CN105498824A - Hydrocarbon reforming catalyst containing mesoporous molecular sieve, and preparation method thereof - Google Patents
Hydrocarbon reforming catalyst containing mesoporous molecular sieve, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrocarbon reforming catalyst containing a molecular sieve. The hydrocarbon reforming catalyst comprises a molecular sieve catalyst and an alumina catalyst with an alumina carrier according to a mass ratio of 1-5:1-30, wherein the molecular sieve catalyst comprises the following active components (calculated as the dry-based molecular sieve): 0.1-5.0% by mass of a platinum group metal and 0.1-4.0% by mass of a group IIIB metal, the molecular sieve is a mesoporous molecular sieve with a pore diameter of 2-50 nm, and the alumina catalyst comprises the following active components (calculated as the dry-based alumina): 0.1-4.0% by mass of a platinum group metal, 0.1-5.0% by mass of a group VIIB metal, and 0.5-10.0% by mass of a halogen. According to the present invention, the catalyst is suitable for the reforming reaction of hydrocarbons and naphtha, and has characteristics of high isoparaffin yield and high aromatic hydrocarbon yield, and the preparation method is simple and easy to operate.
Description
Technical field
The present invention is a kind of reforming catalyst and preparation method thereof, specifically, is a kind of hydrocarbons reforming catalyst containing molecular sieve and preparation method thereof.
Background technology
Catalytic reforming take naphtha cut as raw material, under the effect of certain reaction condition and catalyst, produces the process of high-knock rating gasoline blend component, light aromatics and cheap hydrogen.The reforming catalyst overwhelming majority of current commercial Application is (as halogen-containing γ-Al by active component (platinum), co-catalyst (as rhenium, tin etc.) and acid carrier
2o
3) formed, this kind of catalyst has carried out the extensive and deep research of over half a century since invention.Weigh catalytic reforming evolution and the level of catalyst made from platonic according to the concept of " theoretical yield ", under existing catalyst system, the actual yield of reforming reaction is more and more close to theoretical yield.Further raising catalytic reforming technical merit, explores the new reaction mechanism mechanism of reaction, and exploitation new catalytic material is significant for the preparation of the reforming catalyst of high activity, high arenes selectivity.
Molecular sieve, owing to having regular pore passage structure and special surface nature, becomes a class catalysis material of extensive concern.In recent years, scientific research personnel has carried out large quantifier elimination to molecular screen material for catalytic reforming reaction.Wherein Pt/KL molecular sieve catalyst and ZSM-5 Type Zeolites agent achieve commercial Application.But the weak point of this two classes catalyst be alkalescence the anti-carbon deposit of Pt/KL catalyst and sulfur resistance poor, to reaction environment require harshness; The Si-Al molecular sieve acidity of the routine such as ZSM-5 is excessively strong, and during for reforming reaction, strong cracking activity is appeared in performance, the aromatics yield of impact reaction and liquid yield.
CN1384176A discloses a kind of phosphorous and the modenite of alkali metals modified and/or the reforming catalyst of β zeolite, this catalyst is used for reforming reaction and is suitable for operating under the condition of high temperature, high-speed, higher aromatics yield and liquid yield can be obtained, and the benefit chlorine dose in course of reaction can be reduced.
CN1640993A discloses a kind of hydrocarbons reforming catalyst containing molecular sieve, and this catalyst comprises carrier and platinum, rhenium, chlorine isoreactivity component, and described carrier is by aperture SAPO-34 molecular sieve and γ-Al
2o
3composition.This catalyst is applicable to the catalytic reforming reaction of naphtha, has higher liquid yield and activity stability.
CN101172252A discloses a kind of reforming catalyst containing ZSM-5 molecular sieve, antimony oxide and inorganic refractory oxide.The antimony oxide contained in this catalyst and ZSM-5 molecular sieve surface contact, make the strong acidic site on molecular sieve surface occur poisoning and reduce the chain carrier of poor selectivity, and maintain selective higher duct reacting environment.Adopt phosphorus pentoxide to carry out modification to molecular sieve simultaneously, modulation is carried out to the inner surface of molecular sieve and pore size, the generation of constraint ortho-xylene and meta-xylene, thus improve the selective of paraxylene.
