CN1177647C - Catalyst containing Si-P-Al molecular sieve and its preparing process - Google Patents
Catalyst containing Si-P-Al molecular sieve and its preparing process Download PDFInfo
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- CN1177647C CN1177647C CNB01115618XA CN01115618A CN1177647C CN 1177647 C CN1177647 C CN 1177647C CN B01115618X A CNB01115618X A CN B01115618XA CN 01115618 A CN01115618 A CN 01115618A CN 1177647 C CN1177647 C CN 1177647C
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Abstract
A catalyst containing Si-P-Al molecular sieves contains at least one Si-P-Al molecular sieve. The crystallinity of the Si-P-Al molecular sieve is at least 70%. A preparing process of the Si-P-Al molecular sieve comprises: drying and calcining a mixture of a Si-P-Al molecular sieve containing organic template agents and the water solution of an acid. The weight ratio of the acid to the molecular sieve is from 0.001 to 1.
Description
Technical field
The invention relates to a kind of Catalysts and its preparation method that contains molecular sieve, more specifically say so about a kind of Catalysts and its preparation method of silicon-aluminum containing phosphorus molecular sieve.
Background technology
The sial phosphorus molecular sieve is the molecule sieve that is made of silicon-oxy tetrahedron, aluminum-oxygen tetrahedron and phosphorus oxygen tetrahedron, this molecular sieve analog can be widely used as the catalyst of various chemical reactions, as to have mesopore be that the aperture is the sial phosphorus molecular sieve in 5.3-6.5 dust hole, is especially suitable for use as catalyst to the selective splitting dewaxing process of waxy petroleum distillate as SAPO-11, SAPO-31, SAPO-41.
The sial phosphorus molecular sieve is that the mixture by silicon compound, aluminium compound and phosphorus compound is synthesized after the crystallization in water or organic media and in the presence of the agent of organic amine template, therefore, contain the agent of a large amount of organic amine template in the sial phosphorus molecular sieve that newly is synthesized, make the sial phosphorus molecular sieve have catalytic activity, must remove organic formwork agent wherein.
The conventional method that removes organic amine template agent in the molecular sieve is the method for high-temperature roasting, promptly in oxygen-containing atmosphere, the molecular sieve that will contain the agent of organic amine template is roasting direct at high temperature, and the organic amine template agent of molecular sieve intracrystalline is decomposed fully, with the duct of the form effusion molecular sieve of gas.The method of this high-temperature roasting is for constitutionally stable molecular sieve, as the ZSM-5 zeolite is effective, and for structural stability relatively poor Si-Al zeolite and sial phosphorus molecular sieve, when removing wherein organic amine template agent by traditional method of roasting, the structural deterioration of molecular sieve is serious, degree of crystallinity reservation degree all drops to below 70%, and this has directly influenced siliceous phosphorus molecular sieve catalyst catalytic performance.With the molecular sieve catalyst that contains SAPO-11 is example, when waxy feeds oil is dewaxed, the proportion that the non-selective cracking reaction (being the cracking reaction of less molecular hydrocarbon) that contains the catalyst of the molecular sieve that adopts the conventional high-temperature method of roasting to remove the agent of organic amine template accounts for cracking reaction is bigger, causes the purpose product yield lower.
CN1041618C discloses the removal methods of organic amine in a kind of Si-Al zeolite or its composition, this method is included in zeolite or contains and adds the oxidant that is selected from perchloric acid, hypochlorous acid, perchloric acid or hypochlorous sylvite, sodium salt, ammonium salt and aluminium salt that accounts for zeolite weight 1-40% in the composition of zeolite, in 300-500 ℃, in air roasting 1-5 hour.
CN1041617C discloses the removal methods of organic amine in a kind of Si-Al zeolite or its composition, this method is included in zeolite or contains in the composition of zeolite, press 3-20: 1 solvent and solute weight ratio, add concentration and be the containing or the not water of ammonium salt-containing or the alkaline solution of ethanol of reducing agent of the salt that is selected from hydrazine, oxyammonia, hydrazine or oxyammonia of the heavy % of 0.2-5, at room temperature to 100 ℃ stirring reaction 1-10 hour, after the drying, in 450-550 ℃ of air roasting 1-6 hour.
Above-mentioned two kinds of methods are applicable to and remove the mesopore that comprises Beta, Ω, VPI-5, MCM series zeolite and the organic amine template agent in the macropore Si-Al zeolite, when the amine effect is taken off in raising, Si-Al zeolite crystallization reservation degree are improved.
