Following example will be described further Catalysts and its preparation method provided by the invention.
In example, the content of rare earth in the sample catalyst is measured with XRF, and phosphorus content is measured with chemical colorimetry, and specific surface and pore volume are measured with low-temperature nitrogen adsorption method.
The catalyzer that is used for the little anti-and fixed fluidized bed evaluation of light oil is in advance through aging 4 hours or 17 hours of 800 ℃, 100% water vapour.
The little anti-appreciation condition of light oil is: 235~335 ℃ huge port solar oil is a raw material, and agent-oil ratio is 3.2, and weight space velocity is 16h
-1, temperature is 460 ℃.
Fixed fluidized bed appreciation condition is: temperature of reaction is 520 ℃, weight space velocity 20h
-1, the catalyzer loading amount is 90 grams, and agent-oil ratio is 5, and reaction raw materials is the defeated VGO+20% vacuum residuum of 80% pipe.
Olefin(e) centent is by gas Chromatographic Determination in the gasoline.
Example 1
With 32 gram REHY molecular sieve (RE
2O
3Content 3.4 heavy %, Na
2The heavy % of O content 4.5, silica alumina ratio is 5.6, the Shandong catalyst plant is produced) with after ammonium phosphate (chemical pure) solution of 43.8 grams, 7.8 weight % (in the ammonium phosphate amount) mix, stirred 0.5 hour, 120 ℃ after lower dry 2 hours, roasting 40 minutes in air is taken out and is pulverized under 480 ℃.
In 41 gram boehmites (solid content 34.8 heavy %, Shandong Aluminum Plant's production), add 78 gram water, after stirring, take by weighing again rare earth chloride (production of Inner Mongol Baotou rare earth factory, the RE of 3.0 grams
2O
3Content 46 heavy %, RE
2O
3Consist of La
2O
353.2%, CeO
213.0%, Pr
6O
1113.0%, Nd
2O
320.8%), is dissolved in 10 gram water, mixes with boehmite solution, stir after 10 minutes, take by weighing 15 grams, 37 heavy % hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) and dropwise add in the mixed liquor, stir.The gained mashed prod wore out 1.5 hours down at 90 ℃.The phosphorous REHY molecular sieve after pulverizing and 2 gram MFI structure molecular screen (Na
2The heavy % of O content 3.0, silica alumina ratio 30, the Shandong catalyst plant is produced), behind 39.4 gram kaolin (solid content 85.0 heavy %, the China Kaolin Co., Ltd's industrial products) mixing, (contain Al with aged boehmite and 24 gram aluminium colloidal sols
2O
321 heavy %, the Shandong catalyst plant is produced) mix after, in 500 ℃ of lower roastings 2 hours.
Baked catalyst is pulverized, crossed 20 mesh sieves, washing in water, ammoniacal liquor and the exhaustion of yang water in 20 times of PH3 to stem-based catalyst~4 respectively under 60 ℃, be washed till Na after sieving
2O<0.25%, after the filtration, filter cake processed 1 hour under 20-80 ℃ in the elemental phosphorous phosphoric acid solution of counting 0.70 heavy % after, 120 ℃ lower dry 2 hours, namely get phosphorous REHY molecular sieve catalyst A provided by the invention.
Consisting of of catalyst A: kaolin 36.9%, the aluminium oxide 15.8% from boehmite, the aluminium oxide 5.6% from aluminium colloidal sol, Y zeolite 34.1%, MFI structure molecular screen 2.2%, RE
2O
32.7%, P
2O
52.7%.
Evaluation result sees Table 1.
Comparative Examples 1
Prepare catalyzer by the method described in the example 1, but the roasting in the 1st step is in 100% water vapour.This comparative catalyst's note is made A '.
Catalyst A ' consist of: kaolin 36.9%, aluminium oxide 21.4%, Y zeolite 34.1%, MFI structure molecular screen 2.2%, RE
2O
32.7%, P
2O
52.7%.
The evaluation result data are listed in table 1.
Table 1
Catalyst | A | A ' |
Specific surface, rice
2/ gram
| 229 | 198 |
Pore volume, milliliter/gram | 0.32 | 0.27 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 82 67 | 79 62 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 17.4 51.8 19.2 3.6 20.2 | 16.2 49.1 20.6 4.2 24.5 |
Data from table 1 can be found out: catalyst A has comparison than catalyst A ' higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 2
To 21 gram REY molecular sieve (RE
2O
3Content is 19.5 heavy %, Na
2O content is 1.6 heavy %, silica alumina ratio is 5.4, Chang Ling catalyst plant production) adding 32 gram concentration in is ammonium dihydrogen phosphate (ADP) (chemical pure) solution of 4.1 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stir and evenly mix 2 hours, 120 ℃ of lower dryings are after 2 hours, roasting is 3 hours in 500 ℃ of lower air, takes out and pulverizes.
