CN111068771B - Isomerization pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate oil and preparation method and application thereof - Google Patents
Isomerization pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate oil and preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- 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
Abstract
The invention relates to an isomerism pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate oil, a preparation method and application thereof, wherein the catalyst comprises an active component composed of VIII family noble metal and transition metal, and a modified composite molecular sieve carrier composed of a silicon aluminum phosphate molecular sieve, a silicon aluminum molecular sieve and a binder; the preparation method comprises the steps of firstly mixing a silicon aluminum phosphate molecular sieve with a silicon aluminum molecular sieve, immersing the silicon aluminum molecular sieve in an acidic solution, filtering, washing, drying and roasting the mixture, kneading the mixture with a binder and a forming acid uniformly, forming, crushing, screening, drying and roasting the mixture, mixing the mixture with a mixed salt solution of a VIII noble metal and a transition metal, and drying and roasting the mixture to obtain the catalyst. Compared with the prior art, the catalyst can effectively convert long straight-chain alkane in distillate oil into multi-branched isoparaffin, and has higher isomerism selectivity, and the obtained isomerisation product has low pour point and high viscosity index and is suitable for serving as lubricating oil base oil.
Description
Technical Field
The invention belongs to the technical field of lubricating oil, relates to an isomerism pour point depressing catalyst, a preparation method and application thereof, and in particular relates to an isomerism pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate oil, a preparation method and application thereof in preparing lubricating oil base oil
Background
With the development of environmental protection and mechanical industry, more severe requirements are put on the quality of lubricating oil products. The lubricating oil has high oxidation stability, better viscosity-temperature property, better low-temperature fluidity and excellent shear stability and abrasion resistance. Because the method of improving the service performance of the lubricating oil by only adjusting the additive formula cannot meet the related requirements, higher requirements are placed on the quality of the lubricating base oil. In addition, the quality of mineral lubricating oil produced by the traditional process is difficult to further improve, and the crude oil resources suitable for producing lubricating oil worldwide are increasingly reduced, so that the production of lubricating oil must face inferior heavy crude oil, which is also a difficult problem for the traditional processing process.
With the development of coal chemical industry, all products obtained by Fischer-Tropsch synthesis do not contain or have low sulfur, nitrogen and aromatic hydrocarbon, are colorless, odorless and clean in combustion, and are not only very good clean fuels, but also very good petrochemical raw materials and special chemicals. Fractionating the Fischer-Tropsch synthesis product, and subjecting the separated base oil precursor fraction to a catalytic dewaxing process to produce base oils of different grades; the separated heavy distillate oil is subjected to hydroisomerization catalyst dewaxing process, so that base oil with different grades can be produced. The lubricating oil base oil produced by the Fischer-Tropsch synthesis product has no sulfur, high viscosity index and high biodegradability, is very suitable for preparing new-generation engine oil, and can replace part of PAO to prepare high-grade lubricating oil and grease products. Fischer-Tropsch synthesis processes provide a variety of sources for lubricating oil base oil raw materials.
US5834522a discloses a process for producing a lube base oil from a fischer-tropsch synthesis product which comprises hydroisomerising the non-hydrotreated or hydrotreated fischer-tropsch synthesis product in a hydroisomerisation reaction zone, distillating the isomerised oil, dewaxing the bottoms of the distillation to obtain an oil and a non-oil fraction. Wherein the operating conditions of the hydroisomerization reaction zone are: the reaction temperature is 200-450 ℃, the pressure is 2-25MPa, and the airspeed is 0.1-10h -1 The hydrogen/carbon volume ratio is 100-2000. The catalyst comprises a deposit on an amorphous silica-alumina carrier, the deposit contains 0.05-100wt% of reduced noble metal of VIII group, the catalyst does not contain zeolite molecular sieve and halogen element, the content of silica in the carrier is 5-45wt%, and the BET specific surface is 100-500m 2 And/g, the silicon oxide is uniformly distributed, the average pore diameter of the catalyst is 1-12nm, the pore volume of pores with the average pore diameter of more than 3nm and less than 3nm exceeds 40% of the total pore volume, and the dispersion coefficient of noble metal in the catalyst is more than 0.1.
CN1364188 discloses a process for the preparation of a lubricant base oil, which comprises contacting a synthetic wax obtained by a fischer-tropsch process and not subjected to hydroisomerisation treatment with a catalyst comprising at least a hydrogenation component, dealuminated aluminosilicate zeolite crystallites and a low acidity high melting point oxide binder material which is substantially free of alumina, and fractionating the resulting product to form the lubricant base oil.
CN1703490 discloses a process for converting fischer-tropsch wax to isoparaffinic lube base stock, which process comprises: first, a Fischer-Tropsch wax and hydrogen are co-fed over a beta-catalyst comprising a beta-zeolite and one or more group VIII metals to produce an intermediate product; secondly, passing the intermediate product over a one-dimensional molecular sieve catalyst comprising a one-dimensional mesoporous molecular sieve having a pore structure approximating a circle having an average diameter of between 0.50 nm and 0.65 nm, wherein the difference between the maximum diameter and the minimum diameter is less than or equal to 0.05 nm, and one or more group VIII metals; thereby producing an isoparaffinic lube basestock.
CN105032478B discloses a catalyst for isomerization and pour point depressing of F-T synthesized middle distillate and a special core-shell structure composite molecular sieve thereof. Wherein, the composite molecular sieve takes a microporous ZSM-22 molecular sieve as a core and a mesoporous MCM-41 molecular sieve as a shell, and the relative proportion of the two molecular sieves is adjustable. The catalyst prepared by taking the ZSM-22/MCM-41 composite molecular sieve with the core-shell structure as a carrier is applied to hydroisomerization reaction of F-T synthesized middle distillate oil, and under the condition of 91.4 percent conversion rate, the isomerism selectivity is maintained to be more than 90 percent, wherein the multi-branched chain isomerism selectivity reaches 55.6 percent.
