CN1247744C - Olefin cracking catalyst for increasing diesel oil yield and preparation method thereof - Google Patents
Olefin cracking catalyst for increasing diesel oil yield and preparation method thereof Download PDFInfo
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Abstract
The olefin-reducing cracking catalyst for high-yield diesel oil contains 5-45 wt% of phosphorus and rare earth composite modified Y zeolite (or ultrastable rare earth Y zeolite), and the ultrastable rare earth Y zeolite is obtained by using sodium Y zeolite as a raw material, performing rare earth exchange and first roasting, reacting with rare earth, phosphorus-containing substances and ammonium salt, and performing second roasting. The recommended catalyst comprises 5-45 wt% of ultrastable rare earth Y zeolite, 0.5-30 wt% of one or more other zeolites, 0.5-70 wt% of clay and 1.0-65 wt% of high temperature resistant inorganic oxide, wherein the components comprise 0.3-2.5 wt% of phosphorus and 1.5-6.0 wt% of rare earth oxide. The preparation method of the catalyst comprises the steps of homogenizing the zeolite component, the clay and the precursor of the high-temperature resistant inorganic oxide according to a required proportion, and carrying out spraying and post-treatment to obtain a finished catalyst product. The obtained catalyst has strong olefin reducing capability, high diesel oil yield, low coke yield and strong heavy oil cracking capability.
Description
Technical field
What the present invention relates to a kind of high-yield diesel oil falls the cracking of olefins Catalysts and its preparation method, more specifically, is a kind of high-yield diesel oil olefine lowering catalyst that is applicable to catalytic cracking process and preparation method thereof.
Background technology
In the domestic gasoline total amount nearly the olefin(e) centent of 80% pressure gasoline between 40-60%, bigger from national new standard (olefin(e) centent is no more than 35v%) gap, and the olefin content in gasoline height is the one of the main reasons that causes the motor vehicle exhaust amount high.Exploitation has falls the research emphasis that the strong cracking catalyst of alkene ability becomes present catalytic field.
Market from the FCC catalyzer of the world, famous AKZO catalyst Co. and GRACE company have corresponding catalyst prod, from the RFG catalyst prod test data analysis that obtains, mainly adopted similar REY molecular sieve as main active ingredient, shown certain alkene ability of falling, outstanding problem is the coke yield height, and gasoline octane rating and diesel yield obviously descend.People such as Japan COSMO graduate Tan-no disclose two relevant patents that suppress gasoline olefins, and [USP 5646082, USP5705142], its core technology is to have adopted a kind of super stable molecular sieve, repeatedly exchange and the repeatedly roasting of different warm areas are adopted in the preparation of this molecular sieve, the technological process more complicated, especially the thermal oscillation of molecular sieve is handled and is difficult to realize in industrial production, has limited the application in making olefine lowering catalyst of this molecular sieve active ingredient.
In the domestic disclosed patent, CN12989923 and CN1304980A have reported the method for falling the alkene active ingredient with the modified ZSM-5 preparation, the catalyzer or the auxiliary agent that contain modified ZSM-5 have the function of certain reduction content of olefin in gasoline, and gasoline octane rating increases to some extent simultaneously.In the HY that has developed, REY, REHY, USY, REUSY, ZSM-5 equimolecular sieve, REY generally adopts twice rare earth ion exchanged and twice high-temperature roasting to make, and the content of rare earth height (contains RE
2O
3The heavy % of 16-22), hydrogen transfer activity is the highest, has the very strong alkene ability of falling, but coke and diesel oil poor selectivity.CN1147420A adopts REY, one of REHY or REX are zeolite seed crystal, crystal seed is evenly dispersed in the colloidal state system of being made up of water glass, aluminium salt, mineral acid and water, synthesized the molecular sieve that contains rare earth with MFI structure by crystallization, at high temperature handle with phosphorus-aluminium activator then, obtained phosphorous and molecular sieve rare earth, when being used for hydro carbons pyrolytic conversion reaction, shown excellent hydrothermal stability and good low-carbon alkene selectivity of product.CN1317547 discloses a kind of method of making the olefine lowering catalyst active ingredient, be composited with 0.5-5%ZSM-5,0.5-15% rare earth exchanged Y zeolite and 20-40% phosphorus and the composite modified overstable gamma zeolite of rare earth, wherein the content of rare earth of phosphorus and the composite modified Y zeolite of rare earth is 2-12%, unit cell parameters is 2.445-2.465nm, phosphorus content 0.2-3% (in P), its method is rare earth modified for carrying out earlier, carries out the phosphorus modification again and handles; CN1217231A discloses the preparation method of P-contained zeolite molecular sieve, with solution containing phosphate dipping modcfied faujasite molecular sieve, drying is in 450～600 ℃ of roastings more than 0.5 hour, the catalyzer that contains this molecular sieve has increased diesel yield, but the effect that reduces gasoline olefin is not described.