US4741820 discloses a kind of reforming catalyst, and the non-silicate molecular sieve containing mesopore in this catalyst, comprising silicoaluminophosphamolecular molecular sieve, as SAPO-11, SAPO-31, SAPO-40, SAPO-41.Content preferably 5 ~ 40 heavy % of catalyst Middle molecule sieve, carry out reforming reaction to raw materials such as naphthas and can obtain high-octane gasoline blending component.
US5972203 has the different structure molecular sieve binding agent based on phosphorus aluminum oxide by two kinds is sticked together and makes catalyst.Binding agent used is aluminium oxide, and catalyst preparing is combined with binding agent by the first molecular sieve, then puts it in the autoclave containing phosphoric acid and organic formwork agent and carry out crystallization.The first described molecular sieve is SAPO molecular sieve, and the second is AlPO molecular sieve.In catalyst, the content of binding agent is about 10 ~ 60 heavy %, is applicable to the reactions such as reformation, olefin oxidation, dewaxing, dehydrogenation, cracking.
The people such as Liu Quanjie (Industrial Catalysis, 2009,17:37 ~ 40) are studied the catalytic performance containing ZSM-5 zeolite reforming catalyst.Result shows, ZSM-5 catalyst has the aromatization activity higher than conventional reforming catalyst, and in product, the content of benzene and dimethylbenzene is higher, and the content of paraxylene is higher than its thermodynamical equilibrium content.When Zn mass fraction is 2.0% in catalyst, show better catalytic performance, the generation of increase to heavy aromatics of platinum content has obvious inhibitory action.
Summary of the invention
The object of this invention is to provide a kind of hydrocarbons reforming catalyst containing mesopore molecular sieve and preparation method thereof, this catalyst has higher isoparaffin productive rate and aromatics yield, and preparation method is simple, be easy to operation.
Hydrocarbons reforming catalyst containing mesopore molecular sieve provided by the invention, comprise molecular sieve catalyst that mixed uniformly mass ratio is 1 ~ 5:1 ~ 30 and carrier is the aluminium oxide catalyst of aluminium oxide, described molecular sieve catalyst comprises with the following active component of the butt molecular sieve content that is benchmark:
Platinum group metal 0.1 ~ 5.0 quality %,
III B race metal 0.1 ~ 4.0 quality %,
The mesopore molecular sieve of described molecular sieve to be bore dia be 2 ~ 50nm,
Described aluminium oxide catalyst comprises with the following active component of the butt aluminium oxide content that is benchmark:
Platinum group metal 0.1 ~ 4.0 quality %,
VII B race metal 0.1 ~ 5.0 quality %,
Halogen 0.5 ~ 10.0 quality %.
The present invention by platinum group metal and III B race Metal Supported in mesopore molecular sieve, then with aluminium oxide catalyst compound, the catalyst obtained, for the catalytic reforming reaction of hydro carbons and naphtha, while having higher aromatics yield, can significantly improve isoparaffin productive rate.
Detailed description of the invention
The aluminium oxide catalyst Homogeneous phase mixing that the mesoporous molecular sieve catalyst of supporting platinum-group metals and III B race metal and carrier are aluminium oxide by the present invention obtains bi-component composite catalyst, described molecular sieve catalyst coordinates with aluminium oxide catalyst, for hydrocarbon catalytic reforming reaction, while raising aromatics yield, the productive rate of isoparaffin can be improved.
The aluminium oxide catalyst that catalyst of the present invention is aluminium oxide by the mesoporous molecular sieve catalyst of supporting platinum-group metals and III B race metal and carrier mixes, described molecular sieve catalyst and the mass ratio of aluminium oxide catalyst preferably 1 ~ 3:1 ~ 25.
In described molecular sieve catalyst, preferably include with the following component of the butt molecular sieve content that is benchmark:
Platinum group metal 0.1 ~ 4.0 quality %,
III B race metal 0.1 ~ 3.0 quality %.
One or more in described mesopore molecular sieve preferred SBA-15, MCM-41 and MCM-48.
Described aluminium oxide catalyst preferably includes with the following active component of the butt aluminium oxide content that is benchmark:
Platinum group metal 0.1 ~ 1.0 quality %,
VII B race metal 0.1 ~ 2.0 quality %,
Halogen 0.6 ~ 3.0 quality %.
The preferred γ of the carrier-Al of described aluminium oxide catalyst
2o
3, η-Al
2o
3or the mixture of the two, more preferably γ-Al
2o
3.
