CN1055301C - Cracking catalyst for producing isomeric olefine and gasoline with high yield - Google Patents
Cracking catalyst for producing isomeric olefine and gasoline with high yield Download PDFInfo
- Publication number
- CN1055301C CN1055301C CN96100782A CN96100782A CN1055301C CN 1055301 C CN1055301 C CN 1055301C CN 96100782 A CN96100782 A CN 96100782A CN 96100782 A CN96100782 A CN 96100782A CN 1055301 C CN1055301 C CN 1055301C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- heavy
- earth
- rare
- described catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a cracking catalyst for producing isoalkene and high-octane gasoline with high yield, which is prepared from 5 to 70% of composite aluminium-base binding agent, 5 to 65% of clay and 23 to 50% of mixed zeolite (measured according to the catalyst weight as the reference). The catalyst is suitable for the catalytic cracking of raw oil, such as wax oil, residual oil, raw oil having a high vanadium content, having various properties. The catalyst in used can make the total yield of isobutylene and isoamylene reach 10.11 to 13.73 wt%, make the gasoline yield reach 41.5 to 48.5 wt%, make the RON yield reach 95.6 to 96.4 wt% and make the MON yield reach 80.5 to 81.3 wt%.
Description
The invention relates to a kind of cracking catalyst, specifically.Be to be used for the cracking catalyst that catalytic cracking petroleum hydrocarbons is produced low-carbon (LC) isomeric olefine and stop bracket gasoline about a kind of.
Along with the petrochemical complex industrial expansion, catalytic cracking process is not only the important means that light-end products are provided, and also provides simultaneously a kind of processing mode of basic Organic Chemicals such as alkene.Because readjusting of gasoline prescription, requiring in the gasoline has certain oxygen level, and oxygenatedchemicalss such as MTBE, TAME will progressively add in the gasoline.As raw material-iso-butylene and the isopentene of MTBE, TAME, its demand will increase day by day.Therefore require cracking catalyst that the selectivity of isomeric olefine is improved to some extent.Common catalytic cracking is only producing lightweight oil, though also by-product liquefied gas.But output seldom, only accounts for below the 10 heavy % of stock oil, and wherein the output of iso-butylene and isopentene just still less only accounts for about 5 heavy % of raw material.
In order to improve gasoline octane rating and olefin yield, people had once done a large amount of effort, for example CN 1072201A, CN 1093101A, CN 1098130A and CN 1085825A etc.But in the process of catalytic cracking, it is still rare to improve gasoline output and octane value and increase the research of isomeric olefine yield aspects.For example in NPRA meeting in 1992, the result of study of the Davison of U.S. W.R.Grace company chemistry branch report shows, add ZSM-5 and help high yield of isobutene, isopentene in the OCTACAT catalyzer, but the productive rate of gasoline but decreases
In CN1103105A, disclosed the cracking catalyst of a kind of high yield of isobutene and isopentene, by HZSM-5,1～5% high silicon HZSM-5 of 5～25% modifications, 5～20%USY zeolite, four kinds of active ingredients of 1～5% β zeolite and form as 30～60% natural claies of carrier and 15～30% inorganic oxides.Use this catalyzer, though RON can reach 93～94, MON is 81～82, and gasoline yield is 36.84～45.09%, and the overall yield of iso-butylene and isopentene only is 9.40～10.61%.
A kind of catalysis conversion method of low-carbon olefines high-output is disclosed among the CN1102431A, wherein used the catalyzer of being made up of 0～70% clay, 5～90% inorganic oxides and 10～35% zeolites, to be the y-type zeolite that contains rare earth by 0～75% type-Y high silicon zeolite and 0～25% become to be grouped into for three kinds with the five-ring supersiliceous zeolite of 25～100% phosphorous and rare earth active ingredient.Use this catalyzer, the overall yield of iso-butylene and isopentene reaches as high as 13%, and this moment, gasoline yield was 26～43%.
Disclosed a kind of producing in high-yield olefin catalyzer among the CN1099788A is made up of the ZSM-5 zeolite of the y-type zeolite of 20～80% semi-synthetic carriers of being made up of kaolin and al binder and 10～50% lattice constants≤2.450nm, 2～40% modifications, beta-zeolite and composition thereof.Use this catalyzer, though the overall yield of iso-butylene and isopentene can reach 10～13%, gasoline yield only is 35～42%.
