CN101823726B - Modified Y molecular sieve - Google Patents
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Abstract
The invention discloses a modified Y molecular sieve, which is prepared by performing a primary exchange reaction on a NaY molecular sieve and rare earth solution, then introducing a phosphorus compound into an exchange serous fluid for further reaction, filtering and washing the mixture after the reaction, and roasting a filter cake under a vapor condition. The lattice constant of the modified Y molecular sieve is 2.450 to 2.479 nanometers, and the modified Y molecular sieve comprises the following components in percentage by weight: 2.0 to 6.0 percent of sodium oxide, 0.01 to 2.5 percent of phosphorus and 11 to 23 percent of rare earth oxide. Most of the rare earth of the modified molecular sieve is positioned in a sodalite cage of the Y molecular sieve, so the stability of the molecular sieve in a high-temperature hydrothermal environment is increased; and the structural acidity of the molecular sieve plays a good role in modulation. The modified Y molecular sieve used as an active component of a cracking catalyst has strong heavy oil conversion capacity and good coke selectivity.
Description
Technical field
The invention relates to a kind of modified Y molecular sieve, further say so about a kind of " one hands over a roasting " rare earth and the composite modified Y molecular sieve of phosphorus.
Background technology
Along with the increase of oil production difficulty, world's crude oil heaviness trend is fairly obvious in recent years, when crude quality becomes heavy variation, the world to the clean or white demand but increasing.The reserves ratio of heavy oil and conventional crude is respectively 53% and 25% in the world; The most crude oil of China also all belong to heavy crude; Heavy oil productive rate greater than more than 350 ℃ accounts for more than 70% of crude oil; In addition, the ratio that FCC technology is mixed refining residual oil also improves constantly, and RCC (RFCC) is being brought into play more and more important effect in heavy oil conversion.Not only contain the macromolecular cpd of easy green cokes such as colloid and bituminous matter in the residual oil, and contain than multi-metal (like nickel, vanadium etc.), metal deposition such as nickel, vanadium is on catalyzer in cracking reaction; Cause catalyst activity to reduce; Particularly the vanadium of high oxidation state transport property under the high-temperature water thermal environment is strong, and the structure of molecules of active components sieve causes the irreversible inactivation of catalyzer in the havoc catalyzer; Make the catalyzer consumption increase, process cost significantly improves.In the composition of FCC catalyzer, the molecular sieve active ingredient has material impact to the combined reaction performance of catalyzer, and the production cost of molecular sieve component is one of prime cost of preparation catalyzer.The main active component of general FCC catalyzer all is a modified Y molecular sieve, and this requires modified Y molecular sieve that high activity should be arranged, and has good product to distribute again.
Y molecular sieve activity after rare earth modified is greatly improved, like CN91101221.4, and CN97116833.4, CN02103909.7 etc., but rare earth oxide content is not higher than 16m% among the REY of general preparation.It has been generally acknowledged that have in the REY molecular sieve sufficiently high content of rare earth be the prerequisite of molecular sieve with Gao Re and hydrothermal stability (USP3140249, USP3140250, USP3140253).And high rare earth REY is often with the shortcoming of coke selectivity difference.In recent years, adopted cracking activity and the selectivity of method to improve cracking catalyst of rare earth and the composite modified Y molecular sieve of phosphorus both at home and abroad, like CN1436600A, CN02155600.8 etc.The preparation method of the Y molecular sieve of a kind of phosphorous and rare earth that patent CN00133566.9 provides is earlier with ammonium ion and rare earth ion exchanged and hydrothermal calcine, then with the P of 0.2～10 weight % on itself and the phosphide reaction bonded with the NaY molecular sieve
2O
5, carry out hydrothermal calcine again.This method rare earth utilization ratio is not high, and through double roasting, complex process.The preparation method of that patent CN02103910.0 provides is a kind of " one hands over a roasting " modcfied faujasite.Modcfied faujasite is to carry out permutoid reaction one time through faujusite and phosphorus compound and ammonium compound, in the exchange slurries, introduces earth solution then and further reacts, and obtains through filtration, washing, steam calcination process.By this zeolite is the catalyst activity good stability that active ingredient is processed, and yield of gasoline is high, and coke yield is low, but cracking activity is not high, and the heavy oil conversion rate is low.