In sum, the olefine lowering catalyst of prior art for preparing has certain alkene ability of falling, and main drawback shows as the coke yield height, and the lightweight oil productive rate is low, and especially diesel yield descends obviously.Present status in China is that the diesel oil demand increases considerably, and diesel oil is in the situation that supply falls short of demand, and the disparities between supply and demand that adopt the olefine lowering catalyst of prior art exploitation to aggravate diesel oil have undoubtedly influenced the economic benefit of refinery.In order to adapt to refinery's processing heavy raw oil, produce the demand of clean gasoline and increase economic benefit, the cracking of olefins catalyzer that falls that the exploitation performance is excellent more seems very urgent.
Summary of the invention
The object of the present invention is to provide olefine lowering catalyst of a kind of high-yield diesel oil and preparation method thereof, the characteristics of this cracking catalyst are to have the strong alkene ability of falling, and coke yield is moderate, the diesel yield height.
Olefine lowering catalyst of high-yield diesel oil of the present invention and preparation method thereof is:
(1) contains phosphorus and the composite modified Y zeolite of rare earth (claiming super steady rare earth exchanged Y zeolite again) of 5～45 heavy % in the catalyzer, the composite modified Y zeolite of this phosphorus and rare earth is that (silica alumina ratio is greater than 4.0 with the sodium Y zeolite, degree of crystallinity is greater than 75%) be raw material, through rare earth exchanged and roasting for the first time, obtain " one hands over a roasting " rare earth sodium Y; Again with rare earth, phosphorus containg substances and ammonium salt reaction, carry out that calcination process for the second time obtains; The condition of " one hand over one roasting " rare earth sodium Y and rare earth, phosphorus containg substances and ammonium salt reaction and the roasting second time can for: P/Y zeolite (weight) is 0.005～0.04, and is best 0.007～0.035, RE
3O
3/ Y zeolite (weight) is 0.05～0.15, and is best 0.07～0.13, NH
4 +/ Y zeolite (weight) is 0.02～0.5, best 0.03～0.4, pH=2.0～5.0, react certain hour down at 65～95 ℃, filter washing, filter cake is at 400～700 ℃, roasting is 0.3～3.5 hour under 1～100% steam, best 0.5～2.5 hour, obtains the super steady rare earth exchanged Y zeolite that the present invention prepares.
(2) contain phosphorus 0.3～2.5 heavy % in the catalyzer, rare earth oxide 1.5～6.0 heavy %, and the phosphorus and the composite modified Y zeolite of rare earth (claiming super steady rare earth exchanged Y zeolite again) that wherein contain 5～45 heavy %, the composite modified Y zeolite of this phosphorus and rare earth is that (silica alumina ratio is greater than 4.0 with the sodium Y zeolite, degree of crystallinity is greater than 75%) be raw material, through rare earth exchanged and roasting for the first time, obtain " one hands over a roasting " rare earth sodium Y; Again with rare earth, phosphorus containg substances and ammonium salt reaction, carry out that calcination process for the second time obtains.
(3) provide a kind of preferred catalyzer to form among the present invention: phosphorus and the composite modified Y zeolite of rare earth (claiming super steady rare earth exchanged Y zeolite again), one or more other zeolites of 0.5～30 heavy %, the clay of 0.5～70 heavy %, the high-temperature inorganic oxide of 1.0～65 heavy % by 5～45 heavy % are formed, contain phosphorus 0.3～2.5 heavy %, rare earth oxide 1.5～6.0 heavy %.
(4) the Preparation of catalysts method is the precursor homogeneous with above-mentioned zeolite component, clay and high-temperature inorganic oxide, sprays and aftertreatment acquisition catalyzer finished product.
