CN101204668B - Propylene production increasing cracking catalyst and preparation method thereof - Google Patents
Propylene production increasing cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalytic cracking catalyst for producing more propene, which is characterized in that: the invention is a compound that comprises ZSM-5 zeolite, Y zeolite, ferric oxide modified silicon alumina oxide, kaolin, phosphoric oxide and alumina adhesive, wherein, the ZSM-5 zeolite accounts for 1 to 4 percent, the Y zeolite accounts for 20 to 40 percent, the ferric oxide modified silicon alumina oxide accounts for 5 to 20 percent, the phosphoric oxide accounts for 0.5 to 10 percent, the kaolin accounts for 10to 40 percent and the alumina adhesive accounts for 15 to 40 percent. Sodium silicate and aluminum sulfate are precipitated according to the proportion of 75 to 80 percent of SiO2 and 20 to 25 percent of Al2O3 before being washed by deionized water, and the ferric oxide modified silicon alumina oxide is obtained after being modified by 0.1 to 2 percent of the ferric oxide. The compounds are moulded through spray drying and the chemical composition is that: Al2O3 >= 25 percent, NaO2 <= 0.1 percent, 2 to 6 percent of RE2O3, 0.1 to 1.0 percent of Fe2O3, 0.5 to10 percent of P2O5 and the balance of SiO2. When the catalyst prepared by the method is used in a catalytic cracking unit, liquefied gas yield is increased and the yield of the propene in the liquefied gas is evidently improved as well.
Description
The present invention relates to the catalytic cracking catalyst and preparation method thereof of a kind of producing more propylene of petroleum refining and petrochemical industry, the present invention relates to or rather a kind of in catalytic cracking process, can effectively improve product distribute in catalytic cracking catalyst and preparation method thereof of productivity of propylene.
Propylene is one of important foundation raw material of development petrochemical industry, is mainly used in to produce polypropylene, acrylonitrile, expoxy propane, isopropylbenzene, oxo-alcohols, isopropyl alcohol and acrylic acid etc.Propylene is fastest-rising in the world petrochemical industry product, world's propylene demand was from 1,800 ten thousand tons of 5,000 ten thousand tons of rising to 2000 in 1980, average annual growth by 6.3%, estimate to reach about 7,800 ten thousand tons in 2008, a period of time from now on, propylene is the product that is considered to have the very big market potentiality, if do not manage to increase the output of propylene, the propylene breach will reach more than 500 ten thousand tons in 2010.
Steam cracking is traditional preparation method, and as CN1665911A, CN10035138 were disclosed, CN1753973A, CN1753974A and CN1756829A disclosed a kind of common method from naphtha pyrolysis production propylene.
CN1182089C, CN1189434C, CN1192994C, CN1704389A, CN1151105C, CN1156417C, CN1259293C, CN1235845C, CN1274645C series of patents disclose under 400-600 ℃ of steam condition the prior art that the lower carbon four of superfluous relatively added value and above cut alkene thereof are carried out catalytic cracking for producing propylene using that adopts the ZSM-5 zeolite catalyst.CN1176213A similar with it, CN1272295C, CN1762931A, CN1274342A, CN1653020A, EP1061116A1, EP010905, EP0305720, USP5981818, USP5981819A, USP6049017, WO99/57226, WO99/29805, WO2004/009519, WO00/26163 adopt pentasil type zeolite catalyst that the light olefin catalyzed conversion is produced propylene; It is raw material to the alkane of carbon 12 that WO90/11338 then adopts carbon four; USP5414181 and USP5447622 produce light olefin with low-carbon alkanes.These patented technologies have disclosed and have adopted the ZSM-5 zeolite can be very effectively carbon four to be converted into propylene to alkene or the alkane cracking of carbon 12.
It is to come from some preparation methods not too commonly used that 2% propylene is arranged approximately, discloses with the low-carbon alkene disproportionation as CN1277608C, CN1721376A, CN1033246A, USP6271430, USP5898091, USP6166279, USP5300718, USP5877365, USP6624338, USP5120894, USP373785957, USP6271430, USP2002/0175110A1, EP0304515A, EP1379489, WO0014038 etc. and has produced propylene; CN1639091A, USP6207115 and CN1642887A have then adopted the rapid polymerization-cleavage method of double decomposition, metathesis reaction and multistep to produce propylene from low-carbon alkene.