In sum, after Y zeolite process rare earth and phosphorus are composite modified, can obviously improve its activity stability and cracking selectivity.But it is complicated that the shortcoming of prior art is a modified technique, carries out such as the super stabilizing and the distribution of phosphorus modifying process of molecular sieve, and the production cycle is long, and the rare earth utilization ratio is not high; Existing " one hands over a roasting " modified molecular screen can not possess high activity and good coke selectivity simultaneously.In order to adapt to heavy oil upgrading, it is simple to develop a kind of preparation technology, and it is significant with the modified Y molecular sieve of good coke selectivity to have high reactivity concurrently.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare that process is simple, the rare earth and the composite modified Y molecular sieve of phosphorus of high rare-earth content.This Modified Zeolite Y has high activity and good coke selectivity, its preparation technology's clean environment firendly, and rare earth can utilize fully.
Modified Y molecular sieve of the present invention obtains through following manner:
Y zeolite and earth solution carry out permutoid reaction, water and molecular sieve weight ratio 2～30, pH=2.5～7.0; Temperature is 0～100 ℃, 0.1～3.5 hour swap time, the precursor of introducing phosphorus in the exchange slurries then; 1～70 minute reaction times; Through filtration, washing, filter cake is at 180～650 ℃, roasting 0.5～6 hour under 5～100% steam and obtaining.These molecular sieve lattice constant 2.450～2.479 sodium rice, sodium oxide 2.0～6.0 weight %, phosphorus 0.01～2.5 weight %, rare earth oxide 11～23 weight %.
Earth solution of the present invention can be the single or mixed rare earth solution of any composition, as can being that re chloride also can be rare earth nitrate solution, preferably Lanthanum trichloride or lanthanum nitrate hexahydrate; The precursor of described phosphorus can be phosphoric acid such as ortho-phosphoric acid, phosphorous acid, tetra-sodium etc., also can be soluble phosphate such as ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate etc., can be one or more.
Y zeolite modified condition of the present invention is: water and molecular sieve weight ratio 2～30, preferred 4～12; Earth solution adds according to rare earth oxide and molecular sieve weight ratio 0.1～0.30; Preferred 0.12～0.20; PH=2.5～7.0, preferred 3.0～6.0, temperature is 0～100 ℃, 0.1～2.5 hour swap time; When in the exchange slurries, adding the precursor of phosphorus, the weight ratio 0.01～4.5% of phosphorus and molecular sieve, preferred 0.02～2.0%; Reaction times is 1～70 minute, filters, washs, and filter cake is at 180～650 ℃, and preferred 220～550 ℃, roasting is 0.5～6 hour under 5～100% (preferably 20～100%) steam.
The filter cake roasting process carries out under 180～650 ℃ among the present invention; Preferably 220～550 ℃; Rising along with temperature; The rare earth that gets in the Y zeolite supercage will more migrate to move, the structural stability that this helps the exchange of sodium and improves molecular sieve, the too high then easy saboteur's sieve skeleton shelf structure of maturing temperature certainly.
Modified Y molecular sieve is introduced through first exchanged rare earth again and is carried out roasting behind the phosphorus and obtain among the present invention, different from the pastly introduces phosphorus again after introducing behind the phosphorus exchanged rare earth or first exchanged rare earth roasting earlier again, carries out roasting.Modified Y molecular sieve rare earth oxide content of the present invention can reach about 20 weight %, and increases operation rate with the phosphorus interaction, reaches best performanceization.
Contain rare earth and composite modified Y zeolite lattice constant 2.450～2.479 sodium rice of phosphorus, sodium oxide 2.0～6.0 weight %, phosphorus 0.01～2.5 weight %, rare earth oxide 11～23 weight % according to the present invention preparation.Wherein exchange the rare earth and the phosphorus reaction formation composite oxides that get into molecular sieve in the modified Y molecular sieve and be evenly distributed on the surface of molecular sieve, rare earth is fully exploited.This method of modifying makes the rare earth major part be arranged in the move of Y molecular sieve, has increased the stability of molecular sieve under the high-temperature water thermal environment; Structure acidity to molecular sieve plays good promotor action.
