CN1393403A - Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition - Google Patents
Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition Download PDFInfo
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- CN1393403A CN1393403A CN 01119907 CN01119907A CN1393403A CN 1393403 A CN1393403 A CN 1393403A CN 01119907 CN01119907 CN 01119907 CN 01119907 A CN01119907 A CN 01119907A CN 1393403 A CN1393403 A CN 1393403A
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Abstract
A stepped crystallizing process for synthesizing the composition of mesoporous and microporous molecular sieves includes such steps as preparing the mixture gel for synthesizing microporous molecular sieve (Y-molecular sieve, ZSM-5, etc), then stage-one crystallizing at 30-300 deg.C for 3-300 hr, regulating pH value to 9.5-12, adding the template agent for synthesizing mesoporous molecular sieve, Si-source (sodium silicate), Al-source (aluminium sulphate), and other additives, and then stage-two hydrothermal crystallizing at 30-170 deg.C for 15-480 hr.
Description
The present invention relates to the synthetic method of molecular sieve, specifically about the step crystallizing process for synthesizing of mesoporous-microporous composite molecular sieve composition in a kind of.
Zeolite molecular sieve is to have good shape selectivity and adjustable acid sites as two key propertys of catalyst activity constituent element, utilizes its regular pore passage structure, can realize the screening of molecule and cuts out, and realizes so-called shape selective catalysis.Because geometrical constraint and some correlative factors, there is certain limitation in micro porous molecular sieve in the catalytic process that relates to the large volume molecule.The division of said here micropore, mesopore and macropore is to stipulate according to international material association: the material aperture is a poromerics (Microporous) less than 2nm's; The aperture is at the genus mesopore of 2-50nm or be mesoporous material (Mesoporous); Greater than 50nm is large pore material (Macroporous).
Since the eighties,, required crude oil secondary processing means such as catalytic cracking, hydrocracking to process particularly inferior heavy oil of more heavy oil as vacuum residuum along with crude oil and heaviness day by day that processes raw material and poor qualityization.The heavy oil molecules diameter is big, generally between 1.5～15nm, want pressure fuel just the active centre that macromole can be contacted must be arranged, and traditional FCC catalyzer all is to be the cracking activity component with the Y zeolite, because its orifice diameter is no more than 0.9nm, therefore be difficult to satisfy the requirement of heavy oil fluid catalytic cracking.For this reason, wide-aperture novel molecular sieve catalytic material all is devoted to develop in countries in the world.The beginning of the eighties, VPI-5 molecular sieve with eighteen ring structure synthesizes successfully (Nature, 1983,31,698), the molecular sieve aperture of having broken through synthetic can not surpass the traditional view of twelve-ring, but the about 1.2nm in the aperture of VPI-5 molecular sieve is obviously still big inadequately, and thermostability is too poor, temperature surpasses 500 ℃, and structure is just destroyed.Therefore, be difficult to obtain industrial application.
The main method of the solution heavy oil bulky molecular catalysis cracking problem that prior art is used is, active matrix by the carrying molecular sieve is cracked into less molecule in advance to heavy (slag) oily macromole, or secondary pore or lattice imperfection by producing on established zeolite crystal by certain technology (as hydrothermal treatment consists), making heavily, (slag) oily macromole is cracked into than small molecules.The pore size distribution of made matrix of prior art and molecular sieve secondary pore usually is that several nanometers are to the hundreds of nanometer normally in a very wide scope.Therefore, no matter be by active matrix, secondary pore, still, all make the functions such as shape selective catalysis of molecular sieve have a greatly reduced quality by the zeolite crystal outside surface.In addition, the narrow and small pore passage structure of (Y type, ZSM-5 and the Beta) molecular sieve of active component in the prior art catalyzer, the rapid diffusion that also influences reacted product molecule is overflowed, thereby easily causes secondary cracking and green coke amount to increase; A spot of coke can stop up the narrow and small duct that oil gas is rely and passed through, inner a certain part or all of molecular sieve of isolated fully crystal grain and extraneous passage, thereby that part of molecular sieve can not be played a role, also make the green coke amount increase, this is very disadvantageous to heavy oil catalytic cracking reaction.In heavy (slag) oil distillate, molecular diameter occupies ratio considerably greater than the molecule of 1nm, realize macromolecular controlled cracking, and exploitation has molecular sieve homogeneous, larger aperture and seems very necessary.
