CN114471679B - Catalyst for preparing lubricating oil base oil and preparation method of carrier of catalyst - Google Patents

Catalyst for preparing lubricating oil base oil and preparation method of carrier of catalyst Download PDF

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Publication number
CN114471679B
CN114471679B CN202011264594.9A CN202011264594A CN114471679B CN 114471679 B CN114471679 B CN 114471679B CN 202011264594 A CN202011264594 A CN 202011264594A CN 114471679 B CN114471679 B CN 114471679B
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acid
molecular sieve
catalyst carrier
catalyst
preparing
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CN114471679A (en
Inventor
杨晓东
陆雪峰
张全国
张国甲
王新苗
高善彬
刘彦峰
王燕
孙生波
董春明
郭立艳
姜维
赵檀
姜丽丽
马东海
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Petrochina Co Ltd
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Petrochina Co Ltd
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • B01J37/0201—Impregnation
    • 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
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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    • C10G2300/304—Pour point, cloud point, cold flow properties
    • 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
    • C10G2400/10—Lubricating oil

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a catalyst carrier of low cloud point base oil, which involves two main steps in the preparation process of the catalyst carrier, namely: preparation of molecular sieve fragment structural units and preparation of catalyst carriers. Preparing turbid liquid containing molecular sieve fragment structural units, an auxiliary agent and deionized water into solution, dripping the solution into powder formed by ten-membered ring structural molecular sieve and amorphous inorganic porous material, and performing forming, homogenization, drying and roasting to obtain the catalyst carrier. The base oil produced by the catalyst carrier has the advantages of high viscosity index, less viscosity index loss, low pour point, low cloud point and high total yield, and has good application prospect.

Description

Catalyst for preparing lubricating oil base oil and preparation method of carrier of catalyst
Technical Field
The invention relates to the field of preparing lubricating oil base oil, in particular to a preparation method of a catalyst carrier for preparing lubricating oil base oil, and a catalyst for preparing the lubricating oil base oil, which comprises the carrier prepared by the preparation method.
Background
Waxes are contained in mineral-based lubricating oil feedstocks, particularly petroleum-based lubricating oil feedstocks and intermediate-based lubricating oil feedstocks, which generally refer to long-chain normal paraffins or long-chain paraffins with small amounts of short side chains, including long-chain paraffins with small amounts of short side chains, long-chain alkyl aromatics, and long-chain alkyl alkane exchanges. Since the presence of these waxes affects the low temperature fluidity of the lubricant, dewaxing the processed lubricant stock is a necessary manufacturing step to obtain a lubricant product with good fluidity at low temperatures. Because the boiling point of wax is similar to that of lubricating oil fraction, it can not be separated by simple distillation method, and it needs to adopt necessary dewaxing process to remove.
The traditional dewaxing process adopts a solvent dewaxing method, wherein a solvent with high oil solubility and low wax solubility is added into a lubricating oil raw material to dilute the lubricating oil, a benzene solvent can well dissolve the lubricating oil, the solubility of the benzene solvent to the wax is high, and the solubility of a ketone solvent to the wax is low, so that acetone or methyl ethyl ketone is usually added into the benzene solvent to reduce the solubility of the benzene solvent to the wax, which is a so-called ketone-benzene dewaxing process, but the main defects of the process are high operation cost and high energy consumption, the reduction range of the condensation point of the lubricating oil is limited, and the produced lubricating oil foundation can only meet the I standard requirement of an API.
Catalytic dewaxing is another disclosed dewaxing process in which a waxy feed is contacted with hydrogen in the presence of a zeolite-containing catalytic dewaxing catalyst to selectively crack or isomerize the wax molecules, thereby achieving dewaxing. Catalytic dewaxing is more economical than solvent dewaxing, which has the disadvantage of higher yields of low molecular weight products, and lower yields of the desired product, lubricant oil.
The catalytic dewaxing generally adopts molecular sieve catalysts such as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and the like, and the special pore structure only allows normal paraffins and isoparaffins with a small amount of short side chains to enter the pore channels of the molecular sieve, but isoparaffins, naphthenes, aromatic hydrocarbons and the like cannot enter, so that the effect of selectively removing wax components is achieved.
