CN1353086A - Process for preparing Y-type molecular sieve - Google Patents

Process for preparing Y-type molecular sieve Download PDF

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CN1353086A
CN1353086A CN 00133566 CN00133566A CN1353086A CN 1353086 A CN1353086 A CN 1353086A CN 00133566 CN00133566 CN 00133566 CN 00133566 A CN00133566 A CN 00133566A CN 1353086 A CN1353086 A CN 1353086A
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molecular sieve
content
weight
ammonium
preparation
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CN1111136C (en
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罗一斌
宗保宁
达志坚
李明罡
宋家庆
田辉平
庄立
张剑秋
何鸣元
龙军
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

A process for prparing the pand rare earth-contained Y-type molecular sieve from NaY one includes such steps as exchanging with ammonium ions and rare-earth ions, hydrothermal calcining, reaction with phosphorus compound to bind P2O5 (0.1-10 wt%), and further hydrothermal calcining. This invented molecular sieve can greatly reduce the content of olefin in FCC gaseline and has good coke selectivity.

Description

A kind of preparation of Y zeolite
The present invention relates to a kind of preparation method of Y zeolite, particularly relate to the active component that mainly can be used as in fluid catalytic cracking (FCC) technology catalyst for heavy oil catalytic cracking that reduces gasoline olefin, have a preparation method of the Y zeolite of high hydrogen transfer activity and low coke yield.
For environmental protection requirement, offshore company begins to develop the technology of FCC reduction gasoline olefin catalyzer from the nineties middle and later periods.U.S. Grace Davison company has reported that in american petroleum NPRA (NPRA) in 1998 annual meeting trade names are industrial application data (the NPRAAnnual Mtg. of the catalyzer of RFG, 1998, AM-98-11), guaranteeing to reduce alkene 5-10v% under the condition that product distributes.Akzo Nobel Catalysts company has reported the industrial application data of olefine lowering catalyst in Japanese Kashima Oil company in American Chemical Society (ACS) in 1999 annual meeting, report declares that its catalyzer that reduces alkene is under the condition that guarantees product distribution and gasoline octane rating, can reduce gasoline olefin 8v% (ACS PREPRINTS, 43 (3), 1999,515).Consider that for coml these concrete technical intelligence that reduce gasoline olefin activity of such catalysts constituent element there is no the play-by-play of document.
The key that reduces the FCC content of olefin in gasoline is the hydrogen transference ability that will increase in the FCC reaction, with the alkene in the saturated gasoline, catalysis is burnt to be increased but also can make simultaneously, mix refining residual oil ability drop, therefore require Y zeolite when reducing the FCC content of olefin in gasoline, should keep good coke selectivity and product to distribute.
According to the existing understanding of people, in all kinds of Y zeolites, be followed successively by by the big minispread of hydrogen transference ability: REY＞REHY＞REUSY＞USY, visible rare earth is to the influence of molecular sieve hydrogen transfer activity.
The Y molecular sieve that does not contain rare earth is carried out the existing patent report of phosphorus modification.As active component, being about to solution containing phosphate is 3～8 with the Y zeolite that does not contain rare earth at PH with phosphorus containing molecular sieve for USP4,970,183 catalytic cracking catalysts of being reported, temperature is to contact under the condition of room temperature to 100 ℃, makes molecular sieve have 0.3～15 weight % (with P 2O 5Meter) phosphorus content, then with it 400～800 ℃ of following hydrothermal calcines 1～6 hour, obtain said phosphorus containing molecular sieve.USP5, the phosphorus containing molecular sieve of 312,792 reports similarly.Show higher gasoline yield and thermostability preferably through the USY molecular sieve of phosphorus modification.
In CN1217231A, mention the method that various Y molecular sieves such as comprising HY, REY, REHY, USY are carried out the phosphorus modification: the aqueous solution of molecular sieve and P contained compound is even, leave standstill, dry, 450～600 ℃ do roasting more than 0.5 hour.Catalyzer with the preparation of gained molecular sieve shows higher diesel yield and diesel and gasoline ratio.
