CN1073198A - Catalyst for dehydroaromatizationof of alkane and preparation method - Google Patents
Catalyst for dehydroaromatizationof of alkane and preparation method Download PDFInfo
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- CN1073198A CN1073198A CN 91111491 CN91111491A CN1073198A CN 1073198 A CN1073198 A CN 1073198A CN 91111491 CN91111491 CN 91111491 CN 91111491 A CN91111491 A CN 91111491A CN 1073198 A CN1073198 A CN 1073198A
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Abstract
The invention discloses a kind of Catalysts and its preparation method that is used for dehydroaromatizationof of alkane.This catalyzer is by a kind of macropore alkalescence L zeolite and a kind of inorganic oxide binder mixing moulding, flood jointly with the tetrammine salt that contains noble metal platinum and certain density basic metal or alkaline earth metal chloride solution, make on the catalyzer except that containing a certain amount of reactive metal platinum and basic metal or alkaline-earth metal, also contain a certain amount of chlorine.By adjusting muriatic concentration in the steeping fluid, the cl content on the may command finished catalyst in the scope that requires, thereby help improving selectivity of catalyst and activity stability.
Description
The present invention is a kind of Catalysts and its preparation method that is used for the alkane dearomatization, belongs to the reformation technical field of hydrocarbon ils.
The petroleum naphtha that octane value is very low is converted into stop bracket gasoline or petrochemical complex important source material aromatic hydrocarbons is the purpose of reforming process, but existing dual-function reforming catalyst is only good to the naphthenic hydrocarbon changing effect in the petroleum naphtha, and to paraffinic hydrocarbons (C particularly
6, C
7Paraffinic hydrocarbons) it is all lower to change into the activity and the selectivity of aromatic hydrocarbons.For this reason, the paraffin dehydrogenation aromatized catalyst of seeking high reactivity and highly selective is the noticeable problem in the petrochemical complex catalytic field in recent years.In this respect, the L zeolite catalyst that carries platinum is wherein a kind of representational catalyzer.Since patent documentation US in 1978 4,104,320 have proposed first piece of L zeolite that carries platinum and are used for the patent of alkane aromatization, manyly up till now delivered in technologic application patent about Pt-L catalyzer and its.All be better than existing dual-function reforming catalyst owing to carry the L zeolite catalyst aromatization activity and the selectivity of platinum, but stability is relatively poor, so many patents all are devoted to the improvement of this respect, as US 4,435,283 propose to carry out ion-exchange system Ba-L zeolite with nitrate of baryta and L zeolite, and resulting intermediate carries out ion-exchange with the platiniferous aqueous solution again and makes the Pt-Ba-L aromatized catalyst that carries platinum after roasting.US 4,458, and 075 proposes to mix with the L zeolite with nitric acid peptization aluminum oxide again, then in the hydro-oxidation potassium with the acidity of nitric acid, through the extruded moulding carrier, carry out ion-exchange with the platiniferous aqueous solution again after the roasting and become Pt-Ba-L-AL
2O
3Catalyzer.EP 184, and 451A proposes a kind of method for preparing the Pt-L catalyzer, this method be when carrying platinum, add a small amount of sylvite with in and the acidity that produces when the reduction of platinum.US4,619906US 4780223 and CN 86107521A are the patent of Uop Inc. about preparation Pt-L catalyzer, have introduced and have introduced three kinds of different methods that surpass the surface deposition basic metal constituent element of loading capacity on the L zeolite.EP 334, and the method that 562A1 and US 4,595,669 proposition L zeolite catalysts are handled with high-temperature water chlorine after soaking platinum is with the dispersity of raising platinum on the L zeolite, and then the method for raising aromatization activity.US 4,618, and 865 disclose a kind of L zeolite catalyst that contains halogen family element and platinum, handle the L zeolite with halogenated alkane, flood to carry platinum with the platiniferous aqueous solution then.Though above-mentioned Pt-L zeolite catalyst in the process of preparation, has used platiniferous chloride aqueous solution dipping or has handled with containing the muriatic aqueous solution, does not all propose the content requirement of chlorine constituent element in catalyzer.