By combining the characteristics of Fischer-Tropsch synthesis products, the method for converting the Fischer-Tropsch synthesis products into lubricating oil base oil through isomerization and pour point depressing has good development prospect, and the development of a catalyst with higher isomerization reaction selectivity is particularly critical.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an isomerism pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate, a preparation method and application thereof, which are used for solving the problem of low selectivity of long-chain straight-chain hydrocarbon isomerisation reaction in the Fischer-Tropsch synthesis distillate.
The aim of the invention can be achieved by the following technical scheme:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight:
0.05 to 1.0 percent of VIII noble metal, 0.1 to 5.0 percent of transition metal, 50 to 80 percent of silicon aluminum phosphate molecular sieve, 10 to 30 percent of silicon aluminum molecular sieve and 5 to 20 percent of binder;
the silicon aluminum phosphate molecular sieve, the silicon aluminum molecular sieve and the binder together form a modified composite molecular sieve carrier of the catalyst;
the VIII noble metal and the transition metal are used as active components of the catalyst in the form of corresponding compounds and are loaded on the modified composite molecular sieve carrier.
As a preferable technical scheme, the weight part content of the VIII group noble metal is 0.05-0.6, and more preferably 0.1-0.3.
As a preferable technical scheme, the weight part content of the transition metal is 0.2-4.0, and more preferably 0.5-3.0.
As a preferred technical scheme, the weight part content of the silicon aluminum phosphate molecular sieve is 60-80, and more preferably 65-80.
As a preferred technical scheme, the weight part content of the silicon-aluminum molecular sieve is 15-30, and more preferably 15-25.
As a preferable technical scheme, the content of the binder in parts by weight is 10-30, and more preferably 15-30.
Further, the VIII noble metal comprises at least one of Pt, pd and Ru;
the transition metal comprises at least one of Zn, zr, mn, cr, ni;
the silicon aluminum phosphate molecular sieve comprises one of SAPO-11, SAPO-31 and SAPO-41;
the silicon-aluminum molecular sieve comprises one of ZSM-5, ZSM-22, beta-molecular sieve and SBA-15;
the binder is one of aluminum sol, pseudo-boehmite and silica sol.
As a preferable technical scheme, the VIII noble metal is Pt or Pd.
As a preferable technical scheme, the transition metal is Zn or Zr.
As a preferable technical scheme, the silicoaluminophosphate molecular sieve is SAPO-11.
As a preferable technical scheme, the silicon-aluminum molecular sieve is beta-molecular sieve.
As a preferable technical scheme, the binder is pseudo-boehmite.
A process for the preparation of a catalyst suitable for isomerisation of long chain hydrocarbons in fischer-tropsch derived distillate as described above comprising the steps of:
1) Mixing a silicon aluminum phosphate molecular sieve with a silicon aluminum molecular sieve, adding the mixture into an acidic solution for modification treatment, and sequentially carrying out filtering, washing, drying and roasting to obtain an acid treatment mixed molecular sieve;
2) Kneading the acid-treated mixed molecular sieve in the step 1) with a binder and a molding acid uniformly, and sequentially performing molding, drying, roasting, crushing and screening to obtain a molded modified composite molecular sieve;
3) Preparing mixed salt solution of VIII noble metal and transition metal, immersing the molding modified composite molecular sieve in the step 2) in the mixed salt solution, and sequentially drying and roasting to obtain the catalyst.
In the step 1), the dosage of the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve is determined according to a required formula;
as a preferable technical scheme, the mixing mass ratio of the silicon aluminum phosphate molecular sieve to the silicon aluminum molecular sieve is (2-5) 1;
the concentration of the acid solution is 0.1-0.5mol/L;
the addition amount of the acid solution is 10-40mL/10g of a mixed molecular sieve of the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve;
the acidic solution comprises one of oxalic acid, citric acid, acetic acid, hydrochloric acid and nitric acid;
in the modification treatment, the treatment temperature is 50-90 ℃ and the treatment time is 0.5-3h;
in the washing process, deionized water is adopted for washing until the pH value of the filtrate is 6.8-7, and then the filtrate can enter a drying process;
in the drying process, the drying temperature is 100-120 ℃;
in the roasting process, the roasting temperature is 400-600 ℃, and the roasting time is 1-6h.
In the step 1), the mixing mass ratio of the silicon aluminum phosphate molecular sieve to the silicon aluminum molecular sieve is (2-4): 1.
As a preferred technical scheme, in the step 1), the concentration of the acid solution is 0.1-0.3mol/L.
In a preferred embodiment, in step 1), the acidic solution is a citric acid solution.
In the preferred technical scheme, in the step 1), the treatment temperature is 60-80 ℃ and the treatment time is 0.5-1.5h.
In a preferred technical scheme, in the step 1), the drying temperature is 110 ℃.
In the step 1), the roasting temperature is 450-550 ℃ and the roasting time is 2-4h.
In the step 2), the molding acid is 5-20wt% nitric acid solution;
the addition amount of the molding acid is 8-15mL/60-80g of acid treatment mixture formed by the mixed molecular sieve and the adhesive;
the molding process is tabletting molding or strip extrusion molding;
in the drying process, the drying temperature is 100-120 ℃;
in the roasting process, the roasting temperature is 400-600 ℃ and the roasting time is 1-6h;
and crushing and screening, and taking 20-40 mesh fine powder to obtain the molded modified composite molecular sieve.
