CN102029186B - Bicomponent naphtha reforming catalyst and preparation method thereof - Google Patents
Bicomponent naphtha reforming catalyst and preparation method thereof Download PDFInfo
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- CN102029186B CN102029186B CN 200910177172 CN200910177172A CN102029186B CN 102029186 B CN102029186 B CN 102029186B CN 200910177172 CN200910177172 CN 200910177172 CN 200910177172 A CN200910177172 A CN 200910177172A CN 102029186 B CN102029186 B CN 102029186B
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Abstract
The invention relates to a bicomponent naphtha reforming catalyst which comprises a molecular-sieve catalyst and an alumina catalyst, wherein the molecular-sieve catalyst is used for platinum exchange, the carrier of the alumina catalyst is alumina, the mass ratio of the molecular-sieve catalyst to the alumina catalyst is 1-9:9-1, the platinum content in the molecular-sieve catalyst on the calculating basis of a dry-basis molecular sieve is 0.1-2.0 percent by mass, the molecular sieve is a borosilicate molecular sieve or a low-aluminum borosilicate molecular sieve, and the alumina catalyst comprises the following active components with the content on the calculating basis of dry-basis alumina: 0.1-3.0 percent by mass of platinum-family noble metal, 0.1-5.0 percent by mass of VIIB-family metal and 0.5-10.0 percent by mass of halogen. The catalyst is applicable to naphtha catalytic reforming and has higher liquid yield and aromatics yield.
Description
Technical field
The present invention is a kind of catalyst for reforming naphtha and preparation method thereof, specifically, is a kind of bicomponent naphtha reforming catalyst that contains molecular sieve and preparation method thereof.
Background technology
Along with the increase to the aromatic hydrocarbons demand of the fast development of auto industry and petrochemical industry, more and more stricter environmental protection standard particularly, catalytic reforming is being brought into play more and more important effect as the important oil refining process of producing high-knock rating gasoline, light aromatics (benzene,toluene,xylene) and cheap price and excellent quality hydrogen in oil-refining chemical industry.The reforming catalyst overwhelming majority of commercial Application is as carrier take aluminium oxide at present, Pt is two (many) metallic catalysts of major components, the development of this class reforming catalyst is in a metastable period, and their common weakness is lower to the aromatization activity of low-carbon paraffin.
The eighties in 20th century, people begin to contain the research and development of the catalytic reforming catalyst of molecular sieve, wherein the most representative is Pt/KL basic zeolite catalyst, this catalyst is to alkane, especially n-hexane, the normal heptane that traditional reforming catalyst is difficult to aromatisation has excellent aromatization activity and selective, but extremely sensitive to the water in the environment and sulfur content, stability is not ideal enough.And for acid Si-Al molecular sieves such as ZSM-5, β, Y, USY, clinoptilolite, modenite, when being applied in the catalytic reforming, because the highly acid of himself often causes strong cracking reaction to occur, produce the C of a large amount of low values
1～C
4Gas.
Borosilicate zeolite is a kind of class sial hetero-atom molecular-sieve, i.e. a kind of molecular sieve of being replaced by the boron atom fully of aluminium on the Si-Al molecular sieve skeleton.The acidity of borosilicate zeolite is starkly lower than Si-Al molecular sieve, changes Si/B than acidity that can the regulatory molecule sieve, and the catalyzed conversion of alkane is shown special catalytic performance.(J.Chem.Soc., Chem.Commun., 1241-1242,1994) such as Van derWaal directly synthesize the borosilicate beta-molecular sieve without aluminium, and comparing hydrophobicity with the sial beta-molecular sieve obviously increases.The micropore borosilicate SSZ Series Molecules sieve of Chevron company development, such as SSZ-24, SSZ-25, SSZ-31, SSZ-33, SSZ-35, SSZ-37, SSZ-42 etc., be used for catalytic reforming reaction, FCC heavy petrol and LCO upgrading are produced high-knock rating gasoline, benzene,toluene,xylene, the process of ethylbenzene and naphthalene shows good catalytic performance.
USP5,114,565 disclose a kind of naphtha reforming method of carrying out with the macropore boron-containing molecular sieve, and this method uses hole dimension to be
Aluminium content carry out hydrocarbon feed less than the macropore borosilicate zeolite of 1000ppm and reform, described borosilicate zeolite cation-bit exchanges with platinum, also can further exchange again cobalt, zinc or caesium, molecular sieve after the exchange can be directly used in catalytic reforming reaction after reduction, also can be used further to catalytic reforming reaction after presulfurization.Catalyst after the presulfurization has higher arenes selectivity.
Summary of the invention
The purpose of this invention is to provide a kind of bicomponent naphtha reforming catalyst and preparation method thereof, this catalyst is take borosilicate zeolite or low aluminium borosilicate zeolite and aluminium oxide as carrier, the carried metal active component, can significantly improve liquid yield and the aromatics yield of catalyst, simple, the easy row of method for preparing catalyst.
Bicomponent naphtha reforming catalyst provided by the invention, comprise that mass ratio is that molecular sieve catalyst and the carrier of 1～9: 9～1 platinum exchange is the aluminium oxide catalyst of aluminium oxide, platinum content take the butt molecular sieve as the calculating benchmark in the described molecular sieve catalyst is as 0.1～2.0 quality %, described molecular sieve is borosilicate zeolite or low aluminium borosilicate zeolite, and described aluminium oxide catalyst comprises take the butt aluminium oxide as calculating the following active component of content of benchmark:
Platinum family noble metal 0.1～3.0 quality %
VIIB family metal 0.1～5.0 quality %
Halogen 0.5～10.0 quality %.