Though propylene has 66% to come from steam cracking method production approximately, but because the easy coking of high-temperature cracking furnace, therefore steam cracking device only is suitable for processing lightweight material oil, as natural gas, naphtha and light diesel fuel, but because crude oil is more and more heavier, yield of light oil such as naphtha are tending towards on the low side, the raw material imbalance between supply and demand of steam cracking and catalytic reforming is serious day by day, adopt the catalytic cracking process producing more propylene of heavy charge just particularly important, it is to come from catalytic cracking process that 32% propylene is arranged in fact approximately, fluid catalytic cracking (FCC) is the main processes of heavy oil lighting in the petroleum refining industry always, but the general propone output of conventional catalytic cracking process only is 3-5%.The ZSM-5 class is selected the type zeolite and is begun to be used for catalytic cracking catalyst and be used to improve octane number and increased low-carbon alkene simultaneously since the beginning of the eighties, as USP4309280, USP3758083, USP3758403, USP5318696, USP5997728, CN1124892C, CN1031834A, CN1085885, CN1124892C, CN1170030A, CN1465527A are disclosed.
Utilizing catalytic cracking process to produce propylene generally has four methods, and carbon two and C 4 olefin metathesis reaction production propylene in catalyst system (3) selectivity circulation naphtha component (4) catalytic cracking process are optimized in (1) high severity operation (2).
Prior art by change catalytic cracking process condition increased low carbon olefine output is a lot, is exactly to have adopted higher reaction temperature and oil ratio such as harsher reaction condition (Deep Catalytic Cracking process) USP4826586, USP4966681, USP4980053, USP6566293, USP5904837, WO00/31215A1, CN1667089A, CN10223333A, CN1069016A, CN1072203A, CN1034223C, ZL93119748.1 etc.
CN1332781A, CN1760342, CN02116786.9, CN02139064.9, CN02123817.0, USP4830728, USP5389232, USP5456821, USP5879535, USP6106697, USP3928172 and US2002/0003103A1 then are that the Cracking catalyst that has adopted duo-lift tube reactor and faujasite and ZSM-5 zeolite to form increases light olefin output.
Adopting the lighter hydrocarbons circulation also is the process of a class propylene enhancing, as CN1753973A, CN1753974A, CN1756829A, CN1710031A, EP490435B, EP372632B, EP385538A, USP5069776, USP3928172, USP6037294A etc., CN1643112A then adopts heavy charge and lightweight material to mix mutually and produces propylene and gasoline, and CN1380898A, CN1380899A, CN1383448A, CN1205154C are the raw material propylene enhancing with part naphtha C-4-fraction then.Though these prior arts have increased the output of low-carbon alkene or the output of liquefied gas, but change process conditions and increase the inconvenience that propone output often brings scrap build investment increasing and product distribution causing aspects such as bigger variation, lighter hydrocarbons then bring the problem of the raw material anxiety identical with steam cracking again as part material.
In order to satisfy global growing wilderness demand, still must explore the channel of various production propylene to propylene.By optimizing catalyst formulation or in catalytic cracking process, using the co-catalyst of propylene enhancing to be undoubtedly very simple and feasible method, adopt the liquid adjuvants pattern to increase the productivity of propylene of catalytic cracking process such as CN1690166, USP5997728 uses the solid additive pattern to allow in system's reserve the ratio of ZSM-5 zeolite reach 3% increases productivity of propylene, CN1796498A, adopted the ZSM-5 zeolite co-catalyst of metal and phosphorous oxides modification to come propylene enhancing, be undoubtedly method very easily by new catalyst volume increase catalytic cracking production propylene, as USP3758403, USP5110776, USP6566293, USP2002/0049133, adopt modified ZSM-5 to combine to be prepared into Cracking catalyst and be used in the catalytic cracking process increased low carbon olefine output with the Y zeolite facies, it has used a large amount of ZSM-5 zeolites, even up to more than 30% to improve the productive rate of alkene, the easy so very big change that causes the catalytic cracking process product to distribute brings inconvenience.Except adopting the ZSM-5 zeolite, some has also introduced the zeolite constituent element of other structure, and introducing SAPO-34 zeolite activity constituent element as USP6049017 increases propone output in the catalytic cracking process.