Wherein the addition amount of the binder is determined according to the required formula.
In the step 3), the mixed salt solution is immersed on the molding modified composite molecular sieve by adopting an isovolumetric immersion method, and the immersion time is 1-12h;
in the drying process, the drying temperature is 100-120 ℃;
in the roasting process, the roasting temperature is 400-600 ℃, and the roasting time is 1-6h.
Further, in the step 3),
in the mixed salt solution, the VIII noble metal salt comprises at least one of chloroplatinic acid, chloropalladic acid, ruthenium trichloride, tetraamineplatinum dichloride and tetraaminepalladium dichloride;
in the mixed salt solution, the transition metal salt comprises at least one of zinc nitrate, zirconium nitrate, manganese nitrate, chromium nitrate and nickel nitrate.
In the mixed salt solution, the concentration of the VIII noble metal salt and the transition metal salt is determined according to the design load.
As a preferable technical scheme, in the step 3), the soaking time is 2-10h.
In a preferred technical scheme, in the step 3), the drying temperature is 110 ℃.
In the step 3), the roasting temperature is 450-550 ℃ and the roasting time is 2-4h.
The roasting atmosphere in the roasting process is one of oxygen or air.
Use of a catalyst as described above in the preparation of a lubricating base oil.
Further, the catalyst is used for preparing the lubricating oil base oil by catalyzing the isomerization and pour point depressing reaction of long-chain straight-chain hydrocarbon in the Fischer-Tropsch synthesis distillate oil.
Further, the isomerization and pour point depressing reaction is carried out in a fixed bed;
the reaction conditions of the isomerism pour point depressing reaction comprise: the reaction temperature is 260-440 ℃, the reaction pressure is 2-8MPa, the hydrogen-oil ratio is 200-1000, and the volume airspeed is 0.5-2.5h -1 。
Compared with the prior art, the invention has the following characteristics:
1) The isomerization pour point depressing catalyst has higher isomerization reaction selectivity, can effectively convert long straight-chain alkane in Fischer-Tropsch synthesis distillate into multi-branched isoparaffin when being used for catalyzing hydroisomerization pour point depressing reaction of Fischer-Tropsch synthesis distillate, shows higher isomerization reaction selectivity, and simultaneously, the obtained isomerization product has low pour point and high viscosity index, and is suitable for being used as lubricating oil base oil;
2) According to the invention, the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve are mixed and subjected to acid treatment together, so that the acid distribution on the surface of the molecular sieve and the distribution proportion of strong acid to weak acid are effectively improved, the interaction between the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve is effectively enhanced, and the problem that the interaction between the silicon aluminum molecular sieve and the silicon aluminum molecular sieve is not obvious due to large space of a simple mechanical mixed molecular sieve is solved;
3) The invention simplifies the manufacturing process of the composite molecular sieve by the method of carrying out acid treatment on the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve together, and can better play the synergistic effect of the two molecular sieves, thereby showing excellent performance in the catalysis process;
4) The invention mixes and dips the transition metal and the noble metal on the composite molecular sieve carrier, can better play the synergistic effect of the transition metal and the noble metal, promote the dispersion of the active metal, reduce the consumption of the noble metal and reduce the cost of the catalyst.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
Comparative example 1:
the preparation method of the isomerism pour point depressing catalyst comprises the following steps:
1) Uniformly mixing 50g of SAPO-11 molecular sieve and 10g (calculated by weight of dry alumina) of pseudo-boehmite SB powder, adding 10mL of 10wt% dilute nitric acid, uniformly kneading, tabletting and forming sequentially, drying at 110 ℃ for 24 hours, roasting at 500 ℃ for 1 hour, crushing and screening to 20-40 meshes to obtain a formed molecular sieve carrier;
2) Soaking 50g of molded molecular sieve carrier in 0.1mol/L H 2 PtCl 6 Mixing the aqueous solution for 6 hours, and then drying at 110deg.C for 12 hoursThen roasting at 500 ℃ for 2 hours to prepare the catalyst, and recording as: 0.3wt% Pt/SAPO-11 molecular sieve.
Comparative example 2:
the preparation method of the isomerism pour point depressing catalyst comprises the following steps:
1) 50g of SAPO-11 molecular sieve and 20g of beta-molecular sieve are uniformly mixed, and the mixture is directly immersed in the mixture with equal volume and contains 1mol/LZn (NO) 3 ) 2 、0.3mol/L H 2 PtCl 6 And standing for 6 hours, then drying for 12 hours at 110 ℃ and roasting for 2 hours at 500 ℃, tabletting and forming, crushing to 20-40 meshes, preparing the modified catalyst and marking as: 1wt% Zn-0.3wt% Pt/SAPO-11/beta-molecular sieve.