U.S. patent No. 4,176,050 discloses a method for preparing a catalytic dewaxing catalyst, using large grain ZSM-5 molecular sieve as acid component and nickel as hydrogenation component. The selectivity of the catalyst is improved, but the activity is poor, and the liquid yield is low.
U.S. patent No. 4,428,819 discloses a ZSM-5 molecular sieve catalytic dewaxing catalyst for catalytic dewaxing of heavy lubricant oils, which has been found to be incapable of removing certain petroleum waxes, the dewaxed oil having a high cloud point and having to be dewaxed further with a noble metal catalyst to meet the cloud point requirements.
The isomerization dewaxing method is a first advance dewaxing technology of lubricating oil base oil disclosed after solvent dewaxing and catalytic dewaxing, and the dewaxing technology is characterized in that isomerization reaction is mainly carried out by an isomerization dewaxing catalyst and a processed oil product and a small amount of cracking reaction is auxiliary hydrogenation reaction under the hydrogen atmosphere, and the technology has the advantages of low product viscosity loss, low pour point and high liquid yield.
U.S. patent No. 6,699,385 discloses a method for reducing the cloud point of lubricating base oils by fractionating waxy feeds such as bright stock, heavy neutral stock, F-T synthetic oil, etc., isodewaxing the lighter fractions using a noble metal type catalyst with a cloud point reduced to only about 0 ℃.
In the prior published patent reports, although base oils of different grades can be produced, the low temperature flow properties (such as pour point and congealing point) and cloud point properties of the base oils cannot be effectively solved, and some techniques have a certain effect on pour point and cloud point, but the viscosity index loss of the base oils is larger.
Disclosure of Invention
In order to solve the above problems in the prior art, an object of the present invention is to provide a method for preparing a catalyst carrier for preparing a lubricant base oil, in which a molecular sieve fragment structural unit having a ten-membered ring structure is introduced during the preparation of the catalyst carrier, on the one hand, the molecular sieve having the ten-membered ring structure has better catalytic performance in the production of the lubricant base oil, on the other hand, the molecular sieve fragment structural unit has abundant molecular sieve defect sites with special catalytic performance in certain catalytic fields, and on the other hand, more molecular sieve defect sites (defect zeolite) having a shape selective catalytic effect are introduced on the catalyst carrier, so that the overall catalytic performance of the catalyst is improved, and it is required to explain that the molecular sieve defect sites (defect zeolite) refer to irregularities of the molecular sieve structure in the regular molecular sieve structure by a modification method.
The invention also aims to provide a catalyst for preparing the lubricating base oil, and the base oil produced by the catalyst has the advantages of no more than-5 ℃ of cloud point, low pour point and low viscosity index loss.
To this end, the present invention provides a method for preparing a catalyst carrier for preparing a lubricating base oil, comprising the steps of:
(1) Preparation of molecular sieve fragment structural units:
Placing a raw material molecular sieve in an acidic or alkaline solution, fully stirring for 5-60 min to obtain turbid liquid A, and continuously adjusting the pH value of the acidic or alkaline solution to 6-8 to obtain turbid liquid B containing molecular sieve fragment structural units;
(2) Preparation of the catalyst support:
mechanically and uniformly mixing a molecular sieve, an amorphous inorganic porous material and a binder to obtain mixed powder, preparing turbid liquid B obtained in the step (1), an auxiliary agent and deionized water into turbid liquid, dripping the turbid liquid B into the mixed powder, continuously kneading and forming, homogenizing, drying and roasting to obtain the catalyst carrier.
The preparation method of the catalyst carrier of the present invention is preferably that the mass ratio of the raw material molecular sieve, the amorphous inorganic porous material and the binder is 5-20:30-80:20-50:5-15.
The preparation method of the catalyst carrier of the present invention is preferably such that the mass ratio of the raw material molecular sieve, the amorphous inorganic porous material and the binder is 10-15:40-70:30-40:5-10.
The method for producing a catalyst carrier according to the present invention is preferably such that the raw material molecular sieve and the molecular sieve are the same or different.
In the method for preparing a catalyst carrier of the present invention, it is preferable that the raw material molecular sieve has a ten-membered ring structure.
The method for producing a catalyst carrier according to the present invention is preferably such that the molecular sieve has a ten-membered ring structure.
