals has stability preferably, the catalyzer cost can improve greatly, and the aromizing selectivity that adds affiliation reduction catalyzer of platinum, and sulfur poisoning easily takes place.Therefore, people introduce the base metal constituent element and carry out modification in the Zn-HZSM-5 catalyzer, disclose a kind of with Al and/or rare earth modified aromatized catalyst as CN1063121A, the active improving agent of two or three compound in Zn, Al and the rare earth that is selected from that contains 0.3～15 heavy % in this catalyzer, 5.0 the silica alumina ratio of～94.5 heavy % is 10～500 hydrogen type molecular sieve, comprise HZSM-5, HZSM-7 etc., all the other are the binding agent that is selected from aluminum oxide, silicon oxide, the clay any one.This Preparation of catalysts adopts conventional pickling process to introduce active modifier, only uses single rare earth element nitrate in the example, as La (NO
3)
3And/or Ce (NO
3)
2The formulations prepared from solutions catalyzer.
For solving the zinc losing issue of Zn-HZSM-5 catalyzer, CN1057476A discloses a kind of preparation method who contains the zinc zeolite catalyst of Zincleaching-resistant, difficult reductive zinc compound is stated from the ZSM-5 zeolite on this method employing thermodynamics, and described zn cpds is selected from ZnS, ZnSO
4, ZnSiO
4, ZnTiO
4, ZnAl
2O
4The catalyzer that makes is used for the aromizing of liquefied petroleum gas (LPG), and the reaction times is 168 hours, and aromatics yield drops to 32% from 42%.
Light naphthar aromatization process (the will Sekiyu Gakkaishi of institute of Petroleum of Japan Energy company exploitation, 37, (1) 77～83 (1994)) adopts the directly zinciferous close grain zinc-silicon-aluminium zeolite catalyst (Appl.Catal. of preparation of hydrothermal synthesis method with ZSM-5 structure, V.93,35 (1992)) pass through particular processing again, reduce the loss of zinc, prolonged the one way work-ing life of catalyzer.When being zeolite synthesis, shortcoming need use the organic formwork agent TPAOH, the cost height, and problem of environmental pollution is arranged, the Preparation of catalysts technology also has certain degree of difficulty.
In the prior art, for this class supersiliceous zeolite of HZSM-5, all be difficult to quantitatively or near introducing required metal ion quantitatively with common dipping or ion-exchange techniques, therefore often need carry out repetitious ion-exchange under 85～95 ℃ being heated to excessive zinc solution before the carrier moulding, catalyst preparation process is numerous and diverse like this, and yield is low.If adopt the saturated extent of adsorption pickling process and behind dipping the method for excessive steeping fluid evaporate to dryness, then be difficult for making zinc to be evenly distributed at preformed carrier granule surfaces externally and internally.
In addition, though steam-treated is usually used in the modification of zeolite catalyst,, then not a method of modifying that generally adopts for aromatizing catalyst for light hydrocarbon.Because light-hydrocarbon aromatized is a complex process that comprises a succession of reactions such as cracking, polymerization, cyclisation, dehydrogenation, especially for the aromizing of alkane, the controlled step of speed of response is the scission reaction on the strong acidic site, high-temperature water vapor is handled the strongly-acid active centre that might destroy on the catalyzer, and aromatization activity is descended significantly.Thereby must select suitable steam-treated condition, and the acidic cleavage and the dehydrogenation functionality of the agent of ability hormany catalyt, thus make catalyzer both have good activity, selectivity, have satisfactory stability again.
The objective of the invention is on the basis of above-mentioned prior art, a kind of noble metal component that do not contain is provided, both had excellent activity, selectivity, have aromatized catalyst of good stability and preparation method thereof again.
We find to introduce the mishmetal component in the Zn-HZSM-5 aromatized catalyst, and with [Zn (NH
3)
4]
2+Complex ion solution is introduced Zn, adopts high-temperature water vapor to handle the aromatized catalyst that can obtain to have superperformance to catalyzer again.
