CN109201093B - Multi-metal continuous reforming catalyst and preparation and application thereof - Google Patents

Multi-metal continuous reforming catalyst and preparation and application thereof Download PDF

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CN109201093B
CN109201093B CN201710540736.1A CN201710540736A CN109201093B CN 109201093 B CN109201093 B CN 109201093B CN 201710540736 A CN201710540736 A CN 201710540736A CN 109201093 B CN109201093 B CN 109201093B
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mass
water
tin
alumina
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CN109201093A (en
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王春明
马爱增
潘锦程
任坚强
周怡然
刘昌呈
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/24—Chlorinating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

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Abstract

A multi-metal continuous reforming catalyst comprises an alumina carrier, and 0.1-2.0 mass% of platinum, 0.1-2.0 mass% of tin, 0.01-0.5 mass% of calcium, 0.05-0.7 mass% of phosphorus and 0.5-5.0 mass% of chlorine calculated by element content. The catalyst is suitable for naphtha reforming reaction, is particularly suitable for the reforming operation process for producing gasoline under medium severity, has higher gasoline yield and higher stability, reduces the content of aromatic hydrocarbon in a gasoline product and increases the content of isomeric hydrocarbon, and is more suitable for being used as a blending component of clean gasoline.

Description

Multi-metal continuous reforming catalyst and preparation and application thereof
Technical Field
The invention relates to a continuous reforming catalyst and preparation and application thereof, in particular to a multi-metal reforming catalyst containing platinum and tin and preparation and application thereof.
Background
The catalytic reforming process is an important petroleum processing process, in the process, naphtha components are converted into products with higher aromatic hydrocarbon content under the action of a catalyst, and high-octane gasoline and aromatic hydrocarbon can be produced, and hydrogen is produced as a byproduct. With the deterioration of crude oil quality and the upgrading of environmental protection indexes of finished oil products, the demand of refineries for cheap hydrogen is continuously increased, so that catalytic reforming becomes a necessary process for modern oil refining enterprises. The reforming apparatus can be classified into an aromatic type apparatus for producing aromatic hydrocarbons such as benzene, toluene and xylene as a target product and a gasoline type apparatus for producing a high-octane gasoline blending component as a target product, according to the target product classification of the reforming process. For gasoline type reformers, obtaining higher yields of gasoline products is a sought after goal. With the upgrading of national gasoline quality, the benzene and aromatic hydrocarbon content in the gasoline is required to be limited. Since aromatic hydrocarbons are important components for increasing the octane number of gasoline, in order to maintain a high octane number of gasoline products, the content of aromatic hydrocarbons in gasoline is reduced while the content of isomeric hydrocarbons with a high octane number is increased.
Typical metrics for catalyst performance include activity, selectivity, and stability. For a reforming catalyst, activity refers to the ability of the catalyst to convert reactants to the desired product under the given reaction conditions. Generally, activity is expressed as the magnitude of the octane number of the product obtained at a given feed and reaction conditions, or as the magnitude of the reaction temperature at a given liquid product octane number; selectivity refers to the yield of aromatics or the yield of C5+ gasoline product at a given activity level; stability refers to the change in catalyst activity or selectivity per unit time or unit throughput. Generally speaking, the octane number of the liquid product in the reforming process is higher or lower corresponding to the reaction severity, and higher reaction temperature and lower reaction pressure correspond to higher severity.
In the catalytic reforming process, several competing reactions occur simultaneously. These reactions include dehydrogenation of cyclohexane to aromatics, dehydroisomerization of alkylcyclopentanes to aromatics, dehydrocyclization of paraffins to aromatics, hydrocracking of paraffins to lighter hydrocarbon products outside the gasoline boiling range, dealkylation of alkylbenzenes and isomerization of paraffins. Among these reactions, the yield of gasoline is unfavorable because of the generation of light hydrocarbon gas by the hydrocracking reaction. In addition to the above reaction, another very unfavorable reaction process is a coking reaction, which proceeds to convert the raw material into a high carbon-to-hydrogen ratio substance attached to the catalyst, and is oxidized and burned off during the regeneration of the catalyst, thereby also lowering the yield and selectivity of the target product. Carbon deposits on the catalyst can cover the active sites on the surface of the catalyst, reducing the activity of the catalyst and therefore generally requiring a catalyst with a lower carbon deposition rate.
