CN1035316A - The hydrocarbon reforming catalyst that contains the β zeolite - Google Patents
The hydrocarbon reforming catalyst that contains the β zeolite Download PDFInfo
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- CN1035316A CN1035316A CN 88100760 CN88100760A CN1035316A CN 1035316 A CN1035316 A CN 1035316A CN 88100760 CN88100760 CN 88100760 CN 88100760 A CN88100760 A CN 88100760A CN 1035316 A CN1035316 A CN 1035316A
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Abstract
The hydrocarbon reforming catalyst that contains the β zeolite in a kind of carrier is made up of the carrier that one or both VIII class precious metal elements of the heavy % of 0.1-1.0 are active component and surplus.Vehicle group becomes: aluminum oxide or the silicon oxide of the modified beta zeolite of the heavy % of 10-100 and the heavy % of 0-90.Modified beta zeolite is for containing the heavy % of 0.5-2.5, and preferably 1.0-2.0 weighs the potassium of % or contains the heavy % of 0.5-2.5, preferably the H β zeolite behind the dealuminzation of heavy % potassium of 1.0-2.0 and the heavy % barium of 0.1-0.5.It is high activity, good sulfur resistance and arenes selectivity that this catalyzer has than industrial agent.The characteristic that has the unexistent alkylating aromatic hydrocarbon of industrial agent in addition.
Description
The invention relates to hydrocarbon reforming catalyst, specifically about containing the hydrocarbon reforming catalyst of β zeolite in the carrier.
The β zeolite is a kind of high silica alumina ratio zeolite, and its aperture is between the ZSM-5 zeolite of the faujusite of macropore and mesopore, and diameter is about 6
The Na β zeolite that synthesizes has following constitutional chemistry formula:
Wherein X is less than 1, preferably less than 0.75; R represents the template ion; Y greater than 5 less than 100; The W value can reach 4, depends on dehydration conditions and metal ion character.Sodium ion can be replaced by hydrogen ion or other positively charged ion by ion-exchange method on this zeolite, can be expressed as through the β zeolite after ion-exchange and the roasting:
Wherein M is the n valence metal ion.
The β zeolite has very high hydrocracking, hydroisomerizing catalytic activity and to the adsorptive power of straight-chain paraffin, and good anti-sulphur, nitrogen poisoning capability, abroad mainly be to be used for process (USP3308069 such as hydrocracking, hydroisomerizing, hydrodewaxing, dewaxing at present with some metal constituent element of its load or through modification, USP3923641, USP4568655, EP0164,208).Though once mentioning the β zeolite that contains hydrogenation component in EP0164208 can be used for reforming, but do not see the report that is useful on catalytic reforming, this is because the acidity of β zeolite is stronger, thereby it is directly applied to the effect unsatisfactory (too much cracking caused low aromizing and isomerization) of reforming process.
Purpose of the present invention is exactly with the modification in addition of existing β zeolite, so that the novel hydrocarbon reforming catalyst that contains the β zeolite in a kind of carrier to be provided.
Hydrocarbon reforming catalyst provided by the invention is one or both VIII class precious metal elements by 0.1～1.0 heavy %, and preferably platinum is the carrier composition of active component and surplus.Vehicle group becomes: aluminum oxide or the silicon oxide of the modified beta zeolite of 10～100 heavy % and 0～90 heavy %.Modified beta zeolite is for containing 0.5～2.5 heavy %, the potassium of best 1.0～2.0 heavy % or contain 0.5～2.5 heavy %, the H β zeolite behind the dealuminzation of the potassium of best 1.0～2.0 heavy % and 0.1～0.5 heavy % barium.H β zeolite behind the dealuminzation has following constitutional chemistry formula:
Wherein X is less than 1, preferably less than 0.75; Y is greater than 35; The W value can reach 4, depends on dehydration conditions and metal ion character; M is that valency is the metal ion of n.