In sum, existing cracking catalyst all can not keep higher gasoline output and octane value when improving the isomeric olefine productive rate.
In addition, disclose a kind of composite aluminum base binding agent in CN1098130A, this binding agent has improved the wear resistance and the coke selectivity of semi-synthetic carrier cracking catalyst
The objective of the invention is to provide on the basis of above-mentioned prior art a kind of new catalyst, it can improve iso-butylene and isopentene productive rate, can make gasoline output and octane value maintain higher level again.
Catalyzer provided by the invention has following composition (is benchmark in the catalyst weight): 5～70% the composite aluminum base binding agent of being made up of according to 1: 9 to 9: 1 weight ratio pseudo-boehmite and aluminium colloidal sol, 5～65% clay and 23～50% zeolite, said zeolite are that the phosphorus content of 15～82% y-type zeolite and surplus is (with P
2O
5Meter) is the mixture that contains rare-earth five-membered ring supersiliceous zeolite and/or HZSM-5 zeolite of 0～10 heavy %, wherein when said phosphorus content was containing rare-earth five-membered ring supersiliceous zeolite and said HZSM-5 zeolite and existing simultaneously of 0～10 heavy %, phosphorus content was that the rare-earth five-membered ring supersiliceous zeolite content that contains of 0～10 heavy % is no more than 65%.
In this catalyzer used clay be natural or synthetic, through or handle without various chemistry and/or physical method, usually as the various clays of cracking catalyst carrier.As kaolin, halloysite etc.
Used y-type zeolite is that content of rare earth is (with RE in this catalyzer
2O
3Meter) is y-type zeolite and/or the REHY zeolite of 0～5 heavy %, lattice constant＜2.455nm.Said content of rare earth is that the y-type zeolite of 0～5 heavy %, lattice constant＜2.455nm obtains through chemistry and/or physical method stabilization treatment, the ultrastable Y that obtains with hydrothermal method for example, the type-Y high silicon zeolite that obtains with liquid phase method or vapor phase process aluminium-eliminating and silicon-replenishing.The content of rare earth of said REHY zeolite is (with RE
2O
3Meter) is 2～16 heavy %.
Phosphorus content used in this catalyzer is (with P
2O
5Meter) be 0～10 heavy % to contain rare-earth five-membered ring supersiliceous zeolite (following brief note is the ZRP zeolite) be by USP5,232, method preparation disclosed in 675, be raw material promptly with water glass, aluminum phosphate, mineral acid, with REY or REHY zeolite is crystal seed, 130～200 ℃ of following crystallizations 12～60 hours, promptly getting not, phosphorated contained the rare-earth five-membered ring supersiliceous zeolite;
Exchanging processing as the five-ring supersiliceous zeolite that contains rare earth with above-mentioned gained in advance with ammonium ion makes its sodium content (with Na
2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al
2O
3: P
2O
5=1: 1～3 aluminum phosphate colloid is according to P
2O
5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and have roasting down 5～6 hours in 300～600 ℃, 10～100% water vapors, can obtain phosphorous and the rare-earth five-membered ring supersiliceous zeolite.
Catalyzer method for making provided by the invention is as follows:
(1) preparation zeolite water slurries: zeolite is mixed with decationized Y sieve water, glue be milled to granularity less than 6 μ m till;
(2) preparation support of the catalyst slurries: decationized Y sieve water, binding agent and clay are mixed, and being mixed with solid content is the slurries of 10～50 heavy %, stirs, under 20～80 ℃, left standstill aging 0～2 hour,
(3) above-mentioned zeolite water slurries are joined in the support of the catalyst slurries, and mix, homogeneous, spraying drying;
(4) roasting or optional with ammonium hydroxide and/or ammonium phosphate solution washing and dry.
The advantage of catalyzer provided by the invention is
1. applicable raw materials wide ranges, the stock oil that can be used for various character, for example the catalytic cracking of wax oil, residual oil, high content of vanadium stock oil is for example on medium-sized riser arrangement, catalyzer provided by the invention is the stock oil of 5.2ppm for content of vanadium, still can make the overall yield of iso-butylene and isopentene reach 10.74%, C
5 +Gasoline output reaches 46.30 heavy %;
2. cracking conversion rate height, C
3 =～C
5 =Productive rate and iso-butylene, isopentene productive rate height, gasoline output and octane value height.For example on heavy oil microreactor, under identical appreciation condition, catalyzer provided by the invention is than single binding agent and do not contain transformation efficiency height, the C of the catalyzer of y-type zeolite
3 =～C
5 =Overall yield height, the gasoline output height of total olefin productive rate height, iso-butylene and isopentene; Under the same conditions, catalyzer of the present invention is also than the transformation efficiency and the gasoline output height of the catalyzer of high ZRP zeolite content.