Mesoporous molecular sieve is novel molecular sieve (Nature, 1992,359, the 710-712 that a class is at first succeeded in developing in 1992 by the Mobil oil company; J.Am.Chem.Soc., 1992,114,10834-10843; USP5108725), that has reported at present has types such as MCM-41 and MCM-48, its aperture can be in 1.5～10nm scope modulation, broken through the limitation that conventional molecular sieve bore diameter can not surpass 1.2nm.Because this molecular sieve analog has the pore passage structure of big homogeneous, have broad prospects as the catalyst activity constituent element of macromolecular reaction.Stability is better studied maximum working as and is counted MCM-41 among the M41S, because this molecular sieve analog has the one-dimensional tunnel structure of big homogeneous, is used for catalyzer (Appl.Catal.A1999,176, the 1-10 of macromolecular reaction rapidly; Catal.Taday, 1998,43,261-272; J.Am.Chem.Soc., 1998,120,12289-12296; J.Inclusion Phenomena Mol.Rec., 1995,21,215-237), demonstrate application promise in clinical practice.For example, high richness etc. utilize synthetic MCM-41 make the FCC promotor (Petroleum Processing and Petrochemicals, 1997,28 (5), 16-20.), its performance is evaluated at the small fixed flowing bed device.In common commercial catalysts LC-7, mix a certain proportion of MCM-41 promotor, can improve propylene, butylene and the gasoline of residual oil catalytic cracking, the product yield of diesel oil effectively, reduce the green coke amount.This mainly is to carry out shape selective catalysis because the bigger residual oil molecule of diameter can enter the inside in MCM-41 duct, intermediate product that cracking generates such as gasoline and diesel oil molecules break away from the main body duct easily as early as possible, suppress the generation of secondary cracking reaction to a certain extent, so gasoline and diesel yield increase to some extent, and help improving gasoline output, amount of coke descends, therefore MCM-41 is in the cracking process of heavy oil, demonstrate good reactivity worth, be expected to become the main active component of heavy oit pyrolysis catalyzer from now on.
But the pore wall thickness of such mesoporous molecular sieve only is about 0.5nm usually, and hole wall is unbodied, and hole wall very easily penetrates because of local hydrolysis or heat effect, even the caving in of whole molecular sieve lattice.Cause its thermostability and hydro-thermal thermostability very poor.In addition, because the amorphous hole wall of mesoporous molecular sieve, it can not provide similar micro porous molecular sieve such acid sites basically, and its acidity is very weak in other words.Also have, mesoporous molecular sieve is selected the shape effect to the heavy oil macromole, then can not bring into play its shape selective catalysis effect well to the fragment (small molecules) that is cracked into.Thereby restricted the industrial application of mesoporous molecular sieve.
Be heat and the hydrothermal stability that improves mesoporous molecular sieve, worldwide scientist has carried out a large amount of experiments, as the Mobil oil company at its disclosed patent USP5,126, announced a kind of post-modification method of mesoporous molecular sieve in 829, the crystallization reservation degree in the time of molecular sieve can effectively be improved taking off amine.This method adopts the alkoxy compound of a kind of silicon, aluminium, titanium as the skeleton propping agent mesoporous molecular sieve to be modified to improve its structure stability.People such as Nicole (J.Chem.Soc., Chem.Commun, 1994, (8) are 967-968) by control synthesis condition such as OH
-/ Si, H
2O/Si, factor such as aging makes the mesoporous molecular sieve pore wall thickness that synthesizes adjustable in 0.4～1.6nm scope.The mesoporous molecular sieve wall thickness increases, and can effectively improve its thermostability.
But the technology of above-mentioned increase mesoporous molecular sieve thermostability can not be given the acid sites of this molecular sieve like micropore simultaneously.