Embodiment
Further set forth characteristics of the present invention below, but these examples can not limit the present invention with embodiment.
(1) invents main analytical procedure
1, rare earth oxide, sodium oxide, phosphorus content are by x-ray fluorescence spectrometry
2, lattice constant: x-ray diffraction method.
3, percent crystallinity retention rate: x-ray diffraction method.
(2) use raw materials used specification in the embodiments of the invention
1, rare earth chloride: industrial goods, rare earth oxide 200 grams per liters; Rare earth nitrate: industrial goods, rare earth oxide 200 grams per liters.
2, primary ammonium phosphate: solid, industrial goods; Secondary ammonium phosphate: solid, industrial goods; Ortho-phosphoric acid: industrial goods, phosphorous 25 heavy %.
3, NaY molecular sieve: CNPC's Catalyst Factory of Lanzhou Petrochemical Company is produced.
4, hydrochloric acid is analytical pure.
Embodiment 1:
Get 5 kilograms of NaY (butt), add 50 liters deionized water, making beating under agitation slowly adds 5 liters of re chlorides; The hydrochloric acid adjusting slurry pH that uses 3 mol is 4.5,30 ℃ of exchanges 0.5 hour, adds 83.3 gram Secondary ammonium phosphates then; Continue reaction 1 hour, filter, wash, filter cake is at 500 ℃; Roasting is 1.5 hours under 80% water vapor conditions, obtains the present invention's " hands over a roasting " modification Y sieve, is designated as P-1.
Embodiment 2:
Get 5 kilograms of NaY (butt), add 40 liters deionized water, making beating under agitation slowly adds 3.2 liters of re chlorides; The hydrochloric acid adjusting slurry pH that uses 2 mol is 5.5,40 ℃ of exchanges 50 minutes, adds 83.3 gram Secondary ammonium phosphates then; Continue reaction 0.5 hour, filter, wash, filter cake is at 550 ℃; Roasting is 1 hour under 100% water vapor conditions, obtains the present invention's " hands over a roasting " modification Y sieve, is designated as P-2.
Embodiment 3:
Get 5 kilograms of NaY (butt), add 25 liters deionized water, making beating under agitation slowly adds 5.0 liters of rare earth nitrate solutions; The hydrochloric acid adjusting slurry pH that uses 2 mol is 6.0,20 ℃ of exchanges 2 hours, adds 416.5 gram primary ammonium phosphates then; Continue reaction 1 hour, filter, wash, filter cake is at 350 ℃; Roasting is 3 hours under 100% water vapor conditions, obtains the present invention's " hands over a roasting " modification Y sieve, is designated as P-3.
Embodiment 4:
Get 5 kilograms of NaY (butt), add 50 liters deionized water, making beating under agitation slowly adds 4.5 liters of re chlorides; The hydrochloric acid adjusting slurry pH that uses 3 mol is 5.0,65 ℃ of exchanges 1.5 hours, adds 192.2 gram ammonium phosphate then; Continue reaction 10 minutes, filter, wash, filter cake is at 450 ℃; Roasting is 1.5 hours under 100% water vapor conditions, obtains the present invention's " hands over a roasting " modification Y sieve, is designated as P-4.
Embodiment 5:
Get 5 kilograms of NaY (butt), add 50 liters deionized water, making beating under agitation slowly adds 4.5 liters of rare earth nitrate solutions; The hydrochloric acid adjusting slurry pH that uses 2 mol is 4.0,85 ℃ of exchanges 0.5 hour, adds 10 gram ortho-phosphoric acid then; Continue reaction 1 hour, filter, wash, filter cake is at 500 ℃; Roasting is 1.5 hours under 100% water vapor conditions, obtains the present invention's " hands over a roasting " modification Y sieve, is designated as P-5.