Said modified beta zeolite can have following several preparation method among the present invention:
The method for making I:
(1) will be by prior art (USP3308069 for example, EP0159846, EP0159847, the Na β zeolite that EP0164208) synthesizes are 500～550 ℃ of following roastings after 2～4 hours, take out the part framework aluminum by method described in the EP095304 with acid, obtain silica alumina ratio greater than 70 H β zeolite.
(2) with potassium content (for example greater than the commutative capacity of positively charged ion on the zeolite with H β zeolite, potassium content is 3～5 times of commutative capacity), the soluble potassium salts solution that comprises Repone K, saltpetre, Potassium ethanoate, exchange one or many down at 85～100 ℃, potassium content is 0.5～2.5 heavy % to the zeolite, 110～120 ℃ of dryings then, 500～600 ℃ roasting 2-4 hour, promptly get the modified beta zeolite (K β) that contains 0.5～2.5 heavy % potassium.
The method for making II:
(1) with (1) of I method.
(2) the H β zeolite that (1) is made with contain weakly alkaline salt solution mix potassium ion, that comprise salt of wormwood, saleratus and Potassium ethanoate, the consumption of salt with 50～75% acid site in the energy and on the zeolite (for example, can be that the solution of potassium carbonate of 0.1～4 heavy % mixes with zeolite with 10: 1 liquid-solid ratio with concentration) be advisable, make that potassium content is 0.5～2.5 heavy % on the zeolite; Again after filtration, washing was to neutral, dry, 500～600 ℃ of roastings 2～4 hours.
(3) (2) gains are exchanged 1～2 hour with the soluble barium salt solution that comprises bariumchloride, nitrate of baryta, barium acetate down at 85～100 ℃, making on the zeolite barium content is 0.1～0.5 heavy %, (for example, nitrate of baryta solution with 2～10 heavy % exchanges under 15: 1 condition of liquid-solid ratio), filter then, the free barium ion of flush away, 110～120 ℃ of dryings, 500～590 ℃ of roastings 2～4 hours, promptly get the modified beta zeolite (KBa β) that contains 0.5～2.5 heavy % potassium and 0.1～0.5 heavy % barium.
The method for making III:
The K β zeolite of I method gained and II method (2) step gains by 5～1: 1～5 mixed, are promptly got the modified beta zeolite (K β) that contains 0.5～2.5 heavy % potassium.
Hydrocarbon reforming catalyst provided by the invention can have following two kinds of preparation methods:
The method for making I:
To consist of the modified beta zeolite of 10～100 heavy % and 0～99 heavy %(in butt) aluminum oxide or the shaping carrier of its precursor or silicon oxide or its precursor, carry out ion-exchange or dipping with the diacyloxy four ammino type compounds of VIII class precious metal, drying, roasting, reduction are made then.Moulding also can be carried out after ion-exchange or dipping.
The method for making II:
Carry out ion-exchange or dipping with accounting for the modified beta zeolite of vehicle weight 10～100 heavy % and the diacyloxy four ammino type compounds of VIII class precious metal, and then make with (in the butt) aluminum oxide that accounts for the heavy % of vehicle weight 0～99 or its precursor or silicon oxide or its precursor mixing moulding, drying, roasting, reduction.
It is high pure hydrocarbon reforming activity that the hydrocarbon reforming catalyst that contains modified beta zeolite in the carrier provided by the invention has more industrial platinum-rhenium reforming catalyst CB-6, and the former active comparable latter improves more than 15% under same reaction conditions, even can reach more than 90%.Catalyzer provided by the invention also has good sulfur resistance, can keep arenes selectivity constant under the situation of high sulfur content.In addition, catalyzer provided by the invention also has the characteristic of alkylating aromatic hydrocarbon, and this is that industrial agent is unexistent.
Following example will the invention will be further described.
Example 1～2
Prepare modified beta zeolite K β provided by the present invention with the I method.