In a word, in transformation efficiency is the scope of 76.4～87.0 heavy %, when can reaching 10.11～13.73% in the overall yield of iso-butylene and isopentene, catalyzer provided by the invention make gasoline output reach 41.5～48.5 heavy %, and gasoline octane rating is higher, research octane number (RON) (RON) reaches 95.6～96.4, and motor-method octane number (MON) reaches 80.5～81.3.
By means of embodiment the present invention is further specified below, but these embodiment should not be construed as any restriction to the scope of the invention.
(1) raw materials used place of production specification is as follows in the embodiment of the invention:
1. aluminium colloidal sol: Qilu Petrochemical company catalyst plant Industrial products contain Al
2O
321.6 heavy %;
2. kaolin: hard paste porcelain God in charge of the Earth Sigong industry product, solid content 78.6 heavy %;
3. pseudo-boehmite: Shandong Aluminum Plant's Industrial products, solid content 34.2 heavy %;
4.DASY zeolite: Qilu Petrochemical company catalyst plant Industrial products are y-type zeolites made from the hydrothermal dealumination method, and lattice constant is 2.445nm;
5.ZRP zeolite: Qilu Petrochemical company catalyst plant Industrial products, Na
2The heavy % in O＜1;
6.REDASY zeolite: Qilu Petrochemical company catalyst plant Industrial products are y-type zeolites made from re chloride exchange, hydrothermal dealumination method, and lattice constant is 2.452nm;
7.HZSM-5 zeolite: the commercial industrial product of silica alumina ratio 60;
8.REHY zeolite: Qilu Petrochemical company catalyst plant Industrial products, content of rare earth is (with RE
2O
3Meter) is 6.1 heavy %.
(2) method of the evaluate catalysts that adopts in the embodiment of the invention and condition:
1. the condition of evaluate catalysts on heavy oil microreactor:
Temperature of reaction is 520 ℃, weight space velocity 16h
-1, catalyst sample consumption 4 grams.Before catalyst sample is estimated in advance through normal pressure, 800 ℃, 100% steam-treated 8 hours.The performance of testing raw materials used oily A is as follows:
| Density (20 ℃), g/cm 3 | 0.8652 |
| Viscosity, mm 2/s 50℃ 100℃ | 14.58 4.37 |
| Carbon residue, heavy % | 0.04 |
| S content, heavy % | 0.42 |
| Boiling range, ℃ | 227～75 |
2. go up the condition of evaluate catalysts at small-sized cyclic catalytic cracking device (ARCO):
Temperature of reaction is 520 ℃, agent-oil ratio 8.0, atomized water 5.0 heavy %.Before catalyst sample is estimated in advance through normal pressure, 790 ℃, 100% steam-treated 10 hours.The performance of testing raw materials used oily B is as follows:
| Density (20 ℃), g/cm 3 | 0.8764 |
| Condensation point, ℃ aniline point, ℃ carbon residue, heavy % basic nitrogen, ppm | 41 97.2 0.12 304 |
| Constituent content, heavy % C H S N | 86.01 13.47 0.24 0.072 |
| Boiling range, ℃ | 223～544 |
3. the condition of evaluate catalysts on medium-sized riser arrangement:
Temperature of reaction is 530 ℃, reaction pressure 127KPa.Before catalyst sample is estimated in advance through normal pressure, 790 ℃, 100% steam-treated 4 hours.The performance of testing used stock oil C and D is as follows:
| The stock oil title | C | D |
| Density (20 ℃), g/cm 3 | 0.8788 | 0.8884 |
| Viscosity, mm 2/s 80℃ 100℃ | - - | 15.45 9.17 |
| Condensation point, ℃ aniline point, ℃ carbon residue, heavy % basic nitrogen, ppm | 45 101.5 0.1 232 | 40 94.8 2.04 704 |
| Constituent content, heavy % C H S N | 86.22 13.29 0.27 0.20 | 86.79 12.70 0.32 0.16 |
| Boiling range, ℃ | 278～506 | 232～538 |
| Heavy metal content, ppm Fe Ni Cu V Na | - - - - - | 5.8 3.6 0.1 5.2 1.2 |
Embodiment 1～2
Preparation of catalysts provided by the invention and the cracking performance of on heavy oil microreactor, estimating thereof.
