CN113908817A - Carrier for catalyst, preparation method of carrier, pour point depressing catalyst, preparation method of pour point depressing catalyst and application of pour point depressing catalyst - Google Patents

Carrier for catalyst, preparation method of carrier, pour point depressing catalyst, preparation method of pour point depressing catalyst and application of pour point depressing catalyst Download PDF

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Publication number
CN113908817A
CN113908817A CN202010655584.1A CN202010655584A CN113908817A CN 113908817 A CN113908817 A CN 113908817A CN 202010655584 A CN202010655584 A CN 202010655584A CN 113908817 A CN113908817 A CN 113908817A
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carrier
catalyst
pour point
content
point depressing
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CN113908817B (en
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马辉
李虎
艾军
杨加义
胡云剑
邢爱华
余海鹏
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J35/615—
    • B01J35/633—
    • B01J35/635—
    • B01J35/647—
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group

Abstract

The invention relates to the field of catalysts, and discloses a carrier for a catalyst, a preparation method of the carrier, a pour point depressing catalyst, a preparation method of the pour point depressing catalyst and application of the pour point depressing catalyst. The carrier for the catalyst comprises silicon oxide and aluminum oxide, wherein SiO is used based on the total weight of the carrier2The content of the silicon oxide is 4-36 wt% calculated by Al2O3The content of the alumina is 64-96 wt%; in the carrier, silicon oxide and aluminum oxide are amorphous; the acidity of the carrier is 1.1-3.25 mmol/g. The surface of the carrier for the catalyst belongs to medium-strength acid and is prepared by the medium-strength acidThe diesel pour point depressing catalyst has larger specific surface area, wider mesoporous aperture distribution and excellent isomerization catalytic activity, can prepare high-isomerization diesel products, and is suitable for Fischer-Tropsch synthesis with cracking hydrogenation reaction.

Description

Carrier for catalyst, preparation method of carrier, pour point depressing catalyst, preparation method of pour point depressing catalyst and application of pour point depressing catalyst
Technical Field
The invention relates to the field of catalysts, and particularly relates to a carrier for a catalyst and a preparation method thereof, a pour point depressing catalyst and a preparation method and application thereof.
Background
In northern areas of China, the demand of low-freezing diesel oil is large in winter, diesel oil produced by a 400-million-ton indirect liquefaction device of Ningdan is mainly paraffin, the condensation point of the diesel oil fraction is high, the low-temperature fluidity is poor, and the pour point reduction treatment is required to improve the low-temperature fluidity of the diesel oil. In the diesel oil dewaxing process, the hydrogenation pour point depressing technology has the advantages of less investment, low operation cost, mild operation condition, etc. and has obvious technological advantages.
The diesel oil hydrogenation pour point depressing principle is that under the condition of hydrogen gas, normal paraffin with short side chain, naphthenic hydrocarbon with long side chain, arene with long side chain and other high condensation point components in the raw oil are made to produce hydrogenation isomerization reaction on the catalyst with shape selective isomerization performance to produce isomeric paraffin with low condensation point or long side chain isomeric paraffin, so as to reach the aim of depressing condensation point. The key of diesel oil hydrogenation pour point depression technology is hydrogenation pour point depression catalyst. The hydrogenation pour point depression catalyst is a bifunctional catalyst, the metal component provides a hydrogenation dehydrogenation active center, and the molecular sieve provides an acid center.
CN107570206A discloses a diesel oil hydrogenation pour point depression catalyst, which is prepared by adopting TON/MFI shape selective isomerism in-situ composite molecular sieve, adding a small amount of adhesive, extruding into strips, forming into a carrier, and drying/roasting the carrier to load metal active components. Wherein the TON/MFI shape selective isomerism in-situ composite molecular sieve is obtained by in-situ synthesis by a sol-gel method, the molar ratio of silicon-aluminum oxide is 30-180, and the TON structure accounts for 1-60%. The catalyst is suitable for diesel oil hydrogenation pour point depression process, and has the characteristics of high diesel oil product yield, large pour point depression range and the like.
CN1448475A discloses a catalyst for producing low freezing point clean diesel, which adopts modified beta zeolite as an acid component, the modification method of the zeolite uses a silicon-containing organic matter with larger kinetic diameter to contact with the zeolite under certain conditions, so that the silicon-containing organic matter is combined with acid centers on the outer surface of the zeolite to be passivated, and the acid centers inside zeolite pore channels are reserved.