Get 42.5 gram boehmites, after adding 100 gram water stir, add again 20 gram HCl, after stirring, that pastel is lower aging 2 hours at 70 ℃.Again the phosphorous REY molecular sieve after the above-mentioned pulverizing, 2 gram MFI structure molecular screen (Na
2The heavy % of O content 3.0, silica alumina ratio 30, the Shandong catalyst plant is produced), 20.1 gram kaolin with aging after boehmite and after 51.3 gram aluminium colloidal sols mix, in 500 ℃ of lower roastings 2 hours.
Same with the 3rd step in the example 1, just solution containing phosphate is the ammonium phosphate solution of phosphorous 0.30 heavy %, gets phosphorated REY molecular sieve type catalyst B provided by the invention.
Consisting of of catalyst B: kaolin 25.5%, the aluminium oxide 22.1% from boehmite, the aluminium oxide 16.1% from aluminium colloidal sol, Y zeolite 25.2%, MFI structure molecular screen 3.0%, RE
2O
36.0%, P
2O
52.0%.
Evaluation result sees Table 2.
Comparative Examples 2
Prepare catalyzer by the method described in the example 2, but the solution containing phosphate that adds in the 1st step is that 32 gram concentration are the ammonium dihydrogen phosphate of 7.1 heavy % (in primary ammonium phosphate), roasting is in 100% water vapour, and the 3rd solution containing phosphate of no use in the step filter cake is handled, the comparative catalyst that obtains note is made B '.
Catalyst B ' consist of kaolin 25.5%, aluminium oxide 38.2%, Y zeolite 25.2%, MFI structure molecular screen 3.0%, RE
2O
36.0%, P
2O
52.0%.
Relevant Analysis and evaluating data are listed in table 2.
Comparative Examples 3
According to disclosed preparation method in USP511 0776 example 3, the preparation comparative catalyst.
Get REY molecular sieve (RE
2O
3Content is 19.5 heavy %, Na
2O content is 1.6 heavy %, and silica alumina ratio is 5.4, and the Chang Ling catalyst plant is produced) 101.4 grams, 0.61 gram dispersant, 11.0 gram ammonium dihydrogen phosphate (ADP)s and 133.8 gram water mix and stirred 16 hours, and then add 163.8 gram deionized waters.In addition 96.5 gram kaolin, 385 gram sodium metasilicate (are contained SiO
226.8 heavy %, Na
2The heavy % of O7.8, the Qilu Petrochemical Company catalyst plant is produced) and 2134 gram water mix, add at last the molecular sieve pulp that has prepared, mix, dry, wash to there not being acid ion, reslurry, spray-drying obtains comparative catalyst B ".
Catalyst B " consist of kaolin 25.4%, silica 41.2%, Y zeolite 25.2%, RE
2O
36.1%, P
2O
52.1%.
Relevant Analysis and evaluating data are listed in table 2.
Table 2
Catalyst | B | B ' | B " |
Specific surface, rice
2/ gram
| 238 | 211 | 218 |
Pore volume, milliliter/gram | 0.32 | 0.29 | 0.29 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 83 67 | 78 60 | 81 63 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 15.8 49.8 21.0 4.0 19.9 | 14.8 47.8 22.4 5.4 23.2 | 15.6 48.9 22.0 5.2 22.5 |
Can find out from table 2 data: catalyst B has comparison than catalyst B ' higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.Catalyst B has comparison than catalyst B " olefin(e) centent in higher activity, activity stability and lower coking yield, the gasoline fraction.
Example 3
To 22 gram USY molecular sieve (Na
2O content is 0.87 heavy %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced) in to add 30 gram concentration be the ammonium dihydrogen phosphate of 1.85 heavy % (in the primary ammonium phosphate amount), stirring and evenly mixing 4 hours, 120 ℃ drying is after 2 hours down, and 550 ℃ of following roastings 30 minutes, taking-up was pulverized.
Get 26 gram boehmites, add 32 gram water and stir, stir after 10 minutes, dropwise add 10.5 and restrain HCl, after stirring, that pastel is lower aging 1.5 hours at 70 ℃.Then the phosphorous USY molecular sieve after pulverizing, 1 gram MFI structure molecular screen (Na
2The heavy % of O content 3.0, silica alumina ratio 30, the Qilu Petrochemical Company catalyst plant is produced), 30 gram kaolin restrain the aluminium colloidal sols with above-mentioned boehmite and 30 after aging and mix, behind the mixing in 500 ℃ of lower roastings 2 hours.
With the 3rd step in the example 2 with, just solution containing phosphate be elemental phosphorous be the ammonium phosphite solution of 0.15 heavy %, get phosphorous USY molecular sieve type catalyst C provided by the invention.