Purpose of the present invention is exactly at the weak point of carrying the L zeolite catalyst aromizing poor stability of platinum at present, the L zeolite catalyst of a kind of year platinum is proposed, this catalyzer should have greater activity and selectivity to the dehydrocyclization reaction of alkane, and stability is preferably arranged again.
For reaching this purpose, catalyzer of the present invention is not only different with the used catalyzer of prior art on constituent element, and has also done improvement on the method for catalyzer preparing.
Catalyzer of the present invention contains the VIII family precious metals pt that the heavy % of 0.1-1.5 has catalytic activity; Contain the heavy % of 0.1-1.5, be preferably the Cl of the heavy % of 0.2-1.2; Contain the heavy % of 7-13, be preferably alkali or alkaline-earth metal constituent element K or the Na of the heavy % of 9-12, Cs, Ba; Surplus is a carrier, and this carrier is by L zeolite and a kind of inorganic oxide binder Al
2O
3Or SiO
2, be preferably γ-Al
2O
3Form.The silica alumina ratio of L zeolite is 5-7, and degree of crystallinity is greater than 85%, and its content is the Al of carrier gross weight 50-85%
2O
3Or SiO
2Its content is the 15-50% of carrier gross weight.The total content of basic metal and alkaline-earth metal constituent element surpasses the tradable positively charged ion total amount of L zeolite on the catalyzer on this catalyzer.
Preparation of catalysts method of the present invention is as follows: (according to US 3,216, the disclosed L zeolite preparation method of 789 patent specifications is with containing SiO with the L zeolite
2, Al
2O
3Make through hydro-thermal is synthetic with the aqueous solution of raw material such as KOH, it consists of 0.9-1.1K
2OAl
2O
35-7SiO
2) with an amount of α-Al(OH)
3Mix, add an amount of aqueous acetic acid, mediate evenly back extrusion,,, become the strip carrier of diameter at the 1.0-2.5 millimeter at 500-650 ℃ of following roasting 4-6 hour through 120 ℃ of oven dry 2-8 hour.α-Al(OH)
3Consumption with Al
2O
3Be calculated as the 15-50% of carrier gross weight.Acetic acid consumption during extrusion is the 1-10% of carrier gross weight, is preferably 2-5%.As use SiO
2During for binding agent, then mix extrusion with the L zeolite with the form of neutral gel.The silicon gel is formed with hydrochloric acid or acetic acid neutralization by alkaline silica sol, and its add-on is pressed SiO
2Be calculated as the 15-50% of carrier gross weight.Carrier after the moulding in 120 ℃ dry 2-8 hour down, 500-650 ℃ roasting 4-6 hour, go up the Pt(NH of amount Pt with containing the phase of giving
3)
4Cl
2And any aqueous solution in the muriate of the potassium of 0.2-0.5M or sodium, caesium, barium at room temperature soaked 1-24 hour, and liquid-solid ratio is 1/1-7/1.Pull carrier after soaking out, remove redundant solution, descended dry 4-12 hour at 50-120 ℃, activation is 4-6 hour in the 200-350 ℃ of following air, and reduction is 1-6 hour in the last hydrogen under 300-500 ℃.
Catalyzer of the present invention, its platinum content can reach the 90-98% of when dipping charging capacity, have very high activity and selectivity for the aromatization of alkane, and stability is preferably arranged.This is because catalyzer of the present invention not only has basic metal or the alkaline-earth metal more than L zeolite exchangeable cation total amount, thereby suppressed the acidic cleavage function of catalyzer, simultaneously also owing to also contain a certain amount of chlorine constituent element, the alkalescence of catalyzer has also been played adjusting and poising action and helped promoting the dispersion state and the stability of platinum component.