The preferred platinum in platinum group metal described in catalyst of the present invention, the preferred gallium of III B race metal, the preferred rhenium of VII B race metal, the preferred chlorine of halogen.
Described aluminium oxide catalyst also comprises the 3rd metal constituent element of 0.1 ~ 4.0 quality %, the described preferred yttrium of the 3rd metal constituent element.
The preparation method of catalyst of the present invention, comprising:
(1) be made into maceration extract with the compound containing III B race metal, dipping mesopore molecular sieve, by solid drying, roasting, then is made into impregnation fluid with the compound of cation platinum group metal, by molecular sieve catalyst obtained after solid drying, roasting,
(2) with the impregnation fluid alumina support of the compound containing anion platinum group metal, VII B race metallic compound and halogen, by aluminium oxide catalyst obtained after the solid drying after dipping, roasting, reduction, presulfurization,
(3) by the mass ratio of 1 ~ 5:1 ~ 30, aluminium oxide catalyst obtained with (2) step for molecular sieve catalyst obtained for (1) step is mixed.
In said method, (1) step is for preparing molecular sieve catalyst, the described preferred gallium nitrate hydrate of compound containing III B race metal, gallium sulfate hydrate, gallium dichloride, borontrifluoride gallium, gallium trichloride, tribromide gallium, triiodide gallium or three isopropyl alcohol galliums.The preferred tri-chlorination platinum of compound of described cation platinum group metal, platinum tetrachloride, platinum nitrate, dichloro four ammonium conjunction platinum, dinitroso diammonia platinum, dinitro are the solution of diaminourea platinum or dichloride dicarbapentaborane platinum, and more preferably dichloro four ammonium closes the solution of platinum.
When said method floods introducing III B race's metal and platinum group metal in molecular sieve, Gu the liquid/volume ratio of dipping is 1.0 ~ 6.0:1, dipping temperature is 15 ~ 50 DEG C, preferably 20 ~ 35 DEG C, after dipping, baking temperature is 90 ~ 130 DEG C, sintering temperature preferably 400 ~ 600 DEG C, roasting time preferably 4 ~ 8 hours.
The inventive method (2) step prepares aluminium oxide catalyst, (2) compound of the anion platiniferous described in step is selected from chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, tetrachloro conjunction platinic acid, potassium tetrachloroplatinate, ammonium chloroplatinite or bromoplatinic acid, the described compound containing VII B race metal is selected from perrhenic acid, ammonium perrhenate or potassium perrhenate, and described halogen is chlorine.
(2) also the 3rd metallic compound can be contained in the maceration extract described in step.3rd metallic compound is six nitric hydrate yttriums, yttrium fluoride, yttrium chloride, nine hydrate yttrium oxalates, yttrium isopropoxide or eight hydrated sulfuric acid yttriums, more preferably six nitric hydrate yttriums preferably.The preferred chlorine of described halogen, the preferred hydrochloric acid of halogen-containing compound.
(2) the preferred γ of the alumina support-Al that step is used
2o
3, the preferred bar shaped of shape of carrier.
In said method, when (2) step introduces active component in alumina support, the dipping method of use can be saturated dipping or supersaturation dipping.During saturated dipping, Gu the liquid/volume ratio of maceration extract and carrier is less than 1.0, be preferably 0.4 ~ 0.8, maceration extract loaded body absorbs completely.During supersaturation dipping, Gu liquid/the volume ratio of maceration extract and carrier is greater than 1.0, preferably 1.05 ~ 2.0, after dipping, remaining maceration extract is removed by the method for filtration or vacuum evaporating solvent.
The present invention preferably adopts vacuum rotating infusion process to introduce active component in alumina support, concrete operation method is: by the compound of anion platinum group metal, be made into maceration extract containing the compound of VII B race metal and halogen-containing compound, oxide impregnation alumina supporter under the condition of 0.005 ~ 0.03MPa and rotation, Gu the liquid/volume ratio of maceration extract and carrier is 1.1 ~ 5.0, during dipping, limit heating edge rotates, heating-up temperature and dipping temperature preferably 20 ~ 90 DEG C, more preferably 30 ~ 70 DEG C.Dip time preferably 1 ~ 8 hour, more preferably 2 ~ 4 hours.After vacuum rotating dipping, in maceration extract, moisture evaporates substantially, and catalyst is drying regime, is taken out by catalyst dry, then roasting.Baking temperature is 80 ~ 130 DEG C, preferably 100 ~ 120 DEG C.