Catalyst C consists of: kaolin 20.7%, the aluminium oxide 22.3% from boehmite, the aluminium oxide 11.1% from aluminium colloidal sol, Y zeolite 43.4%, MFI structure molecular screen 1.5%, P
2O
51.0%.
It is analyzed and evaluation result sees Table 3.
Comparative Examples 4
Prepare USY molecular sieve type comparative catalyst by the method described in EP397183 example I-IV, this comparative catalyst C '.
Catalyst C ' consists of kaolin 20.5%, aluminium oxide 19.1%, Y zeolite 45.7%, P
2O
50.4%, aluminium oxide dry powder 14.3%.
The data of Relevant Analysis and evaluation are listed in table 3.Table 3
Catalyst | C | C ' |
Specific surface, rice
2/ gram
| 252 | 234 |
Pore volume, milliliter/gram | 0.34 | 0.32 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 78 67 | 76 62 |
Heavy oil is little anti-, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 16.8 48.9 20.8 3.2 25.2 | 15.4 47.6 21.5 4.1 33.5 |
Data from table 3 can be found out: catalyst C has comparison than the higher activity stability of catalyst C ' and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 4
To 25 gram REUSY molecular sieve (Na
2O content is 1.2 heavy %, RE
2O
3Content is 1.5 heavy %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced) in add 45 grams in the ammonium phosphate amount, concentration is the ammonium phosphate solution of 5.1 heavy %, stirs after 3 hours, and 120 ℃ of lower dryings are after 2 hours, roasting is 2 hours in 600 ℃ of lower air, takes out and pulverizes.
Get 21.7 gram boehmites, add 42 gram water and stir, add again 0.37 gram rare earth chloride, stir after 10 minutes, dropwise add 10 and restrain HCl, after stirring, that pastel is lower aging 1.5 hours at 80 ℃.Then the phosphorous REUSY molecular sieve after the above-mentioned pulverizing, 3 gram MFI structure molecular screen (Na
2The heavy % of O content 3.0, silica alumina ratio 30, the Qilu Petrochemical Company catalyst plant is produced), 44.6 gram kaolin with aging after boehmite and after 12 gram aluminium colloidal sols mix, in 500 ℃ of lower roastings 4 hours.
Identical with the 3rd step of example 1, just solution containing phosphate be elemental phosphorous be the ammonium dihydrogen phosphate of 0.30 heavy %, obtain phosphorous REUSY molecular sieve type catalyst D provided by the invention.
Catalyst D consists of kaolin 48.8%, boehmite 9.8%, aluminium colloidal sol 3.2%, Y zeolite 31.7%, MFI structure molecular screen 3.9%, RE
2O30.7, P
2O
51.9%.
It is analyzed and evaluation result sees Table 4.
Comparative Examples 5
Press the method Kaolinite Preparation of Catalyst described in the example 4, but with solution containing phosphate molecular sieve is not processed in the 1st step, other prepares comparative catalyst D ' all with example 4.
Catalyst D ' consists of: kaolin 49.5%, binding agent 13.2%, Y zeolite 32.2%, MFI molecular sieve 3.9, RE
2O
30.7%, P
2O
50.5%.
Relevant Analysis and evaluating data are listed in table 4.
Comparative Examples 6
Prepare comparative catalyst D by the 8 described methods of example among the CN1062750 " (this comparative catalyst's composition is adjusted in the scope that its patent comprises).
Catalyst D " consist of: kaolin 48.8%, aluminium oxide 13.0%, Y zeolite 31.7%, MFI structure molecular screen 3.9%, RE
2O
30.7%, P
2O
51.9%.
Relevant Analysis and evaluating data are listed in table 4.Table 4
Catalyst | D | D ' | D " |
Specific surface, rice
2/ gram
| 231 | 242 | 240 |
Pore volume, milliliter/gram | 0.32 | 0.34 | 0.33 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 79 66 | 83 62 | 82 64 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 16.2 49.8 22.9 3.0 24.0 | 17.7 50.8 19.0 4.4 28.2 | 16.9 50.2 19.6 4.2 27.4 |
As can be seen from Table 4, catalyzer D has comparison than catalyzer D ', D " higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 5
With 50 gram NaY (Na
2The heavy % of O content 11, silica alumina ratio is 5.6, the Chang Ling catalyst plant is produced) at the ammonium chloride solution of 1 liter of 0.15M 60 ℃ of lower exchanges 1 hour, the filter cake after the filtration obtained Na in 2 hours 550 ℃ of roastings
+Pre-exchange degree is 65% HNaY.It again by above-mentioned steps exchange twice, is obtained the HY molecular sieve.