US5,143,879 disclose a kind of method that reclaims organic formwork agent from the porous synthetic material, described template agent is adsorbed in the described synthetic material, this method comprises that (1) contacts a kind of porous synthetic material with the polar solvent that is dissolved with a kind of cation trapping agent, (2) under higher temperature, make described porous synthetic material, described polar solvent and described cation trapping agent keep in touch time enough, desorption segment template agent at least from described synthetic material.Described polar solvent is selected from one group that is made up of aromatic series or aliphatic ethers, alcohols, amine, lipid, halogenated hydrocarbons and carboxylic acid, and the content of water is lower in the described polar solvent, preferably is substantially free of water.Described cation trapping agent is soluble in the described polar solvent, can be inorganic acid and salt thereof, comprises HCl, H
2SO
4, HNO
3, HBr, HPO
4, be preferably HCl and HBr.This method is applicable to and reclaims organic formwork agent from synthetic material, still, owing to use non-aqueous organic solvent, has increased the cost that removes the agent of organic amine template.On the other hand, remove organic amine template agent whole in the synthetic material, still need high-temperature roasting, and the use of a large amount of organic solvents is easily caused danger during roasting.
Summary of the invention
The purpose of this invention is to provide a kind of new catalyst that contains aluminium silicophosphate molecular sieve with better catalytic performance, another purpose provides this Preparation of catalysts method.
The catalyst that contains aluminium silicophosphate molecular sieve provided by the invention contains aluminium silicophosphate molecular sieve, described aluminium silicophosphate molecular sieve is selected from one or more in SAPO-11 molecular sieve, SAPO-31 molecular sieve and the SAPO-41 molecular sieve, it is characterized in that the degree of crystallinity of described aluminium silicophosphate molecular sieve is at least 70%.
Preparation of catalysts method provided by the invention comprises a kind of preparation method of aluminium silicophosphate molecular sieve, described aluminium silicophosphate molecular sieve is selected from SAPO-11, in SAPO-31 and the SAPO-41 molecular sieve one or more, the degree of crystallinity of this aluminium silicophosphate molecular sieve is at least 70%, the preparation method of described aluminium silicophosphate molecular sieve comprises and will contain the dry and roasting of mixture of aluminium silicophosphate molecular sieve and a kind of aqueous acid of organic formwork agent, described acid is selected from nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, hydrobromic acid and carbon number are one or more in the organic acid of 1-5, and the weight ratio of described acid and molecular sieve is 0.001-1.
The degree of crystallinity of described aluminium silicophosphate molecular sieve is at least 70%, the preparation method of this molecular sieve comprises and will contain the dry and roasting of mixture of aluminium silicophosphate molecular sieve and a kind of aqueous acid of organic formwork agent that described acid is selected from nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, hydrobromic acid and C
1-C
5Organic acid in one or more, the weight ratio of described acid and molecular sieve is 0.001-1.
Owing to used the higher aluminium silicophosphate molecular sieve of the unexistent degree of crystallinity of a kind of prior art, catalyst provided by the invention has than the better catalytic performance of prior art.With the degree of crystallinity that consists of provided by the invention is 77% SAPO-11 molecular sieve, 75.0 heavy %, the catalyst for hydrogenation de-waxing provided by the invention of aluminium oxide 24.7 heavy % and platinum 0.3 heavy % is identical with composition, just the degree of crystallinity of SAPO-11 molecular sieve is that 67% reference catalyst for hydrogenation de-waxing is an example, in reaction temperature is 330 ℃, 340 ℃ and 350 ℃, reaction pressure 6.0 MPas, liquid hourly space velocity (LHSV) are 1 hour
-1Hydrogen to oil volume ratio is under 400 the condition, hydrocracking tail oil is carried out Hydrodewaxing, and the result shows, compares during with the employing reference catalyst, when employing the invention provides catalyst, under same reaction temperature, purpose product boiling point is higher greater than the yield of 370 ℃ of lubricating oil, and purpose product boiling point is close or lower greater than the pour point of 370 ℃ of lubricating oil, and with the rising of reaction temperature, purpose product boiling point increases greater than this difference of 370 ℃ of yield of lubricating oil.This illustrates that this catalyst for hydrogenation de-waxing provided by the invention has the selectivity higher than prior art.