These prior arts generally all are that the ZSM-5 zeolite is carried out metal and phosphorus modification, but find in actual the use because ZSM-5 zeolitic acid density is low, adopt metal oxide to zeolite direct modification often cover the performance that the acid site influences the shape selective catalysis performance.At present, at the overwhelming majority's catalytic cracking unit, under the prerequisite of identical liquefied gas yield, the concentration that improves the propylene in the liquefied gas is the important channel of improving the catalytic cracking unit benefit.The catalytic cracking catalyst of the disclosed propylene enhancing of prior art or co-catalyst, owing to only paid attention to modification to the ZSM-5 zeolite, not focusing on the secondary that forms rational crackate in the cracking process transforms, thereby just improved the selectivity of low-carbon alkene, and the selectivity for propylene is very not desirable in the catalytic cracking reaction process of reality, thereby the amplitude that improves productivity of propylene in the liquefied gas also is restricted.
At above the deficiencies in the prior art, the purpose of this invention is to provide a kind of improved catalytic cracking catalyst that in catalytic cracking process, can effectively improve productivity of propylene in the product distribution and preparation method thereof.It mainly is to have introduced the sial active component that a class has the ferriferous oxide modification that increases medium size olefin hydrocarbon molecules productive rate in carrier, and make with the mixed-forming such as main active component Y zeolite, ZSM-5 zeolite on the catalyst, to be the active component that can adopt different apertures to greatest extent be converted into the hydrocarbon molecule echelon reaction of large-size middle-sized alkene and finally be converted into propylene product advantage, thereby obtain the purpose of productivity of propylene in the increase cracking liquefied gas of better effect.
The prepared catalytic cracking producing more propylene catalyst of the present invention has adopted three kinds of active components with different aperture sizes and catalysis to achieve these goals, be that the Y zeolite is brought into play as main active component outside the cracking function of similar zeolite in the general Cracking catalyst, the ZSM-5 zeolite that the large-size hydrocarbon molecule is cracked into the sieve and silica-sesquioxide of medium size olefin hydrocarbon molecules function and has a shape selective catalysis function that has of metal oxide modified carries out complementary other two kinds of active components.In order to keep other functions such as the due intensity of catalyst, big molecule conversion capability, anti-metallic pollution ability, also adopted aluminium oxide, kaolin as binding agent and filler, and provide necessary surface area and pore volume, in order to keep the hydrothermal stability under the superheated vapor condition of regenerator in the use, also introduced phosphorous oxides catalyst has been carried out modification.
The composition of the catalytic cracking catalyst of this producing more propylene comprises: a kind of composition that the sieve and silica-sesquioxide of ZSM-5 zeolite, Y zeolite, a kind of ferriferous oxide modification, kaolin, phosphorous oxides and alumina binder constitute, wherein the ZSM-5 zeolite accounts for 1～4%, the Y zeolite accounts for 20～40%, the sieve and silica-sesquioxide of ferriferous oxide modification accounts for 5～20%, phosphorous oxides accounts for 0.5～10%, kaolin accounts for 10～40%, alumina binder accounts for 15～40%, spray-dried moulding is prepared into the microspheric catalytic cracking catalyst with said composition, and its chemical composition is: Al
2O
3〉=25%, Na
2O≤0.1%, RE
2O
30～6%, Fe
2O
30.1 P～1.0%,
2O
50.5～10%, surplus is SiO
2
ZSM-5 zeolite in the catalytic cracking catalyst of this producing more propylene accounts for 1～4%, and preferably 2～3%.
The sieve and silica-sesquioxide of ferriferous oxide modification is by SiO by sodium metasilicate and aluminum sulfate
275～80%, Al
2O
3After 20～25% ratio co-precipitation and the deionized water washing, ferriferous oxide modification with 0.1～2%, 400～600 ℃/0.5～4 hour steam roasting and grind that the back obtains, the content of the sieve and silica-sesquioxide of this ferriferous oxide modification in catalyst is 5～20%, preferably 10～15%.
Wherein the ferriferous oxide used of modification is the soluble salts of iron, as ferric nitrate, ferric sulfate, iron chloride etc., and forms ferriferous oxide in roasting process.
Content as the aluminium oxide of binding agent is 10～40%, preferably 20～30%; Aluminium oxide can adopt aluminium colloidal sol or sour molten boehmite etc.
