CN109701625A - A kind of production method of isomerization-visbreaking catalyst and biology boat coal - Google Patents
A kind of production method of isomerization-visbreaking catalyst and biology boat coal Download PDFInfo
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- CN109701625A CN109701625A CN201711023173.5A CN201711023173A CN109701625A CN 109701625 A CN109701625 A CN 109701625A CN 201711023173 A CN201711023173 A CN 201711023173A CN 109701625 A CN109701625 A CN 109701625A
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Abstract
The present invention relates to biology boat coal production fields, and in particular to a kind of production method of isomerization-visbreaking catalyst and biology boat coal.The catalyst is containing there are two types of twelve-ring Si-Al molecular sieves, wherein at least one twelve-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.Biology boat coal is produced using isomerization-visbreaking catalyst of the present invention, preferable depression effeCt can be obtained, and target product yield is high.
Description
Technical field
The present invention relates to biology boat coal production fields, and in particular to a kind of production of isomerization-visbreaking catalyst and biology boat coal
Method.
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.
CN103964458A discloses a kind of Beta zeolite and preparation method thereof of high silica alumina ratio multistage pore canal.Beta boiling
There is pore-size distribution in the duct of stone in 2nm or less, 5-11nm and 50nm or more, wherein micro pore volume 0.19cm3/ g or more,
Mesoporous and macropore total volume is 0.35cm3/ g or more, silica alumina ratio are 90 or more, specific surface area 400m2/ g or more.The preparation
Method is the following steps are included: carry out the first hypo acid processing for raw material Beta zeolite；By the first hypo acid treated Beta zeolite into
Row roasts for the first time；Beta zeolite after first time is roasted carries out the second hypo acid processing, and it is multistage to obtain the high silica alumina ratio
The Beta zeolite in duct.The preparation method of the invention is easy to operate efficiently, the Beta for the high silica alumina ratio multistage pore canal being prepared
Zeolite has very strong acid, heat and hydrothermal stability and good diffusion.
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 processing Fischer-Tropsch wax.The invention is related to a kind of by Fischer-Tropsch
The method that wax is converted into the base constituent of lubricating oils of high quality, this method are urged using the molecular sieve β-for being followed by one-dimensional mesoporous molecular sieve
Agent, the one-dimensional mesoporous molecular sieve have average diameter between 0.50 nanometer to 0.65 nanometer, maximum diameter and minimum diameter
Between difference≤0.05 nanometer close to circular pore structure.Two kinds of catalyst contain one or more group VIII metals.
For example, a kind of series connection two-bed catalyst that first by being followed by second Pt/ZSM-48 catalyst bed Pt/ beta catalyst forms
Agent system has the selectivity of height in the case where gas generating amount is minimum to wax isomerization and lube oil hydrogenation dewaxing.
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 production methods of a kind of isomerization-visbreaking catalyst and biology boat coal, using institute of the present invention
The isomerization-visbreaking catalyst production biology boat coal stated, can obtain preferable depression effeCt, and target product yield is high.
The present invention provides a kind of isomerization-visbreaking catalyst, which contains there are two types of twelve-ring Si-Al molecular sieve,
In, at least one twelve-ring Si-Al molecular sieve has the following characteristics that silica/alumina molar ratio is 120~300；Contain
Meso-hole structure and occur a closure hysteresis loop at low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and described closes
The initial position of hysteresis loop is closed at P/P0=0.4-0.7.
The present invention also provides a kind of production method of biology boat coal, this method includes being catalyzed feedstock oil and isomerization-visbreaking
Agent haptoreaction, the isomerization-visbreaking catalyst are isomerization-visbreaking catalyst of the present invention.
In isomerization-visbreaking catalyst of the present invention, by by two kinds of twelve-ring Si-Al molecular sieves (especially
Beta molecular sieve and ZSM-12 molecular sieve) at least one of it is combined use, and both is made there is special physico-chemical property,
Allow the catalyst in the production technology for being applied to biology boat coal when obtain obvious preferable depression effeCt, and can be with
Improve target product yield.
