CN109701623A - A kind of hydrotreating method of hydroisomerisation catalysts and hydrocracking tail oil - Google Patents
A kind of hydrotreating method of hydroisomerisation catalysts and hydrocracking tail oil Download PDFInfo
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Abstract
The present invention relates to the hydrotreating fields of hydrocracking tail oil, and in particular to the hydrotreating method of hydroisomerisation catalysts and preparation method thereof and hydrocracking tail oil.The catalyst is containing there are two types of ten-ring Si-Al molecular sieves, wherein at least one ten-ring Si-Al molecular sieve has the following characteristics that silica/alumina molar ratio is 120~300；Occurs a closure hysteresis loop containing meso-hole structure and at low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the initial position of the closure hysteresis loop is at P/P0=0.4-0.7.Hydrotreating is carried out to hydrocracking tail oil using hydroisomerisation catalysts of the present invention, the Viscosity Index of target product obtained is higher, pour point is lower and yield is higher.
Description
Technical field
The present invention relates to the hydrotreating fields of hydrocracking tail oil, and in particular to a kind of hydroisomerisation catalysts and plus
The hydrotreating method of hydrogen cracking tail oil.
Background technique
Molecular screen material has peracidity and high-specific surface area, is a kind of outstanding acidic catalyst.Meanwhile molecular sieve material
Material has very strong chemical stability and hydrothermal stability, is difficult to be destroyed by reactant corrosion dissolution.Relative to usually being made
Homogeneous catalyst, molecular screen material catalyst can be reused directly without being separated, while will not be to environment
It is polluted with product.The cellular structures such as specific surface area of molecular screen material parameter has the catalytic performance of molecular sieve important
It influences, thus preparing the molecular sieve with special duct is one important research direction of chemical field.
CN104353484A discloses a kind of preparation method of cheap highly acid multi-stage porous Beta zeolite, is related to a kind of multistage
The preparation method of hole Beta zeolite.The invention is to solve the acidity of existing desiliconization post-processing multi-stage porous Beta zeolite molecular sieve to subtract
Weak problem.Method includes: (1) by Beta zeolite calcination, obtains micropore Hydrogen Beta zeolite；(2) by micropore Hydrogen Beta zeolite
It is added in aqueous slkali and stirs, wash, it is dry, obtain sodium form desiliconization multi-stage porous Beta zeolite；(3) by sodium form desiliconization multi-stage porous
Beta zeolite is added to aqueous ammonium nitrate solution exchange, and Hydrogen desiliconization multi-stage porous Beta zeolite is obtained after calcining；(4) by Hydrogen desiliconization
Multi-stage porous Beta zeolite, which is added in acid solution, to be stirred, and is washed, dry, then repeatedly step (3) to get arriving highly acid multi-stage porous
Beta zeolite.
CN103073020A discloses a kind of hierarchical zeolite molecular sieve and its preparation method and application.Preparation method tool
Body are as follows: utilizing cationic surfactant is template, assembles silanization zeolite seed crystal under hydrothermal conditions, prepares multistage pore canal boiling
The method of stone molecular sieve.Causing the method overcome the mismatch between common cationic surfactant and zeolite template cannot
Prepare the problem of hierarchical zeolite.Prepared material realizes micropore and mesoporous compound, be have it is highly crystallized
Hierarchical zeolite molecular sieve.But this method is substantially to be grafted organosilan to crystal seed using specific functional group reactions,
Cooperate with cationic surfactant and then prepare mesopore molecular sieve, the generation of this process intermediary hole is lived by cationic surface
Property agent, which guides, to be formed, and acts on forming aperture in the mesoporous of 2.4nm or so using the hard template of organosilan.What the invention was selected
Crystal seed is micro porous molecular sieve, will be added among preparation system after its silanization, increases it to surface-active using its hydrophobicity
The effect at agent micellar hydrophobic end is to reduce the interaction between two kinds of directed agents, but the mesoporous of formation does not have rule still
Whole structure, and whether the addition of crystal seed reduces the dosage of template and does not report.
CN104891526A discloses a kind of preparation method of mesoporous molecular sieve with high hydrothermal stability.This method includes following
Step: (1) preparation of the first Y type molecular sieve presoma: (2) crystallization: crystal seed is added in the first Y type molecular sieve presoma, is adjusted
Section pH value is 0.5-5, after 20 DEG C of -50 DEG C of stirring 10h-24h, then in 20 DEG C of -50 DEG C of aging 2h-24h, obtains assembling product,
Assembling product is transferred to the microreactor with teflon lined, then is transferred in reaction under high pressure Fu together with reactor, in
100 DEG C of -200 DEG C of crystallization 10h-48h, are filtered, washed, are dried to obtain high stability mesopore molecular sieve.Microporous molecular is prepared first
The presoma of sieve is used for the preparation of mesopore molecular sieve using mesoporous-microporomolecular molecular sieve as crystal seed, combines molecular sieve precursor assembling
With two methods of crystal seed, the mesopore molecular sieve of high stability has been obtained under conditions of not using organic formwork agent.Not only substantially
The preparation cost of molecular sieve is reduced, and eliminates calcining template process and reduces energy consumption.