The specific embodiment
According to catalyst provided by the invention, can only contain at least a aluminium silicophosphate molecular sieve in the catalyst.In the catalyst provided by the invention, the degree of crystallinity of described molecular sieve is relative crystallinity, diffracted intensity [Lin (CPS)] with the main diffraction maximum in the described aluminium silicophosphate molecular sieve x-ray diffraction spectra calculates, the degree of crystallinity of taking off the aluminium silicophosphate molecular sieve before the amine is 100%, and take off behind the amine degree of crystallinity of aluminium silicophosphate molecular sieve and is calculated by following formula: aluminium silicophosphate molecular sieve/Lin (CPS) took off the preceding aluminium silicophosphate molecular sieve of amine * 100% after degree of crystallinity=Lin (CPS) took off amine.With the catalyst that contains the SAPO-11 molecular sieve is example, the degree of crystallinity of molecular sieve is the diffracted intensity Lin (CPS-21) of 21.0 ± 0.4 ° of main diffraction maximums of locating in SAPO-11X optical diffraction spectrogram 2 θ angles, takes off behind the amine degree of crystallinity=Lin (CPS-21) of SAPO-11 molecular sieve and takes off behind the amine SAPO-11/Lin (CPS-21) and take off SAPO-11 * 100% before the amine.The X-ray diffraction experiment can be gone up at any X-ray diffractometer (as SIMENS D5005 type X-ray diffractometer) and measure, and adopts CuK α radiation, and condition determination is generally 44KV, 40mA, sweep speed is 2 °/minute.
Described aluminium silicophosphate molecular sieve is selected from existing various aluminium silicophosphate molecular sieve, be preferably SAPOS series molecular sieve, as among SAPO-4, SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42, the SAPO-44 one or more.Wherein, the effective aperture of SAPO-11, SAPO-31 and SAPO-41 is the 5.3-6.5 dust, is particularly suitable for waxy feeds oil is carried out Hydrodewaxing.
According to catalyst provided by the invention, introducing at least a group VIII metal component in described aluminium silicophosphate molecular sieve, obtain catalyst for hydrogenation de-waxing, is benchmark in simple substance and with the total catalyst weight, the content of described group VIII metal component is the heavy % of 0.01-10, is preferably the heavy % of 0.1-5.In described group VIII metal chosen from Fe, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, the platinum one or more, preferred group VIII metal is platinum and/or palladium.Described group VIII metal component can exist with the form of simple substance, oxide and/or sulfide.This catalyst for hydrogenation de-waxing is applicable to waxy feeds oil is carried out Hydrodewaxing as content of wax lubricating oil, content of wax jet fuel, content of wax diesel oil, has lubricating oil, jet fuel and the low-coagulation diesel oil of good fluidity with production.
Can also contain heat-resistant inorganic oxide in the catalyst provided by the invention, described heat-resistant inorganic oxide plays binding agent, catalyst carrier in catalyst, it can improve the intensity of catalyst, and can improve and regulate the physico-chemical property of catalyst, as improving the pore structure of catalyst.Described heat-resistant inorganic oxide is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for catalyst carrier and/or matrix.For example, one or more in the optional self-alumina of described heat-resistant inorganic oxide, silica, titanium oxide, magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, the clay.Preferred silica of described anti-inorganic oxide and/or aluminium oxide.With the total catalyst weight is benchmark, and the content of described heat-resistant inorganic oxide in catalyst is the heavy % of 10-80, is preferably the heavy % of 15-60.
According to Preparation of catalysts method provided by the invention, the concentration of described aqueous acid is 0.001-1 as long as make the acid and the weight ratio of molecular sieve without limits, is preferably 0.005-0.5 and gets final product.If aqueous acid concentration is less, can adopt molecular sieve or contain combination of molecular sieve and mix with aqueous acid, filter out the method for remaining acid solution.Can not make after this method mixed once acid and the weight ratio of molecular sieve reach 0.001-1 if adopt, after can drying,, filter, reach requirement until the weight ratio that makes acid with molecular sieve once more with molecular sieve or contain combination of molecular sieve and mix.If the concentration of aqueous acid is bigger, can adopts molecular sieve and aqueous acid are mixed the method for pinching.Under the preferable case, it is 0.2-50, more preferably 0.35-20 that the concentration of acid should make the solvent and solute weight ratio of the mixture of molecular sieve and acid solution.
The weight ratio of described acid and molecular sieve is 0.001-1, is preferably 0.005-0.5.
Described acid is preferably nitric acid, hydrochloric acid and C
1-C
5In the organic acid one or more, more preferably one or more in nitric acid, hydrochloric acid, oxalic acid, the acetate.
Described drying can adopt the drying means of various routines, as airing, oven dry etc., and the preferred method that adopts oven dry.Dry temperature can be a room temperature to 200 ℃, is preferably 100-150 ℃.