Roasting is carried out in air atmosphere, temperature preferably 300 ~ 700 DEG C, more preferably 400 ~ 600 DEG C.Gas/solid volume ratio during roasting preferably 300 ~ 1200:1, more preferably 500 ~ 1000:1.Roasting time preferably 3 ~ 12 hours, more preferably 4 ~ 8 hours.
Above-mentioned aluminium oxide catalyst needs could use through reduction and presulfurization after baking.Reduction is carried out in hydrogen atmosphere, reduction temperature preferably 350 ~ 550 DEG C, more preferably 400 ~ 500 DEG C.Gas/agent volume ratio preferably 300 ~ 1800:1, more preferably 500 ~ 1500:1.Preferably 3 ~ 12 hours recovery time, more preferably 4 ~ 8 hours.
The method for pre-sulphuration of above-mentioned aluminium oxide catalyst is: in the hydrogen of reducing catalyst, add sulfur-containing compound carry out presulfurization to catalyst, sulfur content in hydrogen is 0.01 ~ 1.0%, preferably 0.04 ~ 1.0% (relative to butt quality of alumina), pre-curing temperature preferably 350 ~ 470 DEG C, more preferably 370 ~ 450 DEG C.
(3) step of method for preparing catalyst of the present invention is mixing of two kinds of catalyst, and preferred mixed solid forming, shaping method can be compressing tablet, also can be extrusion.
Apply the method that catalyst of the present invention carries out hydrocarbon catalytic reformation to comprise hydrocarbon raw material at 0.1 ~ 9.0MPa, preferably 0.3 ~ 2.5MPa, 370 ~ 600 DEG C, preferably 450 ~ 550 DEG C, hydrogen/hydrocarbon volume ratio is 800 ~ 2000, preferably 1000 ~ 1500, feedstock quality air speed 0.1 ~ 18.0 hour
-1, preferably 0.5 ~ 6.0 hour
-1condition under with reforming catalyst haptoreaction of the present invention.
Described hydrocarbon feed is selected from the gasoline component that boiling range is the gasoline of 40 ~ 230 DEG C or its blending coking, process is produced, preferred straight-run naphtha or its mix coking in refining PETROLEUM PROCESSING, catalytic cracking, hydrocracked naphtha.
Further illustrate the present invention below by example, but the present invention is not limited to this.
Example 1
(1) SBA-15 molecular sieve is prepared
By 100g PEO-PPOX-PEO (template, referred to as P123, molecular weight 5800, Aldrich company of the U.S. produces) be dissolved in 2250mL deionized water, add hydrochloric acid that 1500g concentration is 4mol/L and stir, 40 DEG C slowly add 212.5g ethyl orthosilicate, stir 4 hours.Then moved in autoclave by gained mixture, 140 DEG C are aging 24 hours, filter, after washing in 120 DEG C of dryings 8 hours, 550 DEG C of roastings 4 hours, obtaining white powder, is SBA-15 molecular sieve.
(2) Ga/SBA-15 molecular sieve is prepared
Be the Ga (NO of 14.5mg/mL by Ga concentration
3)
3solution and appropriate amount of deionized water are mixed with maceration extract, wherein Ga content is made to be 1.0 quality % (relative to butt molecular sieve quality), Gu liquid/volume ratio is 5:1,25 DEG C with impregnation fluid SBA-15 molecular sieve 10 hours, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, the obtained Ga/SBA-15 molecular sieve containing 1.0 quality %Ga.
(3) Pt-Ga/SBA-15 molecular sieve is prepared
Be the Pt (NH of 9.8mg/mL by Pt concentration
3)
4cl
2solution and appropriate amount of deionized water are mixed with maceration extract, wherein Pt content is made to be 0.5 quality % (relative to butt molecular sieve quality), Gu liquid/volume ratio is 5:1,25 DEG C with the obtained Ga/SBA-15 molecular sieve of impregnation fluid (2) step 10 hours, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, 480 DEG C with hydrogen reducing 2 hours, the obtained Pt-Ga/SBA-15 molecular sieve catalyst containing 0.5 quality %Pt, 1.0 quality %Ga (relative to butt molecular sieve quality).