CN102050459A discloses a kind of method for preparing high-silica zeolite, wherein this method is included in inert carrier gas
Under the carrying of stream, flow molecular sieve with inert carrier gas, and with gas phase SiCl4It is contacted under flow regime, molecular sieve and gas
Phase SiCl4Time of contact be 10 seconds to 100 minutes.The method for preparing high-silica zeolite that the invention provides can be realized molecule
Sieve and SiCl4Haptoreaction be carried out continuously, by control carrier gas flow velocity and tubular reactor length, molecule can be controlled
Sieve and SiCl4The time of contact, so as to make molecular sieve and SiCl4Haptoreaction adequately carried out in tubular reactor.
CN1703490A discloses a kind of catalyst combination method for producing lube base oil.The invention is related to a kind of logical
It crosses using unidimensional intermediate pore molecular sieve, then using molecular sieve beta zeolite catalyst, the wax containing heavy ingredient is made to be converted into high quality
There is the subcircular hole that average diameter is 0.50nm~0.65nm to tie for the method for lube basestock, the unidimensional intermediate pore molecular sieve
Structure, wherein difference≤0.05nm of maximum diameter and minimum diameter.Two kinds of catalyst all include one or more group VIII metals.
For example, by first Pt/ZSM-48 catalyst cascade two bed type catalyst system that then second Pt/ beta catalyst forms
Promote the processing of heavy grease.
CN1803998A discloses a kind of dewaxing catalyst containing composite molecular screen, which contains a kind of with one-dimensional
The molecular sieve of central hole structure, a kind of molecular sieve with macroporous structure, wherein the molecular sieve with one-dimensional central hole structure with
The weight ratio of molecular sieve with macroporous structure is 80-99: 1-20, and the molecular sieve with macroporous structure contains non-skeleton
Silicon, is counted by oxide and on the basis of the molecular sieve, and the content of the silicon is 1-20 weight %.
Summary of the invention
The object of the present invention is to provide the hydrotreating methods of a kind of hydroisomerisation catalysts and hydrocracking tail oil, adopt
The hydrotreating of hydrocracking tail oil is carried out with hydroisomerisation catalysts of the present invention, target product obtained sticks
Degree index is higher, pour point is lower and yield is higher.
The present invention provides a kind of hydroisomerisation catalysts, which contains there are two types of ten-ring Si-Al molecular sieve,
In, at least one ten-ring Si-Al molecular sieve has the following characteristics that silica/alumina molar ratio is 120~300；Contain Jie
Pore structure and one closure hysteresis loop of appearance at low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the closure
The initial position of hysteresis loop is at P/P0=0.4-0.7.
The present invention also provides a kind of hydrotreating methods of hydrocracking tail oil, this method comprises: in hydroisomerization
Under reaction condition, by hydrocracking tail oil and catalyst haptoreaction, wherein the catalyst is that of the present invention plus hydrogen is different
Structure catalyst.
In hydroisomerisation catalysts of the present invention, by by two kinds of ten-ring Si-Al molecular sieves (especially
ZSM-22 molecular sieve and ZSM-48 molecular sieve) it is combined use, and make at least one of the two with special materialization
Matter, allow the catalyst in the hydrotreating production technology for being applied to hydrocracking tail oil when obtain obvious preferable drop
Solidifying effect, the Viscosity Index of target product obtained is higher, pour point is lower and yield is higher.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Hydroisomerisation catalysts of the present invention are containing there are two types of ten-ring Si-Al molecular sieves.At least one ten-ring silicon
Aluminum molecular screen has the characteristics that high silicon, containing mesoporous.Under preferable case, two kinds of ten-ring Si-Al molecular sieves all have high silicon, contain
Have the characteristics that mesoporous.
In the preferred case, the ten-ring molecular sieve has the characteristics that high silicon.According to conventional method in that art preparation
The silica/alumina molar ratio of ten-ring molecular sieve is generally less than 100.The oxidation of ten-ring molecular sieve of the present invention
Silicon/alumina molar ratio is 120~300, specifically, such as can for 120,130,140,150,160,170,180,190,
200,210,220,230,240,250,260,270,280,290,300 and these point values in the model that is constituted of any two
Arbitrary value in enclosing.Under preferable case, the silica/alumina molar ratio of the ten-ring molecular sieve is 150~200.