" one hands over a roasting " of the present invention rare earth sodium Y adopts the rare earth exchanged of sodium Y zeolite and the method for roasting for the first time to make, and can be RE as condition
2O
3/ Y zeolite (weight) is 0.10～0.25, and is best 0.12～0.22, pH=3.0～4.0,75～95 ℃ of exchange temperature, 0.2～1.5 hour time, best 0.3～1.2 hour, filter washing, filter cake is at 450～650 ℃, and roasting is 0.3～3.5 hour under 1～100% steam, best 0.5～2.5 hour.
Rare earth compound of the present invention is that rare earth chloride, rare earth nitrate are or/and sulfuric acid rare earth, preferably rare earth chloride and rare earth nitrate; Described phosphorus containg substances is meant that one or more are selected from ortho-phosphoric acid, phosphorous acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tetra-sodium etc.; Described ammonium salt is meant that one or more are selected from ammonium chloride, ammonium nitrate, volatile salt, bicarbonate of ammonia, ammonium oxalate, ammonium sulfate, monoammonium sulfate.
Other zeolite during catalyzer of the present invention is formed is selected from y-type zeolite, L zeolite, ZSM-5 zeolite, β zeolite, aluminum phosphate zeolite, omega zeolite for one or more, preferred y-type zeolite, ZSM-5 zeolite, β zeolite, or the above-mentioned zeolite of conventional physics of process or chemical modification, comprise HY, USY, REY, REHY, REUSY, H-ZSM-5, H β.
The said clay of the present invention is selected from kaolin, halloysite, polynite, sepiolite etc. for one or more; Said high-temperature inorganic oxide is selected from Al for one or more
2O
3, SiO
2, SiO
2-Al
2O
3, AlPO
4, its precursor comprises that silica-alumina gel, silicon sol, aluminium colloidal sol, sial complex sol are or/and pseudo-boehmite.
Among the present invention the Preparation of catalysts method be precursor with above-mentioned zeolite component, clay and high-temperature inorganic oxide in required ratio, homogeneous is sprayed and aftertreatment obtains the catalyzer finished product.
Spray condition of the present invention is the operational condition of the preparation cracking catalyst of routine, and wherein temperature out is 300～800 ℃, 100～400 ℃ of exhaust temperatures; The microballoon sample that described post-treatment condition forms for spraying is 200～700 ℃ of following roastings, and preferred 300～650 ℃, 0.05～4 hour time, preferred 0.1～3.5 hour.
One of main active ingredient of the cracking catalyst of the present invention's preparation is phosphorus and the promptly super steady Rare Earth Y of the composite modified Y zeolite of rare earth, a phosphorus and a rare earth part may enter molecular sieve by exchange in modification, another part then may form composite oxides by phosphorus and rare earth reaction and be evenly distributed on the surface of molecular sieve, the interaction of this physics and chemistry, structure acidity and surface properties to molecular sieve can play special promotor action, thereby outstanding active ingredient the alkene ability is fallen and the time, coke selectivity and diesel oil selectivity have been improved, in addition, by regulating the pore structure and the acidity of matrix, further increased the selectivity of diesel oil distillate.Adopt catalyzer of the present invention, it is strong that it falls the alkene ability, the diesel yield height, and coke yield is low simultaneously, and heavy oil cracking ability is strong.
Embodiment
The following examples are described further characteristics of the present invention, but these embodiment can not limit the present invention.
(1) used main analysis test method in the example.
1. lattice constant (a
0): the x-ray diffraction method.
2. degree of crystallinity (C/C
0): the x-ray diffraction method.
3. silica alumina ratio: x-ray diffraction method.
4.Na
2O content: flame photometry.
5.P content: phosphorus molybdenum colorimetry.
6. acid: pyridine adsorption infrared spectrometer method.
7.RE
2O
3Content: colorimetry.
8. specific surface: chromatography is analysed in pyrolysis
9. micro-activity: sample was handled 4 hours under 800 ℃, 100% water vapor conditions in advance.Reaction raw materials is the huge port solar oil, 460 ℃ of temperature of reaction, in 70 seconds reaction times, catalyzer loading amount 5.0 gram, agent weight of oil be than 3.2, with total conversion rate as micro-activity.
(2) raw materials used specification in the example
1. sodium Y molecular sieve, silica alumina ratio 4.8, degree of crystallinity 85%; Catalyst Factory of Lanzhou Petrochemical Company is produced.