The preparation method who the purpose of this invention is to provide a kind of Y zeolite, this method gained Y zeolite can significantly reduce the olefin(e) centent of FCC gasoline, can keep good coke selectivity simultaneously.
The preparation method of Y zeolite provided by the present invention comprises the following steps:
(1). the NaY molecular sieve is carried out ion-exchange according to a conventional method with the mixing solutions of rare earths salt or rare-earth salts and inorganic ammonium salt filter then, make the Na of molecular sieve 2O content is 1～5 weight %, RE 2O 3Content is 2～20 weight %, then with products therefrom in stoving oven under 100% steam atmosphere in 450～700 ℃ of roastings 0.5～4 hour;
(2). with step (1) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to molecular sieve (butt): total ammonium salt: P 2O 5: water=1: (0.1～1): (0.002～0.1): the weight ratio of (5～40) is mixed making beating evenly, and these slurries are warmed up to 40～100 ℃, and preferred 50～95 ℃ were stirred 0.5～5 hour, and filtered and wash with water;
(3). with the roasting 0.5～5 hour under 350～700 ℃ and 100% water vapour atmosphere of step (2) products therefrom.
The content of above-mentioned said rare earth, phosphorus and sodium is benchmark with the butt weight of molecular sieve all.
The said rare-earth salts of step among the preparation method of Y zeolite provided by the present invention (1) is meant the rare-earth salts that is used for the rare earth exchanged of molecular sieve well known to those skilled in the art, generally be to be muriate, nitrate or the vitriol of main ingredient with lanthanum and/or cerium, preferred muriate; Wherein the content of lanthanum and/or cerium (in oxide compound) is more than or equal to 50 weight %, is preferably greater than to equal 60 weight %, more preferably greater than equaling 70 weight %.
The said ion-exchange of step among the preparation method of Y zeolite provided by the present invention (1) is carried out according to the condition of prior art, and the present invention has no particular limits it; Condition commonly used is that temperature is a room temperature to 100 ℃, is preferably 50～90 ℃, and the time is more than 10 minutes, is preferably 0.5～2 hour; The consumption of inorganic ammonium salt and rare earth ion is to exchange the Na of back products therefrom 2O content and RE 2O 3Content is standard in said scope.
Said inorganic ammonium salt can be ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium chloride or their mixture in step among the preparation method of Y zeolite provided by the present invention (1) and the step (2).The effect of this inorganic ammonium salt is the sodium content that ammonium ion exchange reduces molecular sieve, and its consumption is according to the requirement of molecular sieve sodium content is decided.
Said titanium pigment compound is ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid or their mixture in the step among the preparation method of Y zeolite provided by the present invention (2).
RE in the last gained Y zeolite of the method provided by the invention product 2O 3Content is 2～20 weight %, preferred 5～18 weight %; P 2O 5Content be 0.2～10 weight %, preferred 1.0～7.0 weight %.
The invention is characterized in the process of the Y molecular sieve that preparation rare earth-phosphorus is composite modified, rare earth and phosphorus will be introduced respectively on the molecular sieve, promptly earlier with rare earth exchanged to molecular sieve and carry out the calcination process of 100% steam atmosphere, and then on molecular sieve, introduce phosphorus quantitatively by the inorganic phosphate ammonium salt, by the calcination process of 100% steam atmosphere, the aluminium on phosphorus and the molecular sieve is had an effect at last.
Feature of the present invention is that also rare earth-phosphorus type the Y molecular sieve that contains for preparing thus compares with general rare-earth type Y molecular sieve, acid distribution table reveals the strong acid center number and reduces (＞350 ℃ of desorptions), and the acid site number of medium tenacity increases (250～350 ℃ of desorptions) (seeing Table 2).This acid the distribution for the coke selectivity that improves molecular sieve is favourable.
Feature of the present invention also is molecular sieve through after the phosphorus modification and since phosphorus aluminium in conjunction with have-the OH number increases, i.e. molecular sieve acid density increases, and can improve the ability that reduces gasoline olefin.