In the preferred case, ten-ring molecular sieve of the present invention contains meso-hole structure.According to conventional method in that art
The ten-ring molecular sieve of preparation is usually micro porous molecular sieve, does not contain meso-hole structure.In ten-ring molecular sieve of the present invention
Low temperature nitrogen adsorption-desorption curve on, absorption branch and desorption branch P/P0=0.4-0.99 at appearance one closure hysteresis loop,
And the initial position of hysteresis loop is closed at P/P0=0.4-0.7, and the ten-ring molecular sieve of prior art preparation does not have then
This feature, i.e., in the section without the initial position of hysteresis loop or hysteresis loop at higher partial pressure (usually P/P0 >
At 0.7).In the preferred case, the initial position of the closure hysteresis loop is at P/P0=0.4-0.6.
In the preferred case, ten-ring molecular sieve of the present invention is through nitrogen adsorption BET (Brunner-Emmet-
Teller) method characterizes, and the mesoporous area in the molecular sieve can be 50m2/g~250m2/g, the ratio table of the molecular sieve
Area can be 150m2/g~400m2/g, and the ratio of mesoporous area accounting surface area can be 20%~70%, preferably
25%~65%.
In the preferred case, in the precursor of ten-ring molecular sieve of the present invention be rich in pentacoordinate aluminium, and molecular sieve at
The content of pentacoordinate aluminium is seldom in product, or even substantially free of pentacoordinate aluminium.Specifically, in the precursor of the ten-ring molecular sieve
The content of pentacoordinate aluminium is 4-30 weight %, preferably 10-30 weight %；And in the finished product of the molecular sieve pentacoordinate aluminium content
For 3% weight hereinafter, preferably 2.5 weight % hereinafter, more preferably 2 weight % hereinafter, further preferably 1.5 weight % with
Under, still more preferably for 0.5 weight % hereinafter, being most preferably to be free of pentacoordinate aluminium.
In general, aluminium containing molecular sieve preparation can be divided into plastic, crystallization, post-treating and other steps.In order to obtain with high silicon, contain
There is mesoporous ten-ring molecular sieve, needs the post-processing step in aluminium containing molecular sieve synthesis process specially treated.Preferred
In the case of, the ten-ring molecular sieve is prepared according to the following steps:
(1) mother liquor after crystallization is filtered, forms the filter cake that contents on dry basis is 5-30 weight %；
(2) filter cake is directly roasted, obtains molecular sieve precursor；
(3) molecular sieve precursor is subjected to hydro-thermal process；
(4) hydro-thermal process product is filtered, washed, be dried.
It is removal synthesis mother liquid to the purpose that the mother liquor after crystallization is filtered in step (1).The present invention is to filtering shape
At the contents on dry basis of filter cake carried out special restriction.Specifically, contents on dry basis is 5-30 weight % in the filter cake, preferably
For 6-15 weight %.When in the filter cake contents on dry basis not within the above range when, the physico-chemical property of prepared molecular sieve is not
Within the framework of the present definition.In the present invention, " butt " is defined as: material mass is than upper after roasting 4 hours at 600 DEG C
The percentage of material mass before roasting.
In step (2), step (1) formed filter cake directly roasted at high temperature and without drying and processing.?
In the present invention, the temperature of the roasting can be 400-600 DEG C, preferably 450-550 DEG C.Heating rate can be 10 when roasting
DEG C/min~100 DEG C/min, preferably 20 DEG C/min~50 DEG C/min.The time of the roasting can be 1 hour~12
Hour, preferably 2 hours~6 hours.The environment of the roasting can be natural environment, that is, be not required to specially be passed through when roasting oxygen-containing
Gas.Even the water energy in filter cake enough oxidizes away template, while can also be with molecule due to roasting in a natural environment
Aluminium in sieve carries out effect to form non-framework aluminum.Particularly, product (the i.e. molecule handled in the present invention by step (2)
Sieve precursor) contain a large amount of pentacoordinate non-framework aluminum (i.e. pentacoordinate aluminium).The definition of pentacoordinate non-framework aluminum is in 27Al NMR
Chemical shift б is the peak of 15~40ppm in map.27Al NMR spectra measuring condition may refer to open source literature, such as
Guoliang Zhao et al,Applied Catalysis A:General 299(2006)167–174。
In the present invention, the content of pentacoordinate aluminium is 40-80 weight in the product (i.e. molecular sieve precursor) of step (2) processing
Measure %, preferably 50-70 weight %；In step (2), sample can be cooled down after calcination process with natural cooling, and target temperature is excellent
It is selected as room temperature.