Comparative Examples 1:
Press the CN02103910.0 method, get 3 kilograms of NaY (butt), add 22.2 liters deionized water, making beating adds 1.44 kilo sulfuric acid ammoniums and 115.3 gram ammonium phosphate in addition.Using the hydrochloric acid adjusting slurry pH of 3 mol is 3.8, heats up, and reacts 50 minutes down at 82 ℃; Under agitation slowly add 2.68 liters of re chlorides then, continue reaction 30 minutes, filter, wash; Drying, filter cake are at 630 ℃, and roasting is 1.5 hours under 80% water vapor conditions; Obtain contrasting modified molecular screen, be designated as D-1.
Comparative Examples 2:
Press the CN00133566.9 method, get 5 kilograms of NaY (butt), after 100 liters of deionized water making beating; Add 1.5 kilo sulfuric acid ammoniums, add concentration again and be 12 liters of the earth solutions of 100g/l, in 90 ℃ of exchanges 1 hour; Filter and use water wash; Then with filter cake at 520 ℃, roasting is 3 hours in 100% steam atmosphere, obtains the REUSY molecular sieve.Get 100 these REUSY molecular sieves (in butt) of gram,, behind the adding 40 gram ammonium chlorides, add 3.8 gram Secondary ammonium phosphates again, be warming up to 85 ℃ and stirred 3 hours, filter then, wash, dry with 2000 gram deionized water making beating.To dry sample at 550 ℃, roasting is 1 hour under 100% water vapor conditions, obtains contrasting modified molecular screen, is designated as D-2.
The physico-chemical property of the modified Y molecular sieve of embodiment 1～5 and Comparative Examples 1 preparation is listed in table 1.
The character of table 1 modified molecular screen
| Project | P-1 | P-2 | P-3 | P-4 | P-5 | D-1 | D-2 |
| Sodium oxide, weight % | 3.85 | 5.50 | 4.00 | 4.10 | 4.18 | 5.60 | 4.11 |
| Rare earth oxide, weight % | 18.01 | 12.11 | 18.85 | 17.00 | 16.88 | 17.00 | 17.00 |
| Phosphorus, weight % | 0.39 | 0.40 | 1.80 | 0.78 | 0.05 | 0.78 | 0.78 |
| Lattice constant, nanometer | 2.474 | 2.471 | 2.473 | 2.473 | 2.472 | 2.460 | 2.466 |
| The rare earth utilization ratio, % ① | 100 | 100 | 100 | 100 | 100 | 99 | 75 |
1.Amount in theory * 100 of molecular sieve middle-weight rare earths content/rare earth
Can find out that from table 1 among molecular sieve P-1, P-2, P-3, P-4 and the P-5 that embodiment 1-5 obtains, the rare earth of exchange entering molecular sieve can not react with phosphorus, the rare earth utilization ratio reaches 100%.In the Comparative Examples 2, rare earth is after exchange, and the part that does not get into molecular sieve is then lost through filtering entering filtrating, and the rare earth utilization ratio has only 75%.The molecular sieve D-1 sodium oxide content that Comparative Examples 1 obtains is 5.60, is higher than 4.10 of molecular sieve P-4 among the embodiment.This is owing to Comparative Examples 1 is introduced phosphorus earlier, and when carrying out rare earth exchanged again, the supercage and the sodalite opening of the phosphate radical that volume is bigger, phosphoric acid hydrogen radical ion easy blocking Y zeolite influence in the rare earth entering molecular sieve and sodium exchanges.In addition, with respect to Comparative Examples 1, the molecular sieve lattice constant that embodiment obtains is all bigger, explains that the present invention adopts lower maturing temperature, when guaranteeing to reduce the molecular sieve sodium content, can effectively protect the framework of molecular sieve structure.Modified molecular screen sodium oxide prepared in accordance with the present invention between 2.0～6.0 weight %, phosphorus 0.01～2.5 weight %, rare earth oxide 11～23 weight %, lattice constant 2.450～2.479 sodium rice.
For cracking activity and the selectivity of investigating modified Y molecular sieve, carried out following experiment.