8.3 kilograms of aluminium colloidal sols, 10.3 kilograms of kaolin are added in the entry and mix, stir, add 9.5 kilograms of pseudo-boehmites, wore out 2 hours, promptly make carrier pulp at 62 ℃.Get 3.6 kilograms of DASY zeolites respectively, 2.8 kilograms of ZRP zeolites (phosphorous 8 heavy %) add in the entry, mix with colloidal mill, promptly make zeolite slurry.Then carrier pulp is mixed with zeolite slurry, through homogeneous, spray drying forming, roasting promptly obtains catalyst sample A of the present invention.
152.8 kilograms of aluminium colloidal sols, 98 public Room kaolin are added in the entry and mix, add 64.3 kilograms of pseudo-boehmites, stir, promptly make carrier pulp.Get 58.4 kilograms of REDASY zeolites respectively and 34 kilograms of HZSM-5 zeolites add in the entry, mix, promptly make zeolite slurry with colloidal mill.Then carrier pulp is mixed with zeolite slurry,, promptly obtain catalyst sample B of the present invention through homogeneous, spray drying forming washing, drying.
[Comparative Examples 1] this Comparative Examples provide by the preparation of the described method of CN 1093101A, be the semi-synthetic carrier of binding agent, be matrix with the clay, be the cracking catalyst of active ingredient with aluminium colloidal sol with ZRP zeolite (phosphorous 8 heavy %): 16.7 public Room aluminium colloidal sols, 10.3 public Room kaolin are added in the entry and mix, mix, promptly make carrier pulp.Get 6.5 kilograms of ZRP zeolites (phosphorous 8 heavy %) and add in the entry, mix, promptly make zeolite slurry with colloidal mill.Carrier pulp is mixed with zeolite slurry, through homogeneous, spray drying forming.Promptly make comparative sample 1.
[Comparative Examples 2] replaces the ZRP zeolite with the HZSM-5 zeolite, and raw material consumption and preparation method according to Comparative Examples 1 make comparative sample 2.
The composition of above-mentioned four samples is listed in table 1.Evaluation result to above-mentioned sample on heavy oil microreactor is listed in the table 2.
From table 2 heavy oil micro anti-evaluation result as seen: under identical appreciation condition, catalyzer of the present invention is compared transformation efficiency height, C with single binding agent with the comparative catalyst who does not contain y-type zeolite
3 =～C
5 =Total olefin productive rate height, the overall yield height of iso-butylene and isopentene, gasoline output reaches more than the 42.7 heavy %, the performance of catalyzer of the present invention obviously is better than comparative sample 1 and 2.
Table 1
Table 2
| Catalyzer | A | B | Comparative sample 1 | Comparative sample 2 |
| Transformation efficiency, heavy % | 76.4 | 81.9 | 52.6 | 39.6 |
| The product productive rate, heavy % gas coke gasoline (C 5～221 ℃) diesel oil (222～343 ℃) heavy oil (＞343 ℃) | 31.4 230 42.7 16.7 6.9 | 32.6 2.49 46.8 13.1 5.0 | 35.4 1.50 15.7 16.7 30.7 | 20.5 1.20 17.9 22.7 37.7 |
| Olefins yield, heavy % C 3 ＝ C 4 ＝ C 5 ＝ C 3 ＝～C 5 ＝ | 11.43 12.66 10.85 34.94 | 10.97 13.08 9.74 33.79 | 14.09 12.15 3.49 29.63 | 7.88 8.96 5.03 21.87 |
| The isomeric olefine productive rate, heavy % iC 4 ＝ iC 5 ＝ iC 4 ＝+iC 5 ＝ | 4.60 7.30 11.90 | 4.42 6.42 10.84 | 4.87 2.33 7.20 | 3.64 3.41 7.05 |
Embodiment 3～6
Preparation of catalysts provided by the invention and the cracking performance of on heavy oil microreactor, estimating thereof.