Bicomponent naphtha reforming catalyst provided by the invention comprises borosilicate zeolite or low aluminium borosilicate zeolite catalyst and aluminium oxide catalyst.The catalyst of this bi-component is used for the naphtha reforming reaction, has higher liquid yield, alkane aromatization activity and selectivity preferably.
The specific embodiment
The present invention is that the conventional catalyst of aluminium oxide evenly mixes with the molecular sieve catalyst that contains noble metal on the cation-bit and carrier, perhaps molecular sieve and aluminium oxide or aluminium hydrate powder are mixed and made into carrier, carry out roasting after the ion-exchange with the solution that contains precious metal ion, load platinum family noble metal, VIIB family metal and halogen make bicomponent catalyst again.Bicomponent catalyst provided by the invention has higher liquid yield and aromatics yield than single molecular sieve catalyst or aluminium oxide catalyst.
The mass ratio of molecular sieve catalyst of the present invention and aluminium oxide catalyst preferred 3～7: 7～3.
The Si/B atomic ratio of described borosilicate zeolite is 10～400, preferred 15～300.The Si/Al atomic ratio of low aluminium borosilicate zeolite greater than 100, preferred 100～500, the Si/B atomic ratio is 10～400, preferred 15～300.Described molecular sieve can be sodium type or Hydrogen.
Aluminium oxide catalyst of the present invention preferably includes take the butt aluminium oxide as calculating the following active component of content of benchmark:
Platinum family noble metal 0.1～1.0 quality %
VIIB family metal 0.1～2.0 quality %
Halogen 0.5～3.0 quality %.
Preferred η-the Al of the carrier of described aluminium oxide catalyst
2O
3, γ-Al
2O
3Or the mixture of the two.
The preferred platinum of platinum family noble metal of the present invention, the preferred borosilicate beta-molecular sieve of described borosilicate zeolite, borosilicate ZSM-5 molecular sieve, borosilicate β/ZSM-5 composite molecular screen, SSZ-33 molecular sieve or SSZ-42 molecular sieve, described low aluminium borosilicate zeolite be low aluminium borosilicate beta-molecular sieve preferably.
The content of platinum is take the butt molecular sieve as calculating benchmark, preferred 0.5～1.0 quality % of platinum content in the molecular sieve catalyst in the molecular sieve catalyst of the present invention.Also contain in the described molecular sieve catalyst and take the butt molecular sieve as I A family's metal or the II A family metal of 0.1～4.0 quality %, preferred 0.1～3.0 quality % as the content that calculates benchmark.The preferred caesium of described I A family's metal, the preferred barium of II A family metal.
In the bicomponent catalyst of the present invention, the preferred platinum of platinum family noble metal, the preferred rhenium of VIIB family metal, the preferred chlorine of halogen, the preferred gama-alumina of aluminium oxide, the gama-alumina that the aluminium hydroxide that is more preferably obtained by the aluminum alkoxide hydrolysis prepares.
The shape of molecular sieve catalyst of the present invention and aluminium oxide catalyst can be sphere, bar shaped, sheet, graininess or cloverleaf pattern, preferred stripe shape or sphere.
The preparation method of catalyst provided by the invention has three kinds, and first method comprises:
(1) with the solution that contains platinum ion borosilicate zeolite or low aluminium borosilicate zeolite are carried out ion-exchange, solid drying, roasting, reduction make the mealy molecular sieve catalyst after will exchanging,
(2) compound and the VIIB family metallic compound with platinum group noble metal in the anion is made into maceration extract, dipping sphere or powdery aluminum carrier, and solid drying, roasting make aluminium oxide catalyst after will flooding,
(3) by 1～9: the aluminium oxide catalyst that 9～1 mass ratio makes the molecular sieve catalyst that makes of (1) step and (2) step mixes, moulding.
The second preparation method of catalyst provided by the invention comprises:
(1) add extrusion aid kneading, extrusion at borosilicate zeolite or low aluminium borosilicate zeolite, then dry, roasting carry out ion-exchange with the solution that contains platinum ion, and solid drying, roasting, reduction obtain the bar shaped molecular sieve catalyst after will exchanging,
(2) compound and the VIIB family metallic compound with platinum group noble metal in the anion is made into maceration extract, dipping bar shaped alumina support, and solid drying, roasting make the bar shaped aluminium oxide catalyst after will flooding,
(3) by 1～9: the bar shaped molecular sieve catalyst that 9～1 mass ratio makes (1) step goes on foot the bar shaped aluminium oxide catalyst that makes with (2) and mixes.
The third preparation method of catalyst provided by the invention comprises:
(1) by 1～9: 9～1 mass ratio is with borosilicate zeolite or low aluminium borosilicate zeolite and aluminium oxide or aluminium-hydroxide powder mixes, moulding, drying, roasting make mixed carrier,
(2) carry out ion-exchange with the solid of the solution that contains platinum ion after to roasting, will exchange afterwards solid drying, roasting,
(3) compound and the VIIB family metallic compound with platinum group noble metal in the anion is made into maceration extract, the solid of gained behind dipping (2) one-step baking, solid drying, roasting, reduction after will flooding.
In above-mentioned first and second kind method, (1) step is the preparation molecular sieve catalyst, and described borosilicate zeolite or low aluminium borosilicate zeolite are sodium type or Hydrogen.If contain I A family's metal or II A family metal in the described molecular sieve catalyst, available following method preparation: described borosilicate zeolite of (1) step or low aluminium borosilicate zeolite are converted into Hydrogen, solution with I A family's metal or the metallic compound preparation of II A family carries out ion-exchange again, then dry, roasting makes the hydrogen type molecular sieve that contains I A family's metal or II A family metal, then carry out ion-exchange with the solution that contains platinum ion, solid drying, roasting, reduction after will exchanging.