For typical dual-function reforming catalyst, chlorine is a requisite constituent element, and it can also promote platinum at Al except acid function is provided
2O
3Dispersity on the carrier.And the Pt-K-L catalyzer is the catalyzer of single metal function basically, cause its aromatization voltinism optionally to descend though introduce acidity, but the existence of chlorine constituent element also helps the stability of the dispersion state of platinum on the L zeolite, in many relevant patents of Pt-L catalyzer of past, or introduce excessive basic metal or alkaline-earth metal suppressing acid function, or introduce chlorine to promote the dispersion state of platinum on the L zeolite.Though the former can improve selectivity, activity of such catalysts is low, and the life-span is short; But the latter has brought acidity into when introducing chlorine, thereby has reduced selectivity and also accelerated the inactivation that catalyzer causes because of carbon deposit.The characteristics of catalyzer of the present invention are in platinum-impregnated, have both introduced can promote platinum dispersive chlorine constituent element in right amount, also introduce an amount of basic metal or alkaline-earth metal, make the acid, alkalescence of catalyzer can coordinated balance, reach optimum regime.
Compare with the Pt-L zeolite aromatized catalyst that contains of prior art, the characteristics of catalyzer of the present invention are:
1, simultaneously constituent elements such as platinum, basic metal, alkaline-earth metal and chlorine once is stated from the carrier after the moulding with muriatic form with a step co-impregnation, has simplified the repeatedly exchange generally adopted in the prior art or the method for dipping repeatedly.
2, when introducing the metal constituent element, introduce the chlorine constituent element together with the method for competitive adsorbate.Muriatic concentration for well, is preferably 0.2-0.5M with 0.1-0.65M.Muriatic consumption is the 1-12% of carrier weight, is preferably 2-8%.In this concentration range, cl content on the catalyzer finished product is varied to proportional relation with chloride concentration, and the content of the platinum on the catalyzer finished product, basic metal or alkaline-earth metal is constant basically, because of platinum content depends on charging capacity, and basic metal or alkaline earth metal content depend primarily on the consumption of L zeolite.
3, catalyzer of the present invention is when the kneading extrusion of carrier, is to be peptizing agent and L zeolite and α-Al(OH) with aqueous acetic acid
3(or SiO
2Colloidal sol) mix, prior art is then mixed with mineral acids such as nitric acid, hydrochloric acid.The embodiment of the invention shows the catalyzer for preparing gained with acetic acid mixing peptization, and is all good than prior art at many indexs such as pore volume, specific surface and aromizing performances.
Because above-mentioned catalyzer in preparation, shows following several respects are arranged on the property of catalyzer:
1, because the competitive adsorption and the exchange interaction of basic metal or alkaline earth metal cation have promoted platinum at the inside and outside lip-deep uniform distribution of carrier particle;
2, introduce an amount of chlorine constituent element, help promoting the dispersion state stability of platinum on the K-L zeolite, thereby improve Pt-L zeolite catalyst stability of catalytic performance.
3, introduce an amount of basic metal or alkaline-earth metal constituent element, both neutralized because platinum reduces, Al
2O
3Existence and the introducing of chlorine and the acidity that produces, improved the negatron state of platinum again, also improved selectivity of catalyst.
Based on catalyzer of the present invention in above-mentioned preparation method and the characteristics on the physical structure, when therefore comparing with the prior art reforming catalyst, catalyzer of the present invention has higher activity, selectivity and stable preferably to the dehydrocyclization reaction (being aromatization) of alkane.Can find out these advantages significantly by following embodiment.
Embodiment 1
According to US 3,216, the L zeolite (SiO that the hydrothermal synthesis method of 789 patent disclosures makes
2/ Al
2O
3=6) and Al(OH)
3Dry glue powder (production of refinery, BaLing Petroleum Chemical Engineering Co., Ltd Chang Ling) mixes by 7: 3 weight ratios, according to Preparation of catalysts method of the present invention, with the Glacial acetic acid of the heavy % of 2-6 that mixes back dry powder amount and an amount of (be about dry powder heavy 30%) water, mediate extrusion, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 4 hours.Comparative Examples is with aqueous nitric acid peptization mixed dry powder, and nitric acid dosage is identical with acetic acid, uses among the KOH of equivalent again and nitric acid, mixedly pinches, extrusion, drying, roasting condition be identical.Two kinds of above-mentioned carriers all are as the criterion with carrier weight with containing Pt0.6%() Pt(NH
3)
4Cl
2(by H
2PtCl
6Reduction makes) and contain the KCl(analytical pure) 5%(is as the criterion with carrier weight) aqueous solution soaked overnight at room temperature, dipping liquid-solid ratio (being the used liquid volume of every gram carrier, milliliter) is 2.Pull the carrier behind the dipping out, 85 ℃ of dryings, 300 ℃ of roastings are reduced in 400 ℃ of hydrogen streams, are crushed to the 40-60 sieve mesh after the cooling, and this catalyzer is represented with A.Reaction unit is raw material for CDS-804 type pressurization continuous flow micro-reactor (production of american chemical data company) with normal heptane (Hangzhou Refinery production, analytical pure), carries out the dehydrocyclization determination of activity of catalyzer.Reaction product is by online gas chromatographic analysis, and thermal conductance detects, and presses the composition that the chromatographic peak area normalization method is calculated anti-wide product, the results are shown in Table 1.