Example 1:
the preparation method of the modified isomerism pour point depressing catalyst comprises the following steps:
1) 50g of SAPO-11 molecular sieve and 12.5g of beta-molecular sieve are mixed to form a mixed molecular sieve, 250mL of 0.1mol/L citric acid solution is used for treating the mixed molecular sieve for 1 hour at 60 ℃, and then the mixed molecular sieve is filtered, washed by deionized water until the pH value of the filtrate is 7.0, dried at 110 ℃ and roasted at 450 ℃ for 4 hours, so that the acid-treated mixed molecular sieve is obtained;
2) Uniformly mixing 50g of acid-treated mixed molecular sieve with 10g (calculated by weight of dry alumina) of pseudo-boehmite SB powder, adding 10mL of 10wt% of dilute nitric acid, uniformly kneading, tabletting and forming sequentially, drying at 110 ℃ for 24 hours, roasting at 500 ℃ for 1 hour, crushing and screening to obtain 20-40 meshes, and obtaining the formed modified composite molecular sieve;
3) 50g of the molded modified composite molecular sieve and a catalyst containing 1mol/L Zn (NO) 3 ) 2 、0.3mol/L H 2 PtCl 6 Is immersed in the mixed aqueous solution of (a) in an equal volume, is kept stand for 6 hours, is dried at 110 ℃ for 12 hours and is baked at 500 ℃ for 2 hours in sequence, so as to prepare the modified catalyst, and the modified catalyst is recorded as follows: 1wt% Zn-0.3wt% Pt/SAPO-11/beta-molecular sieve.
Example 2:
the preparation method of the modified isomerism pour point depressing catalyst comprises the following steps:
1) 50g of SAPO-11 molecular sieve and 25g of beta-molecular sieve are mixed to form a mixed molecular sieve, 150mL of 0.3mol/L citric acid solution is used for treating the mixed molecular sieve for 1 hour at 70 ℃, and then the mixed molecular sieve is filtered, washed by deionized water until the pH value of filtrate is 7.0, dried at 110 ℃ and baked for 2 hours at 500 ℃ to obtain an acid treatment mixed molecular sieve;
2) Mixing 50g of acid-treated mixed molecular sieve with 15g (calculated by weight of dry alumina) of pseudo-boehmite SB powder uniformly, adding 15mL of 5wt% dilute nitric acid, kneading uniformly, sequentially extruding into strips of 3-5mm, drying at 110 ℃ for 20 hours, roasting at 450 ℃ for 3 hours, crushing and screening to 20-40 meshes to obtain the molded modified composite molecular sieve;
3) 40g of the molded modified composite molecular sieve and the catalyst containing 0.9mol/L Zn (NO) 3 ) 2 、0.03mol/L H 2 PtCl 6 Is immersed in the mixed aqueous solution of (2) in equal volume, is kept stand for 12 hours, is dried at 110 ℃ for 12 hours and is baked at 450 ℃ for 3 hours in sequence, so as to prepare the modified catalyst, and is recorded as: 3wt% Zn-0.1wt% Pt/SAPO-11/beta-molecular sieve.
Example 3:
the preparation method of the modified isomerism pour point depressing catalyst comprises the following steps:
1) Mixing 60g of SAPO-11 molecular sieve and 20g of beta-molecular sieve to form a mixed molecular sieve, treating the mixed molecular sieve with 100mL of 0.2mol/L citric acid solution at 80 ℃ for 0.5 hours, filtering, washing with deionized water until the pH value of the filtrate is 7.0, drying at 110 ℃, and roasting at 550 ℃ for 2 hours to obtain an acid treatment mixed molecular sieve;
2) Mixing 60g of acid-treated mixed molecular sieve with 20g of pseudo-boehmite SB powder (calculated by weight of dry alumina), adding 8mL of 20wt% dilute nitric acid, kneading uniformly, sequentially extruding into strips of 3-5mm, drying at 110 ℃ for 12 hours, roasting at 450 ℃ for 3 hours, crushing, and screening to 20-40 meshes to obtain the molded modified composite molecular sieve;
3) 40g of the molded modified composite molecular sieve and a catalyst containing 0.5mol/L Zr (NO) 3 ) 4 、0.06mol/L(NH 3 ) 4 PtCl 2 Is immersed in the mixed aqueous solution of (2) in equal volume, kept stand for 12 hours, and then dried at 110 ℃ for 18 hours and baked at 600 ℃ for 1 hour in turn to prepareThe modified catalyst was obtained and noted as: 5wt% Zr-0.6wt% Pt/SAPO-11/beta-molecular sieve.
Example 4:
the preparation method of the modified isomerism pour point depressing catalyst comprises the following steps:
1) 50g of SAPO-11 molecular sieve and 10g of ZSM-22 molecular sieve are mixed to form a mixed molecular sieve, 80mL of 0.3mol/L oxalic acid solution is used for treating the mixed molecular sieve for 2 hours at 50 ℃, and then the mixed molecular sieve is filtered, washed by deionized water until the pH value of the filtrate is 7.0, dried overnight at 110 ℃ and roasted for 2 hours at 550 ℃ to obtain an acid treatment mixed molecular sieve;
2) Mixing 50g of acid-treated mixed molecular sieve with 10g (calculated by weight of dry alumina) of pseudo-boehmite SB powder uniformly, adding 10mL of 15wt% dilute nitric acid, kneading uniformly, tabletting and molding sequentially, drying at 110 ℃ for 24 hours, roasting at 600 ℃ for 1 hour, crushing, and screening to 20-40 meshes to obtain the molded modified composite molecular sieve;
3) 40g of the molded modified composite molecular sieve and a catalyst containing 1.0mol/L Zn (NO) 3 ) 2 、0.2mol/L H 2 PtCl 6 Mixing the aqueous solution, soaking for 15 hours in equal volume, drying at 110 ℃ for 12 hours, and roasting at 600 ℃ for 1 hour in sequence to prepare the modified catalyst, wherein the modified catalyst is recorded as follows: 1wt% Zn-0.2wt% Pt/SAPO-11/ZSM-22.