For the third preparation method, (2) step is for carrying out the platinum ion exchange at the molecular sieve cation-bit, if introduce I A family's metal or II A family metal, available following method preparation: first described borosilicate zeolite or low aluminium borosilicate zeolite are converted into Hydrogen, solution with I A family's metal or the metallic compound preparation of II A family carries out ion-exchange, then dry, roasting is carried out ion-exchange with the solution that contains platinum ion again, solid drying, roasting after will exchanging.
In the said method, hydroxide or the nitrate of the preferred caesium of described I A family's metallic compound, the nitrate of the preferred barium of II A family's metallic compound.
In the described method, contain the solution of the preferred platinum ammonium of solution complex ion compound of platinum ion or the solution of tri-chlorination platinum, platinum tetrachloride or dichloride dicarbapentaborane platinum.Described platinum ammonium complex ion compound preferred dinitro diaminourea platinum or dichloro four ammoniums close platinum.
When in alumina support or mixed carrier, introducing platinum family noble metal and VIIB family metal, the compound of platiniferous in the compound preferred anionic of platinum group noble metal in the used anion of preparation maceration extract, the preferred chloroplatinic acid of the compound of platiniferous, ammonium chloroplatinate or bromoplatinic acid, more preferably chloroplatinic acid or ammonium chloroplatinate in the anion.The compound of the used preferred rhenium-containing of VIIB family metallic compound, the preferred perrhenic acid of the compound of rhenium-containing or ammonium perrhenate.
When in alumina support or mixed carrier, introducing active component, preferably adopt the method for total immersion to introduce, dipping can adopt saturated dipping or supersaturation dipping.Gu the liquid/volume ratio of maceration extract and carrier is 0.4～4.0 during dipping.Suitable dipping temperature is 15～40 ℃, preferred 20～30 ℃.Also should contain halogen acids, preferred hydrochloric acid in the maceration extract of preparation, to introduce halogen component and metal component is evenly distributed on whole carrier.Behind the solid drying behind the dipping, in air, carry out roasting, reduction, preferred 400～600 ℃ of sintering temperature.Suitable during roasting gas/the agent volume ratio is 500～1000: 1, preferred 4～8 hours of roasting time.
Catalyst reduction of the present invention is all carried out under hydrogen atmosphere, and suitable reduction temperature is 400～500 ℃, and gas/agent volume ratio is 500～1400: 1, and the recovery time is 4～8 hours.
Before using, the catalyst of above-mentioned supported V IIB family metal, preferred rhenium needs to carry out presulfurization.Presulfurization adds sulfur-containing compound in hydrogen carries out, and the sulfur content in the hydrogen is 0.01～1.0%, preferred 0.04～1.0% (with respect to catalyst quality).Preferred 370～450 ℃ of pre-curing temperature.
Bicomponent catalyst of the present invention is suitable for the catalytic reforming reaction of hydro carbons, the reforming reaction condition is: pressure 0.1～10.0MPa, preferred 0.3～2.5MPa, 370～600 ℃ of temperature, preferred 450～550 ℃, hydrogen/hydrocarbon mol ratio is 1～20, preferred 2～10, feed volume air speed 0.1～20.0 hour
-1, preferred 0.5～5.0 hour
-1Described reformer feed is the full distillation gasoline of 40～230 ℃ of boiling ranges, or the gasoline component of the explained hereafter such as the coking in its blending PETROLEUM PROCESSING, cracking.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
(1) preparation borosilicate beta-molecular sieve.
Be that the tetraethyl oxyammonia solution of 25 quality % mixes with 1.0g borax, 1.1g NaOH and 104.7g concentration, (Cabot company produces to add the 20g superfine SiO 2 again, trade mark CAB-O-SILM-5), the rear immigration reactor that stirs, 140 ℃ of crystallization 15 days.Be cooled to rapidly 40 ℃ after crystallization finishes, product is after the centrifugation washing, the gained solid gets the former powder of borosilicate beta-molecular sieve in 90 ℃ of dryings 10 hours, and it is 0.5Na without hydrochemical compositions (take oxide mol ratio)
2OB
2O
322SiO
2
(2) preparation molecular sieve catalyst.
Be the Pt (NH of 10mg/mL with Pt concentration
3)
4Cl
2Be made into maceration extract with appropriate amount of deionized water, make the Pt (with respect to butt molecular sieve quality) that contains 1.0 quality % in the maceration extract, Gu liquid/volume ratio is 4: 1, dipping borosilicate beta-molecular sieve 24 hours, 120 ℃ of dryings 12 hours, 350 ℃ of roastings 2 hours, 480 ℃ with hydrogen reducing 2 hours, makes the borosilicate beta-molecular sieve catalyst that contains 1.0 quality %Pt (with respect to butt molecular sieve quality).
(3) preparation aluminium oxide catalyst.
Chloroplatinic acid, perrhenic acid and hydrochloric acid are made into maceration extract, make and contain 0.22%Pt, 0.46%Re, the 1.3%Cl quality of butt aluminium oxide (all with respect to) in the maceration extract, Gu liquid/volume ratio is 2: 1, flooded spherical gamma-aluminium oxide carrier (production of Chang Ling catalyst plant) 24 hours, filter, 120 ℃ of dryings 12 hours, 500 ℃ of roastings are 4 hours in the dry air, use H for 480 ℃
2Reduced 4 hours, and added hydrogen sulfide in 425 ℃ of hydrogen streams and carry out presulfurization, make aluminium oxide catalyst, contain the Cl of Re, 1.3 quality % of Pt, 0.46 quality % of 0.22 quality % and the S of 0.16 quality the % quality of butt aluminium oxide (all with respect to).
(4) preparation catalyst of the present invention.