Reaction conditions: 480 ℃, 1.08MPa, H
2/ oil (molecular ratio) 7, weight space velocity 20.6 hours
-1
Annotate (1):
The aromizing selectivity, SA%=(aromatics yield)/(aromatics yield+C
6-Productive rate) * 100
The data of table 1 show: the extrusion carrier with the acetic acid peptization has higher specific surface and higher pore volume, and the catalyzer behind year platinum also has higher aromizing and leads structure selection performance.
Embodiment 2
The present embodiment explanation is according to Preparation of catalysts method of the present invention, after adding different competitive adsorbates, to the aromizing of catalyzer and the influence of isomerization performance.
Take by weighing the strip carrier of catalyzer of the present invention among 4 parts of embodiment 1, every part of 4g immerses the Pt(NH that 7ml respectively contains Pt 24mg respectively
3)
4Cl
2And contain the KCl of 0.32M, CsCl, NaCl, and the BaCl of 0.16M
2In the aqueous solution, soaked 24 hours under the room temperature.Pull the back out in 110 ℃ of oven dry, through 300 ℃ of activation, reduce in 500 ℃ of hydrogen streams, the catalyzer finished product is represented with catalyst B, C, D, E respectively.Its compositional analysis and the results are shown in Table 2 with what do that micro-activity measures positive heptan is only to add Pt(NH
3)
4Cl
2But not adding other muriates makes the catalyzer of competitive adsorbate and contrasts.By catalyzer finished product section as can be seen, platinum is uniform grey and distributes on catalyzer of the present invention, and presents the distribution of eggshell shape on the correlation technique catalyzer.
Reaction conditions: 500 ℃, 0.78MPa, H
2/ oil (molecular ratio) 4, weight space velocity 20.6 hours
-1
Annotate (2): M and represent basic metal or alkaline-earth metal total amount, down together.
By the data in the table 2 as can be seen, no matter use K, Na, Cs, the any basic metal among the Ba or the muriate of alkaline-earth metal be during as competitive adsorbate, and prepared catalyzer of the present invention all has higher aromizing and isomerization performance and stability preferably than prior art catalyzer.
Embodiment 3
When present embodiment is to use the different anions compound of basic metal or alkaline-earth metal to make competitive adsorbate, the performance test of catalyzer.
Take by weighing the strip carrier of catalyzer of the present invention among 3 parts of embodiment 1, every part of 4g immerses the Pt(NH that 7ml contains Pt 24mg respectively
3)
4Cl
2And contain the KNO of 0.32M
3, KOH and 0.16M Ba(NO
3)
2In the aqueous solution, prepare catalyzer by the preparation method of embodiment 2, its finished product is represented with catalyzer F, G, H respectively.With measuring the micro-activity of making stock oil with normal heptane, the results are shown in Table 3 with quadrat method.
Reaction conditions: with embodiment 2
Do after the contrast as can be seen with the data of table 2 among the data of table 3 and the embodiment 2, when the positively charged ion of competitive adsorbate is identical, use the prepared catalyzer of muriatic the inventive method, on aromizing and isomerized performance, more superior than the prior art of making competitive adsorbate with nitrate or oxyhydroxide.