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.
Isomerization-visbreaking catalyst of the present invention is containing there are two types of twelve-ring Si-Al molecular sieves.At least one twelve-ring
Si-Al molecular sieve has the characteristics that high silicon, containing mesoporous.Under preferable case, two kinds of twelve-ring Si-Al molecular sieves all have height
Silicon contains mesoporous feature.
Twelve-ring Si-Al molecular sieve
In the preferred case, the twelve-ring Si-Al molecular sieve has the characteristics that high silicon.According to conventional method in that art
The silica/alumina molar ratio of the twelve-ring Si-Al molecular sieve of preparation is generally less than 100.Twelve-ring of the present invention
The silica/alumina molar ratio of Si-Al molecular sieve 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 appoint
Arbitrary value in two ranges constituted of anticipating.Under preferable case, the silica/alumina of the twelve-ring Si-Al molecular sieve
Molar ratio is 150~200.
In the preferred case, twelve-ring Si-Al molecular sieve of the present invention contains meso-hole structure.It is normal according to this field
The twelve-ring Si-Al molecular sieve of rule method preparation is usually micro porous molecular sieve, does not contain meso-hole structure.Of the present invention
On the low temperature nitrogen adsorption-desorption curve of twelve-ring Si-Al molecular sieve, absorption branch and desorption branch are at P/P0=0.4-0.99
There is a closure hysteresis loop, and is closed the initial position of hysteresis loop at P/P0=0.4-0.7, and the ten of prior art preparation
Two member ring Si-Al molecular sieves do not have this feature then, i.e., appear in the section without the initial position of hysteresis loop or hysteresis loop
At higher partial pressure (usually at P/P0 > 0.7).In the preferred case, the initial position of the closure hysteresis loop is in P/P0=
At 0.4-0.6.
In the preferred case, twelve-ring Si-Al 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 molecular sieve
Specific surface area can be 150m2/ g~400m2/ g, the ratio of mesoporous area accounting surface area can be 20%~70%, preferably
25%~65%.
In the preferred case, it is rich in pentacoordinate aluminium in the precursor of twelve-ring Si-Al molecular sieve of the present invention, and divides
The content of pentacoordinate aluminium is seldom in son sieve finished product, or even substantially free of pentacoordinate aluminium.Specifically, the twelve-ring sial point
The content of pentacoordinate aluminium is 4-30 weight %, preferably 10-30 weight % in the precursor of son sieve；And five in the finished product of the molecular sieve
Be coordinated aluminium content be 3 weight % hereinafter, preferably 2.5 weight % hereinafter, more preferably 2 weight % hereinafter, further preferably
For 1 weight % hereinafter, being still more preferably 0.5 weight % hereinafter, being most preferably without pentacoordinate aluminium.
The preparation method of twelve-ring Si-Al molecular sieve
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 twelve-ring Si-Al molecular sieve, needs the post-processing step in aluminium containing molecular sieve synthesis process specially treated.
In the preferred case, the twelve-ring Si-Al 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%；
(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%, preferably 6- in the filter cake
15%.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 in the present invention
Within the scope of restriction.In the present invention, " butt " is defined as: object before material mass is than upper roasting after roasting 4 hours at 600 DEG C
The percentage of matter quality.
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 be27Al NMR figure
Chemical shift б is the peak of 15~40ppm in spectrum.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 preferably 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
Containing H+H2O solution.Wherein, H2O is the liquid substance that conventional method is known as " water ".H+For organic and or inorganic acids solution
Ion from release.In order to obtain the acid water, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, second can be added in " water "
In acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid at least
One kind, preferably hydrochloric acid and/or citric acid.The content of inorganic acid and/or organic acid can be 0.1M~5M in the acid water,
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), 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), the time of the hydro-thermal process can be 0.5 hour~24 hours, and preferably 1 hour~12 is small
When, more preferably 1 hour~4 hours.