By 1: 1 mass ratio that the catalyst mix of (2) step and the preparation of (3) step is even, be ground to below 150 microns, compression molding makes reforming catalyst ZH-1 of the present invention.
Example 2
(1) preparation borosilicate ZSM-5 molecular sieve.
Be that tetraethyl oxyammonia solution and the 224ml deionized water of 10 quality % mixes with 3.2g borax, 2.0gNaOH, 61g concentration, stir the lower 50g of adding superfine SiO 2, strong agitation is even, 60 ℃ were worn out 4 hours, move into reactor, 150 ℃ of crystallization were cooled to rapidly 40 ℃ in 5 days afterwards, product through centrifugation, wash to the pH value be 8～9, the gained solid was in 120 ℃ of dryings 10 hours, the former powder of borosilicate ZSM-5 molecular sieve, it is 0.4Na without hydrochemical compositions (take oxide mol ratio)
2OB
2O
353SiO
2
(2) by the method in example 1 (2) step the former powder of borosilicate ZSM-5 molecular sieve is carried out the platinum exchange, and then roasting, reduction, make the borosilicate ZSM-5 molecular sieve catalyst that contains 1.0 quality %Pt (with respect to the butt molecular sieve).
(3) method by 1 (3) step of example prepares aluminium oxide catalyst.
(4) the borosilicate ZSM-5 molecular sieve catalyst that (2) step is made by 1: 1 mass ratio and the aluminium oxide catalyst of (3) step preparation mix, and are ground to below 150 microns, and compression molding gets reforming catalyst ZH-2.
Example 3
(1) preparation β/ZSM-5 compound borosilicate molecular sieve.
With the 0.64g borax, 0.4gNaOH, 4.88g being tetraethyl oxyammonia solution and the 52ml deionized water of 25 quality %, concentration mixes, stir the lower 7g of adding and press the borosilicate beta-molecular sieve of example 1 (1) step preparation as crystal seed, add the 10g solid silicone after being stirred to evenly, strong agitation is even, 25 ℃ were worn out 2 hours, then move into reactor, 140 ℃ of crystallization were cooled to rapidly 40 ℃ in 5 days afterwards, product is through centrifugation, wash to the pH value be 8～9, the gained solid was in 100 ℃ of dryings 10 hours, XRD analysis shows that dried product exhibited is that crystalline phase is β/ZSM-5 compound borosilicate molecular sieve, and it is 0.4Na without hydrochemical compositions (take oxide mol ratio)
2OB
2O
339SiO
2, wherein the borosilicate beta-molecular sieve accounts for 29 quality %, and the borosilicate ZSM-5 molecular sieve accounts for 71 quality %.
(2) by the method in example 1 (2) step the former powder of β/ZSM-5 compound borosilicate molecular sieve is carried out the platinum exchange, and then roasting, reduction, make the β that contains 1.0 quality %Pt (with respect to the butt molecular sieve)/ZSM-5 compound borosilicate molecular sieve catalyst.
(3) method by 1 (3) step of example prepares aluminium oxide catalyst.
The aluminium oxide catalyst of the β that (4) by 1: 1 mass ratio (2) step is made/ZSM-5 compound borosilicate molecular sieve catalyst and the preparation of (3) step mixes, and is ground to below 150 microns, and compression molding gets reforming catalyst ZH-3.
Example 4
(1) the low aluminium borosilicate beta-molecular sieve of preparation.
Be that the tetraethyl oxyammonia of 25 quality % is stirred to entirely molten with 0.6g sodium aluminate, 0.5g NaOH and 70.2g concentration, stir the lower 10g of adding superfine SiO 2, mix rear immigration reactor, 140 ℃ of crystallization 3 days, be cooled to rapidly 40 ℃ after crystallization finishes, product is after the centrifugation washing, and the gained solid was in 90 ℃ of dryings 10 hours, the former powder of sial beta-molecular sieve, it is 0.8Na without hydrochemical compositions (take oxide mol ratio)
2O54SiO
2Al
2O
3
Be that the tetraethyl oxyammonia solution of 25 quality % mixes with 1.0g borax, 1.1g NaOH and 104.7g concentration, stir the above-mentioned sial beta-molecular sieve of the lower 0.6g of adding as crystal seed, add again the 20g superfine SiO 2, rear immigration reactor stirs, 140 ℃ of crystallization 5 days, crystallization is cooled to rapidly 40 ℃ after finishing, product is after the centrifugation washing, the gained solid was in 90 ℃ of dryings 10 hours, must hang down the former powder of aluminium borosilicate beta-molecular sieve, it is 0.5Na without hydrochemical compositions (take oxide mol ratio)
2OB
2O
321SiO
20.06Al
2O
3
(2) by the method in example 1 (2) step the low former powder of aluminium borosilicate beta-molecular sieve is carried out the platinum exchange, and then roasting, reduction, make the low aluminium borosilicate beta-molecular sieve catalyst that contains 1.0 quality %Pt (with respect to the butt molecular sieve).
(3) method by 1 (3) step of example prepares aluminium oxide catalyst.
(4) by 1: 1 mass ratio the low aluminium borosilicate beta-molecular sieve catalyst of (2) step preparation and the aluminium oxide catalyst of (3) step preparation are mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-4.
Example 5
(1) preparation borosilicate SSZ-33 molecular sieve.