Add 30 grams in elemental phosphorous in the 23 gram HY molecular sieves, the phosphoric acid of phosphorous 1.7 heavy %, PH4.5 and the mixed liquor of ammoniacal liquor stirred 6 hours, and after 120 ℃ of lower dryings, pulverizing is taken out in roasting 1 hour in air under 500 ℃.
After making the aging pseudo-boehmite of identical weight according to example 3 the 2nd same procedure in the step, with phosphorous HY molecular sieve, the 2 gram beta-molecular sieve (Na of above-mentioned pulverizing
2The heavy % of O content 3.2, silica alumina ratio 28, Qilu Petrochemical company catalyst plant is produced), 28.5 gram kaolin, 17.2 gram aluminium colloidal sols and aging after pseudo-boehmite mix after, in 500 ℃ of following roastings 1.5 hours.
After the step identical with the 3rd step in the example 1, get phosphorus containing molecular sieve type catalyst E provided by the invention.
Catalyst E consists of: kaolin 38.0%, the aluminium oxide 14.2% from boehmite, the aluminium oxide 5.7% from aluminium colloidal sol, Y zeolite 36.1%, β zeolite 3.1%, P
2O
52.9%.
It is analyzed and evaluation result sees Table 5.
Comparative Examples 7
According to disclosed preparation method in the USP4970183 example, preparation HY type comparative catalyst.
Earlier with 80 gram NaY (Na
2O content 11 weighs %, silica alumina ratio 5.6, the Chang Ling catalyst plant is produced) and carry out ion-exchange with ammonium ion solution, make 75 gram HY molecular sieves, again itself and 45 grams 20 are weighed % (with phosphorous acidimeter) H
3PO
4(the NH of solution and 50 grams, 20 heavy %
4)
2SO
4The mixed solution of solution, filters after 0.5 hour at 90 ℃ of lower stirring reactions, and washing obtains phosphorous NH
4Y processes this phosphorous NH in 700 ℃ of lower steam atmospheres
4Y 2 hours obtains phosphorous HY.(Changhong chemical plant, Beijing commerical prod contains 12%SiO 40 gram silicon sol earlier then
2), 20.4 gram kaolin, 14 gram hydrated aluminum oxides (the heavy % of solid content 34.8, Qilu Petrochemical company catalyst plant is produced) mix, the more phosphorous HY of 17.6 grams is mixed with it, drying, washing, dry again, obtain HY type comparative catalyst E '.
Catalyst E ' consists of: kaolin 38.9%, sial binding agent 21.6%, Y zeolite 36.6%, P
2O
52.9%.
Relevant Analysis and evaluating data are listed in table 5.
Comparative Examples 8
Prepare catalyzer by the method described in the example 5, but in the 3rd step not to the filter cake aftertreatment that phosphorates, obtain phosphorated comparative catalyst E ".
Catalyst E " consist of kaolin 38.4%, aluminium oxide 20.0%, Y zeolite 36.5%, β zeolite 3.2, P
2O
51.9%.
Relevant Analysis and evaluating data are listed in table 5.Table 5
Catalyst | E | E ' | E " |
Specific surface, rice
2/ gram
| 233 | 208 | 238 |
Pore volume, milliliter/gram | 0.30 | 0.27 | 0.31 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 76 64 | 73 59 | 77 61 |
Heavy oil is little anti-, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 16.2 48.1 19.8 3.8 24.8 | 14.5 45.8 22.2 4.5 29.2 | 16.8 48.8 19.3 4.7 29.3 |
Can find out from table 5 data: catalyst E has comparison than catalyst E ', E " higher activity stability and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 6
Respectively to 8 gram REHY (RE
2O
3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced) and 8 gram REY molecular sieve (RE
2O
3Content is 19.5 heavy %, the production of Qilu Petrochemical Company catalyst plant) adding 24 gram concentration in is the ammonium dihydrogen phosphate of 2.0 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stirs 5 hours, and 120 ℃ of dryings are after 2 hours, roasting 1 hour in air under 600 ℃ is taken out and is pulverized.
Make 20 phosphorous REHY and the REY molecular sieve (RE that restrain after aging boehmite will be pulverized by method described in the second step of example 3
2O
319.5 heavy %, the Qilu Petrochemical Company catalyst plant is produced), 2 gram MFI structure molecular screen (Na
2The heavy % of O content 3.2, silica alumina ratio 33, the Chang Ling catalyst plant is produced), after 30 gram kaolin, the boehmite after aging and 40 gram aluminium colloidal sols mix, in 500 ℃ of lower roastings 2 hours.
With the 3rd step same steps as of example 1, but solution containing phosphate obtains phosphorated mixed molecular sieve type catalyzer F provided by the invention for being the Secondary ammonium phosphate of 0.40 heavy % in elemental phosphorous concentration.