It is obvious that the catalytic cracking catalyst that the composite modified Y molecular sieve of rare earth-phosphorus that is obtained by the present invention is prepared reduces the gasoline olefin effect, and the better products selectivity is arranged simultaneously, shows than the lower coke yield of general rare-earth type Y molecular sieve catalyzer.Beneficial effect of the present invention specifically can be referring to the fixed fluidized bed evaluating data of embodiment 10.
The following examples will the present invention is further illustrated.
Embodiment 1～6
Get 1000 gram NaY molecular sieves (dry basis, catalyzer agent factory of Chang Ling, Hunan oil-refining chemical factory product, down with), after 10 liters of deionized waters making beating, add 400 and restrain NH 4Cl adds the RECl that concentration is 100g/l again 3(preparation of catalyzer agent factory of Chang Ling, Hunan oil-refining chemical factory, the weight percentage of each component is solution in its total amount of rare earth: Ce 2O 313%, La 2O 379%, Pr 6O 111.8%, Nd 2O 33.4%, Sm 2O 30.4%, other is 2.4% years old; Down with) 1200 milliliters, in 90 ℃ of exchanges 1 hour, filter and also use water wash, with filter cake roasting 2 hours in 550 ℃, 100% steam atmosphere, obtain the REUSY molecular sieve then.Get 100 these REUSY molecular sieves (in butt) of gram,, add 20 gram NH with 1000 gram deionized water making beating 4Behind the Cl, add 0.9 gram, 1.82 grams, 3.67 grams, 5.56 grams, 7.5 grams and 9.47 gram NH more respectively 4H 2PO 4, be warming up to 90 ℃ and stirred 1 hour, filter then, wash, dry.To dry sample and put into a tubular oven, roasting is 3 hours under 600 ℃, 100% water vapor conditions.Obtain the composite modified REPY molecular sieve of rare earth phosphorus at last, be designated as REP0.5, REP1, REP2, REP3, REP4 and REP5 respectively.
Embodiment 7
Get 1000 gram NaY molecular sieves (dry basis), after 20 liters of deionized water making beating, add 300 gram (NH 4) 2SO 4Making beating adds the RECl that concentration is 100g/l again 31800 milliliters of solution in 90 ℃ of exchanges 1 hour, filter and also to use water wash, with filter cake roasting 3 hours in 520 ℃, 100% steam atmosphere, obtain the REUSY molecular sieve then.Get 100 these REUSY molecular sieves (in butt) of gram,, add 40 gram NH with 2000 gram deionized water making beating 4Behind the Cl, add 6.3 gram (NH again 4) 2HPO 4, be warming up to 85 ℃ and stirred 3 hours, filter then, wash, dry.To dry sample and put into a tubular oven, roasting is 1 hour under 550 ℃, 100% water vapor conditions.Obtain the composite modified REPY molecular sieve of rare earth phosphorus at last, be designated as REP6.
Embodiment 8
Get 1000 gram NaY molecular sieves (dry basis), after 10 liters of deionized water making beating, adding concentration is the RECl of 100g/l 32500 milliliters of solution in 90 ℃ of exchanges 1 hour, filter and also to use water wash, with filter cake roasting 2 hours in 600 ℃, 100% steam atmosphere, obtain the REUSY molecular sieve then.Get 100 these REUSY molecular sieves (in butt) of gram,, add 10 gram NH with 2000 gram deionized water making beating 4Behind the Cl, add 10.9 gram (NH again 4) 3PO 4With 3.0 gram H 3PO 4, be warming up to 95 ℃ and stirred 5 hours, filter then, wash, dry.To dry sample and put into a tubular oven, roasting is 4 hours under 500 ℃, 100% water vapor conditions.Obtain the composite modified REPY molecular sieve of rare earth phosphorus at last, be designated as REP7.