The preparation method of the catalyst carrier provided by the invention is characterized in that the raw material molecular sieve and the molecular sieve are preferably selected from one or more of ZSM-5, SAPO-11, EU-1, ITQ-13, ZSM-35, ZSM-48, ZSM-22, MCM-22, NU-87 and ZSM-23 respectively and independently.
The preparation method of the catalyst carrier according to the present invention, wherein preferably, the amorphous inorganic porous material comprises one or more of Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2 and Al 2O3-ZrO2.
In the method for preparing a catalyst carrier of the present invention, it is preferable that the alkaline solution is aqueous ammonia.
The preparation method of the catalyst carrier of the invention is characterized in that the acid solution is preferably inorganic acid or organic acid; when the acid solution is inorganic acid, the acid solution is one or more selected from nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the acid solution is organic acid, one or more of citric acid, acetic acid and tartaric acid are selected.
The preparation method of the catalyst carrier is characterized in that the auxiliary agent is preferably inorganic acid or organic acid, and when the auxiliary agent is inorganic acid, the auxiliary agent is one or more of nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the organic acid is selected from one or more of citric acid, acetic acid and tartaric acid.
In the method for preparing the catalyst carrier, the homogenization time is preferably 30-120 min.
In the method for preparing the catalyst carrier, the homogenization time is preferably 40-60 min.
In the preparation method of the catalyst carrier, in the step (1), the stirring time is preferably 20-40 min.
The invention also provides a catalyst for preparing the lubricating oil base oil, and the carrier of the catalyst is prepared by the preparation method of the catalyst carrier.
Specifically, the scheme adopts the following technical scheme:
In the preparation process of the hydroisomerization catalyst carrier, wherein the preparation of the molecular sieve fragment structural unit is an important ring for the preparation of the catalyst carrier, the raw material for preparing the molecular sieve fragment structural unit is a molecular sieve with a ten-membered ring structure, the first two steps are the preparation process of the molecular sieve fragment structural unit, and the step (1-1): placing a raw material molecular sieve containing a ten-membered ring structure into a certain amount of acidic solution with the concentration of H + to 4mol/L or alkaline solution with the concentration of OH + to 0.5 to 5mol/L, and fully stirring for 5 to 60 minutes to obtain turbid liquid A, wherein the stirring time is preferably 10 to 30 minutes; step (1-2): adjusting the turbid liquid A to pH value of 6-8 by acid or alkali to obtain turbid liquid B containing molecular sieve fragment structural units; step (2): mechanically and uniformly mixing molecular sieve powder, an amorphous inorganic porous material and a binder, preparing turbid liquid, an auxiliary agent and deionized water into deionized water, and dripping the deionized water into the mechanically and uniformly mixed powder; and (3) carrying out kneading molding, homogenization, drying and roasting on the product obtained in the step (2) to obtain the catalyst carrier.
The mass ratio of the preparation raw materials in the preparation method is that the raw material molecular sieve is as follows: molecular sieve: amorphous inorganic porous material: the binder is 5-20:30-80:20-50:5-15, and is further optimized to be 10-15:40-70:30-40:5-10.
Wherein the raw material molecular sieve is the same as or different from the molecular sieve.
Wherein the raw material molecular sieve has a ten-membered ring structure.
Wherein the molecular sieve has a ten-membered ring structure.
Wherein the raw material molecular sieve and the molecular sieve are selected from one or more of ZSM-5, SAPO-11, EU-1, ITQ-13, ZSM-35, ZSM-48, ZSM-22, MCM-22, NU-87 and ZSM-23.
Wherein the amorphous inorganic porous material used in the preparation of the catalyst carrier comprises one or more of Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2 or Al 2O3-ZrO2.
Wherein the alkaline solution used for preparing the molecular sieve fragment structural unit is ammonia water.
Wherein, the acid used for preparing the molecular sieve fragment structural unit is inorganic acid or organic acid, and when the acid is inorganic acid, the acid is selected from one or more of nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the organic acid is selected from one or more of citric acid, acetic acid and tartaric acid.
Wherein the auxiliary agent is inorganic acid or organic acid, and when the auxiliary agent is inorganic acid, the auxiliary agent is one or more of nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the organic acid is selected from one or more of citric acid, acetic acid and tartaric acid.