(4) aluminium oxide catalyst is prepared
Get 50 grams of bar shaped γ-Al
2o
3carrier (production of Sinopec catalyst Chang Ling branch company), maceration extract is made into chloroplatinic acid, perrhenic acid and hydrochloric acid, platiniferous 0.22 quality %, rhenium 0.46 quality % and chlorine 1.5 quality % (all calculating relative to butt aluminium oxide) in maceration extract, maceration extract and bar shaped γ-Al
2o
3gu the liquid/volume ratio of carrier is 1.3.First carrier is placed in reduced pressure atmosphere, makes pressure reach 0.02MPa, maintain 0.5 hour, stop decompression operation, introduce maceration extract, 30 DEG C of rotary dippings 3 hours, then at 60 DEG C, Rotary drying 1 hour under 0.02MPa condition.Solids is taken out, 120 DEG C of dryings 12 hours, in 500 DEG C of roastings 4 hours in dry air, then in 480 DEG C with H
2reduce 4 hours, the hydrogen sulfide adding sulfur content 0.09 quality % (calculating relative to butt aluminium oxide) in 425 DEG C of hydrogen atmospheres carries out presulfurization, the aluminium oxide catalyst of the sulphur (all calculating relative to butt aluminium oxide) of the obtained platinum containing 0.22 quality %, the rhenium of 0.46 quality %, the chlorine of 1.5 quality % and 0.09 quality %.
(5) catalyst of the present invention is prepared
Aluminium oxide catalyst prepared by the molecular sieve catalyst (3) step prepared by the mass ratio of 1:9 and (4) step mixes, and compression molding, grinds to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-1.
Example 2
(1) MCM-41 molecular sieve is prepared
Get 9.9g softex kw, add 205.1mL deionized water, 60 DEG C are stirred 0.5 hour.Drip the ammoniacal liquor that 140.7mL concentration is 25 quality %, continue stirring 0.5 hour, add 50.4mL ethyl orthosilicate and 205.1mL deionized water, stir 6 hours.Moved in autoclave by gained mixture, 110 DEG C aging 4 days, filters, after washing, 120 DEG C of dryings 8 hours, and 550 DEG C of roastings 4 hours, obtaining white powder, is MCM-41 molecular sieve.
(2) MCM-41 molecular sieve is got, by the method Ga (NO of example 1 (2) step
3)
3solution impregnation load gallium, drying, roasting, the obtained MCM-41 molecular sieve containing 1.0 quality %Ga (relative to butt molecular sieve quality).
(3) the MCM-41 molecular sieve containing 1.0 quality %Ga that (2) step obtains is got, by the method Pt (NH of example 1 (3) step
3)
4cl
2solution impregnation Supported Pt Nanoparticles, drying, roasting, reduction, the obtained Pt-Ga/MCM-41 molecular sieve catalyst containing 0.5 quality %Pt, 1.0 quality %Ga (relative to butt molecular sieve quality).
(4) aluminium oxide catalyst is prepared by the method for example 1 (4) step.
(5) aluminium oxide catalyst prepared by the molecular sieve catalyst (3) step prepared by the mass ratio of 1:9 and (4) step mixes, and compression molding, grinds to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-2.
Example 3
(1) MCM-48 molecular sieve is prepared
Get 9.6g softex kw (CTAB), add 200mL deionized water, add the ammoniacal liquor that 200mL ethanol and 24mL concentration are 25 quality % respectively, stir 0.5 hour, dropwise add 13.6g ethyl orthosilicate (TEOS), the mol ratio of the reactant added is made to remain on TEOS:CTAB: ethanol: ammoniacal liquor: water=l:0.4:54:12.5:174,25 DEG C are stirred 6 hours, after filtration, washing, 120 DEG C of dryings 8 hours, 550 DEG C of roastings 6 hours, obtaining white powder, is MCM-48 molecular sieve.
(2) MCM-48 molecular sieve is got, by the method Ga (NO of example 1 (2) step
3)
3solution impregnation load gallium, drying, roasting, the obtained Ga-MCM-48 molecular sieve containing 1.0 quality %Ga (relative to butt molecular sieve quality).
(3) the MCM-48 molecular sieve containing 1.0 quality %Ga that above-mentioned (2) step obtains is got, by the method Pt (NH of example 1 (3) step
3)
4cl
2solution impregnation Supported Pt Nanoparticles, drying, roasting, reduction, the obtained Pt-Ga/MCM-48 molecular sieve catalyst containing 0.5 quality %Pt (relative to butt molecular sieve quality), 1.0 quality %Ga.