Catalyst F consists of: kaolin 35.2%, the aluminium oxide 27.6% from boehmite, the aluminium oxide 11.6% from aluminium colloidal sol, Y zeolite 19.5%, MFI structure molecular screen 2.8%, RE
2O
32.5%, P
2O
50.8%.
Relevant Analysis and evaluating data are listed in table 6.
Comparative Examples 9
Prepare catalyzer by the method described in the example 6, but do not add ZSM-5 in second step, and add REHY, reach same molecular sieve content, this comparative catalyst F '.
Catalyst F ' consists of: kaolin 35.2%, aluminium oxide 39.2%, Y zeolite 22.2%, RE
2O
32.6%, P
2O
50.8%.
Relevant Analysis and evaluating data are listed in table 6.
Data can be found out from table 6, and catalyst F has comparison than the higher activity stability of catalyst F ' and low coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.Table 6
Catalyst | F | F ' |
Specific surface, rice
2/ gram
| 218 | 196 |
Pore volume, milliliter/gram | 0.30 | 0.29 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 77 66 | 74 61 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 17.2 47.2 21.1 4.2 22.8 | 16.1 46.3 22.0 5.6 26.5 |
Example 7
With 30 gram REHY molecular sieve (RE
2O
3Content is 3.4 heavy %, and the Qilu Petrochemical Company catalyst plant is produced) with 45.3 grams in elemental phosphorous, behind the ammonium dibasic phosphate solution mixing of 3.0 heavy %, stirred 6 hours, after 120 ℃ of lower dryings, 650 ℃ of lower roastings were taken out pulverizing after 2 hours in air.
In 20 gram boehmites, add 40 gram water, after stirring, add 7 and restrain HCl, stir after 30 minutes, acidification pseudo-boehmite is lower aging 2 hours in 80 ℃.Then the phosphorous REHY molecular sieve after the above-mentioned pulverizing, 70.5 gram kaolin with aging after boehmite and after 14.3 gram aluminium colloidal sols mix, 500 ℃ of lower roastings 2.5 hours.
With example 2 in the 3rd the step same steps as after, get molecular sieve type catalyst G provided by the invention.
Catalyst G consists of: kaolin 57.6%, the aluminium oxide 6.7% from boehmite, the aluminium oxide 2.9% from aluminium colloidal sol, Y zeolite 27.9%, RE
2O
30.9%, P
2O
54.0%.
Relevant Analysis and evaluating data are listed in table 7.
Comparative Examples 10
Prepare catalyzer by the method described in the example 7, but roasting is in 100% water vapour in the first step, and solution containing phosphate of no use is handled to filter cake in the 3rd step, obtains comparative catalyst G '.
Catalyst G consists of: kaolin 58.1%, aluminium oxide 9.7%, Y zeolite 28.2%, RE
2O
30.9%, P
2O
53.1%.
Relevant Analysis and evaluating data are listed in table 7.
Table 7
Catalyst | G | G ' |
Specific surface, rice
2/ gram
| 212 | 205 |
Pore volume, milliliter/gram | 0.28 | 0.26 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 77 69 | 78 63 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 16.0 47.6 20.8 4.0 22.2 | 16.8 48.0 20.2 4.8 26.4 |
Data can be found out from table 7, and catalyst G has comparison than catalyst G ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 8
With 36 gram USY molecular sieve (Na
2O content 0.87 heavy %, silica alumina ratio 6.8, the Qilu Petrochemical Company catalyst plant is produced) with the ammonium dihydrogen phosphate mixing of 49.8 grams, 6.5 heavy % (in the ammonium dihydrogen phosphate (ADP) amount) after, continue to stir 3 hours, 120 ℃ lower dry 2 hours, then under 500 ℃ in air roasting take out and pulverize after 1.5 hours.
With 4 gram MFI structure molecular screen (Na
2The heavy % of O content 3.0, silica alumina ratio 30, the Qilu Petrochemical Company catalyst plant is produced) with the mixed liquor mixing of 12 grams in the phosphoric acid of elemental phosphorous 1.1 heavy %, PH4.5 and ammoniacal liquor after, stirred 6 hours, after 120 ℃ of lower dryings, 700 ℃ of lower roastings were taken out and are pulverized after 2 hours in air.
In 115 gram boehmites, add 230 gram water, after stirring, add successively 41 and restrain hydrochloric acid, stir after 30 minutes, acidification pseudo-boehmite is lower aging 2.5 hours in 50 ℃.Then the phosphorous USY molecular sieve after the above-mentioned pulverizing, phosphorous MFI structure molecular screen, 2 gram beta-molecular sieve (Na
2The heavy % of O content 3.2, silica alumina ratio 28, Qilu Petrochemical company catalyst plant is produced), after the pseudo-boehmite after aging and 95 gram aluminium colloidal sols mix, 500 ℃ of following roastings 3 hours.