With silica alumina ratio is 33 Na β (Fushun No.3 Petroleum Factory's production), 100 grams, refluxes 1.5 hours down at 100 ℃ with 400 milliliters 0.5N hydrochloric acid (analytical pure), and filtration is washed till P with deionized water
H6～7,110 ℃ of dryings are 2 hours then, and 500 ℃ of roastings 2 hours promptly get silica alumina ratio and be 71 H β.
With concentration is Repone K (Beijing chemical reagent factory, the analytical pure) solution of 0.32M and H β with 15: 1 liquid-solid ratio, refluxes 1 hour down at 100 ℃, filter washing, 120 ℃ of dryings, 500 ℃ of roastings 2 hours promptly get the modified beta zeolite that contains potassium 1.8 heavy %, and note is made K β-a.
With concentration be the hydrochloric acid of 2N according to the method described above to Na β dealuminzation, obtain silica alumina ratio and be 163 H β; Handle H β with Klorvess Liquid as stated above again, must contain the modified beta zeolite of potassium 0.6 heavy % at last, note is made K β-b.
Example 3～4
Prepare modified beta zeolite KBa β provided by the present invention with the II method.
With prepared silica alumina ratio in the example 2 is that 163 H β and concentration are salt of wormwood (Beijing chemical reagent factory of 1.3 heavy %, analytical pure) solution mixes by 10: 1 liquid-solid ratio, be heated to 60 ℃, stir after 10 minutes, naturally cooling, placement is spent the night, filter then, be washed till neutrality, 110 ℃ of dryings 2 hours, 500 ℃ of roastings 2 hours; Adding concentration again is nitrate of baryta (Beijing chemical reagent factory of 8.3 heavy %, analytical pure) solution descends to reflux 1 hour at 100 ℃ with 15: 1 liquid-solid ratio, filter, with the free barium ion of deionized water flush away, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 2 hours promptly get the modified beta zeolite that contains potassium and barium, and note is made KBa β-C.
According to example 1 method concentration is that to make silica alumina ratio in 1 hour be 77 H β for the hydrochloric acid reflux of 1N, be the modified zeolite that the solution of potassium carbonate of 0.062M and nitrate of baryta formulations prepared from solutions that concentration is 0.19M go out to contain potassium and barium with concentration according to the method described above again, note is made KBa β-d.
Example 5
Prepare the modified beta zeolite K β that this discovery provides with the III method.
To be 77 H β carry out ion-exchange with the Klorvess Liquid of 1.34M by method described in the example 1 to the silica alumina ratio that 10 grams are made in the examples 4, drying, and roasting must potassic β zeolite (I).
The silica alumina ratio that 10 grams are made in the examples 4 is that 77 H β concentration is that the solution of potassium carbonate of 0.09M soaks by the method described in the example 3, filters, and drying, roasting must potassic β zeolite (II).
The weight ratio of (I) and (II) two kinds of potassic β zeolites by 1: 1 mixed, promptly get potassic modified beta zeolite, note is made K β-e.
Example 6
With the modified beta zeolite is the preparation of the hydrocarbon reforming catalyst provided by the present invention of carrier.
Be the Pt(NH of 10.03 mg/ml with concentration after the modified beta zeolite moulding that example 1～5 makes
3)
4Cl
2Solution is with 2: 1 liquid-solid ratioes, at ℃ following dipping 24 hours of room temperature, more after filtration, washing, drying, and 300 ℃ of roastings 3 hours, 500 ℃ of reduction 4 hours promptly get hydrocarbon reforming catalyst provided by the present invention, remember successively and make catalyst A～E.See Table 1.
Used Pt(NH
3)
4Cl
2Be with hydrazine hydrochloride (Beijing Chemical Plant, analytical pure) reduction Platinic chloride (productions of Chang Ling refinery), add ammoniacal liquor (a Chaoyang District Beijing gold chemical plant, analytical pure) again and make.
Example 7
Prepare hydrocarbon reforming catalyst provided by the present invention with the I method.