Wherein the homogenization time is 30 min-120 min, preferably 40 min-60 min.
The invention has the beneficial effects that:
According to the invention, molecular sieve fragment structural units are prepared by acidic or alkaline dissolution of molecular sieves, the defect sites generally have special shape-selective catalytic activity, and the molecular sieve fragment structural units are introduced into the catalyst carrier, so that the catalyst carrier has more molecular sieve defect sites, and meanwhile, the molecular sieve defect sites are distributed in the catalyst carrier, so that the catalyst has higher catalytic activity. The lubricating oil base oil produced by the catalyst carrier has the advantages of high viscosity index, less viscosity index loss, low pour point, low cloud point and high total yield of the base oil, and has good application prospect.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The preparation method of the catalyst carrier for preparing the lubricating oil base oil provided by the invention comprises the following steps:
(1) Preparation of molecular sieve fragment structural units:
Placing a raw material molecular sieve in an acidic or alkaline solution, fully stirring for 5-60 min to obtain turbid liquid A, and continuously adjusting the pH value of the acidic or alkaline solution to 6-8 to obtain turbid liquid B containing molecular sieve fragment structural units;
(2) Preparation of the catalyst support:
mechanically and uniformly mixing a molecular sieve, an amorphous inorganic porous material and a binder to obtain mixed powder, preparing turbid liquid B obtained in the step (1), an auxiliary agent and deionized water into turbid liquid, dripping the turbid liquid B into the mixed powder, continuously kneading and forming, homogenizing, drying and roasting to obtain the catalyst carrier.
In some embodiments, the feedstock molecular sieve, the amorphous inorganic porous material, and the binder are in a mass ratio of 5-20:30-80:20-50:5-15.
In some embodiments, the feedstock molecular sieve, the amorphous inorganic porous material, and the binder are in a mass ratio of 10-15:40-70:30-40:5-10.
In some embodiments, the feedstock molecular sieve and the molecular sieve are the same or different.
In some embodiments, the feedstock molecular sieve has a ten membered ring structure.
In some embodiments, the molecular sieve has a ten membered ring structure.
In some embodiments, the feedstock molecular sieve and the molecular sieve are each independently selected from one or more of ZSM-5, SAPO-11, EU-1, ITQ-13, ZSM-35, ZSM-48, ZSM-22, MCM-22, NU-87, and ZSM-23.
In some embodiments, the amorphous inorganic porous material comprises one or more of Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2 and Al 2O3-ZrO2.
In some embodiments, the alkaline solution is aqueous ammonia.
In some embodiments, the acidic solution is an inorganic acid or an organic acid; when the acid solution is inorganic acid, the acid solution is one or more selected from nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the acid solution is organic acid, one or more of citric acid, acetic acid and tartaric acid are selected.
In some embodiments, the auxiliary agent is an inorganic acid or an organic acid, and when the auxiliary agent is an inorganic acid, the auxiliary agent is one or more selected from nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the organic acid is selected from one or more of citric acid, acetic acid and tartaric acid.
In some embodiments, the homogenization time is from 30 minutes to 120 minutes.
In some embodiments, the homogenization time is 40min to 60min.
In some embodiments, in step (1), the stirring time is 20 to 40 minutes.
The catalyst for preparing the lubricating oil base oil is prepared from the catalyst carrier by the preparation method.
Example 1
The molecular sieve used for manufacturing the molecular sieve fragment structural unit and the molecular sieve used for carrier molding in the embodiment are industrial ZSM-5 molecular sieves. The amorphous inorganic porous material is Al 2O3, the auxiliary agent is nitric acid and citric acid, and the binder is sesbania powder.
Preparation of ZSM-5 type fragment building blocks: placing 5g of ZSM-5 molecular sieve into 10ml of ammonia water solution containing 5mol/L, and fully stirring in a water bath at 30 ℃ for 60min to obtain turbid liquid A; and (B) step (B): and (3) regulating the pH value of the turbid liquid A to 6-8 by using 1mol/L acetic acid solution to obtain turbid liquid B containing ZSM-5 type fragment structural units.