Embodiment 4
The present embodiment explanation when using the solution impregnating carrier of platinum, basic metal (or alkaline-earth metal) and chlorine constituent element, should be controlled within the specific limits as the chloride soln concentration of competitive adsorbate in Preparation of catalysts method of the present invention.
Preparation method according to catalyst B among the embodiment 2, with platinum and identical liquid-solid ratio with amount, but six catalyzer that six Klorvess Liquids of different concns (being 0.08M, 0.16M, 0.32M, 0.48M, 0.64M and 0.80M) are prepared, with I, J, K, L, M, N sign, the platinum content of its finished catalyst sees Table 4 respectively.
Table 4
| Catalyzer | I | J | K | L | M | N |
| Dipping KCl concentration, M | 0.08 | 0.16 | 0.32 | 0.48 | 0.64 | 0.80 |
| The platinum-impregnated consumption, heavy % | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 | 0.60 |
| The platinum content of finished catalyst, heavy % | 0.56 | 0.56 | 0.56 | 0.53 | 0.44 | 0.38 |
| Platinum distributes on carrier and presents | Eggshell shape | Evenly | Evenly | Evenly | Evenly | Evenly |
The data of table 4 show that when the KCl concentration in dipping solution was higher than 0.60M, the platinum content of catalyzer finished product had obvious downward trend; When being lower than 0.10M, platinum is skewness on granules of catalyst.
Embodiment 5
The cl content of present embodiment explanation catalyzer of the present invention is to the relation of catalytic activity.
According to the preparation method of catalyst B among the embodiment 2, with the Repone K that contains the platinum of same amount and same amount but the different platinum solution that soaks of dilute strength is made four catalyzer, code name is O, P, Q, R.According to the compositional analysis of these four finished catalysts, the content of platinum and potassium is basic identical, and cl content then reduces with the reduction of potassium chloride concentration in the steeping fluid.Table 5 is four catalyzer on pressurization micro-reactor continuously with normal heptane is the dehydrocyclization determination of activity result that raw material is done.
Reaction conditions: 500 ℃, 0.78MPa, H
2/ oil (molecular ratio) 4.0, weight space velocity 20.6 hours
-1
Annotate (3): relative deactivation rate:
R
A=(react after 1 hour aromatics yield-reaction after 6 hours aromatics yield)/(reacting aromatics yield after 1 hour) * 1/ (5 hours)
The data declaration of table 5, the cl content on the catalyzer is lower than at 0.2% o'clock, and deactivation rate is obviously accelerated, but cl content is when too high, and aromatization activity also will reduce.
Embodiment 6
Present embodiment is the test of catalyzer of the present invention on the continuous flow fixed bed reactor of 10 milliliters of reactor capacity.With embodiment 2 catalyst B 3.0 grams, be reaction raw materials with reforming raffinate oil (Tianjin Petrochemical Company production), carry out the aromizing test of catalyzer, contrasting used catalyzer is the used Pt-Re-Al of industrial reformer
2O
3Catalyzer (model is CB-6).The composition of reforming raffinate oil sees Table 6.Reaction test the results are shown in Table 7.
Table 6 reforming raffinate oil is formed, heavy %
| C 5- | i-C 6 | n-C 6 | Me-Cy -C 5 | Benzene | i-C 7 | n-C 7 | Me-Cy -C 6 | Toluene | C 8 + | Sulphur (ppm) |
| 0.6 | 37.0 | 17.7 | 6.2 | 1.2 | 21.4 | 6.8 | 2.4 | 0.31 | 6.4 | ＜0.3 |
Other reaction conditionss: 0.784MPa, H
2/ oil (molecular ratio) 7
Data in the table 7 show that for containing the higher reforming raffinate oil of isoparaffin amount, catalyzer of the present invention also has the Pt-Re-Al than prior art
2O
3Aromatization activity that catalyzer is much higher and selectivity.