In step (3), the medium of the hydro-thermal process is preferably acid water.In the present invention, the acid water refers to
H2O solution containing H+.Wherein, H2O is the liquid substance that conventional method is known as " water ".H+ is organic and or inorganic acids
Dissociate the ion of release.In order to obtain the acid water, can in " water " addition hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid,
In acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid extremely
Few one kind, preferably hydrochloric acid and/or citric acid.In the acid water content of inorganic acid and/or organic acid can for 0.1M~
5M, preferably 0.2M~2M.
In step (3), it can be 5-200, preferably 20-100 that the liquid of the hydro-thermal process, which consolidates volume ratio,；In step
(3) in, the temperature of the hydro-thermal process can be 100 DEG C~300 DEG C, preferably 100 DEG C~200 DEG C；In step (3), institute
The time for stating hydro-thermal process can be 0.5 hour~24 hours, and preferably 1 hour~12 hours, more preferably 1 hour~4 is small
When；In step (3), the hydro-thermal process is preferably implemented in closed container, and the pressure of the hydro-thermal process is preferably close
Close the pressure certainly that container is formed under hydrothermal conditions.
In step (4), molecular sieve needs after step (3) are handled through being filtered, washed.Wherein, filter method can be
Method well-known to those skilled in the art.The process of the washing can be to spend ionized water to be washed, and washing is until filter
Liquid pH value terminates for 6~8, and preferably 6~7.The pH value measurement of solution can be measured with pH test paper or pH meter, measurement method
The method being well known to those skilled in the art.
In step (4), there is no particular limitation for the drying process of molecular sieve, such as can be conventionally 120
It is 6 hours dry at DEG C.
In the present invention, the mother liquor after the crystallization can be prepared according to the method for this field routine, for example, working as described ten
When member ring Si-Al molecular sieve is ZSM-22 molecular sieve, the preparation method of the mother liquor after crystallization is referred to document O.Muraza et
Al., 136-143 Microporous and Mesoporous Materials 206 (2015).In one embodiment, institute
The preparation process of mother liquor after stating crystallization includes: to prepare siliceous solution, containing aluminum solutions, akaline liquid, and aforesaid liquid is mixed into
Row plastic then carries out crystallization at a certain temperature.
In hydroisomerisation catalysts of the present invention, the type of the ten-ring molecular sieve is not limited particularly
It is fixed, such as can be ZSM-22 molecular sieve, ZSM-23 molecular screen, ZSM-48 molecular sieve, ZSM-5 molecular sieve, SSZ-32 molecular sieve
At least one of with Eu-1 molecular sieve.In the preferred case, the ten-ring molecular sieve is ZSM-22 molecular sieve and/or ZSM-
48 molecular sieves.
In hydroisomerisation catalysts of the present invention, in order to further increase hydrotreating effect, it is preferable that institute
The silica/alumina molar ratio value difference for stating ten-ring molecular sieve is no more than 60, and specifically, the difference of the two for example can be
0,5,10,15,20,25,30,35,40,45,50,55,60 and these point values in the range that is constituted of any two in
Arbitrary value.It is highly preferred that the difference of the two is 20-40.
In hydroisomerisation catalysts of the present invention, it is preferable that the mass ratio of two kinds of ten-ring Si-Al molecular sieves
For 10:90~30:70.On the basis of the total weight of two kinds of ten-ring molecular sieves, the content of one of ten-ring molecular sieve can
Think 20-50 weight %, preferably 25-45 weight %, more preferably 30-45 weight %；Another ten-ring molecular sieve contains
Amount is 50-80 weight %, preferably 55-75 weight %, more preferably 55-70 weight %.
In the present invention, the hydroisomerisation catalysts can be loaded catalyst, and preparation process may include:
Ten-ring molecular sieve and heat-resistant inorganic oxide are mixed, molding, followed by dip loading active metal component, then
It is activated and is restored.
In the present invention, the heat-resistant inorganic oxide is preferably aluminium oxide.
In the present invention, the active metal component can be group VIII metal component.Group VIII metal such as Ru, Os,
Rh, Ir, Pd and Pt.Preferably, the group VIII metal is selected from Pd and Pt.
In the present invention, the active metal component can be provided by active metal component presoma.The active metal
Component presoma is selected from the compound of the precious metal element containing VIII group.The compound of the precious metal element containing VIII group can select
Nitrate, chloride, sulfate, formates, acetate, phosphate, citrate, the oxalic acid of self-contained VIII group precious metal element
Salt, carbonate, subcarbonate, hydroxide, phosphate, phosphide, sulfide, aluminate, molybdate, tungstates and water-soluble
One of property oxide is a variety of.