The carrier that catalyzer provided by the invention is made up of Zn, mixed rare earth oxide and HZSM-5 and gama-alumina is formed.Zn content is that 0.8～3.5 heavy %, mixed rare earth oxide content are 0.2～1.5 heavy % in the catalyzer, vector contg is 95.0～99.0 heavy %, described carrier is made up of the HZSM-5 zeolite of 50～80 heavy % and the gama-alumina of 20～50 heavy %, contains lanthanum trioxide 20～40 heavy %, cerium oxide 40～60 heavy %, Praseodymium trioxide 10～18 heavy %, Neodymium trioxide 2～10 heavy % in the mixed rare earth oxide.
Preparation of catalysts method provided by the invention comprises the steps:
(1) preparation carrier: HZSM-5 zeolite and α-water aluminum oxide powder are pressed zeolite: Al
2O
3=50～80: 50～20 butt weight ratio mixing moulding, dry back makes carrier 400～600 ℃ of roastings.
(2) introduce the zinc constituent element: with the carrier [Zn (NH of preparation in (1)
3)
4]
2+Complex ion solution at room temperature floods 2～24 hours, Gu liquid during dipping/than being 1.0～1.4 milliliters/gram, [Zn (NH
3)
4]
2+The consumption of complex ion solution should make wherein Zn content account for 0.8～3.5 heavy % of catalyzer total amount, makes the catalyzer that draws zinc after the drying.
(3) introduce the rare earth constituent element: the zinc catalyst of making in (2) that draws was flooded 2～24 hours with the aqueous solution of chlorination mishmetal under room temperature, chlorination mishmetal consumption is counted 0.2～1.5% of catalyst weight by its oxide compound, Gu liquid during dipping/than being 0.6～0.9 milliliter/gram, dipping back solid drying, 500～600 ℃ of roastings 2～6 hours in airflow again.
(4) steam-treated: the catalyzer of preparation in (3) is warming up to 500～600 ℃ in airflow after, used the pure water steam treatment instead 1～6 hour, the weight ratio of total water amount and catalyzer is 1～10 during processing.
The also available ammonia type of the described HZSM-5 zeolite of step among the above-mentioned preparation method (1) ZSM-5 zeolite replaces.Ammonia type ZSM-5 zeolite obtains after can being exchanged through ammonium by sodium type ZSM-5 zeolite, and the ammonium exchange can carried out before the preparing carriers or behind the carrier shaping and roasting, adopts ordinary method to get final product, as the NH with 1M
4Cl or NH
4NO
3Solution exchanges 2 hours down at 85 ℃, the washing after drying.Exchange back gained NH
4The ZSM-5 sodium content should be preferably less than 0.02 heavy % less than 0.1 heavy %.Conventional technology is also adopted in the moulding of carrier, can raw material mixes nitric acid or the acetic acid that the back adds suitable quantity of water and 1～3 heavy % and mediates extruded moulding, 60～120 ℃ of dryings 2～4 hours, 400～600 ℃ of roastings 4 hours.
The silica alumina ratio of used zeolite is 30～100 in the described step (1).
Contain elements such as lanthanum, cerium, praseodymium, neodymium in the chlorination mishmetal in the described step (3), its content is counted with oxide compound: lanthanum 20～40 heavy %, cerium 40～60 heavy %, praseodymium 10～18 heavy %, neodymium 2～10 heavy %.
(2) and (3) sequence of steps among the described preparation method can be exchanged, and preferably introduces earlier zinc, introduces mishmetal again, and like this, drawing behind the zinc carrier only needs dryly, needn't roasting just can continue to introduce mishmetal.Also can introduce mishmetal earlier, introduce zinc again, the carrier of mishmetal is essential just to draw zinc through after the roasting but introduce, draw behind the zinc carrier also need just can carry out steam-treated 500～600 ℃ of roastings 2～6 hours.
The steam-treated temperature is preferably 520～580 ℃ in the described step (4), and the treatment time is preferably 1～4 hour, and the weight ratio of total water amount and catalyzer is preferably 2～4 during processing.
Described step (4) also can be carried out after step (1) has prepared carrier, is about to prepared carrier and carries out steam-treated earlier, introduces zinc and mishmetal component more respectively.Introduce earlier zinc and mishmetal component but be more preferably, after carry out steam-treated.