Present embodiment is scale-up and the reaction stability test in 250 hours of embodiment 6, and catalyzer and reaction raw materials oil are all identical with embodiment 6.Test is 100 milliliters of reactor capacity and have and carry out on the fixed-bed reactor of hydrogen recycle.A desulphurization reaction pipe is housed behind fresh feed pump.Catalyst levels 50ml, heavy 41g divides upper and lower two sections packing.Epimere is that the 20ml catalyzer mixes with the quartzy sand facies of 20ml, and hypomere is the 30ml catalyzer, but does not mix quartz sand, and upper and lower two sections separate with quartz sand.In pressure is the recycle hydrogen air-flow of 0.78MPa, beds is warming up to 370 ℃ of laggard stock oils, after the oil-feed bed temperature is risen to 450 ℃ gradually.Reactive system is still kept 0.78MPa, and the hydrogen oil molecule is than 3, charging air speed 2hr
-1Aromaticity content in the controlled liq product is under the precondition of the heavy % of 30-35, progressively improves reaction bed temperature.Because testing data is more, the result of present embodiment is with 4 curve representations.Fig. 1 is that the reactor inlet temperatures in 250 hours reaction process changes (curve A).Aromaticity content changes (curve B) in the product liquid, and the hydrogen purity that liquid product yield changes in (curve C) and the recycle hydrogen changes (curve D).These 4 curves show that catalyzer of the present invention has aromizing selectivity and stability preferably.
Claims (5)
1, a kind of catalyst for dehydroaromatizationof of alkane is loaded in the L zeolite and is to constitute on the carrier of caking agent with the inorganic oxide by Pt, K, Cl constituent element, it is characterized in that:
1. activity of such catalysts component and content are:
The heavy % of Pt 0.1-1.5 (to whole catalyzer, down together);
Comprise K, or Na, Cs, the basic metal of Ba or alkaline-earth metal
The heavy % of 7-13 is preferably the heavy % of 9-12;
The heavy % of Cl 0.1-1.5 is preferably the heavy % of 0.2-1.2;
Surplus is a carrier;
2. the carrier of catalyzer is the L zeolite and comprises Al
2O
3Or SiO
2A kind of mixture of inorganic oxide caking agent, its content is:
The heavy % of L zeolite 50-85 (to whole carriers, down together);
The heavy % of inorganic oxide 15-50 is with Al
2O
3Better, with γ-A I
2O
3Best;
3. simultaneously Pt, basic metal or alkaline-earth metal and Cl are loaded on the carrier after the moulding with chloride soln with a step co-impregnation;
4. be peptizing agent with aqueous acetic acid, L zeolite and inorganic oxide peptization are mixed back kneading, extruded moulding.
2, according to the catalyzer of claim 1, the concentration of the chloride soln during said dipping for well, is preferably 0.2-0.5M with 0.1-0.65M.
3, according to the catalyzer of claim 1, the SiO of said L zeolite
2/ Al
2O
3Be 5-7, degree of crystallinity is greater than 85%.
4,1 catalyzer as requested is the 1-10% of carrier gross weight as the acetic acid amount in the aqueous acetic acid of peptizing agent, is preferably 2-5%.