80G of ZSM-5 molecular sieve, 20g of Al 2O3 and 5g of sesbania powder are taken and uniformly mixed in a container, 10g of 37% nitric acid, 4g of citric acid, turbid liquid B and 40ml of deionized water are prepared into turbid liquid C, the turbid liquid C is dripped into the uniformly mixed powder, the uniformly mixed powder is extruded into a ball shape after kneading, the ball shape is homogenized for 30min, and then dried for 3 hours at 120 ℃, and the catalyst carrier Z1 is obtained after roasting for 6 hours at 550 ℃.
Example 2
In the embodiment, the molecular sieve for manufacturing the molecular sieve fragment structural unit is NU-87 type molecular sieve, and the molecular sieve used for carrier molding is ITQ-13 type molecular sieve. The amorphous inorganic porous material used is Al 2O3 and SiO 2, the auxiliary agent is nitric acid and sulfuric acid, and the binder is sesbania powder.
Preparing NU-87 molecular sieve fragment structural units: taking 20g of NU-87 molecular sieve, placing the molecular sieve in 20ml of hydrochloric acid solution containing 0.5mol/L, and fully stirring the solution in a water bath at 30 ℃ for 5min to obtain turbid liquid A; and (B) step (B): and (3) regulating the turbid liquid A to a pH value of 6-8 through 3mol/L ammonia water solution to obtain turbid liquid B containing NU-87 molecular sieve fragment structural units.
Mixing ITQ-13 type molecular sieve 30g, al 2O3、20g SiO2 g and sesbania powder 8g in a container, preparing turbid liquid C from nitric acid 3g, sulfuric acid 6g, turbid liquid B and deionized water 30ml, dripping into the mixed powder, kneading, extruding into particles, homogenizing for 120min, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 6 hours to obtain the catalyst carrier Z2.
Example 3
In the embodiment, the molecular sieve for manufacturing the molecular sieve fragment structural unit is MCM-22 type molecular sieve, and the molecular sieve used for carrier molding is ZSM-48 type molecular sieve. The amorphous inorganic porous materials used are Al 2O3-SiO2 and Al 2O3-ZrO2, the auxiliary agents are sulfuric acid and phosphoric acid, and the binder is sesbania powder.
Preparing MCM-22 type molecular sieve fragment structural units: 10g of MCM-22 molecular sieve is taken and placed in 15ml of phosphoric acid solution containing 0.5mol/L, and fully stirred in a water bath at 30 ℃ for 20min to obtain turbid liquid A; and (B) step (B): and (3) regulating the turbid liquid A to a pH value of 6-8 through 3mol/L ammonia water solution to obtain turbid liquid B containing MCM-22 molecular sieve fragment structural units.
Mixing 40g of ZSM-48 type molecular sieve, 30g of Al 2O3-SiO2、10g Al2O3-ZrO2 and 10g of sesbania powder uniformly in a container, preparing 2g of sulfuric acid, 7g of phosphoric acid, turbid liquid B and 30ml of deionized water into turbid liquid C, dripping into the uniformly mixed powder, kneading, extruding into a tablet, homogenizing for 60min, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 6h to obtain a carrier Z3.
Example 4
In this example, the molecular sieve used to make the molecular sieve fragment structural unit was EU-1 type molecular sieve, and the molecular sieve used for the carrier formation was SAPO-11 molecular sieve. The amorphous inorganic porous materials used are Al 2O3 and TiO 2, the auxiliary agents are phosphoric acid and citric acid, and the binder is sesbania powder.
Preparation of EU-1 type molecular sieve fragment building blocks: 15g of EU-1 molecular sieve is placed in 20ml of acid solution containing 1mol/L nitric acid and 1mol/L tartaric acid, and fully stirred in a water bath at 80 ℃ for 20min to obtain turbid liquid A; and (B) step (B): and (3) regulating the turbid liquid A to a pH value of 6-8 by 5mol/L ammonia water to obtain turbid liquid B containing ITQ-13 type molecular sieve fragment structural units.
60G of SAPO-11 type molecular sieve, 15g of Al2O3, 5g of TiO2 and 15g of sesbania powder are taken and uniformly mixed in a container, 5g of phosphoric acid, 3g of citric acid, turbid liquid B and 30ml of deionized water are prepared into turbid liquid C, the turbid liquid C is dropwise added into the uniformly mixed powder, the uniformly mixed powder is kneaded into strips, and then homogenized for 60min, and then dried at 120 ℃ for 3 hours, and the carrier Z4 is obtained after roasting at 550 ℃ for 6 hours.