6.9 kilograms of aluminium colloidal sols, 7.6 kilograms of kaolin are added in the entry and mix, stir, add 7.9 kilograms of pseudo-boehmites, mix, wore out 1.5 hours, promptly make carrier pulp at 65 ℃.Get 3.0 kilograms of DASY zeolites, 0.15 kilogram of HZSM-5 zeolite and 1.7 kilograms of ZRP zeolites respectively and add in the entry, mix, promptly make zeolite slurry with colloidal mill.Operate according to the step of embodiment 2 and to make catalyst sample C of the present invention.
Except that digestion time is 2 hours, according to above-mentioned preparation method, make catalyst sample D of the present invention with 125 kilograms of aluminium colloidal sols, 91.6 kilograms of kaolin, 52.6 kilograms of pseudo-boehmites and 28.7 kilograms of REDASY zeolites, 9.5 kilograms of REHY zeolites and 27.8 kilograms of HZSM-5 zeolites.
6.7 kilograms of aluminium colloidal sols and 8.5 kilograms of kaolin are added in the entry mix, add 8.9 kilograms of pseudo-boehmites, stir, promptly make carrier pulp.Get 1.9 kilograms of ZRP zeolites, 1.5 kilograms of HZSM-5 zeolites and 3.8 kilograms of REDASY zeolites respectively and add in the entry, mix, promptly make zeolite slurry with colloidal mill.Preparation method's operation by embodiment 1 makes catalyst sample E of the present invention.
9.3 kilograms of aluminium colloidal sols and 9.4 kilograms of kaolin are mixed, stir, add 11.7 kilograms of pseudo-boehmites, mix, wore out 2 hours, promptly make carrier pulp at 62 ℃.Get 1.2 kilograms of ZRP zeolites, 1.4 kilograms of HZSM-5 zeolites, 0.6 kilogram of REHY zeolite and 3.6 kilograms of REDASY zeolites respectively and add in the entry, mix, promptly make zeolite slurry with colloidal mill.Preparation method's operation according to embodiment 2 obtains catalyst sample F of the present invention.
[Comparative Examples 3] this Comparative Examples provides with aluminium colloidal sol and pseudo-boehmite and has been the semi-synthetic carrier of binding agent, is matrix with the clay, is the cracking catalyst of active ingredient with the zeolite: in zeolite component with 3.3 kilograms of REDASY zeolites replace 3.0 kilograms of DASY zeolites and wherein the consumption of ZRP zeolite become 1.5 kilograms, the preparation method according to catalyzer C among the embodiment 3 makes comparative sample 3 fully.
The composition of above-mentioned five kinds of samples is listed in table 3.Evaluation result to above-mentioned sample on heavy oil microreactor is listed in table 4.
From table 4 heavy oil micro anti-evaluation result as seen: under identical appreciation condition, the comparative sample 3 of catalyzer of the present invention and high ZRP zeolite content relatively, alkene of the two and isomeric olefine productive rate are all than higher, but the transformation efficiency of comparative sample 3 and gasoline output are lower, the gasoline output of catalyzer of the present invention can reach 41.5～48.5 heavy %, apparently higher than the gasoline output of comparative sample 3.
Table 3
Table 4
| Catalyzer | C | D | E | F | Comparative sample 3 |
| Transformation efficiency, heavy % | 78.9 | 81.5 | 85.4 | 81.5 | 74.9 |
| The product productive rate, heavy % gas coke gasoline (C 5～221 ℃) diesel oil (222～343 ℃) heavy oil (＞343 ℃) | 32.6 2.30 44.0 15.2 5.9 | 30.7 2.30 48.5 13.3 5.2 | 41.7 2.20 41.5 11.4 3.2 | 37.1 2.40 42.0 13.2 53 | 33.5 2.17 39.2 16.1 9.0 |
| Olefins yield, heavy % C 3 ＝ C 4 ＝ C 5 ＝ C 3 ＝～C 5 ＝ | 11.38 13.52 10.66 35.56 | 9.83 12.94 10.47 33.24 | 14.77 15.71 12.24 42.72 | 12.32 14.88 10.49 37.69 | 12.32 14.07 10.14 36.53 |
| The isomeric olefine productive rate, heavy % iC 4 ＝ iC 5 ＝ iC 4 ＝+iC 5 ＝ | 4.82 7.12 11.94 | 4.33 6.90 11.23 | 5.62 8.11 13.73 | 5.15 6.95 12.10 | 5.30 6.82 12.12 |
Embodiment 7
Preparation of catalysts provided by the invention and the cracking performance of on small-sized cyclic catalytic cracking device, estimating thereof.