2. ortho-phosphoric acid, industrial goods, phosphorous 25 heavy %; Concentrated hydrochloric acid; Primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium oxalate, solid is industrial goods
3. rare earth chloride contains rare earth oxide 250 grams per liters; Rare earth nitrate contains rare earth oxide 248 grams per liters, is industrial goods.
4. pseudo-boehmite, kaolin, halloysite, solid; Aluminium colloidal sol, salic 23.0 heavy %; Silicon sol, silicon oxide-containing 24.5 heavy % are industrial salable product.
5.REY, REHY, USY, REUSY molecular sieve, conventional cracking catalyst (LR-1: rare earth oxide 2.3%, sodium oxide 0.31%), be qualified industrial goods, Catalyst Factory of Lanzhou Petrochemical Company production; The β zeolite, industrial salable product, Fushun Petrochemical Company production; H-ZSM-5, industrial salable product, Fudan University in Shanghai production.
Embodiment 1
In having the reactor of heating, add 3000 gram (butt) sodium Y molecular sieve and a certain amount of deionized waters, make the slurries that solid content is 150 grams per liters, the rare earth chloride that slowly adds 2.14 liters, regulation system pH=3.2 is warmed up to 90 ℃, exchange 0.5 hour, filter, washing, filter cake was 10% steam and 510 ℃ of following roastings 2.0 hours." one hands over a roasting " the rare earth sodium Y and a certain amount of deionized water that obtain are mixed, make the slurries that solid content is 145 grams per liters, the rare earth chloride that slowly adds 1.2 liters, regulation system pH=3.5, be warmed up to 90 ℃, exchange 1.2 hours, add ammonium phosphate 200 grams and ammonium sulfate 1100 grams then, stir, about 75 ℃, continue 0.5 hour, filter, washing, filter cake makes the promptly super steady Rare Earth Y of the composite modified Y zeolite of phosphorus of the present invention and rare earth 50% steam and 650 ℃ of following roastings 2 hours, and note is modified molecular screen A.
In having the reactor of heating in water bath, it is even to add 5 premium on currency, 995 gram kaolin, 606 gram aluminum oxide and 130 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 452 gram modified molecular screen A, 61 gram H-ZSM-5,596 gram REUSY then successively, mix the slow 1350 gram aluminium colloidal sols that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 400 ℃ of roastings 0.5 hour.Get 2 kilograms of roasting microballoons, add 15 kilograms of deionized waters and 0.102 kilogram of ammonium phosphate, stir, 60 ℃ of washings 15 minutes, filtration drying promptly got the cracking catalyst of the present invention's preparation, and note is a.
Embodiment 2
In having the reactor of heating, add 3000 gram (butt) sodium Y molecular sieve and a certain amount of deionized waters, make the slurries that solid content is 120 grams per liters, the rare earth nitrate that slowly adds 1.69 liters, regulation system pH=3.8 is warmed up to 78 ℃, exchange 1.0 hours, filter, washing, filter cake was 80% steam and 620 ℃ of following roastings 1.0 hours." one hands over a roasting " the rare earth sodium Y and a certain amount of deionized water that obtain are mixed, make the slurries that solid content is 125 grams per liters, slowly add 1.7 liters rare earth nitrate, regulation system pH=3.9, be warmed up to 85 ℃, exchange 1.5 hours, add Secondary ammonium phosphate 120 grams and ammonium oxalate 600 grams then, stir, about 70 ℃, continue 1.0 hours, filter, washing, filter cake makes modified molecular screen B of the present invention 20% steam and 500 ℃ of following roastings 1.5 hours.
In having the reactor of heating in water bath, it is even to add 5.5 premium on currency, 850 gram kaolin, 706 gram pseudo-boehmites and 140 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 375 gram modified molecular screen B, 28 gram β zeolites, 620 gram REHY then successively, mix the slow 1362 gram aluminium colloidal sols that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 400 ℃ of roastings 1.0 hours.Get 2 kilograms of roasting microballoons, add 20 kilograms of deionized waters and 0.052 kilogram of ammonium phosphate, stir, 35 ℃ of washings 40 minutes, filtration drying promptly got the cracking catalyst of the present invention's preparation, and note is b.