With 1.3g borax, 0.8g NaOH, 2.7g1,7,7-trimethyl-spiral shell [4.5]-5-ammonium hydroxide and 110mL deionized water mix, and add the 20g superfine SiO 2 again, and rear immigration reactor stirs, 160 ℃ of crystallization 18 days, be cooled to rapidly 40 ℃ after crystallization finishes, product is after the centrifugation washing, and the gained solid was in 90 ℃ of dryings 10 hours, borosilicate SSZ-33 molecular screen primary powder, it is 0.6Na without hydrochemical compositions (take oxide mol ratio)
2OB
2O
342SiO
2
(2) by the method in example 1 (2) step borosilicate SSZ-33 molecular screen primary powder is carried out the platinum exchange, and then roasting, reduction, make the SSZ-33 molecular sieve catalyst that contains 1.0 quality %Pt (with respect to the butt molecular sieve).
(3) method by 1 (3) step of example prepares aluminium oxide catalyst.
(4) the SSZ-33 molecular sieve catalyst that (2) step is made by 1: 1 mass ratio and the aluminium oxide catalyst of (3) step preparation mix, and are ground to below 150 microns, and compression molding makes reforming catalyst ZH-5.
Example 6
The aluminium oxide catalyst that will go on foot preparation by molecular sieve catalyst and (3) of example 1 (2) step preparation mixes by 3: 7 mass ratio, is ground to below 150 microns, and compression molding makes reforming catalyst ZH-6.
Example 7
The aluminium oxide catalyst that will go on foot preparation by molecular sieve catalyst and (3) of example 1 (2) step preparation mixes by 7: 3 mass ratio, is ground to below 150 microns, and compression molding makes reforming catalyst ZH-7.
Example 8
(1) preparation bar shaped borosilicate beta-molecular sieve catalyst.
Get the borosilicate beta-molecular sieve of example 1 (1) step preparation, adding concentration is the solution of the carboxymethyl cellulose of 5.0 quality %, and the solution quality of adding is 20% of borosilicate beta-molecular sieve quality, kneading, extruded moulding, 120 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours.With the Pt (NH that contains Pt 1.0 quality % (with respect to the butt molecular sieve)
3)
4Cl
2Solution impregnation bar shaped borosilicate beta-molecular sieve 24 hours is Gu liquid/volume ratio is 4: 1 during dipping.12 hours, 350 ℃ roastings of 120 ℃ of dryings 2 hours, reductase 12 hour in 480 ℃ of hydrogen makes the bar shaped borosilicate beta-molecular sieve catalyst that contains 1.0 quality %Pt (with respect to the butt molecular sieve).
(2) preparation bar shaped aluminium oxide catalyst.
Chloroplatinic acid, perrhenic acid and hydrochloric acid are made into maceration extract, make and wherein contain 0.22%Pt, 0.46%Re, the 1.3%Cl quality of butt aluminium oxide (all with respect to), with above-mentioned maceration extract dipping bar shaped gamma-aluminium oxide carrier (production of Chang Ling catalyst plant) 24 hours, Gu liquid/volume ratio is 2: 1 during dipping.Filter, will flood afterwards solid in 120 ℃ of dryings 12 hours, roasting is 4 hours in 500 ℃ of dry air, then uses H in 480 ℃
2Reduced 4 hours, the hydrogen sulfide that adds 0.10% (with respect to catalyst quality) in 425 ℃ of hydrogen streams carries out presulfurization, makes the bar shaped aluminium oxide catalyst that contains 0.22 quality %Pt, 0.46 quality %Re, 1.3 quality %Cl and 0.16 quality %S.
(3) by 1: 1 mass ratio the bar shaped borosilicate beta-molecular sieve catalyst of (1) step preparation and the bar shaped aluminium oxide catalyst of (2) step preparation are mixed, get reforming catalyst ZH-8.
Example 9
(1) preparation bar shaped carrier.
The borosilicate beta-molecular sieve and the gama-alumina powder that 1 (1) step of example are made by 1: 1 mass ratio mix, adding the sesbania powder that accounts for powder gross mass 1.0% mixes, adding the concentration that accounts for powder quality 5.0% again is nitric acid and the acetic acid solution kneading of 35 quality %, extruded moulding, 120 ℃ of dryings 12 hours, 550 ℃ of roastings made mixed carrier in 4 hours.
(2) carry out the platinum ion exchange
The bar shaped carrier that (1) step is made by the method in example 1 (2) step carries out the platinum exchange, and then roasting, reduction, makes the mixed carrier that contains 1.0 quality %Pt (with respect to the butt molecular sieve).
(3) Kaolinite Preparation of Catalyst
Chloroplatinic acid, perrhenic acid and hydrochloric acid are made into maceration extract, make and wherein contain 0.22%Pt, 0.46%Re, 1.3%Cl (with respect to the quality of butt aluminium oxide), the carrier that makes with maceration extract dipping (2) step 24 hours, Gu liquid/volume ratio is 2: 1, filter, 120 ℃ of dryings 12 hours, roasting is 4 hours in 500 ℃ of dry air, uses H in 480 ℃ again
2Reduced 4 hours, and added hydrogen sulfide in 425 ℃ of hydrogen streams and carry out presulfurization, make catalyst Z H-9.The Pt content of deduction molecular sieve cation-bit contains 0.22 quality %Pt, 0.46 quality %Re, 1.3 quality %Cl and 0.16 quality %S (with respect to the quality of butt aluminium oxide) among the ZH-9.
Example 10
(1) preparation Hydrogen borosilicate beta-molecular sieve catalyst.
Get the borosilicate beta-molecular sieve that 1 (1) step of example makes, adding concentration is the ammonium chloride solution of 10 quality %, is 4: 1 Gu make liquid/volume ratio, and 90 ℃ are stirred exchange 4 hours, are cooled to 40 ℃, centrifugation, washing.Repeat above-mentioned ion-exchange step once, the gained solid obtains Hydrogen borosilicate beta-molecular sieve in 12 hours, 550 ℃ roastings of 120 ℃ of dryings 4 hours.