Phosphorous oxides wherein is 0.5～10%, preferably 1～5%, and phosphorous oxides can adopt phosphorus pentoxide, phosphorus ammonium salt class, phosphoric acid etc.
Said kaolinic content is 10～40% in this catalyst, preferably 20～30%; Also can select one or more the mixture in other natural inorganic filler halloysites, roasting china clay, imvite, diatomite, bentonite, attapulgite and the sepiolite for use.
180～280 meters of the specific areas of the catalyst after the spray-dried moulding
2/ gram, pore volume are 0.2～0.4 milliliter/gram, and apparent bulk density is 0.6～0.8g/ml; In the size distribution＜20 microns account for 5%～15%, 40～80 micron account for 50%～60%,＞80 microns account for 20%～30%, abrasion index＜2.5% (m/m).
The step of this catalytic cracking propylene-increasing catalyst of preparation the present invention is:
(1), sodium metasilicate and aluminum sulfate are pressed SiO
275～80%, Al
2O
320～25% ratio co-precipitation, the deionized water washing.
(2), adopt the soluble salt of 0.1～2% ferriferous oxide be immersed on the above-mentioned sieve and silica-sesquioxide, 400～600 ℃/0.5～4 hour water vapor conditions under roasting, grind to form fine powder.
(3), the sieve and silica-sesquioxide after the above-mentioned ferriferous oxide modification is mixed the spray-dried formation microballoon of making beating with ZSM-5 zeolite, Y zeolite, phosphorous oxides, kaolin and aluminium colloidal sol/sour molten boehmite.
Catalyst provided by the invention, can be in becoming the glue process with different charging sequence drying and mouldings, silicoaluminate and phosphorous oxides after zeolite slurry, kaolin slurry, the ferroelectric metal oxide modification both can have been added earlier, add aluminium colloidal sol at last, also can add aluminium colloidal sol earlier, add sieve and silica-sesquioxide, zeolite slurry and phosphorous oxides after the ferriferous oxide modification then, add kaolin slurry at last and mix making beating, obtain finished catalyst through spray-drying, washing, pneumatic conveying drying again.
The spray drying forming of described slurries adopts conventional method and condition, and generally being controlled at exhaust temperature is 160～260 ℃, and atomisation pressure is to carry out under the condition of 50～60 atmospheric pressures.
Producing more propylene catalytic cracking catalyst of the present invention mainly is to use on catalytic cracking unit, can be used for the processing of various feedstock oils, described feedstock oil is selected from various petroleum distillates, as crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/in heavily de-oiling, wax tailings and the coal liquefaction product one or more.Described feedstock oil can contain beavy metal impurities such as nickel, vanadium and sulphur, nitrogen impurity, can be as the content of sulphur up to 3%, and the content of nitrogen can be up to 2%, and the content of metal impurities such as vanadium, nickel can be up to 3000ppm.
Catalytic cracking catalyst provided by the invention is used for catalytic cracking process, and cracking conditions is conventional catalytic cracking condition.In general, comprise that reaction temperature is 400～600 ℃, be preferably 480～520 ℃, air speed is 10～120 hours
-1, preferably 20～80 hours
-1, oil ratio is 1～20, preferably 4～10.
Compared with prior art, the catalyst of catalytic cracking producing more propylene provided by the present invention is in catalytic cracking unit, because it has introduced another active component that helps bringing into play ZSM-5 zeolite shape selective catalysis function, can improve the productive rate of propylene in the use greatly.
The following examples will the present invention is described further but are not thereby limiting the invention.
Little activity test is undertaken by the method for ASTM D-3907, and other detect referring to (" oil and oil product test method national standard " China Standard Press published 1989).
Embodiment 1
With 240 ml water glass (water glass plant, Eastern Mountain, Qingdao, SiO
2250 grams per liters, modulus 3.1) and 180 milliliters of aluminum sulfate solutions (Zibo San Feng chemical industry Co., Ltd, Al
2O
390 grams per liters) stir filtration after 30 minutes, washing, drying in 1 liter of colloid generating kettle, it is dry to flood 10% iron nitrate solution, 40 gram backs again, and the roasting of 550 ℃ of following water flowing steams was ground after 2 hours.