Embodiment 3
In having the reactor of heating, add 3000 gram (butt) sodium Y molecular sieve and a certain amount of deionized waters, make the slurries that solid content is 100 grams per liters, the rare earth nitrate that slowly adds 2.95 liters, regulation system pH=4.0 is warmed up to 82 ℃, exchange 1.5 hours, filter, washing, filter cake was 50% steam and 640 ℃ of following roastings 3.0 hours.Mix with a certain amount of deionized water then, make the slurries that solid content is 160 grams per liters, slowly add 0.80 liter rare earth chloride, regulation system pH=3.1 is warmed up to 80 ℃, exchanges 0.6 hour, add primary ammonium phosphate 250 grams and ammonium nitrate 400 grams then, stir, about 70 ℃, continue 2.0 hours, filter, washing, filter cake makes the olefin component of efficiently falling of the present invention 85% steam and 490 ℃ of following roastings 1.0 hours, and note is modified molecular screen C.
In having the reactor of heating in water bath, it is even to add 4.9 premium on currency, 1095 halloysites, 506 gram pseudo-boehmites and 130 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 825 gram modified molecular screen C, 140 gram H-ZSM-5,250 gram USY then successively, mix the slow 1409 gram silicon sol that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 600 ℃ of roastings 0.3 hour.Get 2 kilograms of roasting microballoons, add 15 and do gram deionized water and 0.19 kilogram of ammonium phosphate, stir, 80 ℃ of washings 30 minutes, filtration drying promptly got the cracking catalyst of the present invention's preparation, and note is c.
Embodiment 4
In having the reactor of heating, " one hands over a roasting " rare earth sodium Y500 gram of preparation among the embodiment 1 is mixed with a certain amount of deionized water, make the slurries that solid content is 146 grams per liters, add ammonium phosphate 36 grams and ammonium chloride 150 grams, stir, regulation system pH=3.9, be warmed up to 86 ℃, exchange 1.2 hours, slowly add 0.22 liter rare earth chloride then, about 77 ℃, kept 0.5 hour, filter, washing, filter cake was 60% steam and 580 ℃ of following roastings 1.5 hours, make the olefin component of efficiently falling of the present invention, note is modified molecular screen D.
In having the reactor of heating in water bath, it is even to add 4.9 premium on currency, 1095 gram kaolin, 506 gram aluminum oxide and 130 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 625 gram modified molecular screen D, 90 gram β zeolites, 250 gram USY and 100 gram REY then successively, mix the slow 1105 gram aluminium colloidal sols that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 400 ℃ of roastings 0.5 hour.Get 2 kilograms of roasting microballoons, add 10 kilograms of deionized waters and 0.085 kilogram of ammonium phosphate, stir, 40 ℃ of washings 20 minutes, filtration drying promptly got the cracking catalyst of the present invention's preparation, and note is d.
Embodiment 5
In having the reactor of heating, " one hands over a roasting " rare earth sodium Y 500 grams and a certain amount of deionized water of preparation among the embodiment 2 are mixed, make the slurries that solid content is 126 grams per liters, add ortho-phosphoric acid 36 grams and ammonium sulfate 500 grams, stir, regulation system pH=3.9, be warmed up to 86 ℃, exchange 1.2 hours, slowly add 0.13 liter rare earth nitrate then, about 77 ℃, kept 0.5 hour, filter, washing, filter cake was 60% steam and 580 ℃ of following roastings 0.5 hour, make the olefin component of efficiently falling of the present invention, note is modified molecular screen E.
In having the reactor of heating in water bath, it is even to add 6.5 premium on currency, 995 gram kaolin, 676 gram aluminum oxide and 130 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 210 gram modified molecular screen E, 19 gram H-ZSM-5,830 gram REUSY then successively, mix the slow 1359 gram aluminium colloidal sols that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 500 ℃ of roastings 0.6 hour.Get 2 kilograms of roasting microballoons, add 19 kilograms of deionized waters and 0.109 kilogram of ammonium phosphate, stir, 80 ℃ of washings 10 minutes, filtration drying promptly got the cracking catalyst of the present invention's preparation, and note is e.
Comparative Examples 1
In having the reactor of heating, " one hands over a roasting " the rare earth sodium Y500 that adds preparation among the embodiment 1 restrains (butt) and a certain amount of deionized water, makes the slurries that solid content is 145 grams per liters, slowly adds 0.20 liter rare earth chloride, regulation system pH=3.5, be warmed up to 90 ℃, exchange 1.2 hours, filter, washing, filter cake makes common REY sieve sample 50% steam and 600 ℃ of following roastings 2 hours, and note is contrast modified molecular screen F.