The condition of described roasting can adopt conventional roasting condition, is 400-700 ℃ as sintering temperature, is preferably 450-650 ℃, and more preferred 450-600 ℃, roasting time is 1-10 hour, is preferably 2-8 hour.Calcination atmosphere can be for the calcination atmosphere of routine, as oxygen-containing atmosphere, and air atmosphere particularly.
According to embodiment preferred of the present invention, method of roasting comprises, under oxygen-containing atmosphere,, be preferably 0.5-5 ℃/minute heating rate with 0.5-10 ℃/minute, be warming up to 400-700 ℃ from room temperature, preferred 450-650 ℃, then, at 400-700 ℃, preferred 450-650 ℃ following roasting 1-10 hour, be preferably 2-8 hour.Adopt this method of roasting, can further improve the degree of crystallinity of taking off the amine molecule sieve, thereby further improve the catalytic performance of catalyst.
According to another embodiment preferred of the present invention, method of roasting comprises, under inert atmosphere, and in 200-600 ℃ of roasting 1-8 hour, then, again under oxygen-containing atmosphere, in 450-650 ℃ of roasting 1-8 hour.Adopt this method of roasting also can further improve to take off the degree of crystallinity of amine molecule sieve, thereby further improve the catalytic performance of catalyst.
Described inert atmosphere refers under sintering temperature, not with mixture in the gas of component generation chemical reaction arbitrarily, inert gas commonly used is selected from one or more in the zero group gas in nitrogen, carbon dioxide, the periodic table of elements, wherein, is preferably nitrogen.Described oxygen-containing atmosphere refers to contain any gas of oxygen, under the preferable case, refers to contain the gas that oxygen is not less than 10 body %, and more excellent is oxygen and/or air.
According to Preparation of catalysts method provided by the invention, when containing the group VIII metal component in the catalyst, described group VIII metal component can adopt existing the whole bag of tricks to introduce, as adopting ion-exchange, dipping, mixing method such as pinch and introduce.
When catalyst contains heat-resistant inorganic oxide, can take off amine to described aluminium silicophosphate molecular sieve earlier, mix with described heat-resistant inorganic oxide or its precursor again, moulding, the group VIII metal component is introduced or is not introduced in roasting then.Also can take off amine to described aluminium silicophosphate molecular sieve earlier, introduce the group VIII metal component, and then with described heat-resistant inorganic oxide or its precursor is mixed, moulding, roasting then.Can also earlier described aluminium silicophosphate molecular sieve be mixed with described heat-resistant inorganic oxide or its precursor, moulding, press preceding method, with the mixture after the moulding mix with described aqueous acid, dry and roasting, introduce or do not introduce the group VIII metal component then.Therefore, according to preparation method provided by the invention, can also contain a kind of heat-resistant inorganic oxide or its precursor in the mixture of described aluminium silicophosphate molecular sieve that contains organic formwork agent and described aqueous acid, to the content of heat-resistant inorganic oxide in the mixture or its precursor without limits, as long as guarantee that the weight ratio of described acid and molecular sieve is 0.001-1, be preferably 0.005-0.5 and get final product.Too high levels in heat-resistant inorganic oxide described in the mixture or its precursor, when heat-resistant inorganic oxide content is higher than the content of heat-resistant inorganic oxide in the catalyst in the mixture of the molecular sieve after causing the heat-resistant inorganic oxide that obtains and taking off amine, this mixture can be mixed with an amount of amine molecule sieve that takes off, again moulding, the content of heat-resistant inorganic oxide in catalyst is met the requirements, otherwise, can add an amount of heat-resistant inorganic oxide or the moulding again of its precursor, the content of heat-resistant inorganic oxide in catalyst is met the requirements.Under the preferable case, the content of heat-resistant inorganic oxide or its precursor in the mixture of the described aluminium silicophosphate molecular sieve that contains organic formwork agent and a kind of aqueous acid, should make the content of heat-resistant inorganic oxide in catalyst is the heavy % of 10-80, is preferably the heavy % of 15-60.Wherein, the precursor of described heat-resistant inorganic oxide refers to can form after the roasting compound of described heat-resistant inorganic oxide, is often referred to its hydroxide, hydrous oxide, contains the gel of its oxide, hydroxide and in the colloidal sol one or more.For example, the precursor of silica can be selected from one or more in Ludox, waterglass, the silicon gel, and the precursor of aluminium oxide can be selected from one or more in various hydrated aluminas, the aluminium colloidal sol.Described moulding can be adopted existing various forming method, as methods such as extrusion molding, compression moldings, can add an amount of adhesive and extrusion aid when extrusion molding.The kind of described adhesive and extrusion aid and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.