The condition of steam-treated also can suitably be adjusted according to the silica alumina ratio of HZSM-5 zeolite raw material used in the step (1), the height of acid cracked activity in the described step (4), is in the state of coordinating most with acid function and the dehydrogenation functionality that guarantees catalyzer.The standard of adjusting the steam-treated condition is to make raw materials used HZSM-5 (measuring method of α value is write " petrochemical complex analytical procedure (RIPP experimental technique) " with reference to Yang Cuiding etc. between 50～250 through the α value after the steam-treated, Science Press publishes, P255 " constant temperature method is measured the α value of an acidic catalyst ").
Catalyzer of the present invention is applicable to C
2～C
12Alkene, alkane, naphthenic hydrocarbon or alkene and the aromizing of the mixture of alkane, for example, contain C in the refinery
2～C
5Coal mine gas, liquefied petroleum gas (LPG), pyrolysis gasoline, light naphthar, oil field light hydrocarbon etc. all can be used as the raw material of aromizing.Reaction conditions is different because of raw material, 400～600 ℃ of temperature of reaction, pressure normal pressure～1.0MPa, feed weight air speed 0.2～10 hour
-1
Catalyzer of the present invention adopts [Zn (NH owing to introduce the mishmetal component in zinciferous HZSM-5 catalyzer
3)
4]
2+Complex ion solution is that steeping fluid is introduced the zinc constituent element, and under suitable condition, catalyzer is carried out steam-treated, make the aromatized catalyst that makes in Zincleaching-resistant ability and stable increasing substantially, still keep good activity and selectivity, and reduced the catalyzer cost.Use catalyzer of the present invention at 520～550 ℃, weight space velocity is 0.6～1.5 hour during feeding liquid
-1Reaction conditions under, to mixed C
4Carry out aromatization, aromatics yield can reach 300～450 hours greater than 40% one way runtime, total aromatic hydrocarbons average yield is 47.5%, and catalyzer is through accumulative total reaction in more than 1200 hour and repeatedly regeneration, and zinc content, aromatization activity and stability all do not have considerable change.
Further specify the present invention below by embodiment, but the present invention is not limited to this.
Example 1
This example is a Preparation of catalysts of the present invention.
(1) preparation carrier: get silica alumina ratio and be 54 HZSM-5 zeolite powder (Qilu Petrochemical company Zhou village catalyst plant) 65 grams, α-one water aluminum oxide powder (SB powder, Germany, Condea company) 35 grams place the mortar ground and mixed even, add the solution that 1～2 milliliter of 1: 1 nitric acid and 30 ml waters are made into, mediate agglomerating, in banded extruder, be squeezed into the bar shaped carrier of 2 millimeters of diameters, 110 ℃ of dryings 4 hours, 540 ℃ of roastings 4 hours.
(2) introduce the zinc constituent element: under constantly stirring, to 5.0 milliliters of Zn (NO that contain 270 milligrams of ZnO
3)
2Splash into ammoniacal liquor (Beijing Chemical Plant's production) in the aqueous solution,, add the Zn (NH that water is made into 12 milliliters again up to the white precipitate dissolving
3)
4(NO
3)
2The aqueous solution is got carrier 10 grams of preparation in (1), at room temperature uses above-mentioned Zn (NH
3)
4(NO
3)
2Liquid when aqueous solution dipping 2 hours, solid dipping/than be 1.2 milliliters/restrain, leach solid behind the dipping, usefulness deionized water rinsing 2 times, 120 ℃ of dryings 6 hours,
(3) introduce mishmetal: get the above-mentioned catalyzer that draws zinc, contain 100 milligrams of chlorination mishmetal (industrial goods with 8 milliliters, Inner Mongol Baotou rare earth industrial produces, wherein lanthanum trioxide accounts for 31%, cerium oxide 51%, Praseodymium trioxide 14%, Neodymium trioxide 4%, x-ray fluorescence method is analyzed) the aqueous solution at room temperature flooded 110 ℃ of dryings 16 hours, 540 ℃ of roastings 4 hours 2 hours.
(4) steam-treated: the catalyzer that will introduce behind zinc and the mishmetal is put into tubular reactor, is warming up to 540 ℃ in airflow, changes logical pure water steam treatment 2 hours then under this temperature, feeds the dry air cooling again.Total inflow is 30 grams in the steam-treated process.