With the 3rd step same steps as in the example 1, just the concentration of solution containing phosphate is the ammonium dihydrogen phosphate in elemental phosphorous 0.50 heavy %, gets phosphorus containing molecular sieve type catalyzer H provided by the invention.
Catalyst H consists of: from aluminium oxide 38.2%, the aluminium oxide 19.0% from aluminium colloidal sol, Y zeolite 34.3%, MFI molecular sieve 3.8, β zeolite 1.9%, the P of boehmite
2O
52.8%.
Relevant Analysis and evaluating data are listed in table 8.
Comparative Examples 11
Press the method Kaolinite Preparation of Catalyst described in the example 8, but roasting is in 100% steam in the first step, and the 3rd the step in not with solution containing phosphate to the capable processing of filter cake, obtain the comparative catalyst and be denoted as H '.
Catalyst H ' consists of: aluminium oxide 57.5%, Y zeolite 34.5%, MFI molecular sieve 3.8, β zeolite 1.9%, P
2O
52.2%.
Relevant Analysis and evaluating data are listed in table 8.
Comparative Examples 12
According to disclosed method among the EP252761, with 50 gram USY molecular sieve (Na
2O content 0.87 heavy %, silica alumina ratio 6.8, the Qilu Petrochemical Company catalyst plant is produced) 700 ℃ of lower processing after 16 hours in 100% steam, get wherein 30 grams, in the ammonium dihydrogen phosphate of 1096.3 grams, 6.3 heavy % (in the ammonium dihydrogen phosphate (ADP) amount) 65.6 ℃ lower process 2 hours after, filter, drying in 538 ℃ of lower roastings 2 hours, is mixed with 47 gram (butt weight) silica-alumina gels that contain 25 heavy % aluminium oxide again, make phosphorous comparative catalyst, be denoted as H ".
Catalyst H " consist of: sial binding agent 59.3%, Y zeolite 37.9%, P
2O
52.8%.
Relevant Analysis and evaluating data are listed in table 8.
Table 8
Catalyst | H | H ' | H " |
Specific surface, rice
2/ gram
| 248 | 230 | 232 |
Pore volume, milliliter/gram | 0.34 | 0.32 | 0.31 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 80 68 | 79 63 | 79 64 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 17.6 49.8 19.9 4.1 26.3 | 16.6 49.3 20.8 5.4 31.7 | 17.1 49.3 20.2 5.0 31.2 |
Data can be found out from table 8, and catalyst H has comparison than catalyst H ' and H " higher activity stability and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 9
Will be in elemental phosphorous, the 450ml ammonium dibasic phosphate solution of phosphorous 100 grams per liters adds 2 kilograms (dry basis) wetting REHY molecular sieve (RE without washing
2O
3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced) after, mixing stirred 8 hours, in 100 ℃ lower dry 2 hours, then roasting 2 hours in air under 500 ℃.
In the making beating tank, in 2.74 kilograms boehmite, add 4 kg of water, pull an oar after 30 minutes, add again the hydrochloric acid of 705 grams, 37 heavy %, stir after 1 hour, 85 ℃ of lower wearing out 2 hours, add then 1.86 kilograms of kaolin, 2 kilograms in water, 1.14 kilograms of aluminium colloidal sols, pulled an oar 30 minutes.
With phosphorous rare earth hydrogen Y zeolite and the 200 gram MFI structure molecular screen (Nas of roasting after 2 hours
2The heavy % of O content 3.2, silica alumina ratio 33, the Chang Ling catalyst plant is produced), 3 kg of water add another making beating tank, pull an oar after 2 hours, join in the making beating tank that second step mentions, the homogeneous 5 hours of pulling an oar again, then spray-drying.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and is that the diammonium hydrogen phosphates of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst I provided by the invention.
Consisting of of catalyst I: kaolin 30.5%, the aluminium oxide 18.4% from boehmite, the aluminium oxide 4.6% from aluminium colloidal sol, Y zeolite 37.4%, MFI structure molecular screen 3.9%, RE
2O
31.3%, P
2O
53.9%.
Relevant Analysis and evaluating data are listed in table 9.
Comparative Examples 13
Press the method Kaolinite Preparation of Catalyst described in the example 9, but the amount of the ammonium dibasic phosphate solution that adds in the first step is 877ml, roasting is in 100% steam, and the 4th the step in not with solution containing phosphate to the capable processing of filter cake.This comparative catalyst's note is made I '.
The catalyst I ' consist of: kaolin 30.5%, aluminium oxide 23.0%, Y zeolite 37.4%, MFI structure molecular screen 3.9%, RE
2O
31.3%, P
2O
53.9%.