The reforming catalyst is a bifunctional catalyst and must have both an isomerization acidity function and a hydrogenation-dehydrogenation metal function. The acidic function of the catalyst is typically provided by a porous acidic inorganic oxide support, such as chlorided alumina, and the metal function of the hydro-dehydrogenation is provided by a group VIII metal. In order to obtain better bifunctional matching, other metal promoters, such as Sn, etc., are usually introduced into the catalyst. The acidity function of the catalyst can catalyze side reactions such as paraffin cracking in addition to isomerization of paraffins, and it is often necessary to adjust the acidity of the catalyst in order to minimize the occurrence of side reactions.
USP4,094,821 discloses a reforming catalyst comprising a group viii metal comprising platinum and iridium and an alkaline earth metal oxide comprising an oxide of calcium, barium or strontium on an acidic refractory inorganic oxide support. The examples illustrate catalysts made containing platinum and calcium oxide, the alkaline earth metals of which increase the stability of the platinum.
USP7,538,063 discloses a reforming catalyst comprising platinum, bismuth phosphorus and chlorine on an alumina support, and further, rhenium may be contained. The obtained catalyst has higher liquid product yield and stability.
US2015/0239802 discloses a reforming catalyst for high temperature reforming reaction comprising platinum group metal, group iva metal and a third metal selected from alkali metal or alkaline earth metal, the catalyst platinum group metal content being 0.01-2 mass%, the group iva metal content being 0.01-5 mass%, the third metal content being 0.01-1 mass%. The temperature of the catalyst used for reforming reaction needs to be controlled to be more than 540 ℃. Examples the catalyst wherein the platinum group metal is platinum, the group IVA metal is tin and the third metal is potassium can be used in a reforming process at high temperatures to achieve higher aromatics yields.
Disclosure of Invention
The invention aims to provide a multi-metal continuous reforming catalyst, a preparation method and application thereof, wherein the catalyst is particularly suitable for a reforming device which is operated under medium-severity and takes high-octane gasoline blending components as target products, and can obtain higher gasoline product yield.
The multi-metal continuous reforming catalyst provided by the invention comprises an alumina carrier and active components with the following contents calculated by taking the carrier as a reference:
Figure BDA0001341772120000021
according to the invention, modification components of phosphorus and calcium are added into the platinum-tin catalyst, and the platinum-tin catalyst is used in the naphtha reforming reaction process under medium severity, so that higher gasoline product yield can be obtained, meanwhile, the aromatic hydrocarbon content in the gasoline product is reduced, the isoparaffin content is increased, and the platinum-tin catalyst is more suitable for being used as a blending component of clean gasoline.
Detailed Description
The invention adds modified components of phosphorus and calcium into the platinum-tin reforming catalyst, reduces the catalytic cracking reaction of acidic function, reduces the yield of light hydrocarbon components outside the gasoline boiling range, improves the isomerization performance and improves the yield of high-octane gasoline products. The catalyst is used in the reforming reaction process under medium severity, and can obtain higher liquid product yield, namely higher gasoline yield. Octane yield, which is the product of the liquid product yield and the liquid product octane number, is typically used to measure the performance of the reforming catalyst in producing high octane gasoline components during the reforming process. Compared with the prior art, the content of isoparaffin components in the gasoline product obtained by the reforming reaction of the catalyst is increased, the content of aromatic hydrocarbon is reduced, and the isoparaffin components are good blending components of clean gasoline, so the gasoline product prepared by the catalyst is more suitable for serving as the blending components of the clean gasoline.