In step (3), the hydro-thermal process is preferably implemented in closed container, and the pressure of the hydro-thermal process is preferred
It is pressed certainly for what closed container was 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 two member ring Si-Al molecular sieves are ZSM-12 molecular sieve, the preparation method of the mother liquor after crystallization is referred to document Srikant
49 (2001) 149-156 of Gopal et al., Microporous and Mesoporous Materials.When described 12
When member ring Si-Al molecular sieve is Beta molecular sieve, the preparation method of the mother liquor after crystallization is referred to U.S. Patent application
US5200168.In one embodiment, the preparation process of the crystallization mother liquor of the twelve-ring Si-Al molecular sieve includes: system
Standby siliceous solution contains aluminum solutions, akaline liquid, and aforesaid liquid is mixed and carries out plastic, then carries out crystallization at a certain temperature.
In isomerization-visbreaking catalyst of the present invention, in order to further increase isomerization-visbreaking effect, it is preferable that two kinds
The silica/alumina molar ratio value difference of twelve-ring Si-Al molecular sieve is no more than 60, and specifically, the difference of the two for example may be used
Think the range that any two in 0,5,10,15,20,25,30,35,40,45,50,55,60 and these point values are constituted
In arbitrary value.It is highly preferred that the difference of the two is 20-40.
In isomerization-visbreaking catalyst of the present invention, the type of two kinds of twelve-ring Si-Al molecular sieves is not special
It limits, such as Beta molecular sieve, ZSM-12 molecular sieve, Y type molecular sieve and USY molecular sieve can be respectively selected from.In preferable case
Under, two kinds of twelve-ring Si-Al molecular sieves are respectively Beta molecular sieve and ZSM-12 molecular sieve.In order to further increase isomery drop
Solidifying effect, it is preferable that the silica/alumina molar ratio value of Beta molecular sieve is greater than silica/oxidation of ZSM-12 molecular sieve
Al mole ratio value.It is highly preferred that the difference of the two is 20-40.
In isomerization-visbreaking catalyst of the present invention, it is preferable that with the total of Beta molecular sieve and ZSM-12 molecular sieve
On the basis of weight, the content of Beta molecular sieve is that the content of 10-30 weight %, ZSM-12 molecular sieve is 70-90 weight %.
In the present invention, the isomerization-visbreaking catalyst can be loaded catalyst, preparation process may include: by
Two kinds of twelve-ring Si-Al molecular sieves and heat-resistant inorganic oxide mixing, molding, followed by dip loading active metal
Then component is activated and is restored.
In the present invention, the heat-resistant inorganic oxide is preferably aluminium oxide.
In hydroisomerisation catalysts of the present invention, the active metal component can be VIII group noble metal group
Point.VIII group noble metal can be at least one of for ruthenium, osmium, palladium, platinum, rhodium and iridium, preferably palladium and/or platinum, most preferably
Platinum.
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 hydroisomerisation catalysts of the present invention, on the basis of the total weight of catalyst, two kinds of twelve-rings
The total content of Si-Al molecular sieve can be 20-60 weight %, preferably 25-55 weight %；Heat-resistant inorganic oxide is (as aoxidized
Aluminium) content be 35-80 weight %, preferably 42-72 weight %；The content of active metal component based on the element is 0.1-5
Weight %, preferably 0.2-3 weight %, more preferably 0.4-1 weight %.
It is of the present invention biology boat coal production method include by feedstock oil and isomerization-visbreaking catalyst haptoreaction,
In, the isomerization-visbreaking catalyst is isomerization-visbreaking catalyst provided by the invention.