The method for preparing semi-synthetic cracking catalyst according to routine; Modified molecular screen with 35%, 20% aluminum oxide, 35% kaolin, 10% aluminium sol adhesive and proper amount of deionized water mix; Through spraying, washing, drying; Process catalyzer; Wherein modified molecular screen is respectively embodiment gained molecular sieve P-1, P-2, P-3, P-4, P-5 and Comparative Examples gained molecular sieve D-1, D-2, processes cracking catalyst a, b, c, d, e, f, g respectively, and the physical and chemical performance of catalyzer is seen table 2.
The catalyzer physical and chemical performance that table 2 embodiment and Comparative Examples gained modified molecular screen are processed
| Project | a | b | c | d | e | f | g |
| Sodium oxide, weight % | 0.11 | 0.13 | 0.12 | 0.12 | 0.12 | 0.14 | 0.12 |
| Rare earth oxide, weight % | 6.30 | 4.23 | 6.59 | 5.95 | 5.91 | 5.95 | 5.95 |
| Phosphorus, weight % | 0.13 | 0.13 | 0.58 | 0.25 | 0.016 | 0.25 | 0.25 |
| Micro-activity, m% ② | 78 | 72 | 72 | 74 | 76 | 69 | 71 |
2.The micro-activity condition determination: catalyzer is under 800 ℃, 100% water vapor conditions after aging 17 hours, 460 ℃ of reactions 70 seconds down.Catalyzer loading amount 5.0g, agent-oil ratio 3.2, raw oil are straight distillation light diesel oil, oil inlet quantity 1.56g.
Can find out that from table 2 the catalyzer micro-activity of being made active ingredient by the modified molecular screen of embodiment gained all is higher than the catalyzer of being made active ingredient by the modified molecular screen of Comparative Examples gained.This is once to accomplish when hydrothermal calcine owing to the invention enables migration of rare earth, phosphorus and molecular sieve to have an effect; The synergistic effect of rare earth and phosphorus effectively gets in the Y zeolite move rare earth, thereby improves structural stability and the activity stability of molecular sieve under harsh hydrothermal condition.The modified Y molecular sieve of this explanation the present invention preparation has good activity stability.The molecular sieve of Comparative Examples 1 is after being prepared into catalyzer, and sodium content still is higher than the catalyzer that embodiment gained molecular sieve is prepared into, and the technology that further illustrates Comparative Examples 1 is unfavorable for that rare earth gets in the Y zeolite and sodium generation permutoid reaction.
The cracking activity and the cracking reaction selectivity of catalyzer and the catalyzer of the modified molecular screen that contains the Comparative Examples preparation that contains the modified Y molecular sieve active ingredient of the present invention preparation through fixed fluidized bed measuring.
Experiment condition: at 800 ℃, 100% water vapor conditions is aging down after 10 hours, 500 ℃ of temperature of reaction, 650 ℃ of regeneration temperatures, weight space velocity 16h
-1, catalyzer loading amount 150 grams, agent-oil ratio 3.75, raw oil are 70% wide fraction oil+30% Xinjiang vacuum residuum.The fixed bed evaluation result is seen table 3, can find out from table 3, and the catalyzer that contains the modified Y molecular sieve active ingredient of the present invention's preparation is compared with the catalyzer f of the modified molecular screen that contains the Comparative Examples preparation, and the heavy oil productive rate is low, and cracking activity is good.The modified molecular screen that the present invention obtains is compared with the molecular sieve that Comparative Examples 1 obtains, and has big lattice constant, promptly possesses good structural integrity; The non-framework aluminum fragment is few; Rare earth is distributed in the ratio height of move simultaneously, makes that the molecular sieve activity is high, the duct is unimpeded, helps reactant and gets into the reaction of molecular sieve supercage smoothly; Product in time comes out of steamer, thereby has improved heavy oil conversion performance.The catalyzer that contains the modified Y molecular sieve active ingredient of the present invention's preparation is compared with the catalyzer g of the modified molecular screen that contains the Comparative Examples preparation, and the heavy oil productive rate is low, and coke selectivity is good.This is because the modified molecular screen that obtains of the present invention is compared with the molecular sieve that Comparative Examples 2 obtains, and the ratio of move that rare earth is positioned at Y molecular sieve is big, has improved the activity stability of molecular sieve; Simultaneously; Middle-weight rare earths migration of the present invention, phosphorus and molecular sieve are had an effect and when hydrothermal calcine, are once accomplished; And phosphorus is not single has an effect with framework of molecular sieve aluminium; In addition some is evenly distributed on the surface of molecular sieve with rare earth formation composite oxides; Play good promotor action to the structure of molecular sieve is acid with surface properties, the synergy of above rare earth and phosphorus makes has the catalyzer of the modified Y molecular sieve active ingredient that the present invention prepares under the prerequisite that guarantees the efficient conversion of heavy oil, coke selectivity.