Example 5:
the preparation method of the modified isomerism pour point depressing catalyst comprises the following steps:
1) 45g of SAPO-11 molecular sieve and 15g of ZSM-5 molecular sieve are mixed to form a mixed molecular sieve, 160mL of 0.2mol/L citric acid solution is used for treating the mixed molecular sieve for 1.5 hours at 60 ℃, and then the mixed molecular sieve is filtered, washed by deionized water until the pH value of the filtrate is 7.0, dried overnight at 110 ℃ and baked for 2 hours at 500 ℃ to obtain an acid treatment mixed molecular sieve;
2) Mixing 50g of acid-treated mixed molecular sieve with 10g (calculated by weight of dry alumina) of pseudo-boehmite SB powder uniformly, adding 12mL of 10wt% dilute nitric acid, kneading uniformly, tabletting and molding sequentially, drying at 110 ℃ for 24 hours, roasting at 500 ℃ for 1 hour, crushing and screening to 20-40 meshes to obtain the molded modified composite molecular sieve;
3) 40g of the molded modified composite molecular sieve and the catalyst containing 0.2mol/L Zn (NO) 3 ) 2 、0.5mol/L H 2 PdCl 6 Is immersed in the mixed aqueous solution of (a) for 15 hours, then dried at 110 ℃ for 12 hours and baked at 500 ℃ for 2 hours, and the modified catalyst is prepared and recorded as: 0.2wt% Zn-0.5wt% Pd/SAPO-11/ZSM-5.
Example 6:
the preparation method of the modified isomerism pour point depressing catalyst comprises the following steps:
1) 50g of SAPO-11 molecular sieve and 10g of beta-molecular sieve are mixed to form a mixed molecular sieve, 100mL of 0.4mol/L citric acid solution is used for treating the mixed molecular sieve for 1 hour at 65 ℃, and then the mixed molecular sieve is filtered, washed by deionized water until the pH value of the filtrate is 7.0, dried overnight at 110 ℃ and roasted for 3 hours at 500 ℃ to obtain an acid treatment mixed molecular sieve;
2) Mixing 50g of acid-treated mixed molecular sieve with 15g (based on dry alumina weight) of pseudo-boehmite SB powder uniformly, adding 15mL of 10wt% dilute nitric acid, kneading uniformly, sequentially extruding into strips of 3-5mm, drying at 110 ℃ for 20 hours, roasting at 500 ℃ for 3 hours, crushing, and screening to 20-40 meshes to obtain the molded modified composite molecular sieve;
3) 40g of the molded modified composite molecular sieve and a catalyst containing 1.0mol/L Zr (NO) 3 ) 4 、0.01mol/L H 2 PdCl 6 Is immersed in the mixed aqueous solution of (2) in equal volume, is kept stand for 12 hours, is dried at 110 ℃ for 12 hours and is baked at 500 ℃ for 2 hours in sequence, so as to prepare the modified catalyst, and is recorded as: 5wt% Zr-0.05wt% Pd/SAPO-11/beta-molecular sieve.
Example 7:
in this example, the hydroisomerization performance of the catalyst prepared in comparative examples and examples 1 to 6 was evaluated on the raw material of the Fischer-Tropsch distillate hydrocracked tail oil (pour point-15 ℃ C.).
Wherein the reactor is a fixed bed reactor, the reaction pressure is 5MPa, the reaction temperature is 325 ℃, and the volume space velocity is 1.5h -1 Hydrogen oil volume ratio 800. Wherein the liquid phase product is condensed and then is analyzed off-line, and the gas phase product is producedAnd (5) carrying out on-line analysis on the substances.
The hydroisomerization mixture was distilled under reduced pressure using the procedure specified in GB/T9168-1997, and the product yield was calculated using the following formula, with the fraction being collected at greater than 370℃:
product yield = (weight fraction greater than 370 ℃ c/weight feed) ×100%.
The viscosity index of the synthetic base oil was calculated using GB/T1995-1998 and the pour point of the fraction above 370℃was determined using the method specified in GB/T3535-2006.
The catalysts prepared in comparative examples and examples 1 to 6 were reduced, respectively, wherein the reduction temperature was 500℃and the reduction time was 4 hours, the reducing gas was hydrogen gas, and the hydrogen gas flow rate was 300 mL/min.
Table 1 evaluation of catalytic performance of each catalyst
| Catalyst | Yield (%) | Viscosity index | Pour point (. Degree. C.) |
| Comparative example 1 | 25.3 | 172 | -57 |
| Comparative example 2 | 30.5 | 176 | -76 |
| Example 1 | 55.6 | 168 | -75 |
| Example 2 | 50.1 | 165 | -70 |
| Example 3 | 42.6 | 168 | -83 |
| Example 4 | 71.1 | 172 | -74 |
| Example 5 | 50.6 | 177 | -77 |
| Example 6 | 43.4 | 165 | -68 |
As can be seen from Table 1, the catalyst prepared according to the invention can effectively convert long straight-chain alkane in the distillate into multi-branched isoparaffin when being used for hydroisomerization reaction of hydrocracking tail oil of Fischer-Tropsch synthesis distillate, and the obtained isomerized product has low pour point and high viscosity index, and is suitable for being used as lubricating oil base oil; in addition, the two molecular sieves are mixed and subjected to acid treatment, so that the interaction between the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve can be promoted, the liquid product yield can be improved when the silicon aluminum phosphate molecular sieve is used as a composite carrier in the isomerization pour point depressing reaction, and the carrier acidity caused by mechanical mixing is avoided.