5, according to the catalyzer of claim 1, carrier in preparation after the moulding in 120 ℃ dry 2-8 hour down, 500-650 ℃ roasting 4-6 hour, the dipping back 50-120 ℃ dry 4-12 hour down, activation is 4-6 hour in the 200-350 ℃ of following air, and reduction is 1-6 hour in the 300-500 ℃ of following hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91111491 CN1030329C (en) | 1991-12-12 | 1991-12-12 | Catalyst for dehydroaromatization of alkane and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91111491 CN1030329C (en) | 1991-12-12 | 1991-12-12 | Catalyst for dehydroaromatization of alkane and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1073198A true CN1073198A (en) | 1993-06-16 |
| CN1030329C CN1030329C (en) | 1995-11-22 |
Family
ID=4910670
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91111491 Expired - Lifetime CN1030329C (en) | 1991-12-12 | 1991-12-12 | Catalyst for dehydroaromatization of alkane and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030329C (en) |
Cited By (11)
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|---|---|---|---|---|
| CN1048426C (en) * | 1994-06-20 | 2000-01-19 | 南开大学催化剂厂 | C5 chain hydrocarbon aromatization catalyst |
| CN1093431C (en) * | 1998-11-25 | 2002-10-30 | 中国科学院大连化学物理研究所 | Catalyst for aromatizing low-carbon paraffin and its preparing process |
| CN1101454C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrodesulfurizing catalyst for fraction oil and its preparing method |
| CN101898148B (en) * | 2009-05-27 | 2012-03-07 | 中国石油天然气股份有限公司 | L-containing molecular sieve catalytic cracking gasoline selective hydrodesulfurization modification catalyst |
| CN101633850B (en) * | 2008-07-24 | 2012-10-10 | 中国石油化工股份有限公司 | Method for preparing catalytic reforming catalyst |
| CN108239554A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | catalytic reforming catalyst containing L T L-type molecular sieve |
| CN108349843A (en) * | 2015-11-04 | 2018-07-31 | 埃克森美孚化学专利公司 | For converting acyclic C5Compound circlewise C5The method of compound and be used for carbon monoxide-olefin polymeric therein |
| CN108993584A (en) * | 2018-06-26 | 2018-12-14 | 中海油天津化工研究设计院有限公司 | A kind of reforming raffinate oil aromatized catalyst and preparation method thereof |
| CN110028079A (en) * | 2019-06-05 | 2019-07-19 | 中海油天津化工研究设计院有限公司 | It is a kind of rich in mesoporous BaKL zeolite and preparation method thereof |
| CN111420698A (en) * | 2020-03-30 | 2020-07-17 | 广西华睿能源科技有限公司 | Bimetallic acid-free aluminosilicate porous composite material for direct aromatization of n-alkanes and preparation method and application thereof |
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-
1991
- 1991-12-12 CN CN 91111491 patent/CN1030329C/en not_active Expired - Lifetime
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| CN1048426C (en) * | 1994-06-20 | 2000-01-19 | 南开大学催化剂厂 | C5 chain hydrocarbon aromatization catalyst |
| CN1093431C (en) * | 1998-11-25 | 2002-10-30 | 中国科学院大连化学物理研究所 | Catalyst for aromatizing low-carbon paraffin and its preparing process |
| CN1101454C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrodesulfurizing catalyst for fraction oil and its preparing method |
| CN101633850B (en) * | 2008-07-24 | 2012-10-10 | 中国石油化工股份有限公司 | Method for preparing catalytic reforming catalyst |
| CN101898148B (en) * | 2009-05-27 | 2012-03-07 | 中国石油天然气股份有限公司 | L-containing molecular sieve catalytic cracking gasoline selective hydrodesulfurization modification catalyst |
| CN108349843A (en) * | 2015-11-04 | 2018-07-31 | 埃克森美孚化学专利公司 | For converting acyclic C5Compound circlewise C5The method of compound and be used for carbon monoxide-olefin polymeric therein |
| CN108239554A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | catalytic reforming catalyst containing L T L-type molecular sieve |
| CN108993584A (en) * | 2018-06-26 | 2018-12-14 | 中海油天津化工研究设计院有限公司 | A kind of reforming raffinate oil aromatized catalyst and preparation method thereof |
| CN108993584B (en) * | 2018-06-26 | 2021-05-28 | 中海油天津化工研究设计院有限公司 | Reforming raffinate oil aromatization catalyst and preparation method thereof |
| CN110028079A (en) * | 2019-06-05 | 2019-07-19 | 中海油天津化工研究设计院有限公司 | It is a kind of rich in mesoporous BaKL zeolite and preparation method thereof |
| CN111420698A (en) * | 2020-03-30 | 2020-07-17 | 广西华睿能源科技有限公司 | Bimetallic acid-free aluminosilicate porous composite material for direct aromatization of n-alkanes and preparation method and application thereof |
| CN114653395A (en) * | 2022-03-09 | 2022-06-24 | 中科合成油技术股份有限公司 | Naphtha reforming catalyst and preparation method and application thereof |
| CN114653395B (en) * | 2022-03-09 | 2024-05-24 | 中科合成油技术股份有限公司 | Naphtha reforming catalyst and preparation method and application thereof |
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| CN1030329C (en) | 1995-11-22 |
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