The fixed fluidized bed evaluating data of table 3
| Catalyzer | a | b | c | d | e | f | g |
| Dry gas | 2.98 | 2.19 | 2.28 | 2.27 | 2.38 | 1.50 | 3.00 |
| Liquefied gas | 20.06 | 18.80 | 19.26 | 18.51 | 19.02 | 22.60 | 18.22 |
| C 5Gasoline | 47.54 | 50.06 | 48.78 | 49.69 | 49.44 | 47.00 | 48.98 |
| Diesel oil | 13.99 | 15.89 | 15.45 | 15.71 | 15.52 | 15.20 | 15.30 |
| Heavy oil | 4.47 | 4.65 | 4.56 | 4.60 | 4.52 | 6.10 | 5.60 |
| Coke | 10.21 | 7.81 | 9.01 | 8.58 | 8.35 | 6.80 | 8.80 |
| Transformation efficiency, m% | 80.79 | 78.86 | 79.33 | 79.05 | 79.19 | 77.90 | 79.00 |
Claims (8)
1. modified Y molecular sieve is characterized in that this modified Y molecular sieve obtains through following manner:
Y zeolite and earth solution carry out permutoid reaction, water and molecular sieve weight ratio 2～30, pH=2.5～7.0; Temperature is 0～100 ℃, 0.1～3.5 hour swap time, the precursor of introducing phosphorus in the exchange slurries then; 1～70 minute reaction times; Through filtration, washing, filter cake is at 180～650 ℃, roasting 0.5～6 hour under 5～100% steam and obtaining; These molecular sieve lattice constant 2.450～2.479 nanometers, sodium oxide 2.0～6.0 weight %, phosphorus 0.01～2.5 weight %, rare earth oxide 11～23 weight %.
2. modified Y molecular sieve according to claim 1 is characterized in that said earth solution is rare earth chloride or rare earth nitrate solution.
3. modified Y molecular sieve according to claim 1, the precursor that it is characterized in that phosphorus are phosphoric acid and/or soluble phosphate.
4. modified Y molecular sieve according to claim 3, the precursor that it is characterized in that phosphorus are one or more in ortho-phosphoric acid, phosphorous acid, tetra-sodium, ammonium phosphate, Secondary ammonium phosphate, the primary ammonium phosphate.
5. modified Y molecular sieve according to claim 1, when it is characterized in that Y zeolite and earth solution carry out permutoid reaction, water and molecular sieve weight ratio are 4～12.
6. modified Y molecular sieve according to claim 1, when it is characterized in that Y zeolite and earth solution carry out permutoid reaction, pH is 3.0～6.0.
7. modified Y molecular sieve according to claim 1, when it is characterized in that in the exchange slurries, adding the precursor of phosphorus, the weight ratio of phosphorus and molecular sieve is 0.01～4.5%.
8. modified Y molecular sieve according to claim 1 is characterized in that filter cake at 220～550 ℃, and roasting is 0.5～6 hour under 20～100% steam.
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| JP2015523907A (en) * | 2012-06-01 | 2015-08-20 | 中国石油天然気股▲ふん▼有限公司 | Heavy oil high-efficiency catalytic conversion cracking catalyst and production method thereof |
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| US9968915B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Phosphorus-containing ultrastable Y-type rare earth molecular sieve and preparation method therefor |
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