In method of the present invention, the feedstock oil can be the conventional selection of this field.In the preferred case, institute
The boiling range for stating feedstock oil is 150-500 DEG C, wherein the mass fraction of S element less than 100 μ g/g, N mass fractions less than 50 μ g/g,
For aromatics quality score less than 0.5%, n-alkane mass fraction is greater than 90%.
In method of the present invention, the catalytic condition may include: that temperature is 250-400 DEG C, preferably
It is 300-350 DEG C；Pressure is 1-30MPa, preferably 5-20MPa, and pressure described herein refers to absolute pressure；Air speed is
0.1-3h-1, preferably 0.5-2h-1；Hydrogen to oil volume ratio is 50-1000, preferably 400-600.
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%.
Prepare twelve-ring Si-Al molecular sieve
Preparation example 1
(1) mother liquor after crystallization is prepared
Take 6.05mL white carbon black, (content is for 0.51 gram of analytically pure aluminium secondary butylate and 18.4mL tetraethyl ammonium hydroxide
40 weight %) it is stand-by.15 grams of deionized waters are mixed with tetraethyl ammonium hydroxide and aluminium secondary butylate and 37 grams of deionized waters, with
White carbon black is added afterwards, is moved into reaction kettle after stirring 1h, crystallization 120 hours at 140 DEG C.
(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%, silica/alumina molar ratio 40.2.
(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 Beta molecular sieve finished product H-1 of acquisition.
As can be seen that the Beta molecular sieve is in low temperature nitrogen adsorption-desorption curve P/ from nitrogen adsorption-desorption curve of the molecular sieve
Occurs a closure hysteresis loop at P0=0.4-0.99, and the initial position of the closure hysteresis loop is at P/P0=0.4-0.5.
Prepare comparative example 1
Beta molecular sieve is prepared according to the method for preparation example 1, the difference is that in step (2), not filtered on filter cake
Liquid timing, 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%.It is made Beta points
Son sieve finished product DH-1.
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 and NH will be obtained4Cl is exchanged 3 times, after dry
Form ammonium type molecular sieve finished product DH-2.
Preparation example 2
(1) mother liquor after crystallization is prepared
38.5mL is taken to contain the SiO of 40 weight %2Silica solution, 1.48 grams of analytically pure sodium aluminates and 17.5mL tetrem
Base ammonium hydroxide (content is 40 weight %) is stand-by.Tetraethyl ammonium hydroxide and sodium aluminate and 37 grams of deionized waters are mixed,
Then silica solution is added, is moved into reaction kettle after stirring 1h, crystallization 132 hours at 160 DEG C.
(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%, silica/alumina molar ratio 30.2.
(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-12 molecular sieve finished product of acquisition
H-2.As can be seen that the ZSM-12 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-12 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
12 molecular sieve finished product DH-3.
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-3 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.
Application Example 1-5 and Comparison study example 1-4
Catalyst prepared by above-described embodiment and comparative example is loaded in high-pressure hydrogenation reactor respectively and is evaluated, is evaluated
Condition is as shown in table 3, and raw materials used oil nature is as shown in table 2.Product is distilled to cut off less than 150 DEG C after reaction
Light component and heavy constituent greater than 280 DEG C.Freezing point analysis is carried out to 150-280 DEG C of component and yield calculates, as a result such as
Shown in table 4.Yield is defined as: quality/charging quality of 150-280 DEG C of component in yield=product.
Table 2
| Analysis project | Analyze data | Analysis method |
| 20 DEG C of density/(kg/m3) | 778.2 | SH/T0604-2000 |
| Pour point/DEG C | +16 | SH/T 0771-2005 |
| Nitrogen content/(μ g/g) | 1.2 | NB/SH/T 0704-2010 |
| Sulfur nutrient/(μ g/g) | 2.1 | SH/T 0842-2010 |
| Boiling range/DEG C | ASTM D-1160 | |
| IBP | 270 | |
| 10% | 279 | |
| 50% | 289 | |
| 95% | 306 | |
| FBP | 320 |
Table 3
Table 4
It, can be with using isomerization-visbreaking catalyst of the present invention production biology boat coal it can be seen from the data of upper table 4
Preferable depression effeCt is obtained, and target product yield 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 (17)
1. a kind of isomerization-visbreaking catalyst, which is characterized in that the catalyst is containing there are two types of twelve-ring Si-Al molecular sieves, wherein
At least one twelve-ring Si-Al molecular sieve has the following characteristics that silica/alumina molar ratio is 120~300；Containing mesoporous
Structure and one closure hysteresis loop of appearance at low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the closure is stagnant
The initial position of ring is at P/P0=0.4-0.7 afterwards.