With the Pt (NH that contains Pt 1.0% (with respect to the quality of butt molecular sieve)
3)
4Cl
2Solution impregnation Hydrogen borosilicate beta-molecular sieve 24 hours, Gu made liquid/volume ratio 4: 1,12 hours, 350 ℃ roastings of 120 ℃ of dryings 2 hours, 480 ℃ with hydrogen reducing 2 hours, makes the Hydrogen borosilicate beta-molecular sieve catalyst that contains 1.0%Pt (with respect to the quality of butt molecular sieve).
(2) method by 1 (3) step of example prepares aluminium oxide catalyst.
(3) by 1: 1 mass ratio the Hydrogen borosilicate beta-molecular sieve catalyst of (1) step preparation and the aluminium oxide catalyst of (2) step preparation are mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-10.
Example 11
Press the method Kaolinite Preparation of Catalyst of example 1, that different is the Pt (NH that uses in (2) step
3)
4Cl
2Solution in to contain Pt amount be 0.6% (with respect to the quality of butt molecular sieve), the borosilicate beta-molecular sieve catalyst that contains Pt 0.6 quality % that makes is mixed with the mass ratio of aluminium oxide catalyst by 1: 1, grinding, compressing tablet make reforming catalyst ZH-11.
Example 12
(1) preparation contains the Hydrogen borosilicate beta-molecular sieve catalyst of Cs.
Method by 10 (1) steps of example prepares Hydrogen borosilicate beta-molecular sieve, with the CsOH solution impregnation Hydrogen borosilicate beta-molecular sieve that contains Cs1.0% (with respect to the quality of butt molecular sieve) 24 hours, Gu making liquid/volume ratio is 4: 1,12 hours, 300 ℃ roastings of 120 ℃ of dryings 2 hours, making Cs content is the Hydrogen borosilicate beta-molecular sieve of 1.0% (with respect to the quality of butt molecular sieve).With the Pt (NH that contains Pt 1.0% (with respect to the quality of butt molecular sieve)
3)
4Cl
2Solution impregnation contains Cs Hydrogen borosilicate beta-molecular sieve 24 hours, Gu maceration extract/volume ratio is 4: 1, reductase 12 hour in 2 hours, 480 ℃ hydrogen of 12 hours, 350 ℃ roastings of 120 ℃ of dryings makes the Hydrogen borosilicate beta-molecular sieve catalyst that contains 1.0 quality %Pt, 1.0 quality %Cs.
(2) method by 1 (3) step of example prepares aluminium oxide catalyst.
(3) by 1: 1 mass ratio the CsPt Hydrogen beta-molecular sieve catalyst of (1) step preparation and the aluminium oxide catalyst of (2) step preparation are mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-12.
Example 13
Press the method Kaolinite Preparation of Catalyst of example 12, different is to contain Cs1.5 quality % (with respect to the butt molecular sieve) in the CsOH solution that uses in (1) step, through roasting, with after the platinum exchange, must contain the Hydrogen borosilicate beta-molecular sieve catalyst of 1.0 quality %Pt, 1.5 quality %Cs again.This CsPt Hydrogen beta-molecular sieve catalyst and the aluminium oxide catalyst mass ratio by 1: 1 is mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-13.
Example 14
Press the method Kaolinite Preparation of Catalyst of example 12, different is to contain Cs2.0 quality % (with respect to the butt molecular sieve) in the CsOH solution that uses in (1) step, through roasting, with after the platinum exchange, must contain the Hydrogen borosilicate beta-molecular sieve catalyst of 1.0 quality %Pt, 2.0 quality %Cs again.This CsPt Hydrogen beta-molecular sieve catalyst and the aluminium oxide catalyst mass ratio by 1: 1 is mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-14.
Example 15
Press the method Kaolinite Preparation of Catalyst of example 12, different is to contain Cs2.5 quality % (with respect to the butt molecular sieve) in the CsOH solution that uses in (1) step, through roasting, with after the platinum exchange, must contain the Hydrogen borosilicate beta-molecular sieve catalyst of 1.0 quality %Pt, 2.5 quality %Cs again.This CsPt Hydrogen beta-molecular sieve catalyst and the aluminium oxide catalyst mass ratio by 1: 1 is mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-15.
Example 16
To mix with the mass ratio of the aluminium oxide catalyst for preparing by example 1 (3) one step process by 3: 7 by the Hydrogen borosilicate beta-molecular sieve catalyst that contains 1.0 quality %Pt, 1.0 quality %Cs of example 12 (1) step preparation, be ground to below 150 microns, compression molding makes reforming catalyst ZH-16.
Example 17
The Hydrogen borosilicate beta-molecular sieve catalyst that contains 1.0 quality %Pt, 2.5 quality %Cs that example 15 (1) step is made and the method by 1 (3) step of example prepare aluminium oxide catalyst and mix by 7: 3 mass ratio, be ground to below 150 microns, compression molding makes reforming catalyst ZH-17.
Example 18
Press the method Kaolinite Preparation of Catalyst of example 12, different is (1) step to use the Ba (NO that contains Ba 2.0 quality % (with respect to the butt molecular sieve)
3)
2Solution impregnation Hydrogen borosilicate beta-molecular sieve through roasting, with after the platinum exchange, must contain the Hydrogen borosilicate beta-molecular sieve catalyst of 1.0 quality %Pt, 2.0 quality %Ba again.This BaPt Hydrogen beta-molecular sieve catalyst and the aluminium oxide catalyst mass ratio by 1: 1 is mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-18.