CN1952074A discloses a diesel fraction pour point depressing catalyst, which comprises a modified molecular sieve carrier and a hydrogenation metal component, wherein the modified molecular sieve is modified by VIB group metal, the weight of a modifier in the modified molecular sieve is 1-40% in terms of oxidation state, the weight content of the molecular sieve in the catalyst is 10-90%, and the weight content of hydrogenation active metal in oxide is 0.1-40%. The modifier can modify the acid property and the orifice size of the surface of the molecular sieve, has good matching between the isomerization function and the shape-selective cracking function of the catalyst, ensures that the isomerization reaction is carried out according to a key reaction mechanism, has proper shape-selective cracking reaction, prevents over-cracking, improves the property of diesel oil and improves the yield of the diesel oil.
However, in the above techniques, the molecular sieve is used as a carrier of the catalyst, which results in a decrease in yield of the isomerate diesel.
Disclosure of Invention
The invention aims to solve the problem of low yield of heterogeneous diesel oil in the Fischer-Tropsch synthetic oil cracking process in the prior art, and provides a carrier for a catalyst, a preparation method of the carrier, a pour point depressing catalyst, a preparation method of the pour point depressing catalyst and application of the pour point depressing catalyst. The surface of the carrier for the catalyst belongs to medium-strength acid, the diesel pour point depressing catalyst prepared from the carrier has larger specific surface area, wider mesoporous aperture distribution and excellent isomerization catalytic activity, can prepare a high-isomerization diesel product, and is suitable for Fischer-Tropsch synthesis with cracking hydrogenation reaction.
In order to achieve the above object, a first aspect of the present invention provides a carrier for a catalyst, wherein the carrier comprises silica and alumina, wherein SiO is provided based on the total weight of the carrier2The content of the silicon oxide is 4-36 wt% calculated by Al2O3The content of the alumina is 64-96 wt%; in the carrier, silica and alumina are amorphous, and the acidity of the carrier is 1.1-3.25 mmol/g.
Preferably in SiO2The content of the silicon oxide is 8-32 wt%, preferably 12-28 wt%; with Al2O3The content of the alumina is 68 to 92 wt%, preferably 72 to 88 wt%.
Preferably, the acidity of the support is in the range of 2.6 to 3 mmol/g.
The second aspect of the present invention provides a method for producing the carrier for a catalyst of the present invention, wherein the method comprises: mixing amorphous silicon-aluminum with a binder, stirring, adding a nitric acid solution, kneading, molding, drying and roasting to obtain the carrier for the catalyst.
Preferably, the binder is selected from at least one of pseudoboehmite, silica sol, alumina sol and water glass, preferably pseudoboehmite.
Preferably, the pseudoboehmite has a peptization index of at least 90 wt%; more preferably, the pseudoboehmite has a peptization index of at least 95 wt%.
Preferably, the pseudo-boehmite contains gibbsite in an amount of at most 5 wt%; more preferably, the pseudo-boehmite contains gibbsite in an amount of at most 2 wt%.
Preferably, the amorphous silicon aluminum has a specific surface area of 200-500m2A/g of preferably 400-500m2/g。
Preferably, the amorphous silicon aluminum has a pore volume of 1 to 1.6mL/g, preferably 1.4 to 1.6 mL/g.
Preferably, SiO in the amorphous silicon-aluminum2The content of (B) is 20 to 70 wt%, preferably 30 to 50 wt%.
Preferably, the nitric acid solution is used in an amount of 4 to 10g, preferably 4 to 7g, relative to 100g of the total weight of amorphous silica-alumina and binder.
Preferably, the method of forming comprises at least one of drop ball forming, extrusion forming and tablet forming, preferably extrusion forming.
Preferably, the drying conditions include: the drying temperature is 40-180 ℃, and preferably 100-150 ℃; the drying time is 0.5-24h, preferably 1-8 h.
Preferably, the conditions of the calcination include: the roasting temperature is 350-700 ℃, and preferably 400-600 ℃; the roasting time is 0.5-24h, preferably 4-8 h.
The third aspect of the invention provides a pour point depressing catalyst, wherein the catalyst comprises a carrier and a metal active component, wherein the carrier is the carrier of the invention or the carrier prepared by the method of the invention.
Preferably, the content of the carrier is 60 to 80 wt% based on the total weight of the catalyst, and the content of the metal active component is 20 to 40 wt% in terms of metal oxide.
Preferably, the content of the carrier is 65 to 75 wt% based on the total weight of the catalyst, and the content of the metal active component is 25 to 35 wt% in terms of metal oxide.
Preferably, the metal active component comprises group VIII and group VIB metal elements.
Preferably, the group VIII metal element is present in an amount of from 1 to 15 wt%, preferably from 4 to 8 wt%, calculated as oxide, based on the total weight of the catalyst; the content of the VIB group metal element is 10-35 wt%, and preferably 20-28 wt%.
More preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten.