Contain in the catalyst A of making as stated above and mix rare earth oxide 0.34 heavy %, Zn 2.1 heavy % (all adopting the analysis of X quantitative fluorescence analysis method).
Example 2
Method by embodiment 1 prepares catalyst B, and the consumption of different is chlorination mishmetal in the preparation process is 200 milligrams, Zn (NO
3)
2Consumption count 180 milligrams with ZnO.Contain in the catalyst B and mix rare earth oxide 0.68 heavy %, Zn 1.4 heavy %.
Example 3
Method by embodiment 1 prepares catalyzer C, and preparing carriers that different is finishes and promptly carries out steam-treated, and then introduces zinc and mishmetal.Contain among the catalyzer C and mix rare earth oxide 0.33 heavy %, Zn 2.2 heavy %.
Example 4
Method by embodiment 1 prepares catalyzer D, and different is that step (2) and (3) are exchanged, and promptly introduces mishmetal earlier, introduce zinc again, but carrier needs 540 roastings 4 hours after drawing zinc, and then carries out steam-treated.Contain among the catalyzer D and mix rare earth oxide 0.34 heavy %, Zn 2.1 heavy %.
Example 5
Method by embodiment 1 prepares catalyzer E, and different is with silica alumina ratio is that 43 HZSM-5 is the feedstock production carrier, and carrier soaked behind zinc and the mishmetal in 560 ℃ of air roasting 4 hours, again 560 ℃ down with steam-treated 4 hours, total inflow is 30 grams.Catalyzer E contains and mixes rare earth oxide 0.34 heavy %, Zn 2.1 heavy %.
Comparative Examples
Dipping method with routine prepares the Zn-HZSM-5 aromatized catalyst.
Get carrier 10 grams of preparation in the example 1, with the Zn (NO that contains 280 milligrams of ZnO
3)
28 milliliters of the aqueous solution at room temperature flooded 24 hours, 80 ℃ of oven dry, and 120 ℃ of dryings 6 hours, roasting is 4 hours in 540 ℃ of air, makes catalyzer F.Contain Zn 2.2 heavy % among the F.
The following example explanation premium properties that catalyzer of the present invention had.
Example 6
This example explanation catalyzer of the present invention has good guarantor's zinc ability.
590 ℃, during volume space velocity 2000
-1Hydrogen stream in catalyst A, C and comparative catalyst F are reached 20 hours reduction, the relatively variation of catalyzer zinc content before and after the reduction.The results are shown in Table 1, catalyzer of the present invention as shown in Table 1 has good Zincleaching-resistant ability, and the catalyzer that carries out steam-treated behind wherein first impregnated zinc and the mishmetal has better guarantor's zinc ability.
Example 7
This example explanation catalyzer of the present invention is to mixed C
4Aromizing has excellent catalytic performance.
Get 10 milliliters of catalyzer D, weigh 7 grams, in the fixed-bed reactor of packing into, carry out mixed C
4Aromatization is reflected at and carries out under the continuous flow isothermal condition, mixed C
4Raw material composed as follows: C
30.1%, C
4Alkane 55.5%, C
4Alkene 44.2%, C
5 +0.1%.Reaction product is separated into gas-liquid two-phase through water cooling, measures respectively and compositional analysis.Reacting after 20 hours, is 0.15MPa, liquid feeding weight space velocity 1.5 hours in reaction pressure
-1, the catalyst inlet temperature is respectively the response data of measuring under 530 ℃ and the 550 ℃ of conditions and sees Table 2.The result shows that catalyzer D is to mixed C
4Aromizing has good activity and selectivity, with C
6～C
8Aromatic hydrocarbons is that main aromatics yield is higher than 50%, BTX content＞90% wherein, C
5 +Virtue in the product contains up to more than 99%.
Example 8
This example explanation catalyzer of the present invention is to C
5～C
8Alkane aromatization has excellent catalytic performance.
Method by example 7 is carried out C respectively to catalyst A, B, C
5～C
8The aromatization experiment of paraffins mixture, reaction raw materials consists of: C
55.1%, C
658.2%, C
731.9%, C
8 +4.8%.Reaction conditions is 550 ℃ of bed temperature ins, pressure 0.15MPa, liquid feeding weight space velocity 1.5 hours
-1, the product yield that reacts after 20 hours sees Table 3.The result shows that catalyzer of the present invention is to C
5～C
8Alkane have good aromatization activity and selectivity, aromatics yield all is higher than 50 heavy %, and coproduct hydrogen tolerance can reach about 3 heavy %.