In the present invention, in the isomerization-visbreaking catalyst, on the basis of the total weight of catalyst, the content of molecular sieve
It can be 20-60 weight %, preferably 25-55 weight %；The content of heat-resistant inorganic oxide (such as aluminium oxide) is 35-80 weight
Measure %, preferably 42-72 weight %；The content of active metal component be 0.1-5 weight %, preferably 0.2-3 weight %, it is more excellent
It is selected as 0.4-1 weight %.
The present invention also provides a kind of hydrotreating methods of hydrocracking tail oil, this method comprises: in hydroisomerization
Under reaction condition, by hydrocracking tail oil and catalyst haptoreaction, wherein the catalyst be it is provided by the invention described plus
Hydrogen isomerization catalyst or the hydroisomerisation catalysts prepared according to the above method.
In the present invention, the boiling range of the hydrocracking tail oil generally can be for 350-500 DEG C (using simulation distillating method
It measures under normal pressure).
In the present invention, there is no particular limitation for the hygrogenating isomerization reaction condition, as long as being enough to make to be hydrocracked tail
Fry dried food ingredients gives birth to hygrogenating isomerization reaction.Generally, it is 200-500 that the hygrogenating isomerization reaction condition, which may include: temperature,
DEG C, preferably 250-400 DEG C, more preferably 300-350 DEG C；Pressure is 1-30MPa, preferably 2-20MPa, more preferably 5-
20MPa, pressure described herein refer to absolute pressure；Air speed is 0.1-5h-1, preferably 0.1-3h-1, more preferably 0.5-
2h-1；Hydrogen to oil volume ratio is 50-3000, preferably 300-3000, more preferably 400-600.
It contacts hydrocracking tail oil with hydroisomerisation catalysts according to the method described in the present invention, carries out hydroisomerizing
Change reaction, higher isomerization product yield can be obtained；Also, isomerization product is same Viscosity Index with higher
When, also there is lower pour point, be suitable for lube base oil.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, using the 3271E type X-ray for being commercially available from Rigaku electric machine industry Co., Ltd.
Fluorescence Spectrometer carries out analysis measurement to the content of each element in measurement sample, roasts 3 hours at 600 DEG C before sample test.
2500 type automatic absorbing of U.S. Micromeritics company DIGISORB is used in following embodiment and comparative example
Instrument measures the specific surface area of sample, external surface area, roasts 3 hours at 600 DEG C before sample test, and measurement method can be according to
ASTM D4222-98 standard method carries out.
In following embodiment and comparative example, butt refers to a certain amount of material in air atmosphere in Muffle furnace 600
DEG C weight of product obtained after roasting 4 hours and before roasting the weight ratio of material percentage.That is butt=(after roasting
The weight of material before the weight ÷ of the product arrived is roasted) × 100%.
Preparation example 1
(1) mother liquor after crystallization is prepared
Take 36.3 grams containing 40 weight % SiO2 silica solution, 1.77 grams of analytically pure Al2 (SO4) 318H2O, 3.94
Gram analytically pure KOH and 8.44 diamines of restraining oneself is stand-by.Hexamethylene diamine is mixed with silica solution, by KOH and Al2 (SO4) 3
18H2O and 89.4 gram of deionized water mixing, then mixes two kinds of solution, moves into reaction kettle after stirring 1h, at 160 DEG C
Crystallization 72 hours.
(2) filter cake is prepared
Mother liquor after the crystallization prepared in process (1) is filtered, not have filtrate timing on filter cake, continues suction filtration 5
Minute, the contents on dry basis of the filter cake F-1 of acquisition, filter cake F-1 are 11.2 weight %, silica/alumina molar ratio 60.
(3) molecular sieve precursor is prepared
Filter cake F-1 is raised to 450 DEG C, constant temperature 4 hours from room temperature with 25 DEG C/min of heating rate.It is roasted in temperature-rise period
Burning furnace is closed roaster, obtains molecular sieve precursor C-1.
(4) molecular sieve finished product is prepared
Molecular sieve precursor C-1 is put into the HCl solution that concentration is 1M and carries out closed hydro-thermal process.Wherein, liquid-solid ratio is
50, the temperature of hydro-thermal process is 180 DEG C, and the time of hydro-thermal process is 3 hours, is filtered product after hydro-thermal process, washing,
Until filtrate pH is 7, after 120 DEG C 4 hours dry, roasted 4 hours at 550 DEG C, the ZSM-22 molecular sieve finished product H- of acquisition
1.As can be seen that the ZSM-22 molecular sieve is bent in low temperature nitrogen adsorption-desorption from nitrogen adsorption-desorption curve of the molecular sieve
Occurs a closure hysteresis loop at line P/P0=0.4-0.99, and the initial position of the closure hysteresis loop is in P/P0=0.4-
At 0.5.