Getting concentration and be 30.0% USY molecular sieve pulp (Wenzhou Hua Hua group) 500 grams, ZSM-5 molecular sieve (Chemical Plant of Nankai Univ.) 15 restrains in 3 liters of colloid generating kettles, add 1200 gram water, 5 gram phosphorus pentoxide (chemical pures more successively, the Beijing Chemical Plant) and 180 the gram kaolin (Suzhou kaolin company), mix with the sieve and silica-sesquioxide of above-mentioned ferriferous oxide modification and to add 375 gram aluminium colloidal sols again after the making beating (yueyang, hunan is built long company and produced, Al
2O
320%) in colloid generating kettle, stir behind 30 clocks in the laboratory and make microballoon on small-sized spray drier, obtain the catalyst of embodiment 1 again through washing, drying.280 meters of its specific areas
2/ gram, pore volume are 0.4 milliliter/gram, and apparent bulk density is 0.71g/ml; In the size distribution＜20 microns account for 13%, 40～80 micron account for 59%,＞80 microns account for 28%, abrasion index＜2.5% (m/m).
Embodiment 2
With 156 ml water glass (water glass plant, Eastern Mountain, Qingdao, SiO
2250 grams per liters, modulus 3.1) and 120 milliliters of aluminum sulfate solutions (Zibo San Feng chemical industry Co., Ltd, Al
2O
390 grams per liters) stir filtration after 30 minutes, washing, drying in 1 liter of colloid generating kettle, it is dry to flood 1% ferric chloride solution, 15 gram backs again, and the roasting of 450 ℃ of following water flowing steams was ground after 3 hours.
Getting concentration and be 28.0% DAY molecular sieve pulp (Wenzhou Hua Hua group) 500 grams, ZSM-5 molecular sieve (Chemical Plant of Nankai Univ.) 10 restrains in 3 liters of colloid generating kettles, add 1300 gram water, 130 gram kaolin (Suzhou kaolin company) more successively, add 250 gram boehmite (Shandong Aluminum Plant, Al again mix making beating with the sieve and silica-sesquioxide of above-mentioned ferriferous oxide modification after
2O
360%) and 33 gram phosphoric acid (chemical pure, 85%, Beijing Chemical Plant) in colloid generating kettle, stir behind 30 clocks in the laboratory and make microballoon on small-sized spray drier, obtain the catalyst of embodiment 2 again through washing, drying.220 meters of its specific areas
2/ gram, pore volume are 0.34 milliliter/gram, and apparent bulk density is 0.68g/ml; In the size distribution＜20 microns account for 13%, 40～80 micron account for 58%,＞80 microns account for 29%, abrasion index＜2.1% (m/m).
Embodiment 3
With 240 premium on currency glass (water glass plant, Eastern Mountain, Qingdao, SiO
2250 grams per liters, modulus 3.1) and 185 liters of aluminum sulfate solutions (Zibo San Feng chemical industry Co., Ltd, Al
2O
390 grams per liters) stir filtration after 30 minutes, washing, drying in 1 liter of colloid generating kettle, flood behind 14 kilograms of 5% copperas solutions dryly again, the roasting of 500 ℃ of following water flowing steams was ground after 2 hours.
Get concentration and be in 30.0% 500 kilograms of REHY molecular sieve pulps (Wenzhou Hua Hua group), 15 kilograms to 3 cubic metres colloid generating kettles of ZSM-5 molecular sieve (Chemical Plant of Nankai Univ.), add 1300 kg water, 125 kilograms of kaolin (Suzhou kaolin company), 125 kilograms of boehmites (Shandong Aluminum Plant, Al more successively
2O
360%), mixes with the sieve and silica-sesquioxide of above-mentioned ferriferous oxide modification and to add 250 kg aluminium colloidal sols again after the making beating (yueyang, hunan is built long company and produced, Al
2O
320%) in colloid generating kettle, add 16 kilograms of industrial phosphoric acids (Hengyang City Raw Materials Company of Chemical Industry, 85%) at last, on spray drying tower, make microballoon after stirring 60 clocks, obtain the catalyst of embodiment 3 again through washing, drying.270 meters of its specific areas
2/ gram, pore volume are 0.4 milliliter/gram, and apparent bulk density is 0.70g/ml; In the size distribution＜20 microns account for 13%, 40～80 micron account for 58%,＞80 microns account for 29%, abrasion index＜2.2% (m/m).