From above situation analysis, to use the technology that makes mesoporous molecular sieve hole wall " crystallization " and when increasing its heat and hydrothermal stability, introduce acid sites and microvoid structure, i.e. mesoporous-microporous composite molecular sieve will be a good technological line during design is synthetic.Promptly take certain technology terms of settlement, make the composition of certain form of formation of mesoporous molecular sieve and micro porous molecular sieve, the i.e. existence of existing mesopore in same zeolite crystal, the existence of micropore is arranged again, make macromole formerly among mesopore, realize shape slective cracking, afterwards, the small molecules that is cracked into further enters micro porous molecular sieve again and carries out micromolecular shape slective cracking.Thereby improve the effect of catalytic cracking reaction, have great potential as residue cracking catalyst active component of new generation.
The investigator of Fudan University has synthesized mesoporous-microporous composite molecular sieve among two kinds of β/MCM-41, the ZSM-5/MCM-41 (the open CN1208718 of Chinese patent, 1999; J.Phys.Chem.B, 2000,104,2817-2823; SCI, 1999,20 (3), 356-358).They are by two step crystallization, adopt two directed agents methods, earlier synthetic MCM-41 mesoporous molecular sieve, again the unbodied crystallization of pore wall of mesoporous molecular sieve is formed micro porous molecular sieve, think that crystallization of pore wall is to follow solid transformation mechanism, the synthetic composite molecular screen is better than the middle micro porous molecular sieve of mechanically mixing in acidic catalyst like this.
Karlsson is with C
6H
13(CH
3)
3NBr and C
14H
29(CH
3)
3NBr is that template changes temperature of reaction, regulates template concentration, and synthetic MFI/MCM-41 type matrix material (Microporous MesoporousMater., 1999,27,181-192.).
But known technology can not be incorporated into important molecule sieves such as present Y zeolite the most frequently used in catalytic cracking, hydrocracking catalyst, rare earth phosphorus ZSM-5, mordenite among the mesopore hole wall, and its range of application will be restricted.
The objective of the invention is to provide a kind of novel a kind of in the step crystallizing process for synthesizing of mesoporous-microporous composite molecular sieve composition, in the gained molecular sieve, both contained the mesoporous molecular sieve composition, the micro porous molecular sieve composition is arranged again.
The synthetic method of the middle mesoporous-microporous composite molecular sieve composition of synthesizing new provided by the present invention is, prepare the reaction mixture gel of synthetic microporous molecular sieve earlier with the method for routine, and then under 30～300 ℃ of conditions, carry out the crystallization of fs, after the crystallization 3～300 hours, the acidity-basicity ph value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, simultaneously also can add silicon source---water glass, silicon sol and/or aluminium source---Tai-Ace S 150, sodium metaaluminate, also can add transistion metal compound---tetrabutyl titanate, iron nitrate is introduced the heteroatoms metal, also can add sodium-acetate again, the sodium-chlor auxiliary agent, then, certainly depress the hydrothermal crystallizing that carries out subordinate phase at 30～170 ℃, crystallization time is 15～480 hours, obtains the said middle mesoporous-microporous composite molecular sieve composition of the present invention.
The characteristics of method provided by the present invention are, the first crystallization stage was utilized the synthetic method of general micro porous molecular sieve fully, the preparation reaction mixture gel is carried out crystallization then under the condition of synthetic microporous molecular sieve, product is without the filter washing step afterwards, but in same reactor, directly add the template of synthesizing mesoporous molecular sieve, and/or the silicon source, and/or the aluminium source, and/or auxiliary agent, and/or heteroatomic compound, carry out the crystallization of subordinate phase again.By grasping suitable reaction depth, realize micro porous molecular sieve crystal grain in some way " assembling " among the hole wall of mesoporous molecular sieve.
Method provided by the present invention is characterized in that the micro porous molecular sieve that adopts is Y zeolite, ZSM-5, contains ZSM-5, ZSM-11, beta-molecular sieve, mordenite, HTS, X type zeolite, APO and the SAPO molecular sieve of rare earth and phosphorus.
Method provided by the present invention is characterized in that the mesoporous molecular sieve that adopts is MCM-41, MCM-48, KIT-1, KIT-2, KIT-3, FSM-16.
Method provided by the present invention, it is characterized in that the crystallization process in the said synthetic middle micropore complex type molecular sieve method for compositions, be divided into two stages: the fs crystallization can next step carries out a temperature, also can be at fractional crystallization under the differing temps; The subordinate phase crystallization also can next step be synthetic a temperature, also can be at fractional crystallization under the differing temps.