Comparative Examples 1
According to USP5,312,792 method is got 200 gram NaY molecular sieves, and the ammoniumsulphate soln with 10% concentration under 80 ℃ exchanges 1.5 hours, filters also washing, dries 12 hours down at 110 ℃.Get this molecular sieve 48 grams, add 320 gram deionized waters, and then add the H of 10 grams 20% 3PO 4, mix and dry, through 550 ℃, 100% steam roasting 2 hours, once wash sodium with the ammonium salt solution exchange more at last again, obtain phosphorous ultra-steady Y molecular sieve, be designated as D1
Comparative Examples 2
Get 1000 gram NaY molecular sieves (dry basis), after 10 liters of deionized water making beating, add 400 gram NH 4Cl adds the RECl that concentration is 100g/l again 31200 milliliters of solution in 90 ℃ of exchanges 1 hour, filter, drip washing, with filter cake roasting 2 hours in 550 ℃, 100% steam atmosphere, exchange molecular sieve with ammonium chloride solution again, make it Na 2O content obtains the rare-earth type molecular sieve D2 of water roasting less than 1 weight %
Comparative Examples 3
Get 100 gram NaY molecular sieves (dry basis), after 1 liter of deionized water making beating, add 40 gram NH 4The Cl making beating adds the RECl that concentration is 100g/l again 3120 milliliters of solution after 1 hour, after filtration, drip washing, the oven dry, are put into the inherent 580 ℃ of air atmosphere roastings of muffle furnace 2 hours in 90 ℃ of exchanges.Pull an oar with the molecular sieve of 2000 gram deionized waters after above-mentioned dried roasting, add 40 gram NH 4Behind the Cl, add 7.5 gram NH again 4H 2PO 4, be warming up to 85 ℃ and stirred 1 hour, filter then, wash, dry.To dry sample and put into a tubular oven, roasting is 1 hour under 550 ℃, 100% water vapor conditions.Obtain molecular sieve D3.
Comparative Examples 4
Get 100 gram NaY molecular sieves (dry basis), after 1 liter of deionized water making beating, add 40 gram NH 4The Cl making beating adds the RECl that concentration is 100g/l again 3120 milliliters of solution, in 90 ℃ of exchanges after 1 hour, filtration, drip washing, then with filter cake roasting 2 hours in 550 ℃, 100% steam atmosphere.Pull an oar with the molecular sieve of 2000 gram deionized waters behind above-mentioned hydrothermal calcine again, add 40 gram NH 4Behind the Cl, be warming up to 85 ℃ and stirred 1 hour, after filtration, washing, oven dry, make the molecular sieve in its sodium oxide content and each example close.
At last, press method among the CN1217231A, add the NH that concentration is 5.25 heavy % in the molecular sieve after above-mentioned oven dry 4H 2PO 4The aqueous solution 142 gram mixes, leave standstill 1 hour after, bake drying is put into sample muffle furnace again in 500 ℃ of air atmosphere roastings 2 hours.Obtain molecular sieve D4.
Embodiment 9
Present embodiment illustrates the physico-chemical property and the micro-activity of each sieve sample.
The materialization data of gained sample see Table 1 in each embodiment and the Comparative Examples, listed P in the table 2O 5, RE 2O 3And Na 2O content is by x-ray fluorescence spectrometry; Lattice constant by X-ray diffraction method (XRD) adopt the RIPP145-90 standard method (see " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure.Micro-activity (MAT) adopts the RIPP92-90 standard method to measure.
The materialization data of several molecular sieves of table 1
Project ????P4 ????P6 ????P7 ????D1 ????D2 ????D3 ????D4
?RE 2O 3(weight %) ??7.5 ??12.6 ??18.1 ??0 ??7.4 ??7.6 ??7.7
?P 2O 5(weight %) ??4.0 ??3.1 ??6.2 ??4.0 ??0 ??3.9 ??4.1
?Na 2O (weight %) ??0.5 ??0.6 ??0.7 ??0.4 ??0.6 ??0.8 ??0.7
Lattice constant (nanometer) ??2.456 ??2.464 ??2.469 ??2.455 ??2.465 ??2.452 ??2.461
Little work (800 ℃/4) ??77 ??80 ??83 ??66 ??78 ??71 ??74
With RE 2O 3D2 among the embodiment 1 of content about 7.5% in each sample and the Comparative Examples 1 measures acid the distribution with ammonia absorption thermogravimetry on Du Pont-990 thermogravimetric instrument, the results are shown in Table 2.