The catalyst comprises an alumina carrier and active components calculated by taking the carrier as a reference, and preferably comprises the following active components:
Figure BDA0001341772120000031
the alumina carrier in the catalyst is a porous and adsorptive substance, and the specific surface area of the alumina carrier is preferably 30-500 m2The specific surface area per gram, the apparent bulk density is preferably 0.4-1.0 g/ml, the pore diameter is preferably 2-50 nm, and the pore volume is preferably 0.2-1.0 ml/g. Its composition should be homogeneous and refractory under the conditions of use. The term "compositionally homogeneous" means that the support is not layered and has no intrinsic componentsA concentration gradient.
The alumina is preferably high-purity alumina prepared by hydrolyzing aluminum alkoxide, and the crystalline form of the alumina can be gamma-A12O3、η-A12O3Or theta-A12O3Preferably gamma-A12O3Or eta-A12O3More preferably gamma-A12O3. The A12O3The carrier is preferably spherical, can be formed by dropping balls by an oil ammonia column method or a hot oil column method, and has a diameter of preferably 1.0-2.5 mm.
The preparation method of the catalyst provided by the invention comprises the steps of impregnating a tin and phosphorus-containing alumina carrier with a water-soluble calcium compound solution, drying and roasting the impregnated solid, impregnating with a platinum compound-containing solution, and then drying and activating.
The tin component of the catalyst of the present invention may be incorporated into the support in any manner and achieve uniform distribution. Such as by coprecipitation during the preparation of the alumina or by ion exchange or impregnation with tin-containing compounds. Wherein the impregnation method is to impregnate the alumina carrier with a solution of a soluble compound of tin so that the solution is impregnated or dispersed in the alumina carrier. Suitable tin-containing compounds are their oxides, chlorides, nitrates, alkoxides or organometallic complexes, such as stannous bromide, stannous chloride, stannic chloride pentahydrate, tetrabutyltin. The preferred method of introducing tin is to mix a tin-containing compound with the alumina or its precursor before shaping the support and then shaping them together so that the tin is uniformly distributed in the alumina support.
The phosphorus in the catalyst of the present invention can be introduced into the carrier by any feasible means, such as coprecipitation, cogelling, coextrusion, ion exchange or impregnation, so that the phosphorus can be uniformly distributed in the alumina carrier. The preferred method is to incorporate the support together with the tin component by co-precipitation, i.e. mixing with the alumina or its precursors before shaping the alumina and then shaping together to give the phosphorus and tin containing alumina support. Preferably, the tin-and phosphorus-containing alumina carrier is prepared by peptizing aluminum hydroxide with acid, adding tin-containing compound and phosphorus-containing compound, dropping ball forming, drying and calcining wet ball, wherein the acid is preferably nitric acid or a mixture of nitric acid and organic acid, and the organic acid can be acetic acid, citric acid or tartaric acid. The phosphorus-containing compound used for introducing phosphorus into the carrier is preferably phosphoric acid, ammonium phosphate or ammonium hydrogen phosphate.
The calcium in the catalyst of the invention may be incorporated into the support by any means, for example by co-precipitation, co-gelling, co-extrusion, ion exchange or impregnation, preferably by impregnating the alumina support with a solution of a water-soluble calcium-containing compound, preferably calcium chloride or calcium nitrate. The catalyst needs to be calcined after the calcium is introduced so that the calcium and the support have a suitable interaction.
The platinum in the catalyst is preferably introduced after the tin, phosphorus and calcium to prevent loss of platinum during impregnation of the other active components. A preferred method is to impregnate the support with a solution of a platinum-containing compound, preferably chloroplatinic acid. Acids such as HCl may be added to the impregnation solution in order to facilitate the introduction of chlorine and to uniformly distribute the platinum component on the support during impregnation. After the impregnation introduction of platinum, the catalyst or its precursor needs to be calcined to provide a more intimate bond between the respective active components introduced by impregnation and the support.
After dipping and platinum introduction, drying and activation are needed. The activation is preferably a water chlorine activation to introduce the appropriate amount of chlorine into the catalyst. The medium used for activating the water chloride is air containing water and HCl, the temperature of the water chloride activation is 370-700 ℃, and the molar ratio of water to HCl in the used air is 5-100: 1. preferably 10-50: 1. the time for activating the water chloride is preferably 2 to 8 hours. The HCl contained in the air used for the water chlorine activation can be derived from HCl, and can also be derived from organic compounds capable of decomposing chlorine, such as tetrachloroethylene, dichloromethane, trichloromethane, carbon tetrachloride.