Example 9
This example explanation catalyzer of the present invention has good aromatization activity stability.
With the senile experiment of accelerating that the catalyzer D and the comparative catalyst F of example 4 preparation carries out aromatization respectively, the activity stability of evaluate catalysts.Reaction raw materials use-case 8 described C
5～C
8Paraffins mixture, reaction pressure 0.15MPa, liquid feeding weight space velocity 5.0 hours
-1, 54 hours test-results of continuous operation is listed in table 4.As can be seen from Table 4, catalyzer of the present invention has aromatization stability preferably.
Example 10
This example explanation catalyzer of the present invention is to mixed C
4Aromatization has satisfactory stability.
Get catalyzer E15 milliliter, weigh 10 grams, be used for mixed C
4The stability experiment of aromatization.Reaction raw materials is formed with embodiment 7, at reaction pressure 0.2MPa, 530 ℃ of temperature, liquid feeding weight space velocity 0.65 hour
-1Reaction conditions under successive reaction 450 hours, aromatics yield is from 50 heavy % of beginning, reduces to the 43 heavy %s of experiment when finishing, average aromatics yield is greater than 47 heavy %, liquid-phase product aromatic hydrocarbons purity height.The changing conditions of BTX and total arenes yield sees Table 5 in 450 hours.Test-results shows that catalyzer of the present invention has good aromatization activity and stability.
Example 11
This example explanation catalyzer of the present invention has good regenerability.
With the catalyst A of example 1 preparation, the method for pressing example 7 is to mixed C
4Carry out aromatisation experiment, 540 ℃ of temperature of reaction, pressure 0.2MPa, liquid feeding weight space velocity 0.8 hour
-1The catalyzer successive reaction is carried out coke-burning regeneration after 300 hours, the regeneration back continues to carry out aromatization by above-mentioned condition, the data contrast active and average yield and live catalyst of each regeneration rear catalyst initial reaction sees Table 6, as shown in Table 6, catalyzer still has high reaction activity and high through behind the repeated regeneration, and always adding up the reaction times is 1200 hours, illustrates that catalyzer of the present invention has good activity stability and regenerability.
Table 1
| Catalyzer | Preparation characteristic | Zn content, heavy % | The Zn number of dropouts, heavy % | ||
| Before the reduction | After the reduction | ||||
| Example 3 | C | Impregnated zinc and rare earth after elder generation's steam-treated | 2.2 | 1.4 | 0.8 |
| Example 4 | A | Steam-treated behind elder generation's impregnated zinc and the rare earth | 2.1 | 1.8 | 0.3 |
| Comparative Examples | F | Only soak Zn and do not carry out steam-treated | 2.3 | 0.9 | 1.4 |
Table 2
| Temperature in, ℃ | Product yield, heavy % | |||||
| H 2 | C 1+C 2 | C 3+C 4 | BTX | Total aromatic hydrocarbons | C 5 +Virtue contains | |
| 530 550 | 2.1 2.6 | 17.0 21.5 | 29.1 21.8 | 46.0 48.7 | 51.0 53.7 | 99.2 99.7 |
Table 3
| The catalyzer numbering | A | B | C | |
| Product yield, heavy % | H 2 | 3.1 | 2.9 | 3.2 |
| Methane ethane | 18.7 | 16.9 | 19.0 | |
| Gaseous olefin | 4.8 | 5.4 | 4.6 | |
| BTX | 48.1 | 47.5 | 51.1 | |
| Total aromatic hydrocarbons | 51.5 | 51.3 | 54.2 | |
| C 5 +The product virtue contains, heavy % | 94.9 | 96.1 | 95.6 | |
Table 4
Table 5
| The successive reaction time, hour | Product yield, heavy % | C 6 +The product virtue contains, heavy % | |
| BTX | Total virtue produces | ||
| 40 90 138 186 234 282 330 378 450 | 43.4 44.0 43.9 43.3 42.4 42.1 42.0 40.7 39.2 | 50.2 49.6 49.3 48.4 47.6 46.2 46.5 45.3 43.2 | 99.99 99.99 99.99 99.99 99.99 99.99 99.98 99.95 99.85 |