The composite modified influence that acidic zeolite is distributed of table 2 phosphorus-rare earth
Sample P 2O 5Content/m% ????NH 3Desorption rate/%
150-250℃ ?250-350℃ ??＞350℃
??D2 ????0 ????40.1 ????40.9 ????19.0
??REP0.5 ????0.5 ????39.8 ????42.8 ????17.4
??REP1 ????1.0 ????35.3 ????47.5 ????17.2
??REP2 ????1.9 ????36.5 ????48.3 ????15.2
??REP3 ????3.1 ????36.9 ????50.9 ????12.2
??REP4 ????4.0 ????34.9 ????51.4 ????13.7
??REP5 ????5.1 ????33.8 ????54.8 ????11.4
By table 2 as seen, with the composite modified molecular sieve of the phosphorus-rare earth of the present invention preparation with only compare with the molecular sieve that rare earth exchanged-dried roasting method makes, acid distribution table reveals under the constant substantially situation of total acid amount, and the strong acid center number reduces, and the acid site number of medium tenacity increases.
Embodiment 10
Use molecular sieve P4 respectively, P6, P7, D1, D2, D3 and D4 sample are active component, according to molecular sieve: kaolin: pseudo-boehmite: aluminium colloidal sol=35: 35: 18: the ratio of 12 (butt weight ratios) is made the catalyst slurry that solid content is 35 weight %, the spray-dried catalyst A of making respectively, B, C, D, E, F and G, through 805 ℃, 100% water vapour is aging after 17 hours, on the small fixed flowing bed FCC apparatus, estimate, to estimate raw materials used oil be VGO and mix 20% vacuum residuum VR (character sees Table 3), temperature of reaction is 500 ℃, agent-oil ratio is 4.0, air speed is 15 hours-1, products obtained therefrom oil cuts out gasoline fraction through distillation, measure its hydrocarbon composition (PONA), evaluation result is listed in table 4.
Table 3 stock oil character
Stock oil VGO+20%VR
Density, g/cm 30.9066
Viscosity, mm 2/ S 20.08 (80 ℃)
Carbon residue, m% 3.1
Stable hydrocarbon, m% 61.2
Aromatic hydrocarbons 23.2
Colloid 14.6
Bituminous matter 1.0
H，％????????????????????????12.60
C，％????????????????????????86.05
S，％????????????????????????0.69
N，％????????????????????????0.29
IBP，℃??????????????????????271
10???????????????????????????360
30???????????????????????????422
50???????????????????????????454
70???????????????????????????495
80???????????????????????????543
Each catalyzer small fixed flowing bed evaluation result of table 4
Catalyst sample ??A ??B ??C ????D ????E ????F ????G
Molecular sieve REP4 ?REP6 ?REP7 ????D1 ????D2 ????D3 ????D4
Molecular sieve preparation method The present invention: rare earth exchanged-water roasting-introducing phosphorus-water roasting No rare earth is introduced phosphorus-water roasting Rare earth exchanged-water roasting Rare earth exchanged-do roasting-introducing phosphorus-water to bake Rare earth exchanged-water roasting-introducing phosphorus-do baking
Molecular sieve RE 2O 3Heavy % ????7.5 ????12.6 ????18.1 ????0 ????7.6 ????7.4 ????7.7
Molecular sieve P 2O 5Heavy % ????4.0 ????3.1 ????6.2 ????4.0 ????0 ????3.9 ????4.1
Material balance/weight % H 2-C 2??C 3-C 4Gasoline, diesel heavy oil coke ? ????1.9 ????14.9 ????51.2 ????17.8 ????7.4 ????6.5 ? ????2.6 ????15.7 ????51.4 ????17.1 ????6.2 ????7.0 ? ????3.1 ????17.0 ????50.5 ????16.8 ????5.2 ????7.4 ? ????1.3 ????11.5 ????48.3 ????21.7 ????11.8 ????5.4 ? ????2.4 ????15.1 ????50.3 ????18.0 ????7.0 ????7.2 ? ????1.6 ????13.2 ????49.2 ????20.0 ????10.0 ????6.0 ? ????1.8 ????14.1 ????50.5 ????18.3 ????8.5 ????6.8
Transformation efficiency/weight % ????74.5 ????76.7 ????78.0 ????66.5 ????75.0 ????70.0 ????73.2
Total liquid receipts/weight % ????83.9 ????84.1 ????84.3 ????81.5 ????83.4 ????82.4 ????82.7
Coke/transformation efficiency ????0.087 ????0.091 ????0.095 ????0.080 ????0.096 ????0.083 ????0.092