The fourth aspect of the invention provides a method for preparing the pour point depressing catalyst, wherein the method comprises the steps of dipping a carrier into dipping solution containing active metal components, drying and roasting to obtain the diesel pour point depressing catalyst.
Preferably, the impregnation comprises at least one of saturation impregnation, spray impregnation, excess impregnation and equal volume impregnation, preferably equal volume impregnation.
Preferably, the drying conditions include: the drying temperature is below 200 ℃, preferably 80-150 ℃; the drying time is 1-10 h.
Preferably, the conditions of the calcination include: the roasting temperature is 350-700 ℃, preferably 450-550 ℃; the roasting time is 0.5-24h, preferably 4-8 h.
In a fifth aspect, the invention provides a use of the pour point depressing catalyst of the invention or the pour point depressing catalyst prepared by the method of the invention in Fischer-Tropsch synthetic oil cracking.
By the technical scheme, the carrier for the catalyst and the preparation method thereof, the pour point depressing catalyst and the preparation method and application thereof provided by the invention have the following beneficial effects:
1. the carrier for the catalyst provided by the invention does not use a molecular sieve as a carrier, but uses amorphous silicon-aluminum as a carrier, the surface of the carrier has medium-strength acid, the prepared catalyst has large specific surface area and wider mesoporous aperture distribution, the diffusion of raw materials and products is easy, the adverse effect of diesel yield reduction caused by secondary cracking of the molecular sieve on the raw materials is reduced, and the production of a high-isomerization diesel product is facilitated;
2. the diesel pour point depressing catalyst provided by the invention uses non-noble metals as active metal components, so that the production cost of the catalyst is greatly reduced.
Drawings
FIG. 1 is an XRD pattern of the catalysts provided in examples 1-2 and comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a carrier for a catalyst, wherein the carrier comprises silica and alumina, wherein the SiO is provided as SiO based on the total weight of the carrier2The content of the silicon oxide is 4-36 wt% calculated by Al2O3The content of the alumina is 64-96 wt%; in the carrier, silica and alumina are amorphous, and the acidity of the carrier is 1.1-3.25 mmol/g.
In the present invention, the acidity of the carrier is obtained by an infrared test using pyridine at 100 ℃.
The distillation range of the raw material Fischer-Tropsch heavy diesel oil subjected to cracking hydrogenation is narrow, the distillation range of the main fraction is at 280-370 ℃, aromatic hydrocarbon, carbon residue and sulfur are not contained, nitrogen is not contained, and more than 90% of the structure of the main fraction is paraffin.
For the cracking reaction of alkanes, it is inevitable to accompany the isomerization. Both isomerization and cracking are carried out under the condition of an acid catalyst through a carbonium ion intermediate, carbonium ions are extremely active and only exist instantly, and once generated, isomerization reaction and cracking reaction are carried out rapidly. It can be seen that the step of desorbing the olefin from the acid sites and adsorbing the olefin to the metal sites during the alkane cracking reaction is very important.
Therefore, the retention time of the isomeric carbonium ions in the acid center is reduced, so that the isomeric carbonium ions are desorbed from the acid center before beta-fragmentation occurs, the cracking reaction can be inhibited, the isomerization reaction is promoted, and the preparation of diesel oil by the Fischer-Tropsch heavy diesel oil isomerization reaction is facilitated.
In the prior art, when the hydroisomerization and pour point depression reaction is carried out on Fischer-Tropsch heavy diesel to prepare diesel, a catalyst taking a molecular sieve as a carrier is generally used.
The research of the inventor finds that just because the Fischer-Tropsch heavy diesel oil has the characteristics, the cracking activity of the catalyst in the prior art which takes the molecular sieve as the carrier is high because the molecular sieve has stronger acidity, so that the yield of the catalyst for preparing the diesel oil by catalyzing the isomerization of the Fischer-Tropsch heavy diesel oil is lower, and the actual requirement cannot be met.
In the present invention, the inventors have employed amorphous oxides, specifically amorphous silicon aluminum (e.g., SiO)2-A12O3) The catalyst is a carrier replacing a molecular sieve in the prior art, and compared with the molecular sieve, the amorphous silica-alumina has weaker acidity, so that the ratio of metallicity to acidity of the catalyst can be greatly improved, the metal/acid value on the hydroisomerization catalyst is improved, the generation of high isomerization products is facilitated, the pour point depressing effect is obviously improved, and the yield of diesel oil is improved.
Further, when the acidity of the carrier is 2.6 to 3mmol/g, the catalyst has more excellent catalytic effect.
Meanwhile, the inventor researches the use amount of amorphous silicon aluminum and a binder in the carrier, and the research shows that when SiO is used2The content of the silicon oxide is 8-32 wt% calculated by Al2O3When the content of the alumina is 68-92 wt%, the provided carrier has more appropriate surface acidity, more appropriate pore size distribution and specific surface area, and the yield of the diesel oil is improved.