K β-a that makes in the example 1 is mixed by 1: 1 weight ratio with SB aluminium hydroxide (West Germany's import) and α-water aluminum oxide (Fushun No.3 Petroleum Factory's product) respectively, compression molding, 550 ℃ of roastings 4 hours are again by the method Pt(NH described in the example 6
3)
4Cl
2Solution impregnation, filtration, washing, drying, roasting, reduction promptly get hydrocarbon reforming catalyst provided by the present invention, and note is made catalyzer F and G respectively, sees Table 1.
Example 8
Prepare hydrocarbon reforming catalyst provided by the present invention with the II method.
(subsidiary factory of Haiyang Chemical Plant, Qingdao produces with silica gel respectively with the catalyst A prepared in the example 6, chromatography with) and SB aluminium hydroxide mix by 70: 30 weight ratio (in butt), behind the compression molding, promptly get hydrocarbon reforming catalyst provided by the present invention, note is made catalyzer H and I respectively, sees Table 1.
Example 9
When methylcyclopentane was model compound, it was high activity that reforming catalyst provided by the present invention has than industrial agent, alkylating aromatic hydrocarbon characteristic and good sulfur resistance.
With methylcyclopentane (Switzerland's import, content is greater than 99%) in pressurization continuous micro-reactor (U.S. CDS-804), at 500 ℃, 9.8 * 10
5Handkerchief pressure, H
2/ hydrocarbon molecule is than 7, under the condition of catalyzer loading amount 0.2 gram, respectively to catalyst A provided by the present invention, B and industrial platinum-rhenium reforming catalyst CB-6(Chang Ling refinery product, and the heavy % of Pt0.3 wherein, the heavy % of Re0.3, carrier is ν-Al
2O
3) estimate, the evaluation result during the Different Weight air speed sees Table 2.
Can be found out that by table 2 result hydrocarbon reforming catalyst provided by the invention can improve more than 30% than the activity of commercial catalysts, with the increase of air speed, the active amplitude that improves increases, even can improve more than 90%.
On normal pressure pulse micro-inverse device, be poisonous substance, at 500 ℃, H with thiophene (Beijing Chemical Plant's product, chemical pure)
2Flow is under the condition of 60 ml/min, catalyzer loading amount 0.1 gram, metal center is poisoned catalyst A provided by the present invention and the last thiophene that injects 2 microlitres earlier of B respectively, remove the sulphur of reversible adsorption then with hydrogen purge, each 2 microlitres of the sample size of methylcyclopentane, prolongation with purge time, catalyst activity progressively recovers, and with the measurement as this catalyzer sulfur poisoning-resistant ability of the speed of this activation recovering, the results are shown in Table 3.
Can be found out that by table 3 result hydrocarbon reforming catalyst provided by the invention has good dehydroisomerization selectivity, the existence of sulphur is favourable on the contrary to the dehydroisomerization performance of catalyzer.
Example 10
When normal hexane was model compound, it was high activity and aromatic hydrocarbons election property, the characteristic of alkylating aromatic hydrocarbon and good sulfur resistance that hydrocarbon reforming catalyst provided by the present invention has than industrial agent.
According to condition described in the example 9 catalyst A .B.C provided by the present invention is estimated on the continuous micro-reactor of pressurization with normal hexane (Hangzhou Refinery product, content is greater than 99.5%), and compare, the results are shown in Table 4 with industrial agent CB-6.
Can find out that by table 4 result hydrocarbon reforming catalyst provided by the present invention can improve more than 15% than the activity of industrial agent.
On normal pressure pulse micro-inverse device, be that poisonous substance carries out the evaluation of sulfur resistance according to condition described in the example 9 to catalyst A .B.F.G provided by the present invention with the thiophene, and with industrial agent high platinum pellet catalyst (Chang Ling refinery product, wherein P
+0.5 heavy %, carrier is η-Al
2O
3) compare, the results are shown in Table 5 and table 6.
Result by table 5 and table 6 can find out that hydrocarbon reforming catalyst provided by the invention has good aromizing performance, and under the situation that sulphur exists, arenes selectivity changes less.