Embodiment 4
The catalyst agent of the above-mentioned embodiment that makes 1～3 after breaking fast wearing out, 800 ℃/4 hours water vapours is carried out performance evaluation on small fixed flowing bed FCC experimental provision.Adopt the commercial heavy oil Cracking catalyst through after the same steam burin-in process as a comparison case and basic value.Feedstock oil character sees Table 1, the suitability for industrialized production index of embodiment 3 sees Table 2, the results are shown in Table 3.
Table 1, feedstock oil character:
| Project | |
| Density (20 ℃), kg/m 3 | 902.2 |
| Boiling range 10%, ℃ | 369 |
| 30％，℃ | 421 |
| 50％，℃ | 463 |
| 300℃，％ | 2 |
| 350℃，％ | 7 |
| Carbon residue, m% | 2.84 |
| Freezing point, ℃ | +36 |
| Total nitrogen, ppm | 2342 |
| Total sulfur, ppm | 2600 |
| Heavy metal Fe ppm | 48.13 |
| Ni?ppm | 2.73 |
| Ca?ppm | 970 |
| V?ppm | 0.8 |
The technical indicator of table 2, producing more propylene catalytic cracking catalyst
| Project | Quality index | Experimental technique |
| Al 2O 3Content, m% | ≥25 | RIPP42-90 |
| Igloss, m% | ≤10％ | RIPP32-90 |
| Abrasion index, m%/h | ≤2.5 | RIPP29-90 |
| Specific area, m 2/g | 180～280 | GB/T5816-1995 |
| Pore volume, ml/g | 0.2～0.4 | RIPP151-90 |
| ＜20um.v％ | 5％～15％ | |
| 40～80um，v％ | 50％～60％ | |
| ＞80um，v％ | 20％～30％ | |
| Apparent density, g/ml | 0.6～0.8 | RIPP32-97 |
Table 3, embodiment 1～3 and Comparative Examples performance evaluation situation:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples |
| Liquefied gas yield increases % | +2.7 | +2.1 | +2.8 | Basic value |
| Productivity of propylene increases % | +1.2 | +1.0 | +1.3 | Basic value |
| Micro-activity MAT% | 69 | 64 | 71 | 72 |
Embodiment 5
The catalytic cracking catalyst of the producing more propylene that embodiment 3 is made and Comparative Examples be the usefulness of its serviceability of check and propylene enhancing on the small-sized process units of a cover riser catalytic cracking respectively, and the performance of feedstock oil, catalyst sees Table 1,2.Main operating condition sees Table 4, and these all are consistent as far as possible, does not make big variation.The sample that product main character that embodiment 3 pilot-scales are produced and prepared in laboratory go out is consistent substantially.Also improved octane number behind the producing more propylene catalyst of use embodiment 3 under the situation with raising productivity of propylene, the variation that major product distributes remains in the reasonable range, sees Table 6.
Table 4, main operating condition:
| Project | Comparative Examples | Embodiment 3 |
| Reaction temperature | 519 | 518 |
| The first regenerator dense phase temperature, ℃ | 699 | 702 |
| The second regenerator dense phase temperature, ℃ | 707 | 706 |
| Reacting-settler pressure, MPa | 0.198 | 0.199 |
| The first regenerator pressure, MPa | 0.235 | 0.235 |
| The second regenerator pressure, MPa | 0.22 | 0.22 |
| The stripped vapor amount, kg/h | 2.0 | 1.9 |
| The feeding preheating temperature, ℃ | 223 | 222 |
| The first regenerator air quantity, m 3/h | 108 | 104 |
| The second regenerator air quantity, m 3/h | 36 | 35 |
| The fresh feed amount, kg/h | 182 | 183 |
Table 5, equilibrium catalyst character:
| Project | Comparative Examples | Embodiment 3 |
| Bulk density, g/ml | 0.8836 | 0.8934 |
| The regenerative agent carbon containing, % | 0.14 | 0.13 |
| Half regenerative agent carbon containing, % | 0.25 | 0.26 |
| Treat the regenerative agent carbon containing, % | 1.03 | 1.02 |
| Micro-activity, % | 72 | 71 |
| Heavy metal Fe, ppm | 5233 | 5214 |
| Ni，ppm | 345.6 | 342.1 |
| Ca，ppm | 970 | 958 |
| V，ppm | 133 | 142 |
Table 6, embodiment 3 prepared producing more propylene catalytic cracking catalyst and Comparative Examples products distribute:
| Project | Comparative Examples | Embodiment 3 |
| Processing capacity, kg/h | 182 | 181 |
| Product distributes, the w% dry gas | 6.2 | 6.3 |
| Liquefied gas | 9.6 | 13.0 |
| Gasoline | 37.2 | 36.0 |