Further, based on the total weight of the carrier, with SiO2The content of the silicon oxide is 12-28 wt% calculated by Al2O3The content of the alumina is 72-88 wt%.
The second aspect of the present invention provides a method for producing the carrier for a catalyst according to the present invention, wherein the method comprises: mixing amorphous silicon-aluminum with a binder, stirring, adding a nitric acid solution, kneading, molding, drying and roasting to obtain the carrier for the catalyst.
According to the invention, the nitric acid solution is added into the mixed amorphous silicon-aluminum and the binder, so that the binder, especially the sol of pseudo-boehmite, can be promoted, the binding property of the amorphous silicon-aluminum is obviously improved, and the carrier for the catalyst with more excellent comprehensive performance is obtained.
According to the invention, the binder is selected from at least one of pseudo-boehmite, silica sol, alumina sol and water glass, and is preferably pseudo-boehmite.
The inventor researches and discovers that the adoption of the pseudoboehmite as the adhesive has remarkable influence on the improvement of the surface acidity of the carrier, the improvement of the pore size distribution of the carrier and the like. The peptization index of the pseudoboehmite is at least 90 wt%, and the content of the gibbsite in the pseudoboehmite is not more than 5 wt%, so that the obtained carrier has excellent performance and the adverse effect of the gibbsite in the pseudoboehmite on the carrier structure is reduced.
Specifically, when the peptization index of the pseudo-boehmite is too low, the binding function of the pseudo-boehmite becomes weak, which is not favorable for binding amorphous silica-alumina powder, and when the content of gibbsite in the pseudo-boehmite is too high, the performance of the catalyst becomes poor.
Further, in the present invention, the pseudoboehmite has a peptization index of at least 95 wt%, and the gibbsite content in the pseudoboehmite is at most 2 wt%.
In the present invention, the inventors have found, through research, that the specific surface area, pore volume and SiO of amorphous silicon-aluminum2The content of (A) has important influence on the surface activity, the pore size distribution and the like of the carrier, and further has obvious influence on the yield of the diesel oil prepared by Fischer-Tropsch heavy diesel oil isomerization. Researches find that in order to ensure the yield of diesel oil prepared by the isomerization of Fischer-Tropsch heavy diesel oil, the specific surface area of the amorphous silicon-aluminum is 400-500m2Per g, preferably 450-2(ii)/g; the pore volume of the amorphous silicon-aluminum is 0.5-1.6mL/g, preferably 0.8-1.6 mL/g; SiO in the amorphous silicon-aluminum2The content of (B) is 20 to 70 wt%, preferably 30 to 70 wt%.
Such as the specific surface area, pore volume and SiO of amorphous Si-Al2When the content of (A) is not in the range defined by the invention, the comprehensive performance of the prepared carrier is poor, and the yield of the carrier used for catalyzing the isomerization of the Fischer-Tropsch heavy diesel oil to prepare the diesel oil is low, so that the actual requirement cannot be met.
According to the invention, the nitric acid solution is used in an amount of 4 to 10g, preferably 4 to 7g, relative to 100g of the total weight of amorphous silica-alumina and binder.
In the present invention, the amount of the nitric acid solution is based on the mass of nitric acid contained in the nitric acid solution.
According to the present invention, the molding method includes at least one of dropping ball molding, extrusion molding and tablet molding, preferably extrusion molding.
According to the invention, the conditions of drying include: the drying temperature is 40-180 ℃, and preferably 100-150 ℃; the drying time is 0.5-24h, preferably 1-8 h.
According to the invention, the conditions of the calcination include: the roasting temperature is 350-700 ℃, and preferably 400-600 ℃; the roasting time is 0.5-24h, preferably 4-8 h.
The third aspect of the invention provides a pour point depressing catalyst, wherein the catalyst comprises a carrier and a metal active component, wherein the carrier is the carrier disclosed by the invention or the carrier prepared by the method disclosed by the invention.
In the invention, the catalyst prepared by matching the carrier provided by the invention and the active metal component has excellent diesel pour point depression effect, and can obviously improve the yield of diesel when being used for isomerization of Fischer-Tropsch heavy diesel.
Meanwhile, the carrier amorphous silicon aluminum used by the invention has weak sensitivity to temperature, so that the reaction temperature is easy to control when the prepared catalyst is used for catalytic reaction, and the requirement on a production device is reduced.
According to the invention, the support is present in an amount of 60 to 80 wt.%, calculated as metal oxide, and the metal active component is present in an amount of 20 to 40 wt.%, based on the total weight of the catalyst.