The roasting temperature of the carrier after the active component is introduced is preferably 350-850 ℃, and more preferably 550-650 ℃. The temperature for introducing calcium and platinum in the impregnation is preferably 15-50 ℃, and the liquid/solid ratio of the impregnation is 0.8-2.0 mL/g.
The catalyst of the invention needs to be reduced before use, and the preferred reducing gas is hydrogen, and other reducing gases such as CO and the like can also be used. The reduction temperature may be 315 to 650 ℃, and the time is preferably 0.5 to 10 hours. The reduction may be carried out before the catalyst is charged into the reactor, or it may be carried out in situ after the catalyst is charged into the reactor and before the reforming reaction is started.
The method for catalytically reforming naphtha by using the catalyst comprises the step of carrying out contact reaction on naphtha and the catalyst under the conditions that the temperature is 495-535 ℃, preferably 500-530 ℃, the pressure is 0.15-3.0 MPa, preferably 0.40-0.8 MPa, and the hydrogen/hydrocarbon molar ratio is 1-20, preferably 1.5-5.
The volume space velocity of the naphtha passing through the catalyst is preferably 0.5-5 hours-1More preferably 1 to 4 hours-1。
Under the operating conditions of the invention, the Research Octane Number (RON) of the liquid product obtained by the catalytic reforming reaction of naphtha can be kept to 97-102.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
Example 1
(1) Preparation of tin and phosphorus-containing gamma-Al with uniformly distributed tin and phosphorus2O3And (4) a small ball.
100 g of SB aluminum hydroxide powder (72 mass% alumina, produced by Sasol Germany) and an appropriate amount of deionized water were mixed, stirred and slurried, and the liquid/solid mass ratio was 2.0. Adding 7.5 ml of the mixture in a volume ratio of 1: 1, 30 g of urea and 10 ml of SnCl containing 0.3450 g of20.9111 g of H3PO4And 0.72 g of HCl, stirring for 1 hour, adding 30 g of kerosene and 3 g of fatty alcohol-polyoxyethylene ether, stirring for 1 hour, and dropping balls in an oil-ammonia column for forming. Solidifying the wet ball in ammonia water for 1 hour, then filtering, washing with deionized water for 2-3 times, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 10 hours, and roasting at 600 ℃ for 4 hours to obtain the gamma-Al containing Sn and P2O3Pellets having a Sn content of 0.30 mass% and a P content of 0.40 mass% calculated on the basis of alumina and a diameter of 1.6mm and a specific surface area of 206 m measured by the BET method2Average pore volume/g, nitrogen adsorption methodThe diameter was 8.1 nm.
(2) And (5) introducing calcium.
160 g of 0.173 mass percent CaCl are taken2The water solution is used as impregnation liquid, 100 g of gamma-Al containing Sn and P prepared by the method in the step (1) is impregnated at 25 DEG C2O3And (3) carrying out a pellet carrier, wherein the impregnation liquid/solid ratio is 1.6ml/g, drying the impregnated solid at 120 ℃ for 12 hours, and introducing air at 600 ℃ for roasting for 4 hours to obtain the calcium-containing carrier.
(3) Platinum is introduced.
Preparing a solution containing chloroplatinic acid and HCl as an impregnation solution, wherein the amount of platinum is 0.29 mass% relative to dry alumina and the amount of HCl is 2.8 mass% relative to dry alumina, and impregnating the carrier obtained in the step (2) with the impregnation solution at 25 ℃ for 4 hours, wherein the impregnation solution/solid ratio is 1.8 ml/g. And (2) evaporating the dipped system to dryness in a rotating manner, drying the system at 120 ℃ for 12 hours, then carrying out water chlorine activation at 510 ℃ for 4 hours, wherein the molar ratio of water to HCl in air used for the water chlorine activation is 45, and reducing the system at 500 ℃ for 4 hours after the activation to obtain a catalyst A, wherein the catalyst A comprises the following components in percentage by weight (composition) calculated by taking alumina as a reference: 0.29 mass% of Pt, 0.30 mass% of Sn, 0.40 mass% of P, 0.10 mass% of Ca, and 1.15 mass% of Cl.