| Diesel oil | 34.8 | 32.8 |
| Slurry oil | 4.3 | 4.0 |
| Coke | 7.5 | 7.4 |
| Loss | 0.4 | 0.5 |
| The productive rate that propylene increases | - | +1.5 |
| Gasoline RON increases | - | +2.0 |
| Gasoline MON increases | - | +0.8 |
Claims (7)
1. the catalytic cracking catalyst of a producing more propylene, it is characterized by this catalytic cracking catalyst is a kind of composition that is made of ZSM-5 zeolite, Y zeolite, a kind of sieve and silica-sesquioxide of ferriferous oxide modification, kaolin, phosphorous oxides, alumina binder; The ZSM-5 zeolite accounts for 1～4% in this catalytic cracking catalyst, the Y zeolite accounts for 20～40%, the sieve and silica-sesquioxide of ferriferous oxide modification accounts for 5～20%, phosphorous oxides accounts for 0.5～10%, kaolin accounts for 10～40%, alumina binder accounts for 15～40%; Its chemical composition is: Al
2O
3〉=25%, rare earth oxide RE
2O
30～6%, Na
2O≤0.1%, Fe
2O
30.1 P～1.0%,
2O
50.5～10%, surplus is SiO
2Wherein the sieve and silica-sesquioxide of ferriferous oxide modification is by SiO by sodium metasilicate and aluminum sulfate
275～80%, Al
2O
3After 20～25% ratio co-precipitation and the deionized water washing, the solution impregnation of the ferric nitrate with 0.1～2%, ferric sulfate or iron chloride, roasting 0.5～4 hour and grinding back obtain under 400～600 ℃ of water flowing steam conditions; Wherein alumina binder is an aluminium colloidal sol.
2. the catalytic cracking catalyst of producing more propylene according to claim 1 is characterized by described ZSM-5 zeolite and accounts for 2～3%.
3. the catalytic cracking catalyst of producing more propylene according to claim 1 is characterized by said Y zeolite and accounts for 25～35%, is selected from a kind of among DAY, USY, REHY, REUSY, the REY.
4. the catalytic cracking catalyst of producing more propylene according to claim 1, the sieve and silica-sesquioxide that it is characterized by described ferriferous oxide modification accounts for 10～15%.
5. the catalytic cracking catalyst of producing more propylene according to claim 1 is characterized by described alumina binder and accounts for 20～30%.
6. the catalytic cracking catalyst of producing more propylene according to claim 1 is characterized by described phosphorous oxides and accounts for 1～5%, and its mode with phosphorus pentoxide, phosphorus ammonium salt, phosphoric acid adds.
7. the catalytic cracking catalyst of producing more propylene according to claim 1 is characterized by described kaolin and accounts for 20～30%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101676182A CN101204668B (en) | 2006-12-19 | 2006-12-19 | Propylene production increasing cracking catalyst and preparation method thereof |
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| CN102229815B (en) * | 2011-05-24 | 2014-03-26 | 卓润生 | Method for preparing low carbon olefin by deep catalytic cracking of inferior oil |
| CN104492479B (en) * | 2014-12-10 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst for preparing pyridine from 3-methylpyridine and preparation method of catalyst |
| CN112657547B (en) * | 2018-06-11 | 2022-06-28 | 山东多友科技有限公司 | Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve |
| CN111748367A (en) * | 2020-06-01 | 2020-10-09 | 四川润和催化新材料股份有限公司 | Method for improving yield of ethylene and propylene by catalytic cracking/thermal cracking of bio-oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN1796496A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for raising density of propylene |
| CN1796498A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for increasing production of propylene |
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| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN1796496A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for raising density of propylene |
| CN1796498A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for increasing production of propylene |
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