Relevant Analysis and evaluating data are listed in table 9.Table 9
Catalyst | I | I ' |
Specific surface, rice
2/ gram
| 238 | 203 |
Pore volume, milliliter/gram | 0.30 | 0.27 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 81 73 | 75 64 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 16.8 49.2 20.2 4.4 23.1 | 15.8 47.2 21.3 4.9 26.8 |
Data can be found out from table 9, and the catalyst I has comparison than catalyst I ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 10
Will be in elemental phosphorous amount, the 400ml phosphoric acid of phosphorous 150g/l and ammoniacal liquor mixed solution add the wetting REHY molecular sieve (RE through washing of 2.7 (with the butt restatements) kilogram
2O
3Content is 6.0 heavy %, and the Qilu Petrochemical Company catalyst plant is produced) after, mixing stirred 5 hours, in 100 ℃ lower dry 2 hours, then roasting 4 hours in air under 500 ℃.
In the making beating jar, add 2 kilograms of kaolin, pull an oar after adding 4 kg of water, the pseudo-boehmite that in the making beating jar, adds 4.9 kilograms then, pull an oar after 2 hours, add the hydrochloric acid of 1.26 kilogram of 37 heavy %, stir after 1 hour, wore out 2 hours down at 75 ℃, add 3.4 kilograms of aluminium colloidal sols then, pulled an oar 1 hour.
With phosphorous REHY type molecular sieve and the 300 gram MFI structure molecular screen (Nas of roasting after 4 hours
2The heavy % of O content 3.0, silica alumina ratio 30, Qilu Petrochemical company catalyst plant is produced), 4.5 kg of water add another making beating jar, pull an oars after 2 hours, join the 2nd and go on foot in the making beating jar of mentioning, the homogeneous 5 hours of pulling an oar again, spraying drying then.
The catalyst that spray-drying is obtained washs in order to the elemental phosphorous phosphoric acid solution of counting 1.0 heavy % on filter under 60 ℃, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst J provided by the invention.
Catalyst J consists of: kaolin 23.1%, the aluminium oxide 23.2% from boehmite, the aluminium oxide 9.7% from aluminium colloidal sol, Y zeolite 34.5%, MFI structure molecular screen 4.1%, RE
2O
32.2%, P
2O
53.2%.
Relevant Analysis and evaluating data are listed in table 10.
Comparative Examples 14
Press the method Kaolinite Preparation of Catalyst described in the example 10, but the amount of the mixed solution that adds in the first step is 691ml, and the 4th the step in not with solution containing phosphate to the capable processing of filter cake.This comparative catalyst's note is made J '.
Catalyst J ' consists of: kaolin 23.1%, aluminium oxide 32.9%, Y zeolite 34.5%, MFI molecular sieve 4.1%, RE
2O
32.2%, P
2O
53.2%.
Relevant Analysis and evaluating data are listed in table 10.Table 10
Catalyst | J | J ' |
Specific surface, rice
2/ gram
| 235 | 209 |
Pore volume, milliliter/gram | 0.31 | 0.27 |
800 ℃/17hr of 800 ℃/4hr | 79 70 | 75 63 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 17.4 50.1 19.8 5.1 22.6 | 16.2 47.8 22.3 5.8 25.8 |
Data can be found out from table 10, and catalyst J has comparison than catalyst J ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 11
To add 3.8 kilograms (dry basis) wetting REHY molecular sieve (RE through washing in 400ml phosphoric acid and the ammoniacal liquor mixed solution of elemental phosphorous amount 150 grams per liters
2O
3Content is 6.0 heavy %, and the Qilu Petrochemical Company catalyst plant is produced) after, mixing continues to stir 3 hours, in 100 ℃ lower dry 2 hours, then roasting 3 hours in air under 650 ℃.
The boehmite that adds 6.5 kilograms in the making beating tank, add again 10 kg of water, pull an oar after 2 hours, the hydrochloric acid that adds 1.67 kilogram of 37 heavy %, stir after 2 hours, 65 ℃ of lower wearing out 1 hour, in the making beating tank, add 12.7 kilograms of aluminium colloidal sols making beating 1 hour then, add again 4 kilograms of kaolin, pulled an oar 2 hours.
With phosphorous REHY type molecular sieve and the 250 gram MFI structure molecular screen (Nas of roasting after 3 hours
2The heavy % of O content 3.0, silica alumina ratio 30, Qilu Petrochemical company catalyst plant is produced), 250 gram beta-molecular sieve (Na
2The heavy % of O content 3.2, silica alumina ratio 28, Qilu Petrochemical company catalyst plant is produced), 6.5 kg of water add another making beating jar, pull an oars after 3 hours, join the 2nd and go on foot in the making beating jar of mentioning, the homogeneous 4 hours of pulling an oar again, spraying drying then.