Example 8:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 0.05% of VIII family noble metal, 0.1% of transition metal, 80% of silicon aluminum phosphate molecular sieve, 10% of silicon aluminum molecular sieve and 9.85% of binder;
wherein the VIII noble metal is Pt, the transition metal is Zn, the silicoaluminophosphate molecular sieve is SAPO-11, the silicoaluminophosphate molecular sieve is ZSM-5, and the binder is alumina sol.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-11 and ZSM-5, adding the mixture into 0.1mol/L oxalic acid solution at 50 ℃ for standing for 3 hours to carry out modification treatment, and then filtering and washing the mixture until the pH value of the filtrate is 6.8-7, drying the filtrate at 100 ℃ and roasting the filtrate at 400 ℃ for 6 hours to obtain an acid treatment mixed molecular sieve, wherein the dosage of the oxalic acid solution is 10mL/10g of a mixed molecular sieve of the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve;
2) Kneading the acid-treated mixed molecular sieve with aluminum sol and 5wt% nitric acid solution uniformly, tabletting and molding, drying at 100 ℃ and roasting at 400 ℃ for 6 hours in sequence, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 8mL/60g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing a mixed salt solution of chloroplatinic acid and zinc nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 1h, and then drying the mixed salt solution at 100 ℃ and roasting the mixed salt solution at 400 ℃ for 6h to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 260 ℃, the reaction pressure is 8MPa, the hydrogen-oil ratio is 200, and the reaction is in a bodyThe volume space velocity is 2.5h -1 。
Example 9:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 1.0% of VIII noble metal, 5.0% of transition metal, 50% of silicon aluminum phosphate molecular sieve, 30% of silicon aluminum molecular sieve and 14% of binder;
wherein the noble metal of VIII family is Pd, the transition metal is Zr, the silicoaluminophosphate molecular sieve is SAPO-31, the silicoaluminophosphate molecular sieve is ZSM-22, and the binder is pseudo-boehmite.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-31 and ZSM-22, adding into a 90 ℃ 0.5mol/L citric acid solution, standing for 0.5h for modification treatment, and then sequentially filtering, washing until the pH of the filtrate is 6.8-7, drying at 120 ℃ and roasting at 600 ℃ for 1h to obtain an acid treatment mixed molecular sieve; wherein, the dosage of the citric acid solution is 20mL/10g of the mixed molecular sieve of the silicon aluminum phosphate molecular sieve and the silicon aluminum molecular sieve;
2) Kneading the acid-treated mixed molecular sieve with pseudo-boehmite and 10wt% nitric acid solution uniformly, extruding and molding, drying at 120 ℃ and roasting at 600 ℃ for 1h in sequence, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 15mL/80g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing a mixed salt solution of palladium chloride acid and zirconium nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 12 hours, and then drying at 120 ℃ and roasting at 600 ℃ for 1 hour in sequence to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 440 ℃, the reaction pressure is 2MPa, the hydrogen-oil ratio is 1000, and the volume space velocity is 0.5h -1 。
Example 10:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 0.6% of VIII family noble metal, 0.2% of transition metal, 75% of silicon aluminum phosphate molecular sieve, 19.2% of silicon aluminum molecular sieve and 5% of binder;
wherein, the noble metal of VIII group is Ru, the transition metal is Mn, the silicoaluminophosphate molecular sieve is SAPO-41, the silicoaluminophosphate molecular sieve is beta-molecular sieve, and the binder is silica sol.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-41 with beta-molecular sieve, adding into acetic acid solution of 0.3mol/L at 60 ℃ and standing for 1.5h to carry out modification treatment, and then filtering and washing until the pH value of the filtrate is 6.8-7, drying at 110 ℃ and roasting at 450 ℃ for 2h to obtain an acid treatment mixed molecular sieve; wherein, the dosage of the acetic acid solution is 40mL/10g of the silicon aluminum phosphate molecular sieve and the mixed molecular sieve of the silicon aluminum molecular sieve;
2) Kneading the acid-treated mixed molecular sieve with silica sol and 8wt% nitric acid solution uniformly, tabletting and molding, drying at 110 ℃ and roasting at 450 ℃ for 2 hours, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 10mL/70g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing a mixed salt solution of ruthenium trichloride and manganese nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 2 hours, and then drying the mixed salt solution at 110 ℃ and roasting the mixed salt solution at 450 ℃ for 2 hours to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 5MPa, the hydrogen-oil ratio is 500, and the volume space velocity is 2h -1 。
Example 11:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 1% of VIII noble metal, 4.0% of transition metal, 50% of silicon aluminum phosphate molecular sieve, 25% of silicon aluminum molecular sieve and 20% of binder;
wherein the VIII noble metal comprises Pt and Pd with equal molar weight, the transition metal comprises Zn, zr and Mn with the molar ratio of 2:1:3, the silicoaluminophosphate molecular sieve is SAPO-11, the silicoaluminophosphate molecular sieve comprises SBA-15, and the binder is pseudo-boehmite.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-11 and SBA-15, adding into a hydrochloric acid solution with the concentration of 0.2mol/L at 80 ℃ and standing for 1h to carry out modification treatment, and then filtering and washing until the pH value of the filtrate is 6.8-7, drying at 110 ℃ and roasting at 550 ℃ for 4h to obtain an acid treatment mixed molecular sieve; wherein, the dosage of the hydrochloric acid solution is 30mL/10g of the silicon aluminum phosphate molecular sieve and the mixed molecular sieve of the silicon aluminum molecular sieve;