Table 6
| Initial 20～40 hours activity, heavy % | The one way average yield, heavy % | Total cumulative time, hour | |||||
| Aromatics yield | H 2Productive rate | Butanes conversion | Reaction times, hour | Aromatic hydrocarbons | H 2 | ||
| Live catalyst | 51.2 | 2.4 | 93.4 | 300 | 47.7 | 2.3 | 300 |
| Regeneration for the first time | 50.9 | 2.6 | 95.1 | 300 | 47.5 | 2.3 | 600 |
| Regeneration for the second time | 51.1 | 2.5 | 94.8 | 300 | 47.2 | 2.3 | 900 |
| Regeneration for the third time | 51.0 | 2.5 | 95.2 | 300 | 47.9 | 2.3 | 1200 |
Claims (10)
1, a kind of aromatizing catalyst for light hydrocarbon contains Zn, rare earth and HZSM-5 component, it is characterized in that this catalyzer has following composition:
Zn 0.8～3.5 heavy %
Mixed rare earth oxide 0.2～1.5 heavy %
Carrier 95.0～99.0 heavy %
Wherein carrier is made up of the HZSM-5 zeolite of 50～80 heavy % and the gama-alumina of 20～50 heavy %, contains lanthanum trioxide 20～40 heavy %, cerium oxide 40～60 heavy %, Praseodymium trioxide 10～18 heavy %, Neodymium trioxide 2～10 heavy % in the mixed rare earth oxide.
2, the described Preparation of catalysts method of a kind of claim 1 is characterized in that comprising the steps:
(1) preparation carrier: HZSM-5 zeolite and α-water aluminum oxide powder are pressed zeolite: the butt weight ratio mixing moulding of Al2O3=50～80: 50～20, dry back makes carrier 400～600 ℃ of roastings,
(2) introduce the zinc constituent element: with the carrier [Zn (NH of preparation in (1)
3)
4]
2+Complex ion solution at room temperature floods 2～24 hours, Gu liquid during dipping/than being 1.0～1.4 milliliters/gram, [Zn (NH
3)
4]
2+The consumption of complex ion solution should make wherein Zn content account for 0.8～3.5 heavy % of catalyzer total amount, makes the catalyzer that draws zinc after the drying,
(3) introduce the rare earth constituent element: the zinc catalyst of making in (2) that draws was flooded 2～24 hours with the aqueous solution of chlorination mishmetal under room temperature, chlorination mishmetal consumption is counted 0.2～1.5% of catalyst weight by its oxide compound, Gu liquid during dipping/than being 0.6～0.9 milliliter/gram, dipping back solid drying, 500～600 ℃ of roastings 2～6 hours in airflow again
(4) steam-treated: the catalyzer of preparation in (3) is warming up to 500～600 ℃ in airflow after, used the pure water steam treatment instead 1～6 hour, the weight ratio of total water amount and catalyzer is 1～10 during processing.
3, in accordance with the method for claim 2, it is characterized in that the described HZSM-5 zeolite of step (1) replaces with ammonia type ZSM-5 zeolite.
4, in accordance with the method for claim 3, it is characterized in that making after ammonia type ZSM-5 zeolite is exchanged through ammonium by sodium type ZSM-5 zeolite, the ammonium exchange is carried out before preparing carriers or after the shaping and roasting, and sodium content is less than 0.1 heavy % in the zeolite after the exchange of gained ammonium.
5, in accordance with the method for claim 4, it is characterized in that sodium content is less than 0.02 heavy % in the zeolite after the ammonium exchange.
6, according to the described any method of claim 2～4, the silica alumina ratio that it is characterized in that used zeolite in the step (1) is 30～100.
7, in accordance with the method for claim 2, it is characterized in that each constituent content in oxide compound is in the middle chlorination mishmetal of described step (3): lanthanum 20～40 heavy %, cerium 40～60 heavy %, praseodymium 10～18 heavy %, neodymium 2～10 heavy %.