(4) aluminium oxide catalyst is prepared by the method for example 1 (4) step.
(5) aluminium oxide catalyst prepared by the molecular sieve catalyst (3) step prepared by the mass ratio of 1:9 and (4) step mixes, and compression molding, grinds to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-3.
Example 4
Mix by the Pt-Ga/SBA-15 molecular sieve catalyst prepared by example 1 (3) one step process with by aluminium oxide catalyst prepared by (4) one step process by the mass ratio of 1:19, compression molding, grind to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-4.
Example 5
Mix by the Pt-Ga/SBA-15 molecular sieve catalyst prepared by example 1 (3) one step process with by aluminium oxide catalyst prepared by (4) one step process by the mass ratio of 3:7, compression molding, grind to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-5.
Example 6
Mix by the Pt-Ga/SBA-15 molecular sieve catalyst prepared by example 1 (3) one step process with by aluminium oxide catalyst prepared by (4) one step process by the mass ratio of 1:1, compression molding, grind to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-6.
Example 7
Mix by the Pt-Ga/SBA-15 molecular sieve catalyst prepared by example 1 (3) one step process with by aluminium oxide catalyst prepared by (4) one step process by the mass ratio of 7:3, compression molding, grind to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst P M-7.
Comparative example 1
The Pt-Ga/SBA-15 molecular sieve catalyst will prepared by example 1 (3) one step process, compression molding, grinds to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst DB-1.
Comparative example 2
The aluminium oxide catalyst will prepared by example 1 (4) one step process, grinds to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst DB-2.
Comparative example 3
By the Pt-Ga/SBA-15 molecular sieve catalyst prepared by example 1 (3) one step process and the aluminium oxide catalyst prepared by (4) one step process, compression molding respectively, grind to form the particle of 0.13 ~ 0.15 millimeter, load than segmentation with the quality of 1:9, molecular sieve catalyst is on top, aluminium oxide catalyst, in bottom, obtains catalyst DB-3.
Comparative example 4
By the Pt-Ga/SBA-15 molecular sieve catalyst prepared by example 1 (3) step and the aluminium oxide catalyst prepared by (4) one step process, compression molding respectively, grind to form the particle of 0.13 ~ 0.15 millimeter, load than segmentation with the quality of 1:9, aluminium oxide catalyst is on top, molecular sieve catalyst, in bottom, obtains catalyst DB-4.
Comparative example 5
(1) SBA-15 molecular sieve is prepared by example 1 (1) step.
(2) Zn/SBA-15 molecular sieve catalyst is prepared
Be the Zn (NO of 21.2mg/mL by Zn concentration
3)
2solution and appropriate amount of deionized water are mixed with maceration extract, wherein Zn content is made to be 1.0 quality % (relative to butt molecular sieve quality), Gu liquid/volume ratio is 5:1,25 DEG C with impregnation fluid SBA-15 molecular sieve 10 hours, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, obtained Zn content is the Zn/SBA-15 molecular sieve of 1.0 quality %.
(3) Pt-Zn/SBA-15 molecular sieve catalyst is prepared
Be the Pt (NH of 9.8mg/mL by Pt concentration
3)
4cl
2solution and appropriate amount of deionized water are mixed with maceration extract, wherein Pt content is made to be 0.5 quality % (relative to butt molecular sieve quality), Gu liquid/volume ratio is 5:1,25 DEG C with the obtained Zn/SBA-15 molecular sieve of impregnation fluid (2) step 10 hours, 120 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, 480 DEG C with hydrogen reducing 2 hours, the obtained Pt-Zn/SBA-15 molecular sieve catalyst containing 0.5 quality %Pt, 1.0 quality %Zn (relative to butt molecular sieve quality).
(4) aluminium oxide catalyst is prepared by example 1 (4) step, wherein platiniferous 0.22 quality %, rhenium 0.46 quality %, chlorine 1.5 quality % and sulphur 0.90 quality % (all calculating relative to butt aluminium oxide).
(5) aluminium oxide catalyst prepared by the molecular sieve catalyst (3) step prepared by the mass ratio of 1:9 and (4) step mixes, and compression molding, grinds to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst DB-5.
Comparative example 6
Borosilicate beta-molecular sieve is prepared by the method for CN102029186A (CN200910177172.5) example 1 (1) step.