The catalyst that spray-drying is obtained washs in order to the elemental phosphorous phosphoric acid solution of counting 0.80 heavy % on filter under 60 ℃, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst K provided by the invention.
Catalyst K consists of: kaolin 26.4%, the aluminium oxide 17.5% from boehmite, the aluminium oxide 20.7% from aluminium colloidal sol, Y zeolite 27.7%, MFI structure molecular screen 1.9%, RE
2O
31.8%, β zeolite 1.9%, P
2O
52.1%.
Relevant Analysis and evaluating data are listed in table 11.
Comparative Examples 15
Prepare catalyzer by the method described in the example 11, but the roasting of molecular sieve is in 100% steam atmosphere in the first step.This comparative catalyst's note is made K '.
Catalyst K ' consists of: kaolin 26.4%, aluminium oxide 38.2%, Y zeolite 27.7%, MFI structure molecular screen 1.9%, RE
2O
31.8%, β zeolite 1.9%, P
2O
52.1%.
Relevant Analysis and evaluating data are listed in table 11.Table 11
Catalyst | K | K ' |
Specific surface, rice
2/ gram
| 230 | 211 |
Pore volume, milliliter/gram | 0.31 | 0.28 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 79 68 | 76 62 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 16.9 48.6 19.6 5.0 23.7 | 16.4 47.4 21.8 5.9 26.2 |
Data can be found out from table 11, and catalyst K has comparison than catalyst K ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.
Example 12
Will be in elemental phosphorous amount, the 540ml phosphoric acid of phosphorous 150g/l and ammoniacal liquor mixed solution add 4 kilograms (with butt restatement) wetting REHY (RE through washing
2O
3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced) behind the molecular sieve, mixing stirred 2 hours, in 100 ℃ lower dry 2 hours, then roasting 2 hours in air under 700 ℃.
In the making beating jar, add 4.7 kilograms of kaolin, pull an oar after adding 6 kg of water, the pseudo-boehmite, the 724 gram rare earth chlorides that in the making beating jar, add 11.9 kilograms then, pull an oar after 3 hours, add the hydrochloric acid of 3.1 kilogram of 37 heavy %, stir after 1 hour, wore out 2 hours down at 70 ℃, add 15.87 kilograms of aluminium colloidal sols then, pulled an oar 1 hour.
With roasting phosphorous REHY molecular sieve and 1 kilogram of REHY molecular sieve (RE after 2 hours
2O
3Content is 3.4 heavy %, and the Chang Ling catalyst plant is produced), 667 gram MFI structure molecular screen (Na
2The heavy % of O content 3.2, silica alumina ratio 33, the Chang Ling catalyst plant is produced), 7 kg of water add another making beating tank, pull an oars after 2 hours, join the 2nd and go on foot in the making beating tank of mentioning, the homogeneous 5 hours of pulling an oar again, then spray-drying.
The catalyst that spray-drying is obtained washs in order to the elemental phosphorous phosphoric acid solution of counting 1.2 heavy % on filter under 60 ℃, and after the filtration, 100 ℃ lower dry, namely gets phosphorus containing molecular sieve catalyst L provided by the invention.
Catalyst L consists of: kaolin 22.4%, the aluminium oxide 23.1% from boehmite, the aluminium oxide 18.6% from aluminium colloidal sol, Y zeolite 27.0%, MFI structure molecular screen 3.7%, RE
2O
32.8%, P
2O
52.4%.
Relevant Analysis and evaluating data are listed in table 12.
Comparative Examples 16
Prepare catalyzer by the method described in the example 12, but solution containing phosphate of no use is handled to molecular sieve in the first step, just the water with equivalent replaces solution containing phosphate, makes comparative catalyst L '.
Catalyst L ' consists of: kaolin 22.6%, aluminium oxide 43.2%, Y zeolite 27.3%, MFI structure molecular screen 3.7%, RE
2O
32.8%, P
2O
51.4%.
Relevant Analysis and evaluating data are listed in table 12.Table 12
Catalyst | L | L ' |
Specific surface, rice
2/ gram
| 236 | 249 |
Pore volume, milliliter/gram | 0.31 | 0.33 |
Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 80 68 | 81 65 |
Fixed fluidized bed, olefin(e) centent in the heavy % casing head gasoling light diesel fuel coke gasoline, heavy % | 17.2 49.2 19.9 4.9 23.7 | 17.6 49.5 19.3 6.1 27.3 |
Data can be found out from table 12, and catalyst L has comparison than catalyst L ' more high-activity stable and lower coking yield, and lower olefin(e) centent is arranged in the gasoline fraction.