According to the invention, the support is present in an amount of 67 to 75 wt.%, calculated as metal oxide, and the metal active component is present in an amount of 25 to 33 wt.%, based on the total weight of the catalyst.
According to the invention, the metal active component comprises elements of the metals of group VIII and group VIB.
In the invention, the content of the VIII group metal element is 1-15 wt% and the content of the VIB group metal element is 10-35 wt% calculated by oxide, and when the content of the metal elements in the metal active component does not meet the range, the obtained catalyst is weak in metal property and the isomerization degree of the product is low.
Further, the content of the group VIII metal element is preferably 4 to 8 wt% in terms of oxide; the content of group VIB metal elements is preferably from 20 to 28 wt.%. The prepared catalyst has more excellent isomerization catalytic activity and can prepare high-isomerization diesel products.
Preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten.
In the invention, because the acidity of the carrier is weakened, non-noble metal can be matched as a metal active component of the catalyst during the preparation of the catalyst, and the production cost of the catalyst can be obviously reduced on the premise of ensuring the heterogeneous catalytic activity of the catalyst.
The fourth aspect of the invention provides a method for preparing the pour point depressing catalyst, wherein the method comprises the steps of dipping a carrier into dipping solution containing active metal components, drying and roasting to obtain the diesel pour point depressing catalyst.
According to the invention, the impregnation comprises at least one of saturation impregnation, spray impregnation, excess impregnation and equal volume impregnation, preferably equal volume impregnation.
According to the invention, the conditions of drying include: the drying temperature is below 200 ℃, preferably 80-150 ℃; the drying time is 1-10 h.
According to the invention, the conditions of the calcination include: the roasting temperature is 350-700 ℃, preferably 450-550 ℃; the roasting time is 0.5-24h, preferably 4-8 h.
In a fifth aspect, the invention provides an application of the pour point depressing catalyst or the diesel oil pour point depressing catalyst prepared by the method in Fischer-Tropsch synthetic oil cracking.
The present invention will be described in detail below by way of examples. In the following examples, N is used as the specific surface area, pore volume and pore distribution of the catalyst2AdsorptionMeasured by the method (BET);
the strength of the catalyst is measured by an intelligent particle strength tester;
the peptization index of the pseudo-boehmite is measured by adopting an EDTA method;
the content of gibbsite in the pseudoboehmite is measured by an XRD method;
testing the content of each component in the carrier by adopting XRF;
pyridine infrared (1540 cm) at 100 DEG was used-1) Testing the acid amount of the carrier and the surface of the amorphous silicon-aluminum powder;
and (3) characterizing the crystal morphology of the catalyst by XRD.
The physical and chemical parameters of the amorphous silicon-aluminum used in the examples and comparative examples are shown in table 1;
TABLE 1
Amorphous silicon-aluminum PA-1 3903 A
Specific surface area, m2/g 320.1 193.97 498
Pore volume, mL/g 0.81 0.64 1.6
Amount of acid，mmol/g 1.781 1.344 4.927
The pseudoboehmite I is purchased from Shandong Enable catalytic technology Limited, and has a peptization index of 95 wt%, a gibbsite content of 2 wt%, a pore volume of 0.45mL/g and a specific surface area of 200m2/g；
The pseudoboehmite II is purchased from Shandong Enable catalytic technology Limited, and has a peptization index of 90 wt%, a gibbsite content of 4 wt%, a pore volume of 0.45mL/g, and a specific surface area of 200m2/g；
The pseudoboehmite III is purchased from Shandong Enable catalytic technology Limited, and has a peptization index of 85 wt%, a gibbsite content of 6 wt%, a pore volume of 0.45mL/g and a specific surface area of 200m2/g。
Example 1
147g of amorphous silica-alumina I (ASA) and 74g of pseudo-boehmite I (SB, unfired), uniformly mixing, adding aqueous solution of nitric acid under stirring, kneading into dough by a mixer, putting into a plodder to extrude clover type with the maximum diameter of 2mm, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 4h to obtain a carrier A, wherein SiO is used as the carrier A2The content of the silicon oxide is 26 wt% in terms of Al2O3The alumina content was 74 wt%. Carrier A was tested for acidity and the results are shown in Table 3.
Preparing 20g of ammonium metatungstate and 18 g of nickel nitrate into impregnation liquid, adding 50g of the obtained carrier A into the impregnation liquid, impregnating in a rotary evaporator at 80 ℃ for 2h, and roasting at 500 ℃ for 2h to prepare the catalyst A, wherein the content of the VIII group metal nickel element is 5 wt% and the content of the VIB group metal tungsten element is 17.5 wt% in terms of oxides. The compositions are shown in Table 3.
The XRD pattern of the catalyst as shown in fig. 1 shows that the catalyst a is in an amorphous shape and the surface support B does not contain molecular sieve.