Get borosilicate beta-molecular sieve, by the method Pt (NH of example 1 (3) step
3)
4cl
2solution impregnation carries out platinum exchange, and then roasting, reduction, the obtained borosilicate beta-molecular sieve catalyst containing 1.0 quality %Pt (relative to butt molecular sieve quality).By the mass ratio of 1:1 by the borosilicate beta-molecular sieve catalyst containing 1.0 quality %Pt (relative to butt molecular sieve quality) with mix by aluminium oxide catalyst prepared by example 1 (4) step, compression molding, grind to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst DB-6.
Comparative example 7
The borosilicate beta-molecular sieve prepared by comparative example 6 method by the CsOH solution impregnation containing Cs1.0% (quality relative to butt molecular sieve) 24 hours, Gu make liquid/volume ratio be 4:1,120 DEG C of dryings, 12 hours, 300 DEG C roastings 2 hours, obtained Cs content is the Cs-borosilicate beta-molecular sieve catalyst of 1.0% (quality relative to butt molecular sieve).
Get Cs-borosilicate beta-molecular sieve, by the method Pt (NH of example 1 (3) step
3)
4cl
2solution impregnation carries out platinum exchange, and then roasting, reduction, the obtained Cs-borosilicate beta-molecular sieve catalyst containing 1.0 quality %Pt (relative to butt molecular sieve quality).By the mass ratio of 1:1 by the Cs-borosilicate beta-molecular sieve catalyst containing 1.0 quality %Pt (relative to butt molecular sieve quality) with mix by aluminium oxide catalyst prepared by example 1 (4) step, compression molding, grind to form the particle of 0.13 ~ 0.15 millimeter, obtained catalyst DB-7.
Example 8
The reactivity worth of catalyst of the present invention and comparative catalyst is evaluated.
In the reactor of micro anti-evaluation device, load 1mL catalyst, pass into normal heptane and react, control that reactor inlet temperature is 500 DEG C, reaction pressure is 1.0MPa, mass space velocity is 6.0 hours
-1, hydrogen/hydrocarbon volume ratio is 1200:1, reaction result is in table 1.
From table 1 data, catalyst of the present invention, than comparative catalyst DB-1, DB-2, DB-3, DB-4, DB-5, has higher aromatics yield and isoparaffin productive rate; Than comparative catalyst DB-6, DB-7, there is higher isoparaffin productive rate.
Example 9
High pressure micro anti-evaluation device loads 2mL catalyst, with refining naphtha for the reactivity worth of catalyst P M-1 of the present invention and comparative catalyst DB-1, DB-2 evaluated respectively by raw material.Naphtha character is in table 2, and reaction temperature is 500 DEG C, reaction pressure is 1.0MPa, and during feeding liquid, volume space velocity is 6.0 hours
-1, hydrogen/hydrocarbon volume ratio is 1200:1, reaction result is in table 3.
From table 3 data, than comparative catalyst, catalyst of the present invention has higher C
5 +liquid yield and aromatics yield.
Table 1
Table 2
Table 3
Claims (16)
1. the hydrocarbons reforming catalyst containing mesopore molecular sieve, comprise molecular sieve catalyst that mixed uniformly mass ratio is 1 ~ 5:1 ~ 30 and carrier is the aluminium oxide catalyst of aluminium oxide, described molecular sieve catalyst comprises with the following active component of the butt molecular sieve content that is benchmark:
Platinum group metal 0.1 ~ 5.0 quality %,
III B race metal 0.1 ~ 4.0 quality %,
The mesopore molecular sieve of described molecular sieve to be bore dia be 2 ~ 50nm,
Described aluminium oxide catalyst comprises with the following active component of the butt aluminium oxide content that is benchmark:
Platinum group metal 0.1 ~ 4.0 quality %,
VII B race metal 0.1 ~ 5.0 quality %,
Halogen 0.5 ~ 10.0 quality %.
2., according to catalyst according to claim 1, it is characterized in that described molecular sieve catalyst comprises with the following component of the butt molecular sieve content that is benchmark:
Platinum group metal 0.1 ~ 4.0 quality %,
III B race metal 0.1 ~ 3.0 quality %.