Annotate: the catalyzer loading amount is 0.2 gram, and the thiophene injection rate is 1 microlitre.
Example 11
When normal heptane was model compound, reforming catalyst provided by the present invention had very high activity and good sulfur resistance equally.
With normal heptane (oil six factory's products, content is greater than 99%) the pressurization continuous micro-reactor on, at 480 ℃, 9.8 * 10
5Handkerchief pressure, H
2/ hydrocarbon molecule is than 7.2, during weight space velocity 21
-1, catalyzer loading amount 0.2 gram condition under, the activity of evaluate catalysts D and E the results are shown in Table 7.
*Cure conditions: under temperature of reaction, hydrogen sulfide is fed beds, to catalyzer absorption saturated after, removed the sulphur of reversible adsorption on the catalyzer again in 4 hours with hydrogen purge.
Example 12
Reforming catalyst provided by the present invention is equally applicable to industrial raw material oil.
On the pressurization micro-reactor, be 7 kilograms per centimeter at 500 ℃, reaction pressure
2, weight space velocity is 10.5 o'clock
-1, the catalyzer loading amount is under the condition of 0.2 gram, is the performance that raw material comes evaluate catalysts H and I with the reforming raffinate oil of general petrochemical works, Kingsoft, Shanghai, the results are shown in Table 8.
Claims (5)
1, a kind of catalyzer that contains β Zeolite support load VIII class precious metal element, its characteristic is:
(1) it is active component and surplus by one or both VIII class precious metal elements of 0.1～1.0 heavy % carrier is formed, vehicle group becomes the modified beta zeolite of 10～100 heavy % and aluminum oxide or the silicon oxide of 0～90 heavy %, modified beta zeolite be contain the potassium of 0.5～2.5 heavy % or contain 0.5～2.5 heavy % potassium and the dealuminzation of 0.1～0.5 heavy % barium after H β zeolite;
(2) modified beta zeolite during carrier is formed can make by following method: Na β zeolite through 500～550 ℃ of roastings after 2～4 hours with acid take out the part framework aluminum to silica alumina ratio greater than 70, under 85～100 ℃ zeolite being carried out ion-exchange to zeolite potassium content greater than the soluble potassium salts solution commutative capacity of positively charged ion on the zeolite, that comprise Repone K, saltpetre, Potassium ethanoate with potassium content is 0.5～2.5 heavy %, 110～120 ℃ of dryings, 500～600 ℃ of roastings got final product in 2～4 hours;
(3) modified beta zeolite during carrier is formed also can make by following method: Na β zeolite after 500～550 ℃ of roasting 2-4 hours with acid take out the part framework aluminum to silica alumina ratio greater than 70, with zeolite behind the dealuminzation with contain potassium ion, comprise salt of wormwood, saleratus, Potassium ethanoate is in interior weakly alkaline salt solution mix, the salt consumption is advisable with 50～75% acid site in the energy and on the zeolite, mixture heating up to 60 ℃, naturally cooling is placed and is spent the night, or mixture was directly placed 8～12 hours in room temperature without heating, making on the zeolite potassium content is 0.5～2.5 heavy %, filter, be washed till neutrality, dry, 500～600 ℃ of roastings 2～4 hours, again with comprising bariumchloride, nitrate of baryta, barium acetate carries out ion-exchange to zeolite barium content to zeolite at interior soluble barium salt solution under 85～100 ℃ be 0.1～0.5 heavy %, filter, the flush away barium ion that dissociates, drying, 500～600 ℃ of roastings got final product in 2～4 hours;
(4) modified beta zeolite during carrier is formed also can make by following method: with obtain in the modified beta zeolite made in (2) and (3) preparation process only contain potassium not the β zeolite of baric according to 5～1: 1～5 weight ratio is mixed and is got final product;
(5) supported catalyst can make by following method: modified beta zeolite and the aluminum oxide of 0～90 heavy % (in butt) or the shaping carrier of its precursor or silicon oxide or its precursor that will consist of 10～100 heavy %, carry out ion-exchange or dipping with the diacyloxy four ammino type compounds of VIII class precious metal, drying, roasting, reduction are made then, and moulding also can be carried out after ion-exchange or dipping;
(6) supported catalyst also can make by following method: will account for the modified beta zeolite of vehicle weight 10～100 heavy % and the diacyloxy four ammino type compounds of VIII class precious metal and carry out ion-exchange or dipping, and then make with (in the butt) aluminum oxide that accounts for the heavy % of vehicle weight 0～90 or its precursor or silicon oxide or its precursor mixing moulding, drying, roasting, reduction.The reduction and make.