Catalyst provided by the invention can be used as various chemical reactions, as the catalyst of the cracking reaction of hydro carbons, isomerization reaction, hydrocracking reaction, hydrotreatment reaction etc.The catalyst provided by the invention that contains the group VIII metal is especially suitable for use as the Hydrodewaxing process of waxy feeds oil.
The following examples will the present invention will be further described.
Example 1
This example illustrates Catalysts and its preparation method provided by the invention.
Press US4, the method for 440,871 examples 16 is synthesized the SAPO-11 molecular sieve.Take by weighing the phosphoric acid of 230.6 grams, 85 heavy %, add 440.0 gram distilled water, 138.0 gram boehmites (alumina content 74.2 heavy %, water content 25.8 heavy %) stir, and obtain mixture I.Taking by weighing concentration is the hydroxyl four n-butylamine aqueous solution 649.2 grams of 40 heavy %, with the silica gel (SiO of being fuming
2Content 92.8 heavy %, water content 7.2 heavy %) 26.0 gram mixing, stir, obtain mixtures II.Mixture I and II are mixed, under agitation add 102.0 gram di-n-propylamines, get reactant mixture.Reactant mixture is packed in the reactor of teflon seal, and 200 ℃ of crystallization 24 hours are filtered, the washing solid product is to neutral, and 120 ℃ of oven dry obtain SAPO-11 molecular sieve (SAPO-11 net content 85.0 heavy %).
Take by weighing 100 gram SAPO-11 molecular sieves, mix with the composite solution of nitric acid of 200 gram deionized waters and 1.0 grams, 68 heavy % that (liquid-solid ratio is 2.01, acid is 0.007 with the weight ratio of molecular sieve), 120 ℃ of oven dry, in air atmosphere, in 500 ℃ of roastings 1 hour, 600 ℃ of roastings 4 hours, obtaining taking off amine SAPO-11 molecular sieve, also is catalyst C provided by the invention
1Taking off the degree of crystallinity and the carbon residue content of amine SAPO-11 molecular sieve lists in the table 1.
Wherein, the assay method of carbon residue amount is referring to " petrochemical industry analytical method (RIPP test method) ", Science Press, P302,1990.Degree of crystallinity is the diffracted intensity [Lin (CPS)] of 21.0 ± 0.4 ° of main diffraction maximums of locating in 2 θ angles in the x-ray diffraction spectra of SAPO-11, the degree of crystallinity of taking off the SAPO-11 before the amine is defined as 100%, and the degree of crystallinity of taking off SAPO-11 behind the amine is for respect to the degree of crystallinity of taking off the SAPO-11 before the amine.The degree of crystallinity of sample is calculated as follows: SAPO-11/Lin (CPS) took off the preceding SAPO-11 of amine * 100% after sample degree of crystallinity=Lin (CPS) took off amine
Wherein, the X-ray diffraction experiment carries out on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep speed is 2 °/minute.
Comparative Examples 1
This Comparative Examples explanation reference catalyst and preparation thereof.
Take by weighing the SAPO-11 molecular sieve of 100 gram examples 1 preparations, directly in air atmosphere, in 500 ℃ of roastings 1 hour, 600 ℃ of roastings 4 hours obtained taking off amine SAPO-11 molecular sieve, also are reference catalyst B
1Taking off behind the amine degree of crystallinity and the carbon residue content of SAPO-11 molecular sieve lists in the table 1.
Example 2
This example illustrates Catalysts and its preparation method provided by the invention.
Remove organic amine template agent among the SAPO-11 by the method for example 1, different is that calcination steps is as follows: with 3 ℃/minute heating rate, be warming up to 500 ℃ of roastings 1 hour from room temperature, again with 2 ℃/minute heating rate, be warming up to 600 ℃ from 500 ℃, 600 ℃ of roastings 4 hours, obtain taking off amine SAPO-11 molecular sieve, also be catalyst C provided by the invention
2Taking off the degree of crystallinity and the carbon residue content of amine SAPO-11 molecular sieve lists in the table 1.
Example 3
This example illustrates Catalysts and its preparation method provided by the invention.
The SAPO-11 molecular sieves that take by weighing 100 gram examples 1 preparations and 50 gram deionized waters and 30 restrain solution that oxalic acid are made into and mix that (liquid-solid ratio is 0.5, acid is 0.3 with the weight ratio of molecular sieve), 120 ℃ of oven dry, earlier in nitrogen atmosphere, in 500 ℃ of roastings 3 hours, then, in air atmosphere, in 600 ℃ of roastings 2 hours, obtain taking off amine SAPO-11 molecular sieve, also promptly the invention provides catalyst C
3Taking off the degree of crystallinity and the carbon residue content of amine SAPO-11 molecular sieve lists in the table 1.