3.5 kilograms of aluminium colloidal sols, 6.7 kilograms of kaolin are added in the entry and mix, stir, add 13.2 kilograms of pseudo-boehmites, mix, wore out 2 hours, promptly get carrier pulp at 62 ℃.Get 1.5 kilograms of DASY zeolites respectively and 3.1 kilograms of HZSM-5 zeolites add in the entry, mix, promptly make zeolite slurry with colloidal mill.Preparation method's operation according to embodiment 2 obtains catalyst sample G of the present invention then.
The composition of above-mentioned sample is listed in table 5.On small-sized cyclic catalytic cracking device, the evaluation result of above-mentioned sample is listed in table 6.
As seen from Table 6.Evaluation result and the above catalyst A～F of catalyzer G of the present invention on the ARCO device has same characteristics, the iso-butylene productive rate reaches 4.68～4.77 heavy %, the overall yield of iso-butylene and isopentene is up to 12.75～12.87 heavy %, gasoline output can also reach 42.28～4334 heavy %, RON reaches 96.1, and MON reaches 80.5.
Table 5
| The catalyzer project | G |
| Form, heavy % aluminium colloidal sol pseudo-boehmite kaolin zeolite is DASY HZSM-5 wherein | 5 30 35 30 33 67 |
Table 6
| Catalyzer | G | |
| Weight space velocity, h -1 | 10.0 | 18.0 |
| Transformation efficiency, heavy % | 79.85 | 75.94 |
| Material balance, heavy % dry gas liquid hydrocarbon gasoline (C 5～221 ℃) diesel oil (222～330 ℃) heavy oil (＞330 ℃) coke | 2.22 32.68 42.28 12.70 7.45 2.67 | 1.67 28.71 43.34 13.71 10.35 2.22 |
| The isomeric olefine productive rate, heavy % iC 4 ＝ iC 5 ＝ iC 4 ＝+iC 5 ＝ | 4.77 8.10 12.87 | 4.68 8.07 12.75 |
| Gasoline octane rating RON MON | 96.1 80.5 | 96.4 80.8 |
Embodiment 8
Preparation of catalysts provided by the invention and the cracking performance of on medium-sized riser arrangement, estimating thereof.
125.0 kilograms of aluminium colloidal sols, 91.6 kilograms of kaolin are added in the entry and mix, stir, add 52.6 kilograms of pseudo-boehmites, mix, wore out 1.5 hours, promptly make carrier pulp at 60 ℃.Get 27.9 kilograms of ZRP zeolites (phosphorous 2 heavy %) respectively, 38.2 kilograms of REDASY zeolites add in the entry, mix with colloidal mill, promptly make zeolite slurry.Preparation method's operation by embodiment 2 obtains catalyst sample H of the present invention then.
The composition of above-mentioned sample is listed in table 7.On medium-sized riser arrangement, adopt stock oil C that the evaluation result of above-mentioned sample is listed in table 8.
From table 8 as seen.Catalyst sample H of the present invention can make gasoline yield under 45.56% situation, makes the overall yield of iso-butylene and isopentene reach 12.88%.
Embodiment 9
Preparation of catalysts provided by the invention and the cracking performance of on medium-sized riser arrangement, estimating thereof.
131.9 kilograms of aluminium colloidal sols, 103.9 kilograms of kaolin are added in the entry and mix, stir, add 55.6 public Room pseudo-boehmites, mix, wore out 1 hour, promptly make carrier pulp at 65 ℃.Get 23.5 kilograms of HZSM-5 zeolites, 16.0 kilograms of REHY zeolites and 24.2 kilograms of REDASY zeolites respectively and add in the entry, mix, promptly make zeolite slurry with colloidal mill.Preparation method's operation according to embodiment 2 obtains catalyst sample I of the present invention then.
The composition of above-mentioned sample is listed in table 7.On medium-sized riser arrangement, adopt stock oil D that the evaluation result of above-mentioned sample is listed in table 8.
From table 8 as seen.When the content of vanadium among the stock oil D was 5.2ppm, the iso-butylene of catalyst I of the present invention and isopentene overall yield can reach 10.11 heavy %, C
5Gasoline output is up to 46.30 heavy %.