2,, it is characterized in that said modified beta zeolite has following constitutional chemistry formula according to the described catalyzer of claim 1:
X＜1 wherein, Y＞35, the W value can reach 4, depends on dehydration conditions and metal ion character, and M is that valency is the metal ion of n.
3,, it is characterized in that X＜0.75 in the constitutional chemistry formula of said modified beta zeolite according to the described catalyzer of claim 1.
4,, it is characterized in that potassium content is preferably 1.0～2.0 heavy % in the said modified beta zeolite according to the described catalyzer of claim 1.
5, the catalyzer of the described β of the containing Zeolite support of claim 1 load VIII class precious metal element is used for the catalytic reforming of hydro carbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100760 CN1015637B (en) | 1988-02-25 | 1988-02-25 | Beta zeolite-containing hydrocarbon reforming catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100760 CN1015637B (en) | 1988-02-25 | 1988-02-25 | Beta zeolite-containing hydrocarbon reforming catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1035316A true CN1035316A (en) | 1989-09-06 |
| CN1015637B CN1015637B (en) | 1992-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100760 Expired CN1015637B (en) | 1988-02-25 | 1988-02-25 | Beta zeolite-containing hydrocarbon reforming catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039818C (en) * | 1995-10-06 | 1998-09-16 | 中国石油化工总公司石油化工科学研究院 | Multiple-metal reforming catalyst |
| CN1100615C (en) * | 1998-12-28 | 2003-02-05 | 北京燕山石油化工公司研究院 | Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol |
| CN102099114B (en) * | 2008-07-23 | 2013-06-19 | 石油资源开发株式会社 | Complex oxide for hydrocarbon reforming catalyst, method for producing the same, and method for producing synthetic gas using the same |
| CN107382646A (en) * | 2016-05-17 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of method of solid acid alkylating |
| CN107376983A (en) * | 2016-05-17 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of solid acid alkylation catalysts and the alkylation catalyst prepared by this method |
| CN107382646B (en) * | 2016-05-17 | 2024-05-17 | 中国石油化工股份有限公司 | Method for alkylating solid acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL99898A (en) * | 1990-11-09 | 1996-10-31 | Eisai Co Ltd | 7-Acyl-3-substituted carbamoyloxy cephem compounds their preparation and antibacterial compositions containing them |
-
1988
- 1988-02-25 CN CN 88100760 patent/CN1015637B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039818C (en) * | 1995-10-06 | 1998-09-16 | 中国石油化工总公司石油化工科学研究院 | Multiple-metal reforming catalyst |
| CN1100615C (en) * | 1998-12-28 | 2003-02-05 | 北京燕山石油化工公司研究院 | Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol |
| CN102099114B (en) * | 2008-07-23 | 2013-06-19 | 石油资源开发株式会社 | Complex oxide for hydrocarbon reforming catalyst, method for producing the same, and method for producing synthetic gas using the same |
| CN107382646A (en) * | 2016-05-17 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of method of solid acid alkylating |
| CN107376983A (en) * | 2016-05-17 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of solid acid alkylation catalysts and the alkylation catalyst prepared by this method |
| CN107382646B (en) * | 2016-05-17 | 2024-05-17 | 中国石油化工股份有限公司 | Method for alkylating solid acid |
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| Publication number | Publication date |
|---|---|
| CN1015637B (en) | 1992-02-26 |
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