8, in accordance with the method for claim 2, it is characterized in that temperature is 520～580 ℃ in the step (4), the steam-treated time is 1～4 hour, and the weight ratio of total water amount and catalyzer is 2～4 during processing.
9, in accordance with the method for claim 2, it is characterized in that introducing mishmetal step (3) earlier, introduce the step (2) of zinc again, drawing the zinc rear catalyst needs to carry out the steam-treated of step (4) again 500～600 ℃ of roastings.
10, in accordance with the method for claim 2, it is characterized in that after step (1) has prepared carrier, promptly to carry out the steam-treated of step (4), and then carry out step (2) and (3).
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|---|---|---|---|
| CN98101358A CN1058284C (en) | 1998-04-10 | 1998-04-10 | Light hydrocarbon aromatization catalyst and its preparing process |
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|---|---|---|---|
| CN98101358A CN1058284C (en) | 1998-04-10 | 1998-04-10 | Light hydrocarbon aromatization catalyst and its preparing process |
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|---|---|
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| CN1058284C true CN1058284C (en) | 2000-11-08 |
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| CN98101358A Expired - Lifetime CN1058284C (en) | 1998-04-10 | 1998-04-10 | Light hydrocarbon aromatization catalyst and its preparing process |
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| CN (1) | CN1058284C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898150B (en) * | 2009-05-25 | 2012-05-30 | 中国石油化工股份有限公司 | Aromatization catalyst and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100124C (en) * | 2000-08-30 | 2003-01-29 | 中国石油化工股份有限公司 | Aromatizing catalyst for light hydrocarbon and its preparing process |
| CN101538184B (en) * | 2008-03-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for aromatizing light hydrocarbons |
| CN105195211B (en) * | 2014-06-16 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of methanol and C4Hydrocarbon aromatizing catalyst and aromatization method |
| CN106140267B (en) * | 2015-03-27 | 2019-02-01 | 中国石油化工股份有限公司 | Aromatizing catalyst for light hydrocarbon and the preparation method and application thereof |
| US11673845B2 (en) * | 2020-09-03 | 2023-06-13 | Saudi Arabian Oil Company | Aromatization of light hydrocarbons using metal-modified zeolite catalysts |
| CN115518679B (en) * | 2021-06-24 | 2024-03-26 | 中国石油化工股份有限公司 | Aromatization catalyst, preparation method and application thereof and butane aromatization method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057476A (en) * | 1991-08-05 | 1992-01-01 | 中国石油化工总公司 | The aromatization of hydrocarbons of Zincleaching-resistant contains the zinc zeolite catalyst |
| CN1062100A (en) * | 1990-12-05 | 1992-06-24 | 中国科学院大连化学物理研究所 | Be used for the light dydrocarbon aromatization reaction modified zeolite catalyst |
| CN1063121A (en) * | 1992-03-05 | 1992-07-29 | 中国石油化工总公司洛阳石油化工工程公司 | Catalytic modification of poor quality gasoline-aromatization |
| CN1070847A (en) * | 1992-10-15 | 1993-04-14 | 大庆石油学院 | Gallium, zinc, platinum modified HZSM-5 catalyst for aromatization of low carbon chain hydrocarbons |
-
1998
- 1998-04-10 CN CN98101358A patent/CN1058284C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062100A (en) * | 1990-12-05 | 1992-06-24 | 中国科学院大连化学物理研究所 | Be used for the light dydrocarbon aromatization reaction modified zeolite catalyst |
| CN1057476A (en) * | 1991-08-05 | 1992-01-01 | 中国石油化工总公司 | The aromatization of hydrocarbons of Zincleaching-resistant contains the zinc zeolite catalyst |
| CN1063121A (en) * | 1992-03-05 | 1992-07-29 | 中国石油化工总公司洛阳石油化工工程公司 | Catalytic modification of poor quality gasoline-aromatization |
| CN1070847A (en) * | 1992-10-15 | 1993-04-14 | 大庆石油学院 | Gallium, zinc, platinum modified HZSM-5 catalyst for aromatization of low carbon chain hydrocarbons |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898150B (en) * | 2009-05-25 | 2012-05-30 | 中国石油化工股份有限公司 | Aromatization catalyst and preparation method thereof |
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| CN1232071A (en) | 1999-10-20 |
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