Example 2
A catalyst was prepared as in example 1, except that the calcium chloride solution used in step (2) had a concentration of 0.416% by mass, and that the catalyst B obtained by platinum-introducing and water-chlorine activating had a composition of: 0.29 mass% of Pt, 0.30 mass% of Sn, 0.40 mass% of P, 0.24 mass% of Ca, and 1.15 mass% of Cl.
Example 3
The catalyst was prepared as in example 1, except that (1) gamma-Al containing tin and phosphorus was prepared2O3H added during pelleting3PO4In an amount of 0.5694 g, catalyst F was prepared having the composition: 0.29 mass% of Pt, 0.30 mass% of Sn, 0.25 mass% of P, 0.10 mass% of Ca, and 1.15 mass% of Cl.
Example 4
The catalyst was prepared as in example 1, except that (1) gamma-Al containing tin and phosphorus was prepared2O3H added during pelleting3PO4In an amount of 0.5694G, and (2) the calcium chloride solution used in the step of introducing calcium had a concentration of 0.416 mass%, and the catalyst G was prepared to have a composition of: 0.29 mass% of Pt, 0.30 mass% of Sn, 0.25 mass% of P, 0.24 mass% of Ca, and 1.15 mass% of Cl.
Comparative example 1
The catalyst was prepared as in example 1, except that there was no calcium introduction step in step (2) and that in step (3) the tin-and phosphorus-containing γ -Al obtained in step (1) was directly used2O3The carrier was used for impregnation of platinum, and the composition of the resulting catalyst C was: 0.29 mass% of Pt, 0.30 mass% of Sn, 0.40 mass% of P, and 1.13 mass% of Cl.
Comparative example 2
A catalyst was prepared as in example 1, except that (1) no H was added during the support formation stage3PO4Obtaining the Sn-containing gamma-Al2O3Pellets having a diameter of 1.6mm and a specific surface area of 203 m by BET method2The average pore diameter measured by nitrogen adsorption method was 8.1 nm. (2) The concentration of the calcium chloride solution used for the calcium introduction in step (a) was 0.416 mass%, and the composition of the obtained catalyst D was: 0.29 mass% of Pt, 0.30 mass% of Sn0.24 mass% of Ca, and 1.15 mass% of Cl.
Comparative example 3
A catalyst was prepared as in example 1, except that (1) no H was added during the support formation stage3PO4Obtaining the Sn-containing gamma-Al2O3Pellets having a diameter of 1.6mm and a specific surface area of 203 m by BET method2The average pore diameter measured by nitrogen adsorption method was 8.1 nm. (3) Directly mixing the tin-containing gamma-Al prepared in the step (1)2O3The pellet carrier was used for impregnation of platinum, and the composition of the obtained catalyst E was: 0.29 mass% of Pt, 0.30 mass% of Sn, and 1.15 mass% of Cl.
Examples 5 to 11
The following examples evaluate the reforming reaction performance of the catalysts.
The inventive and comparative catalysts were evaluated on a 100 ml medium-sized unit with a recycle compressor, starting from straight-run naphtha as shown in table 1. The evaluation conditions were a reaction pressure of 0.7MPa,The space velocity of the feeding volume is 2.0 hours-1The hydrogen/hydrocarbon molar ratio was 2.5 and the evaluation time was 120 hours, during which the temperature of the reaction was adjusted so that the research octane number of the product was maintained at 100, and the results are shown in Table 2. In table 2, the liquid yield is the ratio of the mass of the collected liquid product after the reaction to the total mass of the feed, and the content of the aromatic hydrocarbon and the isoparaffin in the liquid product can be obtained by analyzing the composition of the liquid product.