Example 2
126g of amorphous silica-alumina I (ASA) and 98g of pseudo-boehmite I (SB, unfired), uniformly mixing, adding a nitric acid aqueous solution under the stirring state, kneading into a dough by a mixer, putting into a plodder to extrude a clover shape with the maximum diameter of 2mm, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 4h to obtain a carrier B, wherein SiO is used as the carrier B2The content of the silicon oxide was 22 wt% in terms of Al2O3The alumina content was 78 wt%. Carrier B was tested for acidity and the results are shown in Table 3.
Preparing 20g of ammonium metatungstate and 18 g of nickel nitrate into impregnation liquid, adding 50g of the obtained carrier B into the impregnation liquid, impregnating in a rotary evaporator at 80 ℃ for 2h, and roasting at 500 ℃ for 2h to prepare the catalyst B, wherein the content of the VIII group metal nickel element is 5 wt% and the content of the VIB group metal tungsten element is 17.5 wt% in terms of oxides. The compositions are shown in Table 3.
As can be seen from the XRD pattern of catalyst B shown in fig. 1, catalyst B is in an amorphous shape, and the surface support B does not contain molecular sieve.
Example 3
The carrier was prepared by the same method as in example 1, except that: using amorphous silicon-aluminum II to replace amorphous silicon-aluminum I to prepare a carrier C, wherein SiO is used2The content of the silicon oxide is 26 wt% in terms of Al2O3The alumina content was 74 wt%, and catalyst C was obtained in the same manner as in example 1. Carrier C was tested for acidity and the results are shown in Table 3. Catalyst C composition is shown in table 3.
Example 4
The carrier was prepared by the same method as in example 1, except that: pseudo-boehmite II was used instead of pseudo-boehmite I to prepare a carrier D, and the same method as in example 1 was used to prepare a catalyst D. Carrier D was tested for acidity and the results are shown in Table 3. Catalyst D composition is shown in table 3.
Example 5
The carrier was prepared by the same method as in example 1, except that: and preparing a catalyst E by using 10g of ammonium tungstate and 5.5 g of nickel nitrate, wherein the content of the VIII group metal nickel element is 2 wt% and the content of the VIB group metal tungsten element is 13 wt% in terms of oxides. Carrier E was tested for acidity and the results are shown in Table 3. Catalyst E composition is shown in table 3.
Example 6
The carrier was prepared by the same method as in example 1, except that: using pseudoboehmite III instead of pseudoboehmite I, a carrier F was prepared and the catalyst F was prepared in the same manner as in example 1, wherein SiO was used2The content of the silicon oxide is 26 wt% in terms of Al2O3The alumina content was 74 wt%. Carrier F was tested for acidity and the results are shown in Table 3. The composition of catalyst F is shown in Table 3.
Comparative example 1
Uniformly mixing 147g of amorphous silica-alumina I (ASA), 54g of pseudo-boehmite I (SB, unfired) and 20g of beta molecular sieve (Si/Al is 25), adding aqueous solution of nitric acid under the stirring state, kneading into a mass by a mixer, putting into a squeezer to extrude clover type with the maximum diameter of 2mm, drying at 120 ℃ for 4h, and then roasting at 500 ℃ for 4h to obtain a carrier D1, wherein the carrier D1 is prepared by SiO2The content of the silicon oxide is 38 wt% in terms of Al2O3The content of the alumina was 62 wt%. Carrier D1 was subjected to an acidity test and the results are shown in Table 3.
Preparing 20g of ammonium metatungstate and 18 g of nickel nitrate into an impregnation solution, adding the obtained carrier D150 g into the impregnation solution, impregnating in a rotary evaporator at 80 ℃ for 2h, and then roasting at 500 ℃ for 2h to prepare the catalyst D1, wherein the content of the VIII group metal nickel element is 5 wt% and the content of the VIB group metal tungsten element is 17.5 wt% in terms of oxides. Catalyst D1 composition is shown in table 3.
The XRD spectrum of the catalyst D1 obtained in comparative example 1 is shown in fig. 1. As can be seen from fig. 1, a distinct peak appears at 2 θ ═ 22.4 ° and represents the presence of the molecular sieve.
Comparative example 2
Amorphous silica-alumina I (ASA)147g, pseudoboehmite I (SB, unfired) 62g, beta-moleculeSieving (Si/Al 25)12g, mixing, adding aqueous solution of nitric acid under stirring, kneading into dough, extruding into clover shape with maximum diameter of 2mm, drying at 120 deg.C for 4 hr, and calcining at 500 deg.C for 4 hr to obtain catalyst carrier D2, wherein the catalyst carrier is prepared from SiO2The content of the silicon oxide was 33 wt% in terms of Al2O3The content of the alumina was 67 wt%. Carrier D2 was subjected to an acidity test and the results are shown in Table 3.