2) Kneading the acid-treated mixed molecular sieve with pseudo-boehmite and 10wt% nitric acid solution uniformly, tabletting and molding, drying at 110 ℃ and roasting at 550 ℃ for 4 hours, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 12mL/67g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing mixed salt solution of tetramine platinum dichloride, tetramine palladium dichloride, zinc nitrate, zirconium nitrate and manganese nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 10 hours, and then drying the mixed salt solution at 110 ℃ and roasting the mixed salt solution at 550 ℃ for 4 hours to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 325 ℃, the reaction pressure is 5MPa, the hydrogen-oil ratio is 800, and the volume space velocity is 1.5h -1 。
Example 12:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 0.5% of VIII noble metal, 0.5% of transition metal, 64% of silicon aluminum phosphate molecular sieve, 20% of silicon aluminum molecular sieve and 15% of binder;
wherein, the VIII noble metal is Pt, pd and Ru with equal mass ratio, the transition metal is Cr and Ni with equal mole ratio, the silicoaluminophosphate molecular sieve is SAPO-11, the silicoaluminophosphate molecular sieve comprises beta-molecular sieve, and the binder is pseudo-boehmite.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-11 with beta-molecular sieve, adding into 0.2mol/L nitric acid solution at 70 ℃ and standing for 1h to carry out modification treatment, and then filtering and washing until the pH value of the filtrate is 6.8-7, drying at 110 ℃ and roasting at 500 ℃ for 3h to obtain an acid treatment mixed molecular sieve; wherein, the dosage of the nitric acid solution is 30mL/10g of the silicon aluminum phosphate molecular sieve and the mixed molecular sieve of the silicon aluminum molecular sieve;
2) Kneading the acid-treated mixed molecular sieve with pseudo-boehmite and 10wt% nitric acid solution uniformly, tabletting and molding, drying at 110 ℃ and roasting at 500 ℃ for 3 hours, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 12mL/67g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing a mixed salt solution of chloroplatinic acid, tetraammine palladium dichloride, ruthenium trichloride, chromium nitrate and nickel nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 8 hours, and then drying the mixed salt solution at 110 ℃ and roasting the mixed salt solution at 500 ℃ for 3 hours to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 325 ℃, the reaction pressure is 5MPa, the hydrogen-oil ratio is 800, and the volume space velocity is 1.5h -1 。
Example 13:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 0.2% of VIII noble metal, 3.8% of transition metal, 56% of silicon aluminum phosphate molecular sieve, 20% of silicon aluminum molecular sieve and 20% of binder;
wherein, the VIII noble metal is Pt, the transition metal is Ni, the silicoaluminophosphate molecular sieve is SAPO-11, the silicoaluminophosphate molecular sieve comprises beta-molecular sieve, and the binder is pseudo-boehmite.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-11 with beta-molecular sieve, adding into 0.2mol/L citric acid solution at 70 ℃ and standing for 1h to carry out modification treatment, and then filtering and washing until the pH value of the filtrate is 6.8-7, drying at 110 ℃ and roasting at 500 ℃ for 3h to obtain an acid treatment mixed molecular sieve; wherein, the dosage of the citric acid solution is 12mL/10g of the mixture formed by the acid treatment mixed molecular sieve and the aluminum sol;
2) Kneading the acid-treated mixed molecular sieve in the step 1) with pseudo-boehmite and 10wt% nitric acid solution uniformly, extruding and molding, drying at 110 ℃ and roasting at 500 ℃ for 3 hours, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 15mL/67g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing mixed salt solution of tetramine platinum dichloride and nickel nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 8 hours, and then drying the mixed salt solution at 110 ℃ and roasting the mixed salt solution at 500 ℃ for 3 hours to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 325 ℃, the reaction pressure is 5MPa, the hydrogen-oil ratio is 800, and the volume space velocity is 1.5h -1 。
Example 14:
a catalyst suitable for isomerising long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil comprises the following components in percentage by weight: 0.2% of VIII family noble metal, 2.0% of transition metal, 75% of silicon aluminum phosphate molecular sieve, 20% of silicon aluminum molecular sieve and 20% of binder;
wherein the VIII noble metal is Pd, the transition metal is Zr, the silicoaluminophosphate molecular sieve is SAPO-11, the silicoaluminophosphate molecular sieve comprises beta-molecular sieve, and the binder is pseudo-boehmite.
The preparation method of the catalyst comprises the following steps:
1) Mixing SAPO-11 with beta-molecular sieve, adding into 0.2mol/L citric acid solution at 70 ℃ and standing for 1h to carry out modification treatment, and then filtering and washing until the pH value of the filtrate is 6.8-7, drying at 110 ℃ and roasting at 500 ℃ for 3h to obtain an acid treatment mixed molecular sieve; wherein, the dosage of the citric acid solution is 10mL/10g of the mixture formed by acid treatment mixed molecular sieve and aluminum sol;
2) Kneading the acid-treated mixed molecular sieve with pseudo-boehmite and 10wt% nitric acid solution uniformly, extruding and molding, drying at 110 ℃ and roasting at 500 ℃ for 3 hours, crushing and screening to 20-40 meshes to obtain a molded modified composite molecular sieve; wherein the dosage of the nitric acid solution is 15mL/67g, and the mixture formed by the mixed molecular sieve and the aluminum sol is treated by acid;
3) Preparing mixed salt solution of palladium tetra-chloride and zirconium nitrate, soaking the mixed salt solution on a molding modified composite molecular sieve in an equal volume for 8 hours, and then drying the mixed salt solution at 110 ℃ and roasting the mixed salt solution at 500 ℃ for 3 hours to obtain the catalyst.
The prepared catalyst can be used for preparing lubricating oil base oil by catalyzing isomerization pour point depressing reaction of long-chain straight-chain hydrocarbon in Fischer-Tropsch synthesis distillate oil.