Example 5
The molecular sieve for making the molecular sieve fragment structural unit in the embodiment is a ZSM-35 molecular sieve, and the molecular sieve used for carrier molding is a ZSM-23 molecular sieve. The amorphous inorganic porous materials used are Al 2O3 and ZrO 2, the auxiliary agent is phosphoric acid binder and sesbania powder.
Preparing a ZSM-35 molecular sieve fragment structural unit: 15g of ZSM-35 molecular sieve is taken and placed in 20ml of sulfuric acid solution containing 1mol/L, and the solution is fully stirred in a water bath at 30 ℃ for 20min to obtain turbid liquid A; and (B) step (B): and (3) regulating the turbid liquid A to a pH value of 6-8 by using 4mol/L ammonia water to obtain turbid liquid B containing ZSM-35 type molecular sieve fragment structural unit.
Mixing 40g of ZSM-23 type molecular sieve, 30g of Al 2O3、10g ZrO2 and 10g of sesbania powder uniformly in a container, preparing 5g of phosphoric acid, turbid liquid B and 35ml of deionized water into turbid liquid C, dripping into the uniformly mixed powder, kneading, extruding into strips, homogenizing for 30min, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 6 h to obtain a carrier Z5.
Example 6
The molecular sieve for making the molecular sieve fragment structural unit in the embodiment is a ZSM-22 molecular sieve, and the molecular sieve used for carrier molding is a ZSM-22 molecular sieve. The amorphous inorganic porous material used is Al 2O3 and TiO 2, the auxiliary agent is nitric acid and acetic acid, and the binder is sesbania powder.
Preparing ZSM-22 molecular sieve fragment structural unit: 10g of ZSM-22 molecular sieve is taken and placed in 10ml of ammonia water solution containing 5mol/L, and the solution is fully stirred in a water bath at 30 ℃ for 40min to obtain turbid liquid A; and (B) step (B): and (3) regulating the turbid liquid A to a pH value of 6-8 through 2mol/L hydrochloric acid to obtain turbid liquid B containing ZSM-22 type molecular sieve fragment structural units.
Mixing 70g of ZSM-22 molecular sieve, 20g of Al 2O3, 10g of TiO 2 and 5g of sesbania powder uniformly in a container, preparing 8g of nitric acid, 5g of acetic acid, turbid liquid B and 25ml of deionized water into turbid liquid C, dripping into the uniformly mixed powder, kneading, extruding into strips, homogenizing for 40min, drying at 120 ℃ for 3 h, and roasting at 550 ℃ for 6 h to obtain a carrier Z6.
Comparative example 1
Comparative example 1 support preparation 15g of ZSM-35 from example 5 used to make molecular sieve building blocks was added to the shaped support in the following embodiments: mixing 10g of ZSM-35 molecular sieve, 40g of ZSM-23 molecular sieve, 30g of Al 2O3、10g ZrO2 and 10g of sesbania powder in a container, dripping 75ml of deionized water into the mixed powder, kneading, extruding into strips, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 6 hours to obtain a carrier B5.
Comparative example 2
Comparative example 2 support preparation 10g of ZSM-22 for the preparation of molecular sieve building blocks from example 6 was added to the shaped support in the following embodiments: mixing 80g of ZSM-22 molecular sieve, 20g of Al 2O3、10gTiO2 and 5g of sesbania powder in a container, dripping 75ml of deionized water into the mixed powder, kneading, extruding into strips, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 6 hours to obtain a carrier B6.
Example 7
50G of prepared carriers Z4, Z5, Z6, B5 and B6 are taken, solutions containing chloroplatinic acid and palladium chloride are immersed into the carriers by an isovolumetric immersion method, the platinum content of each prepared catalyst is 0.3%, the palladium content of each prepared catalyst is 0.2%, the prepared catalysts are named ZC4, ZC5, ZC6, BC5 and BC6, the prepared catalysts are filled in a fixed bed reactor and are applied to the hydroisomerization field for producing lubricating oil base oil, the hydrotreated reduced-four-wire wax oil is taken as a raw material, and the reaction conditions are as follows: reaction temperature 380 ℃, hydrogen partial pressure 12MPa and hydrogen oil volume ratio: 700:1, 0.8h -1, and the evaluation results are shown in Table 1.