Preparing 20g of ammonium metatungstate and 18 g of nickel nitrate into impregnation liquid, adding the obtained carrier D250 g into the impregnation liquid, impregnating in a rotary evaporator at 80 ℃ for 2h, and then roasting at 500 ℃ for 2h to prepare the contrast agent D2, wherein the content of the VIII group metal nickel element is 5 wt% and the content of the VIB group metal tungsten element is 17.5 wt% in terms of oxides. Catalyst D2 composition is shown in table 3.
Comparative example 3
The carrier was prepared by the same method as in example 1, except that: using amorphous Si-Al III instead of amorphous Si-Al I, support D3 was prepared, and catalyst D3, in which SiO was used, was prepared in the same manner as in example 12The content of the silicon oxide is 26 wt% in terms of Al2O3The alumina content was 74 wt%. Carrier D3 was subjected to an acidity test and the results are shown in Table 3. Catalyst D3 composition is shown in table 3.
The catalyst B prepared in the invention example 2 and FC-14 pour point depressing catalyst (commercial product) are subjected to N2The adsorption (BET) and the intensity measurements gave the structural parameters shown in Table 2.
TABLE 2 structural parameters of catalyst B and FC pour point depressant prepared in inventive example 2
FC series Example 2
Specific surface area, m2/g 179.44 253.3
Pore volume, ml/g 0.37 0.5
Hole distribution (in dV/dlogD)%
<4nm 13.12 11.23
4-6nm 25.1 22.46
6-12nm 49.05 62.96
>12nm 12.74 3.35
Average pore diameter, nm 8.24 7.97
Strength of catalyst particles 20 19.5
TABLE 3 composition of support and acidity, composition of catalyst
Figure BDA0002576624310000141
Evaluation examples
The hydroisomerization pour point depression reaction is carried out by taking the Fischer-Tropsch heavy firewood after hydrofining as a raw material and the physicochemical parameters of the Fischer-Tropsch heavy firewood are shown in a table 4. Catalysts A-F, D1-D3 were loaded on a 30mL hydrogenation apparatus, respectively, under the following reaction conditions: the hydrogen-oil ratio is 800, the reaction pressure is 7MPa, and the volume space velocity is 1.00h-1The reaction temperature is 320-360 ℃.
TABLE 4 physicochemical parameters of Fischer-Tropsch heavy firewood
Figure BDA0002576624310000142
Figure BDA0002576624310000151
Testing the condensation point of the hydroisomerization product by using a condensation point and pour point tester; the conversion of the hydroisomerization reaction and the yield of diesel were calculated using the simulated distillation data. The results are shown in tables 5 and 6. TABLE 5 product pour point and diesel yield (15% conversion to cracking) at the same conversion for different catalysts
Temperature, C Freezing point of whole fraction product, DEG C Diesel oil yield%
D1 320 -35 60
D2 330 -30 65
D3 360 -15 70
A 348 -35 85
B 353 -30 83
C 356 -20 80
D 348 -30 80
E 348 -10 70
F 348 -25 73
TABLE 6 Diesel yield with the same catalyst at the same product pour point
Figure BDA0002576624310000152
Figure BDA0002576624310000161
As can be seen from Table 2, the catalyst provided by the invention has a large specific surface area, the provided carrier has a wide mesoporous pore size distribution, and the diesel pour point depressing catalyst prepared by the catalyst has excellent isomerization catalytic activity.
As can be seen from Table 3, different amorphous Si-Al and molecular sieves have a great influence on the acidity of the carrier, and the higher the acidity is, the lower the product yield is, which is not favorable for improving the product yield.
As can be seen from Table 5, under the same conversion rate (15%), the diesel pour point depressing catalyst provided by the invention has a lower pour point when used for catalyzing hydroisomerization pour point depressing reaction. In contrast, in comparative examples 1-2, in which the molecular sieve was added to the carrier, the condensation point of the whole product was very low (but the condensation point of the diesel fraction was not reduced) due to cracking into naphtha, and with the increase in the amount of the molecular sieve, the naphtha content of the whole product was increased, which resulted in a further reduction in the condensation point (but the condensation point of the diesel fraction was not reduced), and the yield of diesel was greatly reduced due to the addition of the molecular sieve, indicating that the increase in the molecular sieve content in the catalyst carrier was detrimental to the isomerization reaction.