Wherein, the isomerization and pour point depressing reaction is carried out in a fixed bed, and the reaction conditions are as follows: the reaction temperature is 325 ℃, the reaction pressure is 5MPa, the hydrogen-oil ratio is 800, and the volume space velocity is 1.5h -1 。
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
1. A process for preparing a catalyst suitable for isomerising long chain hydrocarbons in fischer-tropsch derived distillate, comprising the steps of:
1) Mixing a silicon aluminum phosphate molecular sieve with a silicon aluminum molecular sieve, adding the mixture into a citric acid solution for modification treatment, and sequentially carrying out filtering, washing, drying and roasting to obtain an acid treatment mixed molecular sieve;
2) Kneading the acid-treated mixed molecular sieve in the step 1) with a binder and a molding acid uniformly, and sequentially performing molding, drying, roasting, crushing and screening to obtain a molded modified composite molecular sieve;
3) Preparing mixed salt solution of VIII noble metal and transition metal, immersing the molding modified composite molecular sieve in the step 2) in the mixed salt solution, and sequentially drying and roasting to obtain the catalyst;
the catalyst comprises the following components in percentage by weight:
0.05 to 1.0 percent of VIII noble metal, 0.1 to 5.0 percent of transition metal, 50 to 80 percent of silicon aluminum phosphate molecular sieve, 10 to 30 percent of silicon aluminum molecular sieve and 5 to 20 percent of binder; the silicon aluminum phosphate molecular sieve, the silicon aluminum molecular sieve and the binder together form a modified composite molecular sieve carrier of the catalyst; the VIII noble metal and the transition metal are used as active components of the catalyst and are loaded on the modified composite molecular sieve carrier;
in the mixed salt solution, the VIII noble metal salt comprises at least one of chloroplatinic acid, chloropalladic acid, ruthenium trichloride, tetraamineplatinum dichloride and tetraaminepalladium dichloride; in the mixed salt solution, the transition metal salt comprises at least one of zinc nitrate, zirconium nitrate, manganese nitrate, chromium nitrate and nickel nitrate.
2. The method for preparing the catalyst applicable to isomerization of long-chain straight-chain hydrocarbons in Fischer-Tropsch synthesis distillate according to claim 1, wherein the noble metal of the VIII group comprises at least one of Pt, pd and Ru.
3. The method of claim 1, wherein the transition metal comprises at least one of Zn, zr, mn, cr, ni.
4. The method for preparing the catalyst applicable to isomerization of long straight-chain hydrocarbons in Fischer-Tropsch synthesis distillate according to claim 1, wherein the silicoaluminophosphate molecular sieve comprises one of SAPO-11, SAPO-31 and SAPO-41.
5. The method for preparing the catalyst applicable to isomerization of long-chain straight-chain hydrocarbons in Fischer-Tropsch synthesis distillate according to claim 1, wherein the silicon-aluminum molecular sieve comprises one of ZSM-5, ZSM-22, beta-molecular sieve and SBA-15;
the binder is one of aluminum sol, pseudo-boehmite and silica sol.
6. Use of a catalyst prepared according to the method of any one of claims 1 to 5 for preparing a lubricant base oil.
7. The use of a catalyst according to claim 6 for the preparation of a lubricant base oil by catalyzing the isomerisation pour point depressing reaction of long chain hydrocarbons in fischer-tropsch derived cuts.
8. The use of a catalyst according to claim 7 for the preparation of lubricant base oils, wherein the reaction conditions for the isomerisation pour point depressant reaction comprise: the reaction temperature is 260-440 ℃, the reaction pressure is 2-8MPa, the hydrogen-oil ratio is 200-1000, and the volume airspeed is 0.5-2.5h -1 。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721074A (en) * | 2005-06-27 | 2006-01-18 | 中国科学院大连化学物理研究所 | A kind of catalyst for hydroisomerizing and preparation method thereof |
| CN1762594A (en) * | 2005-09-29 | 2006-04-26 | 中国科学院大连化学物理研究所 | A kind of alkane hydroisomerization catalyst and its production and application |
| CN103831135A (en) * | 2013-12-04 | 2014-06-04 | 中国科学院山西煤炭化学研究所 | Catalyst for shape-selective isomerization of Fischer-Tropsch synthetic wax and its preparation method and use |
| CN104209140A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Hydrogenation isomerization catalyst of gasoline fraction and preparation and application thereof |
| CN105728023A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Molecular sieve catalyst for Fischer-Tropsch wax hydroisomerization reaction, and preparation method thereof |
| CN107282097A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of hydroisomerization catalyst and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7704379B2 (en) * | 2002-10-08 | 2010-04-27 | Exxonmobil Research And Engineering Company | Dual catalyst system for hydroisomerization of Fischer-Tropsch wax and waxy raffinate |
-
2019
- 2019-12-29 CN CN201911385588.6A patent/CN111068771B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721074A (en) * | 2005-06-27 | 2006-01-18 | 中国科学院大连化学物理研究所 | A kind of catalyst for hydroisomerizing and preparation method thereof |
| CN1762594A (en) * | 2005-09-29 | 2006-04-26 | 中国科学院大连化学物理研究所 | A kind of alkane hydroisomerization catalyst and its production and application |
| CN104209140A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Hydrogenation isomerization catalyst of gasoline fraction and preparation and application thereof |
| CN103831135A (en) * | 2013-12-04 | 2014-06-04 | 中国科学院山西煤炭化学研究所 | Catalyst for shape-selective isomerization of Fischer-Tropsch synthetic wax and its preparation method and use |
| CN105728023A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Molecular sieve catalyst for Fischer-Tropsch wax hydroisomerization reaction, and preparation method thereof |
| CN107282097A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of hydroisomerization catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 烃类异构化催化剂的研究进展;王春生等;《石油化工应用》;20131025(第10期);第6-10页 * |
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