Gasoline composition/weight % normal paraffin isoparaffin alkene naphthenic hydrocarbon aromatic hydrocarbons ? ????5.96 ????43.40 ????21.52 ????13.02 ????16.40 ? ????5.94 ????43.19 ????20.36 ????13.47 ????17.04 ? ????5.97 ????43.96 ????18.44 ????13.59 ????18.04 ? ????4.99 ????33.54 ????34.55 ????12.67 ????14.25 ? ????5.4 ????40.6 ????26.4 ????12.10 ????15.5 ? ????4.45 ????37.10 ????30.85 ????12.36 ????15.24 ? ????5.11 ????38.29 ????27.60 ????12.80 ????16.20
As seen data are compared with the super steady Y of no rare earth phosphor-containing among the D1 from table 4, with REP4, REP6 and the REP7 activity of conversion and the hydrogen transference ability height of the inventive method preparation, and olefin content in gasoline is low 13～15m%.
REP4 compares with D2, both rare earths introducing modes identical (roasting of exchange-water) and content are close, but REP4 has done further modification by introducing phosphorus and hydrothermal calcine to molecular sieve, reaction result shows, though transformation efficiency is suitable, the former Jiao changes than only being 0.087, the latter is 0.096, therefore, REP4 has excellent coke selectivity, its olefin content in gasoline is also low in the case nearly 5m%.Illustrate that REP4 has good selectivity hydrogen transference ability.
REP4 compares with D3, and the method that both second steps are introduced phosphorus is identical, but REP4 has adopted water roasting mode, makes in the easier little cage of moving to molecular sieve of rare earth ion, and phosphorus and rare earth directly act on the rare-earth phosphorate of generation non-activity in the time of can avoiding back phosphorus modification; The dried roasting mode that D3 adopts makes the migration of rare earth ion insufficient, generates rare-earth phosphorate easily, data show: although content of rare earth is close, the activity of conversion of REP4 is than apparently higher than D3, under the suitable situation of coke selectivity, and content of olefin in gasoline is low nearly 9m%.
REP4 compares with D4, and it is identical that both rare earths are introduced mode, but the water roasting is adopted in the modification of REP4 phosphorus, and D4 then adopts and does roasting.The result shows, under close rare earth and phosphorus content, the former activity, coke selectivity and the ability of falling alkene all are better than the latter, illustrates to adopt the water roasting can make phosphorus to the modulation of acidic zeolite with to improve selectivity hydrogen transference ability favourable.

Claims (4)

1, a kind of preparation method of Y zeolite is characterized in that this method comprises the following steps:
(1). the NaY molecular sieve is carried out ion-exchange according to a conventional method with the mixing solutions of rare earths salt or rare-earth salts and inorganic ammonium salt filter then, make the Na of molecular sieve 2O content is 1～5 weight %, RE 2O 3Content is 2～20 weight %, then with products therefrom in stoving oven under 100% steam atmosphere in 450～700 ℃ of roastings 0.5～4 hour;
(2). with step (1) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to molecular sieve (butt): total ammonium salt: P 2O 5: water=1: (0.1～1): (0.002～0.1): the weight ratio of (5～40) is mixed making beating evenly, these slurries is warmed up to 40～100 ℃ stirred 0.5～5 hour, filters and washes with water;
(3). with the roasting 0.5～5 hour under 350～700 ℃ and 100% water vapour atmosphere of step (2) products therefrom.
2, according to the preparation method of claim 1, wherein said inorganic ammonium salt is ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium chloride or their mixture in step (1) and the step (2).
3, according to the preparation method of claim 1, wherein said titanium pigment compound is ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid or their mixture in the step (2).
4, according to the preparation method of claim 1, the RE of said Y zeolite wherein 2O 3Content is 2～20 weight %, P 2O 5Content is 0.2～10 weight %.
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