TABLE 1 oil Properties of raw materials
The evaluation device was operated for 200 hours and sampled, and the cut base oil was cut at a true boiling point and was cut at a temperature of more than 360℃to obtain the results shown in Table 2.
Table 2 evaluation results
As can be seen from the evaluation results of Table 2, the prepared base oil has the advantages of low congealing point, low pour point, low cloud point, high viscosity index, low viscosity index loss (raw material viscosity index is 141, product viscosity index is > 125), low aromatic hydrocarbon content and high total base oil yield compared with the catalyst carrier without the molecular sieve fragment structural units.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (9)

1. A method for preparing a catalyst support for lubricating base oils, comprising the steps of:
(1) Preparation of molecular sieve fragment structural units:
Placing a raw material molecular sieve in an acidic or alkaline solution, fully stirring for 5 min-60 min to obtain turbid liquid A, and continuously adjusting the pH value of the acidic or alkaline solution to 6-8 to obtain turbid liquid B containing molecular sieve fragment structural units;
(2) Preparation of the catalyst support:
Mechanically and uniformly mixing a molecular sieve, an amorphous inorganic porous material and a binder to obtain mixed powder, preparing turbid liquid B obtained in the step (1), an auxiliary agent and deionized water into turbid liquid, dripping the turbid liquid B into the mixed powder, continuously kneading and forming, homogenizing, drying and roasting to obtain a catalyst carrier;
the alkaline solution is ammonia water;
The acid solution is inorganic acid or organic acid; when the acid solution is inorganic acid, the acid solution is one or more selected from nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the acid solution is organic acid, one or more of citric acid, acetic acid and tartaric acid are selected;
The mass ratio of the raw material molecular sieve to the amorphous inorganic porous material to the binder is 5-20:30-80:20-50:5-15;
the raw material molecular sieve has a ten-membered ring structure;
The molecular sieve has a ten-membered ring structure;
The raw material molecular sieve and the molecular sieve are respectively and independently selected from one or more of ZSM-5, SAPO-11, EU-1, ITQ-13, ZSM-35, ZSM-48, ZSM-22, MCM-22, NU-87 and ZSM-23.
2. The method for producing a catalyst carrier according to claim 1, wherein the mass ratio of the raw material molecular sieve, the amorphous inorganic porous material, and the binder is 10-15:40-70:30-40:5-10.
3. The method for producing a catalyst carrier according to claim 1, wherein the raw material molecular sieve and the molecular sieve are the same or different.
4. The method for producing a catalyst carrier according to claim 1, wherein the amorphous inorganic porous material comprises one or more of Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2 and Al 2O3-ZrO2.
5. The method for preparing a catalyst carrier according to claim 1, wherein the auxiliary agent is an inorganic acid or an organic acid, and when the auxiliary agent is an inorganic acid, the auxiliary agent is one or more selected from nitric acid, sulfuric acid, hydrochloric acid, tartaric acid and phosphoric acid; when the organic acid is selected from one or more of citric acid, acetic acid and tartaric acid.
6. The method for preparing a catalyst carrier according to claim 1, wherein the homogenization time is 30min to 120min.
7. The method for preparing a catalyst carrier according to claim 1, wherein the homogenization time is 40min to 60min.
8. The method for preparing a catalyst carrier according to claim 1, wherein in the step (1), the stirring time is 20 to 40 minutes.
9. A catalyst for preparing a lubricating base oil, characterized in that the catalyst carrier is prepared by the method for preparing a catalyst carrier according to any one of claims 1 to 8.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106669803A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Catalyst applied to production of high-viscosity index hydrocracking tail oil and preparation method thereof
CN111068771A (en) * 2019-12-29 2020-04-28 上海兖矿能源科技研发有限公司 Heterogeneous pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate oil and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106669803A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Catalyst applied to production of high-viscosity index hydrocracking tail oil and preparation method thereof
CN111068771A (en) * 2019-12-29 2020-04-28 上海兖矿能源科技研发有限公司 Heterogeneous pour point depressing catalyst suitable for Fischer-Tropsch synthesis distillate oil and preparation method and application thereof

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