In having the reactor of heating in water bath, it is even to add 10 premium on currency, 1900 gram kaolin, 1200 gram aluminum oxide and 265 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 900 gram modified molecular screen F, 120 gram H-ZSM-5,1205 gram REUSY then successively, mix the slow 2700 gram aluminium colloidal sols that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 400 ℃ of roastings 0.5 hour.Get 4 kilograms of roasting microballoons, add 30 kilograms of deionized waters and 0.205 kilogram of ammonium phosphate, stir, 60 ℃ of washings 15 minutes, filtration drying promptly got this contrast cracking catalyst, and note is f.
Comparative Examples 2
In having the reactor of heating, add modified molecular screen F500 gram (butt) and a certain amount of deionized water, make the slurries that solid content is 145 grams per liters, add ammonium phosphate 36 grams then, stir, be warmed up to 85 ℃, exchange 1.0 hours, filter, washing, filter cake makes the PREY sieve sample 50% steam and 570 ℃ of following roastings 1.5 hours, and note is modified molecular screen G.
In having the reactor of heating in water bath, it is even to add 10 premium on currency, 1900 gram kaolin, 1200 gram aluminum oxide and 265 milliliters of mixed in hydrochloric acid, stirred 1 hour, add 900 gram modified molecular screen G, 120 gram H-ZSM-5,1205 gram REUSY then successively, mix the slow 2700 gram aluminium colloidal sols that add in back and be carried out to glue, through spray shaping, with thus obtained microsphere 400 ℃ of roastings 0.5 hour.Get 4 kilograms of roasting microballoons, add 30 kilograms of deionized waters and 0.205 kilogram of ammonium phosphate, stir, 60 ℃ of washings 15 minutes, filtration drying promptly got this contrast cracking catalyst, and note is g.
The physico-chemical property of the modified molecular screen of embodiment 1～5 and Comparative Examples 1,2 preparations is listed in the table 1.
The character of table 1 modified molecular screen
| Project | Molecular sieve | Na 2O，m％ | P，m％ | RE 2O 3，m％ | C/C 0，m％ | a 0，nm |
| Embodiment 1～5 | A | 1.05 | 1.35 | 19.1 | 40 | 2.470 |
| B | 1.41 | 0.84 | 22.3 | 34 | 2.468 | |
| C | 0.68 | 2.10 | 20.1 | 38 | 2.471 | |
| D | 1.09 | 1.37 | 21.9 | 37 | 2.460 | |
| E | 1.76 | 1.65 | 10.5 | 45 | 2.456 | |
| Comparative Examples 1,2 | F | 1.07 | / | 18.0 | 43 | 2.471 |
| G | 0.98 | 1.20 | 17.8 | 42 | 2.470 |
The physico-chemical property of catalyzer a, b, c, d, e, f and the g of embodiment 1～5 and Comparative Examples 1,2 preparations is listed in the table 2.It can be seen from the table, the sodium oxide of catalyzer of the present invention is lower, and between the rare earth oxide 1.5～6.0%, P content has moderate specific surface and micro-activity between 0.5%～2.5%.
On small fixed flowing bed-tion reacting device (the catalyzer loading amount is 180 grams), be reaction raw materials with the Xinjiang mixing oil, the reactivity worth of catalyzer a, b, c, d, e, f and g to be estimated, the product cloth and the gasoline olefin data of reaction are listed in the table 3.In addition, on riser tube circulating reaction apparatus (5 kilograms of catalyst inventories), catalyzer a and comparative catalyst f that the present invention is prepared estimate again, and the product of evaluation distributes and the gasoline olefin data are listed in the table 4.