Example 4
This example illustrates Catalysts and its preparation method provided by the invention.
Remove organic amine among the SAPO-11 by the method for example 1, different is, and (liquid-solid ratio is 10 with the nitric acid of the salt acid substitutions 1.0 grams 68 heavy % of 1000.0 grams, 3.6 heavy %, acid is 0.36 with the weight ratio of molecular sieve), method of roasting be directly in air in 550 ℃ of roastings 6 hours, obtaining taking off amine SAPO-11 molecular sieve also is catalyst C provided by the invention
4Taking off the degree of crystallinity and the carbon residue content of amine SAPO-11 molecular sieve lists in the table 1.
Example 5
This example illustrates Catalysts and its preparation method provided by the invention.
The SAPO-11 that contains the template agent and the 40 gram boehmites that take by weighing 1 preparation of 50 gram examples (contain Al
2O
374.2 heavy %, H
2O 25.8 heavy %) mix, add the solution that 23.5 gram deionized waters and 1.5 nitric acid that restrain 68 heavy % are made into, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, under air atmosphere, be warming up to 550 ℃ with 2 ℃/minute heating rates and continue roasting 4 hours, obtain taking off amine SAPO-11 combination of molecular sieve, also promptly the invention provides catalyst C
5Taking off the degree of crystallinity and the carbon residue content of SAPO-11 molecular sieve in the amine SAPO-11 molecular sieve lists in the table 1.As calculated, C
5In contain the heavy % of SAPO-11 59.0, Al
2O
341.0 heavy %.
Wherein, the degree of crystallinity of molecular sieve is calculated as follows in the SAPO-11 combination of molecular sieve: SAPO-11 degree of crystallinity=(Lin (CPS) take off amine after SAPO-11 combination of molecular sieve)/(Lin (CPS) take off amine before SAPO-11 combination of molecular sieve * SAPO-11 combination of molecular sieve percentage composition) * 100%.The carbon residue percentage composition is in the SAPO-11 molecular sieve.
Table 1
| Example number | Take off amine SAPO-11 degree of crystallinity, % | Carbon residue content, heavy % |
| 1 | 77 | 0.84 |
| Comparative Examples 1 | 67 | 1.12 |
| 2 | 85 | 0.14 |
| 3 | 79 | 0.31 |
| 4 | 74 | 0.21 |
| 5 | 82 | 0.25 |
Example 6
This example illustrates Catalysts and its preparation method provided by the invention.
Take by weighing the catalyst C of 40 gram examples, 1 preparation
1With 22 gram solid oxide aluminium colloidal sol (alumina content 60 heavy %, Inst., of Alunite Comprehensive Utilization, Zhejiang Prov. produces) to mix, be extruded into circumscribed circle diameter be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours are then with the Pt (NH of platiniferous 0.3 heavy %
3)
4Cl
2H
2The O aqueous solution 53.2 gram dipping, 120 ℃ of oven dry are the hydrogen reducing 4 hours of 800 ml/min at 450 ℃ with flow, obtain catalyst C provided by the invention
6, C
6In to contain degree of crystallinity be 77% SAPO-11 molecular sieve, 75.0 heavy %, aluminium oxide 24.7 heavy %, platinum 0.3 heavy %.
Comparative Examples 2
Reference catalyst and preparation thereof.
Method by example 6 prepares catalyst, the different reference catalyst B that just prepares with Comparative Examples 1
1The reference catalyst C that replaces example 1 preparation
1, must join catalyst B
2, B
2In to contain degree of crystallinity be 67% SAPO-11 molecular sieve, 75.0 heavy %, aluminium oxide 24.7 heavy %, platinum 0.3 heavy %.
Example 7
This example illustrates Catalysts and its preparation method provided by the invention.
Take by weighing the catalyst C of example 5 preparations
550 grams are with the Pt (NH of platiniferous 1.0 heavy %
3)
4Cl
2H
2The O aqueous solution 50 gram dipping, 120 ℃ of oven dry are the hydrogen reducing 4 hours of 1000 ml/min at 450 ℃ with flow, obtain catalyst C provided by the invention
7, C
7In to contain degree of crystallinity be 82% SAPO-11 molecular sieve, 58.4 heavy %, aluminium oxide 40.6 heavy %, platinum 1.0 heavy %.
Example 8-9
This example illustrates the catalytic performance of catalyst provided by the invention.