Table 7
Table 8
| Catalyzer | H | I | |
| Operational condition agent-oil ratio atomized water, heavy % recycle ratio stock oil | 8.0 15 0 C | 8.0 10.0 0.21 D | 7.8 14.6 0 D |
| Transformation efficiency, heavy % | 81.64 | 87.02 | 80.02 |
| Material balance, heavy % dry gas liquid hydrocarbon gasoline (C 5～221 ℃) loss of diesel oil (222～330 ℃) heavy oil (＞330 ℃) coke | 1.62 31.09 45.56 15.31 3.05 2.85 0.52 | 4.01 28.59 4630 12.98 0.00 7.70 0.42 | 2.77 28.26 43.21 14.84 5.14 5.43 0.36 |
| The isomeric olefine productive rate, heavy % iC 4 ＝ iC 5 ＝ iC 4 ＝+iC 5 ＝ | 5.84 7.04 12.88 | 4.53 5.58 10.11 | 5.12 5.62 10.74 |
| Gasoline octane rating RON MON | - - | 95.6 81.3 | - - |
Claims (10)
1. cracking catalyst that is used to produce isomeric olefine, it is characterized in that it is made up of the composite aluminum base binding agent of being made up of according to 1: 9 to 9: 1 weight ratio pseudo-boehmite and aluminium colloidal sol of (is benchmark by catalyst weight) 5～70%, 5～65% clay and 23～50% zeolite, said zeolite is that the phosphorus content of 15～82% y-type zeolite and surplus is (with P
2O
5Meter) is the mixture that contains rare-earth five-membered ring supersiliceous zeolite and/or HZSM-5 zeolite of 0～10 heavy %, when containing rare-earth five-membered ring supersiliceous zeolite and HZSM-5 zeolite and exist simultaneously, contains rare-earth five-membered ring supersiliceous zeolite content and be no more than 65%.
2. according to the described catalyzer of claim 1, it is characterized in that said clay be natural or synthetic, through or handle without various chemistry and/or physical method, usually as the various clays of cracking catalyst carrier.
3. according to the described catalyzer of claim 2, it is characterized in that said clay is kaolin, halloysite.
4. according to the described catalyzer of claim 1, it is characterized in that said y-type zeolite is that content of rare earth is (with RE
2O
3Meter) is y-type zeolite and/or the REHY zeolite of 0～5 heavy %, lattice constant＜2.455mm.
5. according to the described catalyzer of claim 4, it is characterized in that said content of rare earth is (with RE
2O
3Meter) be that the y-type zeolite of 0～5 heavy %, lattice constant＜2.455mm obtains through chemistry and/or physical method stabilization treatment, the type-Y high silicon zeolite that comprises the ultrastable Y that obtains with hydrothermal method, obtains with liquid phase method or vapor phase process aluminium-eliminating and silicon-replenishing.
6. according to the described catalyzer of claim 4, the content of rare earth that it is characterized in that said REHY zeolite is (with RE
2O
3Meter) is 2～16 heavy %.
7. according to the described catalyzer of claim 1, it is characterized in that said phosphorated contains the rare-earth five-membered ring supersiliceous zeolite and handles with aluminum phosphate and contain the rare-earth five-membered ring supersiliceous zeolite and make.
8. according to claim 1 or 7 described catalyzer, it is characterized in that the said rare-earth five-membered ring supersiliceous zeolite that contains is raw material, is crystal seed, made in 12～60 hours at 130～200 ℃ of following crystallizations with REY or REHY zeolite with water glass, aluminum phosphate, mineral acid.
9. according to the described catalyzer of claim 7, it is characterized in that said to handle the method that contains the rare-earth five-membered ring supersiliceous zeolite with aluminum phosphate as follows: zeolite is exchanged to handle with ammonium ion in advance make its sodium content (with Na
2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al
2O
3: P
2O
5=1: 1～3 aluminum phosphate colloid is according to P
2O
5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and have roasting down 5～6 hours in 300～600 ℃, 10～100% water vapors.