Example 19
Press the method Kaolinite Preparation of Catalyst of example 1, different is after the molecular sieve catalyst reduction finishes in (2) step, continuation adds hydrogen sulfide and carries out presulfurization in 425 ℃ of hydrogen streams, make the borosilicate beta-molecular sieve catalyst that contains 1.0%Pt, 0.12%S (with respect to the quality of butt molecular sieve), this borosilicate beta-molecular sieve catalyst and the aluminium oxide catalyst mass ratio by 1: 1 is mixed, be ground to below 150 microns, compression molding makes reforming catalyst ZH-19.
Comparative Examples 1
Take the borosilicate beta-molecular sieve of example 1 (1) step preparation as carrier, with Pt (NH
3)
4Cl
2Solution is maceration extract, Gu pressed 4: 1 amount of liquid/volume ratio dipping 24 hours, 12 hours, 350 ℃ roastings of 120 ℃ of dryings 2 hours, 480 ℃ of hydrogen reducings 2 hours make the borosilicate beta-molecular sieve catalyst DB-1 that contains 1.0%Pt (with respect to the quality of butt molecular sieve).
Comparative Examples 2
Method by Comparative Examples 1 prepares molecular sieve catalyst, different is that used molecular sieve is the borosilicate ZSM-5 molecular sieve by the preparation of example 2 (1) one step process, obtains containing the borosilicate ZSM-5 molecular sieve catalyst DB-2 of 1.0%Pt (with respect to the quality of butt molecular sieve).
Comparative Examples 3
Method by Comparative Examples 1 prepares molecular sieve catalyst, used molecular sieve that different is is for by the borosilicate β of example 3 (1) one step process preparation/ZSM-5 composite molecular screen, obtains containing the borosilicate β of 1.0%Pt (with respect to the quality of butt molecular sieve)/ZSM-5 composite molecular sieve catalyst DB-3.
Comparative Examples 4
Method by Comparative Examples 1 prepares molecular sieve catalyst, different is that used molecular sieve is the low aluminium beta-molecular sieve of borosilicate by the preparation of example 4 (1) one step process, obtains containing the low aluminium beta-molecular sieve catalyst DB-4 of borosilicate of 1.0%Pt (with respect to the quality of butt molecular sieve).
Comparative Examples 5
Method by Comparative Examples 1 prepares molecular sieve catalyst, different is that used molecular sieve is the SSZ-33 molecular sieve by the preparation of example 5 (1) one step process, obtains containing the SSZ-33 molecular sieve catalyst DB-5 of 1.0%Pt (with respect to the quality of butt molecular sieve).
Comparative Examples 6
Take spherical gama-alumina as carrier, prepare PtRe/Al according to example 1 (3) one step process
2O
3Catalyst DB-6.
Example 20
At high-pressure micro-device filling 1mL catalyst, estimate the reactivity worth of each catalyst take normal heptane as raw material, reaction temperature is that 500 ℃, pressure are 1.0MPa, volume space velocity is 6 hours during feeding liquid
-1, hydrogen/hydrocarbon volume ratio is 1200: 1, the results are shown in Table 1.
As shown in Table 1, compare with the comparative catalyst, the reforming catalyst of the inventive method preparation has higher liquid yield and aromatics yield.The evaluation result of ZH-12～ZH-16 catalyst shows, compares with ZH-10, and the introducing of alkalinous metal has facilitation to the liquid yield of catalyst and the raising of aromatics yield, and still along with the increase of alkalinous metal content, conversion ratio is reduction trend.The evaluation result of ZH-19 catalyst shows, molecular sieve catalyst is carried out presulfurization, and catalyst aromatics yield of the present invention is descended.
Example 21
At high-pressure micro-device filling 2mL catalyst, estimate respectively the reactivity worth of DB-1, DB-6 and ZH-1 catalyst take refining naphtha as raw material, naphtha character sees Table 2, and reaction temperature is that 500 ℃, pressure are 1.0MPa, and volume space velocity is 6 hours during feeding liquid
-1, hydrogen/hydrocarbon volume ratio is 1200: 1, the results are shown in Table 3.
As shown in Table 3, take refining naphtha during as raw material, have higher liquid yield and aromatics yield by the catalyst of the inventive method preparation.
Table 1
Table 2
Table 3
| The catalyst numbering | C 1～C 4Yield, quality % | C 5 +Liquid yield, quality % | Aromatics yield, quality % |
| DB-1 | 14.9 | 85.1 | 61.9 |
| DB-6 | 12.6 | 87.4 | 62.3 |
| ZH-1 | 11.8 | 88.2 | 64.3 |
Claims (17)
1. bicomponent naphtha reforming catalyst, comprise that mass ratio is that molecular sieve catalyst and the carrier of 1～9: 9～1 platinum exchange is the aluminium oxide catalyst of aluminium oxide, platinum content take the butt molecular sieve as the calculating benchmark in the described molecular sieve catalyst is as 0.1～2.0 quality %, described molecular sieve is borosilicate zeolite or low aluminium borosilicate zeolite, the Si/Al atomic ratio of described low aluminium borosilicate zeolite greater than 100, the Si/B atomic ratio is 10～400, described aluminium oxide catalyst comprises take the butt aluminium oxide as calculating the following active component of content of benchmark:
Platinum 0.1～3.0 quality %
Rhenium 0.1～5.0 quality %
Chlorine 0.5～10.0 quality %.
2. according to catalyst claimed in claim 1, the mass ratio that it is characterized in that described molecular sieve catalyst and aluminium oxide catalyst is 3～7: 7～3.
3. according to catalyst claimed in claim 1, the Si/B atomic ratio that it is characterized in that described borosilicate zeolite is 10～400.
4. according to catalyst claimed in claim 1, it is characterized in that described aluminium oxide catalyst comprises take the butt aluminium oxide as calculating the following active component of content of benchmark:
Platinum 0.1～1.0 quality %
Rhenium 0.1～2.0 quality %
Chlorine 0.5～3.0 quality %.