Method provided by the present invention, the crystallization temperature that it is characterized in that the said fs is 30～300 ℃, preferably 100～250 ℃; Time is 3～300 hours, preferably 8～72 hours; The crystallization temperature of subordinate phase is 30～170 ℃, preferably 60～140 ℃; Time is 15～480 hours, preferably 24～168 hours;
Method provided by the present invention is characterized in that said crystallization pressure is the autogenous pressure that produces in the crystallization process, or impressed pressure 0.1MPa～15Mpa.
Method provided by the present invention is characterized in that said template general formula is:
R1 is alkyl or the aralkyl of C1～C25 in the formula; R2, R3, R4 are methyl, ethyl or propyl group; X is a halogen, preferably chlorine and bromine.
R
1CH
2CH
2NH-R
2
Or general formula is: R1 is alkyl or the aralkyl of C6～C26 in the formula; R2 is the alkyl of H or C8～C26.
Method provided by the present invention is characterized in that said auxiliary agent comprises: sodium-acetate, sodium-chlor, Repone K, Sodium Fluoride, the sodium salt of ethylenediamine tetraacetic acid (EDTA).
Figure one contains X-ray powder diffraction (XRD) the crystalline phase figure of the molecular screen material roasting front and back of micro porous molecular sieve component NaY and mesoporous molecular sieve component for embodiment one synthetic, spectrogram obviously comprises the characteristic peak of mesoporous molecular sieve and the characteristic peak of NaY simultaneously, illustrates that the gained molecular sieve is middle mesoporous-microporous composite molecular sieve.
The following examples will the present invention is further illustrated.
Embodiment one
With 24 gram high alkali deflection aluminium acid sodium solution (Al
2O
3Be 3 heavy %, Na
2O is 21 heavy %) adding 18ml water glass (Beijing Red Star water glass plant product, SiO
2Weigh 26%, modulus 3.2, proportion 1.384) and the 6.6ml deionized water in, mix, 40 ℃ of ageings 4 hours, obtain the NaY directed agents.
To 13.5ml water glass (Beijing Red Star water glass plant product, SiO
2Weigh 26%, modulus 3.2, proportion 1.384) middle 12% alum liquor, 2 grams that add, add 3.3 again under stirring and restrain directed agents, add 7.7 gram low alkali aluminium acid sodium solution (Al at last
2O
3Be 16 heavy %, Na
2O is 15 heavy %) be made into gel, add behind the 30ml water gel in 100 ℃ of crystallization 20 hours, after the cooling, transfer mixed serum pH value, and add cetyl trimethylammonium bromide solution 60 grams of 18 heavy % with 30%HAc, mixture was in 100 ℃ of crystallization 144 hours, after reaction finishes, product after filtration, washing, drying, identify to have mesopore characteristic peak and NaY crystal phase structure through XRD, 540 ℃ of roastings are after 6 hours in air atmosphere through temperature programming for product, and its XRD spectra is seen figure one.
Embodiment two
Preparation NaY directed agents is identical with embodiment one.
To 13.5ml water glass (Beijing Red Star water glass plant product, SiO
2Weigh 26%, modulus 3.2, proportion 1.384) middle 12% alum liquor, 2 grams that add, add 3.3 again under stirring and restrain directed agents, add 7.7 gram low alkali aluminium acid sodium solution (Al at last
2O
3Be 16 heavy %, Na
2O is 15 heavy %) be made into gel, add behind the 30ml water gel in 100 ℃ of crystallization 20 hours, after the cooling, transfer mixed serum pH value with 30%HAc, and the cetyl trimethylammonium bromide solution 60 that adds 18 heavy % restrains, mixture was in 100 ℃ of crystallization 48 hours, add 30% sodium acetate soln, 22 grams again, again 100 ℃ of crystallization 48 hours, regulate after potential of hydrogen is 10.5, crystallization is 48 hours again, after reaction finishes, product after filtration, washing, drying, temperature programming 550 ℃ of roastings 10 hours in air atmosphere identify to have mesopore characteristic peak and Y crystal phase structure through XRD.
Embodiment three
Preparation NaY directed agents was in 35 ℃ of ageings 7 hours.