Prepare comparative example 1
ZSM-22 molecular sieve and catalyst are prepared according to the method for preparation example 1, the difference is that in step (2), with filter
There is no filtrate timing on cake, the contents on dry basis for continuing to filter 50 minutes, the filter cake DF-1 of acquisition, filter cake DF-1 is 46.5 weights
Measure %.ZSM-22 molecular sieve finished product DH-1 is made.
Prepare comparative example 2
According to the mother liquor after process (1) preparation crystallization in preparation example 1, then filter, and by filtered obtained filter cake
It is 6 hours dry at 120 DEG C, it is then roasted 4 hours at 550 DEG C, solid product will be obtained and exchanged with NH4Cl 3 times, after dry
Form ammonium type molecular sieve finished product DH-2.
Preparation example 2
(1) mother liquor after crystallization is prepared
Take 45 grams of white carbon blacks, 1.25 grams of analytically pure Al2 (SO4) 318H2O, 1.88 grams of analytically pure NaOH and
39.3 diamines of restraining oneself are stand-by.Hexamethylene diamine is mixed with white carbon black and 200 grams of deionized waters, by NaOH and Al2 (SO4) 3
18H2O and 272 gram of deionized water mixing, then mixes two kinds of solution, moves into reaction kettle after stirring 1h, at 160 DEG C
Crystallization 72 hours.
(2) filter cake is prepared
Mother liquor after the crystallization prepared in process (1) is filtered, not have filtrate timing on filter cake, continues suction filtration 5
Minute, the contents on dry basis of the filter cake F-2 of acquisition, filter cake F-2 are 11.2 weight %, silica/alumina molar ratio 60.
(3) molecular sieve precursor is prepared
Filter cake F-2 is raised to 450 DEG C, constant temperature 4 hours from room temperature with 25 DEG C/min of heating rate.It is roasted in temperature-rise period
Burning furnace is closed roaster, obtains molecular sieve precursor C-2.
(4) molecular sieve finished product is prepared
Molecular sieve precursor C-2 is put into the citric acid solution that concentration is 1M and carries out closed hydro-thermal process.Wherein, liquid-solid ratio
It is 100, the temperature of hydro-thermal process is 180 DEG C, and the time of hydro-thermal process is 2 hours, by product filtering, water after hydro-thermal process
It washes, until filtrate pH is 7, after 120 DEG C 4 hours dry, is roasted 4 hours at 550 DEG C, the ZSM-48 molecular sieve finished product of acquisition
H-2.As can be seen that the ZSM-48 molecular sieve is in low temperature nitrogen adsorption-desorption from nitrogen adsorption-desorption curve of the molecular sieve
Occurs a closure hysteresis loop at curve P/P0=0.4-0.99, and the initial position of the closure hysteresis loop is in P/P0=0.4-
At 0.5.
Prepare comparative example 3
ZSM-48 molecular sieve is prepared according to the method for preparation example 2, the difference is that in step (2), not have on filter cake
Filtrate timing, the contents on dry basis for continuing to filter 50 minutes, the filter cake DF-3 of acquisition, filter cake DF-3 is 46.5%.ZSM- is made
48 molecular sieve finished product DH-3.
Prepare comparative example 4
According to the mother liquor after process (1) preparation crystallization in preparation example 2, then filter, and by filtered obtained filter cake
It is 6 hours dry at 120 DEG C, it is then roasted 4 hours at 550 DEG C, solid product will be obtained and exchanged with NH4Cl 3 times, after dry
Form ammonium type molecular sieve finished product DH-4.
Test case 1
(1) using 2500 type automatic absorbing instrument of U.S. Micromeritics company DIGISORB measure above-described embodiment and
The mesoporous area of the molecular sieve finished product of comparative example preparation, specific surface area, and the ratio of mesoporous area accounting surface area is calculated, as a result
As shown in table 1 below.
(2) using the 3271E type Xray fluorescence spectrometer for being commercially available from Rigaku electric machine industry Co., Ltd., to above-mentioned
The content of each element carries out analysis measurement in the molecular sieve precursor and molecular sieve finished product of embodiment and comparative example preparation, determines sial
Than the content with pentacoordinate aluminium, as a result as shown in table 1 below.
Table 1
Embodiment 1
5g (butt) molecular sieve H-1 and 20g (butt) molecular sieve H-2 are ground into 120 mesh respectively, mixed, then and 75g
The mixing of (butt) aluminium oxide, molding roast the Pt metal of 0.4 weight % of back loading through 560 DEG C.3h, 400 DEG C are activated at 400 DEG C
Catalyst is made after lower reduction 3h, is named as Cat-1.