The physico-chemical property of table 2 catalyzer
The evaluation result of table 3 catalyzer
By table 3 data as can be seen, on fixed fluidized bed reaction unit, compare with comparative catalyst f, g, adopt the catalyzer of the inventive method preparation to have low content of olefin in gasoline and high diesel yield, improve the diesel and gasoline ratio value, reduced the coke yield of reaction simultaneously.Found out that by table 4 data the evaluation result on riser tube circulating reaction apparatus shows, compares with conventional cracking catalyst, mixed catalyst of the present invention can reduce by 8 percentage points of gasoline olefins, and diesel yield is lower slightly; Compare with the comparative catalyst, mixed catalyst of the present invention has obviously increased diesel yield, it is suitable to fall the alkene ability, simultaneously, (temperature of reaction is reduced to 495 ℃ from 505 ℃ to adjust the cracking reaction processing parameter, agent-oil ratio brings up to 6.5 from 6.0), then the alkene of gasoline can drop to below 35%, reaches the requirement of national new standard.
The evaluation result of table 4 catalyzer
| Catalyzer | The embodiment of the invention 1 catalyzer a | Comparative Examples catalyzer f | The LR-1 catalyzer | |
| Stock oil | The Xinjiang mixing oil | |||
| Temperature of reaction, ℃ | 505 | 495 | 505 | 505 |
| Agent-oil ratio | 6.0 | 6.5 | 6.0 | 6.0 |
| Dry gas, m% | 1.21 | 1.15 | 1.12 | 0.95 |
| Liquefied gas, m% | 16.21 | 15.98 | 18.82 | 14.58 |
| Gasoline, m% | 55.10 | 55.45 | 56.38 | 54.56 |
| Diesel oil, m% | 15.71 | 15.45 | 13.31 | 16.17 |
| Heavy oil, m% | 6.05 | 6.45 | 4.54 | 7.94 |
| Coke, m% | 5.42 | 5.35 | 5.51 | 5.07 |
| Transformation efficiency, m% | 77.94 | 77.94 | 82.33 | 75.16 |
| Bavin/vapour ratio | 0.29 | 0.28 | 0.24 | 0.30 |
| Gasoline RON | 91.2 | 91.0 | 91.4 | 91.2 |
| Gasoline olefin, v% | 39.8 | 34.7 | 40.6 | 47.8 |
Claims (15)
1. a high-yield diesel oil falls the cracking of olefins catalyzer, the phosphorus and the composite modified Y zeolite of rare earth that contain 5～45 heavy % in the catalyzer, the composite modified Y zeolite of this phosphorus and rare earth is to be raw material with the sodium Y zeolite,, obtains " one hands over a roasting " rare earth sodium Y through rare earth exchanged and roasting for the first time; Again with rare earth, phosphorus containg substances and ammonium salt reaction, carry out that calcination process for the second time obtains; The condition of rare earth sodium Y and rare earth, phosphorus containg substances and ammonium salt reaction and roasting for the second time is: P/Y zeolite weight ratio is 0.005～0.04, and rare earth oxide/Y zeolite weight ratio is 0.05～0.15, NH
4 +/ Y zeolite weight ratio is 0.02～0.5, and pH is 2.0～5.0, reacts 1.7～2.6 hours down at 65～95 ℃; 400～700 ℃ of maturing temperatures, 0.3～3.5 hour time, steam 1～100%.
2. catalyzer according to claim 1, it is characterized in that containing in the catalyzer phosphorus 0.3～2.5 heavy %, rare earth oxide 1.5～6.0 heavy %, and the phosphorus and the composite modified Y zeolite of rare earth that wherein contain 5～45 heavy %, the composite modified Y zeolite of this phosphorus and rare earth is to be raw material with the sodium Y zeolite, through rare earth exchanged and roasting for the first time, obtain " one hands over a roasting " rare earth sodium Y; Again with rare earth, phosphorus containg substances and ammonium salt reaction, carry out that calcination process for the second time obtains.
3. catalyzer according to claim 1 and 2, it is characterized in that catalyzer is made up of the phosphorus of 5～45 heavy % and the composite modified Y zeolite of rare earth, one or more other zeolites of 0.5～30 heavy %, the clay of 0.5～70 heavy %, the high-temperature inorganic oxides of 1.0～65 heavy %, contain phosphorus 0.3～2.5 heavy %, rare earth oxide 1.5～6.0 heavy %; Other zeolite is y-type zeolite, L zeolite, ZSM-5 zeolite, β zeolite, aluminum phosphate zeolite, omega zeolite, or passes through the above-mentioned zeolite molecular sieve of physics, chemical modification.。
4. catalyzer according to claim 3 is characterized in that other zeolite is a y-type zeolite, or the y-type zeolite molecular sieve of process physics or chemical modification.