To 31ml water glass (Beijing Red Star water glass plant product, SiO
2Weigh 26%, modulus 3.2, proportion 1.384) middle 12% alum liquor, 5 grams that add, add 7.6 again under stirring and restrain directed agents, add 18 gram low alkali aluminium acid sodium solution (Al at last
2O
3Be 16 heavy %, Na
2O is 15 heavy %) be made into gel, add behind the 70ml water gel in 100 ℃ of crystallization 24 hours, after the cooling, transfer mixed serum pH value with 30%HAc, and the cetyl trimethylammonium bromide solution 140 that adds 18 heavy % restrains, mixture was in 100 ℃ of crystallization 144 hours, after reaction finishes, product after filtration, washing, drying, temperature programming 540 ℃ of roastings 6 hours in air atmosphere identify to have mesopore characteristic peak and Y crystal phase structure through XRD.
Embodiment four
Aluminum chloride 0.78 gram is added water 20 grams, add 10% (weight) dilute hydrochloric acid again and be mixed, remix 12ml water glass (Beijing Red Star water glass plant product, SiO
2Weigh 26%, modulus 3.2, proportion 1.384) and 20 gram water, stir down and add wherein, 140 ℃ of crystallization of gained gel 24 hours, 180 ℃ of crystallization are 48 hours again, after the cooling, transfer mixed serum pH value with 30%HAc, and the cetyl trimethylammonium bromide solution 27 that adds 25 heavy % restrains, mixture was in 100 ℃ of crystallization 144 hours, after reaction finishes, product after filtration, washing, drying, temperature programming 540 ℃ of roastings 6 hours in air atmosphere identify to have mesopore characteristic peak and ZSM-5 crystal phase structure through XRD.
Claims (6)
1. step crystallizing process for synthesizing that is used for a kind of mesoporous-microporous composite molecular sieve composition of heavy oil upgrading technology, it is characterized in that: its step is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier with the method for routine, under 30～300 ℃ of temperature, carry out the fs crystallization, after the crystallization 3～300 hours, the acidity-basicity ph value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, certainly depress the hydrothermal crystallizing that carries out subordinate phase at 30～170 ℃ then, crystallization time is 15～480 hours, mesoporous-microporous composite molecular sieve composition in obtaining.
2. the step crystallizing process for synthesizing of a kind of middle mesoporous-microporous composite molecular sieve composition according to claim 1, it is characterized in that: when adding the template that synthetic mesoporous molecular sieve uses, add silicon source---water glass or silicon sol, and/or adding aluminium source---Tai-Ace S 150 or sodium metaaluminate, and/or adding other transistion metal compound---tetrabutyl titanate or iron nitrate to be introducing heteroatoms, and/or add sodium-acetate or sodium-chlor auxiliary agent.
3. the step crystallizing process for synthesizing of a kind of middle mesoporous-microporous composite molecular sieve composition according to claim 1, it is characterized in that adopting Y zeolite, ZSM-5, contain ZSM-5, ZSM-11, beta-molecular sieve, mordenite, HTS, X type zeolite, AlPO and the SAPO molecular sieve of rare earth and phosphorus.
4. the step crystallizing process for synthesizing of a kind of middle mesoporous-microporous composite molecular sieve composition according to claim 1 is characterized in that adopting MCM-41, MCM-48, KIT-1, KIT-2, KIT-3, FSM-16.
5. the step crystallizing process for synthesizing of a kind of middle mesoporous-microporous composite molecular sieve composition according to claim 1 is characterized in that the fs crystallization can next step carries out a temperature, also can be at fractional crystallization under the differing temps; The subordinate phase crystallization also can next step be synthetic a temperature, also can be at fractional crystallization under the differing temps.
6. the step crystallizing process for synthesizing of a kind of middle mesoporous-microporous composite molecular sieve composition according to claim 1 is characterized in that general formula is:
R1 is alkyl or the aralkyl of C1～C25 in the formula; R2, R3, R4 are methyl, ethyl or propyl group; X is a halogen.
R
1CH
2CH
2NH-R
2
Or general formula is: R1 is alkyl or the aralkyl of C6～C26 in the formula; R2 is the alkyl of H or C8～C26.
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