10. the described catalyzer of claim 1 is used to comprise that the catalytic cracking petroleum hydrocarbons of wax oil, residual oil and high content of vanadium stock oil produces low-carbon (LC) isomeric olefine and stop bracket gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100782A CN1055301C (en) | 1996-02-08 | 1996-02-08 | Cracking catalyst for producing isomeric olefine and gasoline with high yield |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100782A CN1055301C (en) | 1996-02-08 | 1996-02-08 | Cracking catalyst for producing isomeric olefine and gasoline with high yield |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1143666A CN1143666A (en) | 1997-02-26 |
| CN1055301C true CN1055301C (en) | 2000-08-09 |
Family
ID=5116736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100782A Expired - Lifetime CN1055301C (en) | 1996-02-08 | 1996-02-08 | Cracking catalyst for producing isomeric olefine and gasoline with high yield |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1055301C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134172B (en) | 2006-08-31 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons conversion catalyzer |
| CN101134913B (en) | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| CN101829592B (en) * | 2009-03-10 | 2012-07-18 | 中国石油天然气股份有限公司 | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content |
| CN105728028A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst for highly-producing olefin isomer and high-octane gasoline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093101A (en) * | 1993-03-29 | 1994-10-05 | 中国石油化工总公司 | Produce the catalyst for cracking of low-carbon alkene |
| US5358918A (en) * | 1992-10-22 | 1994-10-25 | China Petro-Chemical Corporation | Hydrocarbon conversion catalyst for producing high quality gasoline and C3 and C4 olefins |
| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1102431A (en) * | 1993-11-05 | 1995-05-10 | 中国石油化工总公司 | Catalytic conversion method of low-carbon olefines high-output |
-
1996
- 1996-02-08 CN CN96100782A patent/CN1055301C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358918A (en) * | 1992-10-22 | 1994-10-25 | China Petro-Chemical Corporation | Hydrocarbon conversion catalyst for producing high quality gasoline and C3 and C4 olefins |
| CN1093101A (en) * | 1993-03-29 | 1994-10-05 | 中国石油化工总公司 | Produce the catalyst for cracking of low-carbon alkene |
| CN1098130A (en) * | 1993-07-29 | 1995-02-01 | 中国石油化工总公司 | A kind of cracking catalyst and preparation method thereof |
| CN1102431A (en) * | 1993-11-05 | 1995-05-10 | 中国石油化工总公司 | Catalytic conversion method of low-carbon olefines high-output |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1143666A (en) | 1997-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1069682C (en) | Layer-column clay catalyst for heavy-oil catalytic thermal cracking and its preparation | |
| CN1031646C (en) | Method for catalytic conversion of hydrocarbons | |
| CN1034223C (en) | Cracking catalyst for processing low-carbon olefines | |
| CN101210187B (en) | Preparing method of catalyst for cracking heavy oil | |
| CN1043520A (en) | A kind of catalyst for cracking of producing low-carbon alkene | |
| CN1055301C (en) | Cracking catalyst for producing isomeric olefine and gasoline with high yield | |
| CN1124892C (en) | Catalytic cracking catalyst for producing gaosline richly-containing paraffinic hydrocarbon, propylene and isobutane | |
| CN1036320C (en) | Cracking catalyst for producing isobutene and isopentene | |
| CN1727445A (en) | Cracking catalyst for hydrocarbon and preparation method | |
| CN1055105C (en) | Cracking catalyst for high yield of isobutene and isopentene | |
| CN1814705A (en) | Heavy-oil catalytic-cracking catalyst and preparing method | |
| CN1088407C (en) | Zeolite containing phosphorus and its preparing process | |
| CN1048428C (en) | Multi-zeolite catalyzer for preparation of low-carbon olefines | |
| CN1072201A (en) | Produce the hydrocarbon conversion catalyst of premium-type gasoline and alkene | |
| CN1053918C (en) | Double zeolite catalyst for prepn. of low carbon olefine | |
| CN1880410A (en) | Process for preparing catalytic cracking catalyst | |
| CN1814707A (en) | Cracking catalyst for preparing high-quality gasoline, and preparing method | |
| CN1056869C (en) | Olefinpoducing-modified layered clay catalyst and its production and use | |
| CN1157259C (en) | Catalytic cracking catalyst for producing gasoline richly-containing paraffinic hydrocarbon | |
| CN1239261C (en) | Fluoride zeolite composition and preparing method thereof | |
| CN100338186C (en) | Petroleum hydrocarbon cracking catalyst | |
| CN1872956A (en) | Catalyst for cracking petroleum hydrocarbons, and preparation | |
| CN1727444A (en) | Cracking catalyst for hydrocarbon and preparation method | |
| CN1749362A (en) | Catalytic cracking aid and its preparing method | |
| CN1743420A (en) | Catalytic cracking adjuvant and its preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20000809 |
|
| EXPY | Termination of patent right or utility model |