5. according to catalyst claimed in claim 1, it is characterized in that described borosilicate zeolite is selected from borosilicate beta-molecular sieve, borosilicate ZSM-5 molecular sieve, borosilicate β/ZSM-5 composite molecular screen, SSZ-33 molecular sieve or SSZ-42 molecular sieve, described low aluminium borosilicate zeolite is low aluminium borosilicate beta-molecular sieve.
6. according to catalyst claimed in claim 1, it is characterized in that also containing in the molecular sieve catalyst and take the butt molecular sieve as I A family's metal or the II A family metal of 0.1～4.0 quality % as the content that calculates benchmark.
7. according to catalyst claimed in claim 6, it is characterized in that described I A family metal is caesium, II A family metal is barium.
8. the preparation method of the described catalyst of claim 1 comprises:
(1) with the solution that contains platinum ion borosilicate zeolite or low aluminium borosilicate zeolite are carried out ion-exchange, solid drying, roasting, reduction make the mealy molecular sieve catalyst after will exchanging,
(2) compound and the rhenium compound with platiniferous in the anion is made into maceration extract, dipping sphere or powdery aluminum carrier, and solid drying, roasting make aluminium oxide catalyst after will flooding, and contain hydrochloric acid in the described maceration extract,
(3) by 1～9: the aluminium oxide catalyst that 9～1 mass ratio makes the molecular sieve catalyst that makes of (1) step and (2) step mixes, moulding.
9. the preparation method of the described catalyst of claim 1 comprises:
(1) add extrusion aid kneading, extrusion in borosilicate zeolite or low aluminium borosilicate zeolite, then dry, roasting carry out ion-exchange with the solution that contains platinum ion, and solid drying, roasting, reduction obtain the bar shaped molecular sieve catalyst after will exchanging,
(2) with containing platinum compounds in the anion and rhenium compound is made into maceration extract, dipping bar shaped alumina support will flood afterwards that solid drying, roasting make the bar shaped aluminium oxide catalyst, contain hydrochloric acid in the described maceration extract,
(3) by 1～9: the bar shaped molecular sieve catalyst that 9～1 mass ratio makes (1) step goes on foot the bar shaped aluminium oxide catalyst that makes with (2) and mixes.
10. the preparation method of the described catalyst of claim 1 comprises:
(1) by 1～9: 9～1 mass ratio is with borosilicate zeolite or low aluminium borosilicate zeolite and aluminium oxide or aluminium-hydroxide powder mixes, moulding, drying, roasting make mixed carrier,
(2) carry out ion-exchange with the solid of the solution that contains platinum ion after to roasting, will exchange afterwards solid drying, roasting,
(3) with containing platinum compounds in the anion and rhenium compound is made into maceration extract, the solid of gained behind dipping (2) one-step baking will flood afterwards solid drying, roasting, reduction, contain hydrochloric acid in the described maceration extract.
11. according to the described any method of claim 8～10, it is characterized in that described borosilicate zeolite of (1) step or low aluminium borosilicate zeolite are sodium type or Hydrogen.
12. according to claim 8 or 9 described methods, it is characterized in that described borosilicate zeolite of (1) step or low aluminium borosilicate zeolite are converted into Hydrogen, solution with I A family's metal or the metallic compound preparation of II A family carries out ion-exchange, then dry, roasting makes the hydrogen type molecular sieve that contains I A family's metal or II A family metal, then carry out ion-exchange with the solution that contains platinum ion, solid drying, roasting, reduction after will exchanging.
13. in accordance with the method for claim 10, it is characterized in that (2) step is converted into Hydrogen with described borosilicate zeolite or low aluminium borosilicate zeolite first, solution with I A family's metal or the metallic compound preparation of II A family carries out ion-exchange, then dry, roasting.
14. according to the described any method of claim 8～10, it is characterized in that containing in the described anion platinum compounds and be selected from chloroplatinic acid, ammonium chloroplatinate or bromoplatinic acid, described rhenium compound is selected from perrhenic acid or ammonium perrhenate.
15. according to the described any method of claim 8～10, it is characterized in that the described solution that contains platinum ion is selected from the solution of platinum ammonium complex ion compound or the solution of tri-chlorination platinum, platinum tetrachloride or dichloride dicarbapentaborane platinum.
16. in accordance with the method for claim 12, it is characterized in that described I A family metallic compound is selected from hydroxide or the nitrate of caesium, II A family metallic compound is selected from the nitrate of barium.
17. in accordance with the method for claim 13, it is characterized in that described I A family metallic compound is selected from hydroxide or the nitrate of caesium, II A family metallic compound is selected from the nitrate of barium.
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| CN103418412B (en) * | 2012-05-15 | 2015-07-01 | 中国石油化工股份有限公司 | Catalytic reforming catalyst and preparation method thereof |
| CN104174427B (en) * | 2013-05-24 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of bi-component reforming catalyst and preparation method and application |
| CN107916131B (en) * | 2016-10-11 | 2021-04-06 | 中国石油化工股份有限公司 | Method for producing isomerized gasoline and aromatic hydrocarbon from alkane |
| CN108238838B (en) * | 2016-12-26 | 2021-02-05 | 中国石油化工股份有限公司 | Method for producing benzene with high yield by using C6 alkane |
| CN110358577B (en) * | 2018-04-10 | 2021-11-16 | 中国石油化工股份有限公司 | Method for converting naphtha into high-octane gasoline and aromatic hydrocarbon |
| US11103856B2 (en) * | 2018-05-07 | 2021-08-31 | Chevron Phillips Chemical Company, Lp | Aromatization catalyst and methods of making and using same |
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