5. described Preparation of catalysts method of claim 1, it is characterized in that precursor homogeneous with phosphorus and the composite modified Y zeolite of rare earth and other zeolite component, clay and high-temperature inorganic oxide, spray and aftertreatment acquisition catalyzer finished product, wherein the preparation method of phosphorus and the composite modified Y zeolite of rare earth is for being raw material with the sodium Y zeolite, through rare earth exchanged and roasting for the first time, obtain " one hands over a roasting " rare earth sodium Y; With rare earth, phosphorus containg substances and ammonium salt reaction, carry out the roasting second time again.
6. Preparation of catalysts method according to claim 5, the silica alumina ratio that it is characterized in that the sodium Y zeolite is greater than 4.0, and degree of crystallinity is greater than 75%.
7. Preparation of catalysts method according to claim 5, it is characterized in that " one hands over a roasting " rare earth sodium Y adopts the rare earth exchanged of sodium Y zeolite and the method for roasting for the first time to make, the condition of rare earth exchanged and roasting for the first time is that rare earth oxide/Y zeolite weight ratio is 0.10～0.25, pH=3.0～4.0,75～95 ℃ of exchange temperature, 0.2～1.5 hour time; 450～650 ℃ of maturing temperatures, roasting time 0.3～3.5 hour, steam 1～100%.
8. Preparation of catalysts method according to claim 5, it is characterized in that " one hands over a roasting " rare earth sodium Y adopts the rare earth exchanged of sodium Y zeolite and the method for roasting for the first time to make, the condition of rare earth exchanged and roasting for the first time is that rare earth oxide/Y zeolite weight ratio is 0.12～0.22, pH is 3.0～4.0,75～95 ℃ of exchange temperature, 0.3～1.2 hour time, filter, washing, filter cake is at 450～650 ℃, and roasting is 0.5～2.5 hour under 1～100% steam.
9. according to claim 5 or 7 or 8 described Preparation of catalysts methods, it is characterized in that the rare earth compound that described rare earth exchanged adopts is that rare earth chloride, rare earth nitrate are or/and sulfuric acid rare earth.
10. Preparation of catalysts method according to claim 5, it is characterized in that described phosphorus containg substances is meant that one or more are selected from ortho-phosphoric acid, phosphorous acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tetra-sodium.
11. Preparation of catalysts method according to claim 5 is characterized in that described ammonium salt is meant that one or more are selected from ammonium chloride, ammonium nitrate, volatile salt, bicarbonate of ammonia, ammonium oxalate, ammonium sulfate, monoammonium sulfate.
12. catalyzer according to claim 5 is characterized in that described high-temperature inorganic oxide precursor comprises that silica-alumina gel, silicon sol, aluminium colloidal sol, sial complex sol, aluminum phosphate colloidal sol are or/and pseudo-boehmite.
13. Preparation of catalysts method according to claim 5 is characterized in that the condition of spraying is: 300～800 ℃ of temperature ins, 100～400 ℃ of exhaust temperatures.
14. the microballoon sample that Preparation of catalysts method according to claim 5, the condition that it is characterized in that described aftertreatment are spraying to be formed was 200～700 ℃ of following roastings 0.05～4 hour.
15. Preparation of catalysts method according to claim 5 is characterized in that microballoon sample that described post-treatment condition forms for spraying was 300～650 ℃ of following roastings 0.1～3.5 hour.
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| US11111152B2 (en) | 2015-08-05 | 2021-09-07 | Petrochina Company Limited | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst |
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| CN102049291B (en) * | 2009-10-30 | 2013-03-27 | 中国石油天然气股份有限公司 | Hydrocarbon catalytic cracking catalyst and preparation method thereof |
| CN104307561A (en) * | 2014-07-15 | 2015-01-28 | 台州欧信环保净化器有限公司 | Oxidative catalyst used for purifying diesel vehicle exhaust, and manufacturing method thereof |
| WO2017020848A1 (en) | 2015-08-05 | 2017-02-09 | 中国石油天然气股份有限公司 | Molecular sieve modification method and catalytic cracking catalyst containing molecular sieve |
| CN113797964B (en) * | 2020-06-17 | 2023-07-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
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| US11111152B2 (en) | 2015-08-05 | 2021-09-07 | Petrochina Company Limited | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst |
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