Respectively with catalyst C
6And C
7Be broken into the particle that diameter is the 0.28-0.40 millimeter, the 20 milliliters of catalyst of in the reactor of 20 milliliters of fixed-bed reactors, packing into, hydrocracking tail oil carries out Hydrodewaxing shown in the his-and-hers watches 2, and reaction condition is that reaction pressure 6.0 MPas, liquid hourly space velocity (LHSV) are 1 hour
-1, hydrogen to oil volume ratio is 400, temperature is respectively 330 ℃, 340 ℃ and 350 ℃.Under the different temperatures, the mid-boiling point that generates oil is listed in the table 3 greater than the pour point of 370 ℃ of lubricating oil greater than the yield and the boiling point of 370 ℃ of lubricating oil.Wherein, boiling point is calculated as follows greater than the yield A of 370 ℃ of lubricating oil.
Comparative Examples 3
This Comparative Examples explanation comparative catalyst's catalytic performance.
Carry out Hydrodewaxing by 8 pairs of same feedstock oils of example, different just catalyst system therefors are the reference catalyst B of Comparative Examples 2 preparations
2, the results are shown in Table 3.
The result of table 3 shows, compared with prior art, employing the invention provides catalyst, under same reaction temperature, purpose product boiling point is higher greater than the yield of 370 ℃ of lubricating oil, purpose product boiling point is close or lower greater than the pour point of 370 ℃ of lubricating oil, reaction temperature high more, and purpose product boiling point is big more greater than this difference of 370 ℃ of yield of lubricating oil.This illustrates that catalyst provided by the invention has the selectivity higher than prior art.
Table 2
| The feedstock oil title | Hydrocracking tail oil |
| Density (20 ℃), g/cm 3 | 0.8311 |
| Index of refraction, 20 ℃ | 1.4610 |
| Kinematic viscosity (100 ℃), mm 2/S | 3.876 |
| Kinematic viscosity (40 ℃), mm 2/S | 15.76 |
| Viscosity index (VI) VI | 14.5 |
| Condensation point, ℃ | 38 |
| Flash-point (opening), ℃ | 205 |
| Sulfur content, ppm | ＜10 |
| Nitrogen content, ppm | ＜5 |
| The alkali nitrogen content, ppm | 0 |
| Boiling range, ℃ | D1160 |
| Initial boiling point | 301 |
| 5％ | 370 |
| 10％ | 380 |
| 30％ | 398 |
| 50％ | 415 |
| 70％ | 432 |
| 83.5％ | 452 |
Table 3
| Catalyst | Reaction temperature, ℃ | Boiling point is greater than the pour point of 370 ℃ of lubricating oil, ℃ | Boiling point weighs % greater than the yield of 370 ℃ of lubricating oil |
| C 6 | 330 | -3 | 82.2 |
| 340 | -12 | 74.0 | |
| 350 | -18 | 71.3 | |
| B 2 | 330 | -3 | 78.8 |
| 340 | -9 | 71.9 | |
| 350 | -18 | 61.8 | |
| C 7 | 330 | -3 | 78.8 |
| 340 | -12 | 71.3 | |
| 350 | -18 | 67.0 |
Claims (24)
1. catalyst that contains aluminium silicophosphate molecular sieve, described aluminium silicophosphate molecular sieve is selected from one or more in SAPO-11, SAPO-31 and the SAPO-41 molecular sieve, it is characterized in that, and the degree of crystallinity of described aluminium silicophosphate molecular sieve is at least 70%; Aluminium silicophosphate molecular sieve/Lin (CPS) took off the preceding aluminium silicophosphate molecular sieve of amine * 100%, Lin wherein (CPS) after so-called degree of crystallinity=Lin (CPS) took off amine] be the diffracted intensity of the main diffraction maximum in the described aluminium silicophosphate molecular sieve x-ray diffraction spectra.
2. catalyst according to claim 1 is characterized in that, described aluminium silicophosphate molecular sieve is the SAPO-11 molecular sieve.
3. catalyst according to claim 1, it is characterized in that, also contain a kind of group VIII metal component in the described catalyst, described group VIII metal component is with simple substance, the form of oxide and/or sulfide exists, in simple substance, and be benchmark with the total catalyst weight, the content of described group VIII metal component is the heavy % of 0.01-10.
4. catalyst according to claim 3 is characterized in that, the content of described group VIII metal component is the heavy % of 0.1-5.
5. according to claim 3 or 4 described catalyst, it is characterized in that described group VIII metal finger platinum and/or palladium.
6. according to claim 1 or 3 described catalyst, it is characterized in that, also contain heat-resistant inorganic oxide in the described catalyst, is benchmark with the total catalyst weight, and the content of described heat-resistant inorganic oxide is the heavy % of 10-80.