3., according to catalyst according to claim 1, it is characterized in that described aluminium oxide catalyst comprises with the following active component of the butt aluminium oxide content that is benchmark:
Platinum group metal 0.1 ~ 1.0 quality %
VII B race metal 0.1 ~ 2.0 quality %
Halogen 0.6 ~ 3.0 quality %.
4. according to any one catalyst described in claims 1 to 3, it is characterized in that described mesopore molecular sieve is selected from SBA-15, MCM-41 and MCM-48 one or more.
5., according to catalyst according to claim 1, it is characterized in that the mass ratio of described molecular sieve catalyst and aluminium oxide catalyst is 1 ~ 3:1 ~ 25.
6. according to catalyst according to claim 1, it is characterized in that described platinum group metal is platinum, III B race metal is gallium, and VII B race metal is rhenium, and halogen is chlorine.
7., according to catalyst according to claim 1, it is characterized in that described aluminium oxide catalyst also comprises the 3rd metal constituent element of 0.1 ~ 4.0 quality %.
8., according to catalyst according to claim 7, it is characterized in that the 3rd described metal constituent element is yttrium.
9. a preparation method for catalyst described in claim 1, comprising:
(1) be made into maceration extract with the compound containing III B race metal, dipping mesopore molecular sieve, by solid drying, roasting, then is made into impregnation fluid with the compound of cation platinum group metal, by molecular sieve catalyst obtained after solid drying, roasting,
(2) with the impregnation fluid alumina support of the compound containing anion platiniferous, VII B race metallic compound and halogen, by aluminium oxide catalyst obtained after the solid drying after dipping, roasting, reduction, presulfurization,
(3) by the mass ratio of 1 ~ 5:1 ~ 30, aluminium oxide catalyst obtained with (2) step for molecular sieve catalyst obtained for (1) step is mixed.
10. in accordance with the method for claim 9, it is characterized in that the compound of the cation platinum group metal described in (1) step is selected from tri-chlorination platinum, platinum tetrachloride, platinum nitrate, the conjunction of dichloro four ammonium platinum, dinitroso diammonia platinum, dinitro diaminourea platinum or dichloride dicarbapentaborane platinum; Compound containing III B race metal is selected from gallium nitrate hydrate, gallium sulfate hydrate, gallium dichloride, borontrifluoride gallium, gallium trichloride, tribromide gallium, triiodide gallium or three isopropyl alcohol galliums.
11. in accordance with the method for claim 9, it is characterized in that the compound of the anion platinum group metal described in (2) step is selected from chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, tetrachloro conjunction platinic acid, potassium tetrachloroplatinate, ammonium chloroplatinite or bromoplatinic acid, the described compound containing VII B race metal is selected from perrhenic acid, ammonium perrhenate or potassium perrhenate, and described halogen is chlorine.
12. in accordance with the method for claim 9, it is characterized in that the maceration extract described in (2) step contains the 3rd metallic compound.
13. in accordance with the method for claim 9, it is characterized in that the 3rd metallic compound is selected from six nitric hydrate yttriums, yttrium fluoride, yttrium chloride, nine hydrate yttrium oxalates, yttrium isopropoxide or eight hydrated sulfuric acid yttriums.
14. in accordance with the method for claim 9, it is characterized in that the aluminium oxide catalyst that molecular sieve catalyst obtained for (1) step and (2) step obtain mixes by the mass ratio of 1 ~ 3:1 ~ 25 by (3) step, shaping.
15. 1 kinds of catalystic reforming method for hydrocarbons, comprise by hydrocarbon raw material 0.1 ~ 9.0MPa, 370 ~ 600 DEG C, hydrogen/hydrocarbon volume ratio 800 ~ 2000, feedstock quality air speed 0.1 ~ 18.0 hour
-1condition under with reforming catalyst haptoreaction according to claim 1.
16. in accordance with the method for claim 15, it is characterized in that described hydro carbons to be boiling range be the gasoline of 40 ~ 230 DEG C or its blending coking, gasoline component that process is produced.
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| CN112570013A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Catalyst containing MCM type molecular sieve, preparation method and application thereof, and gasoline catalytic conversion method |
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| CN106513035A (en) * | 2016-11-16 | 2017-03-22 | 中国海洋石油总公司 | Preparation method for mesoporous-microporous composite hydroisomerization dewaxing catalyst |
| CN112570013A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Catalyst containing MCM type molecular sieve, preparation method and application thereof, and gasoline catalytic conversion method |
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