2. isomerization-visbreaking catalyst according to claim 1, wherein at least one twelve-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 twelve-ring sial point
In son sieve, the mesoporous area in molecular sieve is 50m2/ g~250m2/ g, the ratio of mesoporous area accounting surface area is 20%~
70%, preferably 25%~65%.
4. isomerization-visbreaking catalyst described in any one of -3 according to claim 1, wherein at least one ten binary
In ring 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 binary
It in ring Si-Al molecular sieve, is counted by oxide and on the basis of the total alumina amount of molecular sieve, pentacoordinate aluminium in the precursor of molecular sieve
Content 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 binary
It in ring Si-Al molecular sieve, is counted by oxide and on the basis of the total alumina amount of molecular sieve, pentacoordinate aluminium in the finished product of molecular sieve
Content 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 twelve-ring silicoaluminophosphate 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%；
(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 twelve-ring sial point
The silica/alumina molar ratio value difference of son 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 twelve-ring sial point
Son sieve is respectively selected from Beta molecular sieve, ZSM-12 molecular sieve, Y type molecular sieve and USY molecular sieve.
15. isomerization-visbreaking catalyst according to claim 14, wherein two kinds of twelve-ring Si-Al molecular sieves are respectively
Beta molecular sieve and ZSM-12 molecular sieve；
Preferably, the silica/alumina that the silica/alumina molar ratio value of Beta molecular sieve is greater than ZSM-12 molecular sieve is rubbed
That ratio, and the difference of the two is 20-40；
Preferably, on the basis of the total weight of Beta molecular sieve and ZSM-12 molecular sieve, the content of Beta molecular sieve is 10-30 weight
% is measured, the content of ZSM-12 molecular sieve is 70-90 weight %.
16. a kind of production method of biology boat coal, this method includes by feedstock oil and isomerization-visbreaking catalyst haptoreaction, spy
Sign is that the isomerization-visbreaking catalyst is isomerization-visbreaking catalyst described in any one of claim 1-15.
17. according to the method for claim 16, wherein the boiling range of the feedstock oil is 150-500 DEG C, wherein S element
Mass fraction is less than 100 μ g/g, N mass fractions less than 50 μ g/g, and aromatics quality score is less than 0.5%, n-alkane quality point
Number is greater than 90%.
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|---|---|---|---|---|
| CN102658197A (en) * | 2012-05-16 | 2012-09-12 | 浙江师范大学 | Catalyst for normal paraffin hydroisomerization reaction and preparation method as well as application thereof |
| CN103805255A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low condensation point by catalyst gradation technology |
| CN105582972A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Isomerization pour point depression catalyst, preparation method and application thereof, and a Fischer-Tropsch synthetic wax isomerization pour point depression method |
| CN107282097A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of hydroisomerization catalyst and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658197A (en) * | 2012-05-16 | 2012-09-12 | 浙江师范大学 | Catalyst for normal paraffin hydroisomerization reaction and preparation method as well as application thereof |
| CN103805255A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low condensation point by catalyst gradation technology |
| CN105582972A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Isomerization pour point depression catalyst, preparation method and application thereof, and a Fischer-Tropsch synthetic wax isomerization pour point depression method |
| CN107282097A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of hydroisomerization catalyst and its preparation method and application |
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