Comparative example 1
Catalyst is prepared according to the method for embodiment 1, the difference is that the molecular sieve DH- prepared using preparation comparative example 1
1 replaces molecular sieve H-1, molecular sieve H-2 is replaced using molecular sieve DH-3 prepared by preparation comparative example 3, so that catalyst D- be made
Cat-1。
Comparative example 2
Catalyst is prepared according to the method for embodiment 1, the difference is that the molecular sieve DH- prepared using preparation comparative example 2
2 replace molecular sieve H-1, molecular sieve H-2 are replaced using molecular sieve DH-4 prepared by preparation comparative example 3, so that catalyst D- be made
Cat-2。
Comparative example 3
Catalyst is prepared according to the method for embodiment 1, the difference is that all preparation comparative examples 1 of the molecular sieve used
The molecular sieve DH-1 of preparation, so that catalyst D-Cat-3 be made.
Comparative example 4
Catalyst is prepared according to the method for embodiment 1, the difference is that all preparation comparative examples 3 of the molecular sieve used
The molecular sieve DH-3 of preparation, so that catalyst D-Cat-4 be made.
Embodiment 2
Catalyst is prepared according to the method for embodiment 1, the difference is that the molecular sieve DH- prepared using preparation comparative example 1
1 replaces molecular sieve H-1, so that catalyst Cat-2 be made.
Embodiment 3
Catalyst is prepared according to the method for embodiment 1, the difference is that the molecular sieve DH- prepared using preparation comparative example 3
3 replace molecular sieve H-2, so that catalyst Cat-3 be made.
Embodiment 4
Catalyst is prepared according to the method for embodiment 1, the difference is that (dry using 10g (butt) molecular sieve H-1 and 24g
Base) molecular sieve H-2, so that catalyst Cat-4 be made.
Embodiment 5
Catalyst is prepared according to the method for embodiment 1, the difference is that (dry using 28g (butt) molecular sieve H-1 and 28g
Base) molecular sieve H-2, so that catalyst Cat-5 be made.
Catalyst prepared by above-described embodiment and comparative example is loaded in high-pressure hydrogenation reactor respectively and is evaluated, it is used
Raw material oil nature is as shown in table 2, and evaluation condition is as shown in table 3.Product is distilled to cut off less than 370 DEG C after reaction
Light component.It carries out pour point, Viscosity Index analysis and yield to the component greater than 370 DEG C to calculate, the results are shown in Table 4.It receives
Rate is defined as: be greater than quality/charging quality of 370 DEG C of components in yield=product.
Table 2
| Analysis project | Analyze data | Analysis method |
| 20 DEG C of density/(kg/m3) | 837.2 | SH/T0604-2000 |
| 40 DEG C of dynamic viscosity/(mm2/s) | 16.46 | GB/T 265-88 |
| 100 DEG C of dynamic viscosity/(mm2/s) | 3.812 | GB/T 265-88 |
| Viscosity Index | 130 | GB/T1995-1998 |
| Pour point/DEG C | +36 | SH/T 0771-2005 |
| Nitrogen content/(μ g/g) | 5.2 | NB/SH/T 0704-2010 |
| Sulfur nutrient/(μ g/g) | 2.6 | SH/T 0842-2010 |
| Boiling range/DEG C | IBP | ASTM D-1160 |
| IBP | 370 | |
| 5% | 386 | |
| 10% | 420 | |
| 50% | 436 | |
| 90% | 456 | |
| 97% | 462 | |
| It does | 485 |
Table 3
| Reaction condition | Condition 1 | Condition 2 |
| Pressure, MPa | 12.0 | 12.0 |
| Air speed, h-1 | 1.0 | 1.0 |
| Reaction temperature, DEG C | 300 | 320 |
| Hydrogen-oil ratio, v/v | 500 | 500 |
Table 4
According to the side of hydrocracking tail oil of the present invention production lube base oil it can be seen from the data of table 4
Method can obtain preferable depression effeCt, and lube base oil yield is high, and Viscosity Index is high.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (16)
1. a kind of hydroisomerisation catalysts, which is characterized in that the catalyst is containing there are two types of ten-ring Si-Al molecular sieves, wherein
At least one ten-ring Si-Al molecular sieve has the following characteristics that silica/alumina molar ratio is 120~300；Contain mesoporous knot
Structure and one closure hysteresis loop of appearance at low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the closure lags
The initial position of ring is at P/P0=0.4-0.7.
2. isomerization-visbreaking catalyst according to claim 1, wherein at least one ten-ring Si-Al molecular sieve
In, the silica/alumina molar ratio of molecular sieve is 150~200.
3. isomerization-visbreaking catalyst according to claim 1 or 2, wherein at least one ten-ring silicoaluminophosphate molecular
In sieve, the mesoporous area in molecular sieve is 50m2/ g~250m2/ g, the ratio of mesoporous area accounting surface area are 20%~70%,
Preferably 25%~65%.