As can be seen from Table 6, the diesel pour point depressing catalyst provided by the invention has the advantage that the yield of diesel is remarkably improved when the diesel pour point depressing catalyst catalyzes the hydroisomerization pour point depressing reaction on the premise of ensuring that products of the hydroisomerization pour point depressing reaction have the same pour point. The method shows that compared with a catalyst containing a molecular sieve as a carrier, the catalyst containing amorphous silicon-aluminum as a carrier is more favorable for improving the yield of the product diesel oil.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A carrier for a catalyst, wherein the carrier comprises silica and alumina, wherein SiO is provided based on the total weight of the carrier2The content of the silicon oxide is 4-36 wt% calculated by Al2O3The content of the alumina is 64-96 wt%; in the carrier, silicon oxide and aluminum oxide are amorphous;
the acidity of the carrier is 1.1-3.25 mmol/g.
2. The carrier of claim 1, wherein the carrier is in SiO based on the total weight of the carrier2The content of the silicon oxide is 8-32 wt%, preferably 12-28 wt%; with Al2O3The content of the alumina is 68-92 wt%, preferably 72-88 wt%;
preferably, the acidity of the support is in the range of 2.6 to 3 mmol/g.
3. A method for preparing a carrier for a catalyst, wherein the method comprises: mixing amorphous silicon-aluminum with a binder, stirring, adding a nitric acid solution, kneading, molding, drying and roasting to obtain the carrier for the catalyst.
4. The production method according to claim 3, wherein the binder is selected from at least one of pseudoboehmite, silica sol, alumina sol and water glass, preferably pseudoboehmite;
preferably, the pseudoboehmite has a peptization index of at least 90 wt%; more preferably, the pseudoboehmite has a peptization index of at least 95 wt%;
preferably, the pseudo-boehmite contains gibbsite in an amount of at most 5 wt%; more preferably, the pseudo-boehmite contains gibbsite in an amount of at most 2 wt%.
5. The carrier according to claim 3 or 4, wherein the amorphous silicon aluminum has a specific surface area of 200-500m2A/g of preferably 400-2/g；
Preferably, the pore volume of the amorphous silicon-aluminum is 1-1.6mL/g, preferably 1.4-1.6 mL/g;
preferably, SiO in the amorphous silicon-aluminum2The content of (B) is 20 to 70 wt%, preferably 30 to 50 wt%.
6. The production method according to any one of claims 3 to 5, wherein the nitric acid solution is used in an amount of 4 to 10g, preferably 4 to 7g, based on 100g of the total weight of the amorphous silicon-aluminum and the binder;
preferably, the method of forming comprises at least one of dropping ball forming, extrusion forming and tabletting forming, preferably extrusion forming;
preferably, the drying conditions include: the drying temperature is 40-180 ℃, and preferably 100-150 ℃; the drying time is 0.5-24h, preferably 1-8 h;
preferably, the conditions of the calcination include: the roasting temperature is 350-700 ℃, and preferably 400-600 ℃; the roasting time is 0.5-24h, preferably 4-8 h.
7. A pour point depressing catalyst, wherein the catalyst comprises a carrier and a metal active component, wherein the carrier is the carrier of claim 1 or 2 or the carrier prepared by the method of any one of claims 3 to 6.
8. The pour point depressing catalyst of claim 7, wherein the carrier is present in an amount of 60 to 80 wt%, based on the total weight of the catalyst, and the metal active component is present in an amount of 20 to 40 wt%, calculated as the metal oxide;
preferably, the content of the carrier is 67 to 75 wt% based on the total weight of the catalyst, and the content of the metal active component is 25 to 33 wt% in terms of metal oxide.
9. The pour point depressing catalyst of claim 7 or 8, wherein the metal active component comprises group VIII and group VIB metal elements;
preferably, the group VIII metal element is present in an amount of from 1 to 15 wt%, preferably from 4 to 8 wt%, calculated as oxide, based on the total weight of the catalyst; the content of the VIB group metal element is 10-35 wt%, preferably 20-28 wt%;
more preferably, the group VIII metal element is cobalt and/or nickel, and the group VIB metal element is molybdenum and/or tungsten.
10. A method for preparing the pour point depressing catalyst of any one of claims 7 to 9, wherein the method comprises the steps of dipping a carrier into dipping solution containing metal active components, drying and roasting to obtain the diesel pour point depressing catalyst.
11. The method of claim 10, wherein the impregnation comprises at least one of saturation impregnation, spray impregnation, excess impregnation, and equal volume impregnation, preferably equal volume impregnation;
preferably, the drying conditions include: the drying temperature is below 200 ℃, preferably 80-150 ℃; the drying time is 1-10 h;
preferably, the conditions of the calcination include: the roasting temperature is 350-700 ℃, preferably 450-550 ℃; the roasting time is 0.5-24h, preferably 4-8 h.
12. Use of a diesel pour point depressant catalyst according to any one of claims 7 to 9 or made by the process of claim 10 or 11 in the cracking of fischer-tropsch synthesis oil.
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