7. catalyst according to claim 6 is characterized in that, the content of described heat-resistant inorganic oxide is the heavy % of 15-60.
8. catalyst according to claim 6 is characterized in that described heat-resistant inorganic oxide refers to silica and/or aluminium oxide.
9. claim 1 Preparation of catalysts method, it is characterized in that, this method comprises a kind of preparation method of aluminium silicophosphate molecular sieve, described aluminium silicophosphate molecular sieve is selected from SAPO-11, in SAPO-31 and the SAPO-41 molecular sieve one or more, the degree of crystallinity of this aluminium silicophosphate molecular sieve is at least 70%, the preparation method of described aluminium silicophosphate molecular sieve comprises and will contain the dry and roasting of mixture of aluminium silicophosphate molecular sieve and a kind of aqueous acid of organic formwork agent, described acid is selected from nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, hydrobromic acid and carbon number are one or more in the organic acid of 1-5, and the weight ratio of described acid and molecular sieve is 0.001-1.
10. method according to claim 9 is characterized in that, the weight ratio of described acid and molecular sieve is 0.005-0.5.
11. method according to claim 9 is characterized in that, it is 0.2-50 that the concentration of described acid makes the solvent and solute weight ratio of the mixture of molecular sieve and aqueous acid.
12. method according to claim 11 is characterized in that, described solvent and solute weight ratio is 0.35-20.
13. method according to claim 9 is characterized in that, described acid is selected from nitric acid, hydrochloric acid and C
1-C
5In the organic acid one or more.
14. method according to claim 13 is characterized in that, described acid is selected from one or more in nitric acid, hydrochloric acid, oxalic acid, the acetate.
15. method according to claim 9 is characterized in that, described sintering temperature is 450-650 ℃, and roasting time is 2-8 hour, and calcination atmosphere is an oxygen-containing atmosphere.
16. method according to claim 9 is characterized in that, following method is adopted in described roasting: under oxygen-containing atmosphere, with 0.5-10 ℃/minute heating rate, be warming up to many 400-700 ℃ from room temperature, then at 400-700 ℃ of following roasting 1-10 hour.
17. method according to claim 9 is characterized in that, following method is adopted in described roasting: under inert atmosphere, in 200-600 ℃ of roasting 1-8 hour, and then under oxygen-containing atmosphere in 450-650 ℃ of following roasting 1-8 hour.
18., it is characterized in that described oxygen-containing atmosphere refers to air according to any described method among the claim 15-17.
19. method according to claim 17 is characterized in that, described inert atmosphere refers to nitrogen.
20. method according to claim 9 is characterized in that, also contains a kind of heat-resistant inorganic oxide or its precursor in the mixture of the described aluminium silicophosphate molecular sieve that contains organic formwork agent and the described aqueous solution.
21. method according to claim 20 is characterized in that, the content of heat-resistant inorganic oxide or its precursor makes and contains the heavy % of described heat-resistant inorganic oxide 10-80 in the final catalyst in the described mixture.
22. method according to claim 21 is characterized in that, the content of heat-resistant inorganic oxide or its precursor makes and contains the heavy % of described heat-resistant inorganic oxide 15-60 in the final catalyst in the described mixture.
23. according to claim 9 or 20 described methods, it is characterized in that, this method also is included in the step that claim 9 or 20 obtains introducing in the product group VIII metal component, and the introducing amount of group VIII metal component makes the group VIII metal that contains the heavy % of 0.01-10 in the final catalyst.
24. method according to claim 23 is characterized in that, the introducing amount of group VIII metal component makes the group VIII metal that contains the heavy % of 0.1-5 in the final catalyst.
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| CNB01115618XA CN1177647C (en) | 2001-04-28 | 2001-04-28 | Catalyst containing Si-P-Al molecular sieve and its preparing process |
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| CNB01115618XA CN1177647C (en) | 2001-04-28 | 2001-04-28 | Catalyst containing Si-P-Al molecular sieve and its preparing process |
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| CN1888024B (en) * | 2005-06-30 | 2010-08-25 | 中国石油化工股份有限公司 | Hydrocarbon oil processing method |
| CN103059900B (en) * | 2011-10-19 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method preparing rocket engine fuel |
| CN106554817B (en) * | 2015-09-30 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of method of hydrotreating for preparing low pour point lube base oil |
| CN109465023B (en) * | 2017-09-07 | 2021-12-28 | 中国石油天然气股份有限公司 | Preparation method of isomerization catalyst with MTT-type structure molecular sieve as carrier |
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