4. isomerization-visbreaking catalyst described in any one of -3 according to claim 1, wherein at least one ten-ring
In Si-Al molecular sieve, the initial position of the closure hysteresis loop is at P/P0=0.4-0.6.
5. isomerization-visbreaking catalyst described in any one of -4 according to claim 1, wherein at least one ten-ring
It in Si-Al molecular sieve, is counted by oxide and on the basis of the total alumina amount of molecular sieve, pentacoordinate aluminium contains in the precursor of molecular sieve
Amount is 4-30 weight %, preferably 10-30 weight %.
6. isomerization-visbreaking catalyst described in any one of -5 according to claim 1, wherein at least one ten-ring
It in Si-Al molecular sieve, is counted by oxide and on the basis of the total alumina amount of molecular sieve, pentacoordinate aluminium contains in the finished product of molecular sieve
Amount is 3 weight % hereinafter, preferably 1 weight % is hereinafter, be more preferably free of pentacoordinate aluminium.
7. isomerization-visbreaking catalyst described in any one of -6 according to claim 1, wherein the ten-ring Si-Al molecular sieve
It is prepared according to the following steps:
(1) mother liquor after crystallization is filtered, forms the filter cake that contents on dry basis is 5-30%；
(2) filter cake is directly roasted, obtains molecular sieve precursor；
(3) molecular sieve precursor is subjected to hydro-thermal process；
(4) hydro-thermal process product is filtered, washed, be dried.
8. isomerization-visbreaking catalyst according to claim 7, wherein in step (1), in the filter cake that the filtering is formed
Contents on dry basis is 6-15%.
9. isomerization-visbreaking catalyst according to claim 7 or 8, wherein in step (2), the temperature of the roasting is
400-600 DEG C, preferably 450-550 DEG C.
10. isomerization-visbreaking catalyst according to claim 7 or 8, wherein in step (3), Jie of the hydro-thermal process
Matter is acid water；
Preferably, the acid water contains inorganic acid and/or organic acid, and the content of inorganic acid and/or organic acid be 0.1M~
5M, preferably 0.2M~2M；
It is highly preferred that the acid water contains hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, acetic acid, maleic acid, oxalic acid, amino three
At least one of acetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid.
11. isomerization-visbreaking catalyst according to claim 7 or 8, wherein in step (3), the liquid of the hydro-thermal process
Gu volume ratio is 5-200, preferably 20-100；The temperature of the hydro-thermal process be 100 DEG C~300 DEG C, preferably 100 DEG C~
200℃；The time of the hydro-thermal process be 0.5 hour~24 hours, preferably 1 hour~12 hours, more preferably 1 hour~
4 hours；
Preferably, the hydro-thermal process is implemented in closed container, and the pressure of the hydro-thermal process is closed container in hydro-thermal
Under the conditions of formed from press.
12. isomerization-visbreaking catalyst according to claim 7 or 8, wherein in step (4), the process of the washing is
It is washed with deionized water, washing terminates until filtrate pH value for 6~8, and preferably 6~7.
13. isomerization-visbreaking catalyst described in any one of -12 according to claim 1, wherein two kinds of ten-ring silicoaluminophosphate moleculars
The silica/alumina molar ratio value difference of sieve is no more than 60, preferably the two difference 20-40.
14. isomerization-visbreaking catalyst described in any one of -13 according to claim 1, wherein two kinds of ten-ring silicoaluminophosphate moleculars
Sieve be respectively selected from ZSM-22 molecular sieve, ZSM-23 molecular screen, ZSM-48 molecular sieve, ZSM-5 molecular sieve, SSZ-32 molecular sieve and
At least one of Eu-1 molecular sieve.
15. isomerization-visbreaking catalyst according to claim 14, wherein two kinds of ten-ring Si-Al molecular sieves are respectively ZSM-
22 molecular sieves and ZSM-48 molecular sieve；
Preferably, the silica/alumina molar ratio value of ZSM-22 molecular sieve and the silica/alumina of ZSM-48 molecular sieve are rubbed
Your ratio difference is 5-60, more preferably 20-40；
Preferably, on the basis of the total weight of ZSM-22 molecular sieve and ZSM-48 molecular sieve, the content of ZSM-22 molecular sieve is 10-
The content of 30 weight %, ZSM-48 molecular sieves is 70-90 weight %.
16. a kind of hydrotreating method of hydrocracking tail oil, this method comprises: will add under the conditions of hygrogenating isomerization reaction
Hydrogen cracking tail oil and catalyst haptoreaction, which is characterized in that the catalyst is described in any one of claim 1-15
Hydroisomerisation catalysts.
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