Compared with the comparative catalyst, the catalyst of the invention has the advantages of improved liquid yield, lower carbon deposition amount, reduced aromatic hydrocarbon content in the liquid product, improved isoparaffin content and maintained octane number of the liquid product.
Examples 12 to 18
The following examples evaluate the reaction performance of the inventive and comparative catalysts at varying reaction temperatures.
The inventive catalyst and the comparative catalyst were evaluated on a 100 ml medium-sized unit with a recycle compressor, starting from straight-run naphtha. The composition of the straight-run naphtha used is shown in Table 1, the evaluation conditions being a reaction pressure of 0.7MPa and a volumetric space velocity of the feed of 2.0 hours-1The hydrogen/hydrocarbon molar ratio was 2.5, the inlet temperature of the feed to the reactor was varied, the temperatures considered were 495 ℃, 510 ℃, 525 ℃ and 540 ℃, and the reaction was carried out for 10 hours at each temperature, and the catalysts used in the examples and the octane yields at the different inlet temperatures are shown in table 3.
As can be seen from Table 3, the octane number yield of the catalyst of the present invention is significantly higher than that of the comparative catalyst at the inlet temperatures of the feedstocks of 510 ℃ and 525 ℃, which indicates that the catalyst of the present invention can obtain a higher octane number yield at medium severity level, and is more suitable for producing high octane number gasoline products.
TABLE 1
Figure BDA0001341772120000081
TABLE 2
Figure BDA0001341772120000082
TABLE 3
Figure BDA0001341772120000091

Claims (11)

1. A multi-metal continuous reforming catalyst comprises an alumina carrier and active components with the following contents calculated by taking the carrier as a reference:
Figure FDA0001341772110000011
2. the catalyst of claim 1, wherein the catalyst comprises the following active components:
Figure FDA0001341772110000012
3. a catalyst according to claim 1 or 2, characterised in that the alumina is gamma alumina.
4. A process for preparing the catalyst of claim 1, which comprises impregnating a tin and phosphorus-containing alumina carrier with a solution of a water-soluble calcium-containing compound, drying and calcining the resultant solid, impregnating the solid with a solution of a platinum-containing compound, drying and activating the resultant solid.
5. A method according to claim 4, wherein the water soluble calcium-containing compound is calcium chloride or calcium nitrate and the platinum-containing compound is chloroplatinic acid.
6. A process as claimed in claim 4, wherein the tin and phosphorus containing alumina support is prepared by peptizing aluminum hydroxide with an acid, adding a tin containing compound and a phosphorus containing compound, drop-ball forming, drying the wet balls, and calcining.
7. The method according to claim 4, wherein the calcination temperature is 350 to 850 ℃.
8. The method according to claim 4, wherein the activation is water chlorine activation, the medium used for water chlorine activation is air containing water and HCl, the temperature of water chlorine activation is 370-700 ℃, and the molar ratio of water to HCl in the air is 5-100: 1.
9. a method for catalytically reforming naphtha, comprising a step of bringing naphtha into contact with the catalyst according to claim 1 at a temperature of 495 to 535 ℃, a pressure of 0.15 to 3.0MPa, and a hydrogen/hydrocarbon molar ratio of 1 to 20.
10. The method according to claim 9, wherein the reaction temperature is 500 to 530 ℃ and the reaction pressure is 0.40 to 0.8 MPa.
11. A process according to claim 9, characterised in that the volumetric space velocity of the naphtha over the catalyst is from 0.5 to 5 hours-1The hydrogen/hydrocarbon molar ratio is 1.5 to 5.
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CN1655868A (en) * 2002-05-22 2005-08-17 国际壳牌研究有限公司 Bismuth- and phosphorus-containing catalysts support, reforming catalysts made from same, method of making and naphtha reforming process
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CN1655868A (en) * 2002-05-22 2005-08-17 国际壳牌研究有限公司 Bismuth- and phosphorus-containing catalysts support, reforming catalysts made from same, method of making and naphtha reforming process
CN104511291A (en) * 2013-09-27 2015-04-15 中国石油天然气股份有限公司 Large-aperture high-bulk-density continuous reforming catalyst and preparation and application thereof

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